PREPARATION OF FIXING AGENTS FOR ANIONIC...

PPRREEPPAARRAATTIIOONN OOFF FFIIXXIINNGG AAGGEENNTTSS FFOORR

AANNIIOONNIICC DDYYEESS

A THESIS SUBMITTED TO

THE DIVISION OF SCIENCE AND TECHNOLOGY

OF

THE UNIVERSITY OF EDUCATION LAHORE

BY

SAIMA SHARIF

ROLL NO. 03-138

REGISTRATION NO. 0499056

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE

DEGREE OF DOCTOR OF PHILOSOPHY

IN CHEMISTRY

JUNE 2007

AAPPPPRROOVVAALL OOFF TTHHEE DDIIVVIISSIIOONN OOFF SSCCIIEENNCCEE AANNDD

TTEECCHHNNOOLLOOGGYY// UUNNIIVVEERRSSIITTYY OOFF EEDDUUCCAATTIIOONN,, LLAAHHOORREE

--------------------------------------

Director

I certify that this thesis satisfies all the requirements as a thesis for the award of

the degree of Doctor of Philosophy.

--------------------------------------

Head of Department

This is to certify that we have read this thesis and that in our opinion it is fully

adequate, in scope and quality, as a thesis for the degree of Doctor of

Philosophy.

------------------------------------------------ -------------------------------------

Dr. Mian Muhammad Izhar-ul-Haq Dr. Saeed Ahmad

(Co-Supervisor) (Supervisor)

iii

The selection of dyes and dyeing auxiliaries is a crucial factor in

optimising dyeing processes. Dyeings often show unsatisfactory wet fastness

properties. This is usually encountered with direct dyes and to a lesser extent

with reactive dyes also. Different cationic fixing agents have been used as

pretreatment or aftertreatment to improve the wet fastness properties of these

dyes but none has proved to be totally satisfactory. Therefore, there is still a

need for novel dyeing processes that improve properties in respect of

application and fastness properties of the dyeings.

The present work is therefore concerned with the synthesis of new

cationic fixing agents and their evaluation as fixing agents in improving the wet

fastness properties of anionic dyes on cellulose fibres. Eight mono-reactive

(28a-d and 29a-d) and four bis-reactive (30a-b and 31a-b) 2,3-epoxy / 3-

chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride have

been synthesised and their structures have been characterised using IR and 1H-

NMR spectroscopy. Purity of these compounds has been checked by thin layer

chromatography (TLC).

One mono-reactive (28c) and two bis-reactive (30a and 30b) 2,3-

epoxypropyl derivatives have been used for the cationisation of cellulosic

AABBSSTTRRAACCTT

iv

fabrics under different pretreatment conditions. Pretreated fabrics were then

dyed with a variety of direct, reactive and acid dyes under neutral and alkaline

conditions in the absence of salt. A bis-reactive derivative compound 30b was

also applied as an aftertreatment to the conventional direct dyeings under

neutral and alkaline conditions. The reflectance values and the corresponding

CIE L*, a*, b*, C* and ho colour coordinates of the samples were measured.

From the reflectance values at the λ max. of the dyeings, colour strength (K/S)

values of the dyeings were calculated using Kubelka-Munk equation. Fastness

properties of the dyeings have been determined by following standard methods

for the determination of colour fastness of textiles and leather.

Pretreatment with mono- and bis-reactive cationic fixing agents (30a,

30b, 28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive

and acid) dyes under neutral conditions in the absence of salt. Higher colour

strength (K/S) and good wash fastness properties were obtained with the

pretreated fabrics as compared to the untreated fabrics dyed with the same

direct and reactive dyes. Bis-reactive derivatives showed better wet fastness

properties as compared to the mono-reactive derivative. In addition,

pretreatment has significantly reduced the dyeing time, thus becoming a more

environmentally friendly method for the direct and reactive dyeing of cotton

fabrics. Aftertreatment with cationic agents has shown a slight change in the

colour of the direct dyeings but has beneficial effects on the wash fastness

results.

v

Dedicated to

My Beloved Parents

Whose prayers and affections are the source of strength for me in every step of

life and a sign of success for my bright future.

DDEEDDIICCAATTIIOONN

vi

I would like to express deep appreciation to my supervisor Prof. Dr.

Saeed Ahmad, Chairman, Department of Chemistry, University of Science and

Technology, Bannu for his inspiring guidance, encouraging attitude and

valuable suggestions throughout my research work.

I also express sincere appreciation to my co-supervisor Prof. Dr. Mian

Muhammad Izhar-ul-Haq, Principal, University of Education, Township

Campus, Lahore for his guidance and suggestions throughout the research

work.

I would like to thank Muhammad Fauz-ul-Azeem and Mr. Hamood–ur-

Rehman, Scientific Officers, PCSIR Laboratories complex, Lahore for

providing instrumental facilities. Thanks to Muhammad Naeem Khan and Mr.

Farooq Arif for their cooperation.

Thanks to Mr. Islam, Mr. Muhammad Iqbal, other laboratory staff and

the library staff (PCSIR, Lahore) for their cooperation during my research

work. I also acknowledge the cooperation of Sandal Dyestuff Industries

Limited, Pakistan for providing dyes.

Special thanks to my uncle and Dr. Shahina Waheed, Head (Retd.)

/ACRC PCSIR Laboratories Complex, Lahore.

AACCKKNNOOWWLLEEDDGGEEMMEENNTT

vii

Page

ABSTRACT -----------------------------------------------------------------------------iii

DEDICATION ---------------------------------------------------------------------------v

ACKNOWLEDGEMENT -------------------------------------------------------------vi

TABLE OF CONTENTS -------------------------------------------------------------vii

LIST OF TABLES --------------------------------------------------------------------xiv

LIST OF FIGURES -------------------------------------------------------------------xix

LIST OF SYMBOLS / ABBREVIATIONS -------------------------------------xxiii

CHAPTER

1. INTRODUCTION ------------------------------------------------------------------1

1.1 Dyes and dyeing -----------------------------------------------------------------1

1.2 Classification of dyes -----------------------------------------------------------2

1.3 Anionic dyes ---------------------------------------------------------------------3

1.3.1 Direct dyes ---------------------------------------------------------------3

1.3.2 Reactive dyes ------------------------------------------------------------4

1.3.3 Acid dyes ---------------------------------------------------------------- 5

1.4 The need for auxiliaries -------------------------------------------------------- 5

TTAABBLLEE OOFF CCOONNTTEENNTTSS

viii

1.5 Classification of auxiliaries ----------------------------------------------------6

1.5.1 Classification of surfactants -------------------------------------------7

1.6 Pretreatments and aftertreatments for anionic dyes ------------------------8

1.6.1 Cationic fixing agents --------------------------------------------------9

1.6.1.1 Quaternary ammonium salts ---------------------------------11

1.7 Problems encountered with the fixing agents ------------------------------14

1.8 Plan of work --------------------------------------------------------------------14

2. LITERATURE REVIEW ------------------------------------------------------- 17

2.1 General development ----------------------------------------------------------18

2.2 Monomeric quaternary ammonium salts ----------------------------------- 23

2.2.1 Azetidinium chloride ------------------------------------------------- 25

2.2.2 Epoxy and halohydroxy propyl derivatives ------------------------27

2.2.3 Mono- and bis- reactive haloheterocyclic derivatives ------------34

2.3 Polymeric quaternary ammonium salts -------------------------------------38

3. EXPERIMENTAL WORK -----------------------------------------------------49

3.1 General information -----------------------------------------------------------50

3.2 Synthesis of mono- and bis-reactive 2,3-epoxy / 3-chloro-2-

hydroxy propyl derivatives of quaternary ammonium chloride ---------52

3.2.1 General procedure for the synthesis of mono- and bis-reactive

2,3-epoxypropyl derivatives (28a-d and 30a-b) -------------------55

N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethyl

ammonium chloride (28a) --------------------------------------------55

ix

N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethyl

ammonium chloride (28b) --------------------------------------------56

N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethyl

ammonium chloride (28c) --------------------------------------------57

N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethyl

ammonium chloride (28d) --------------------------------------------57

Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethyl

ammonium chloride] (30a) -------------------------------------------58

Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethyl

ammonium chloride] (30b) -------------------------------------------59

3.2.2 General procedure for the synthesis of mono- and bis-reactive

3-chloro-2-hydroxypropyl derivatives (29a-d and 31a-b) -------59

N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,N-

dimethylammonium chloride (29a) ---------------------------------60

N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,N-

dimethylammonium chloride (29b) ---------------------------------61

N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,N-

dimethylammonium chloride (29c) ---------------------------------62

N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,N-

dimethylammonium chloride (29d) ---------------------------------62

Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-

diethylammonium chloride] (31a) ----------------------------------63

x

Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-

dimethylammonium chloride] (31b) --------------------------------64

3.3 Applications --------------------------------------------------------------------64

3.3.1 Application of cationic fixing agents as pretreatment ------------65

3.3.1.1 Pretreatment of cotton fabrics -------------------------------65

3.3.2 Dyeing conditions for untreated cotton fabrics --------------------66

3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by

conventional method -----------------------------------------66

3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes

by conventional method --------------------------------------66

3.3.2.3 Dyeing of wool fabrics with acid dyes ---------------------67

3.3.3 Dyeing conditions for pretreated cotton fabrics -------------------67

3.3.3.1 Dyeing of pretreated cotton fabrics with direct dyes -----67

3.3.3.2 Dyeing of pretreated cotton fabrics with reactive dyes --68

3.3.3.3 Dyeing of untreated and pretreated cotton fabrics with

acid dyes --------------------------------------------------------69

3.3.4 Application of cationic fixing agents as an aftertreatment -------70

3.3.4.1 Dyeing with direct dyes --------------------------------------70

3.3.4.2 Aftertreatment with cationic fixing agent (30b) ----------71

3.4 Colour measurement ----------------------------------------------------------71

3.5 Fastness testing ----------------------------------------------------------------72

3.5.1 Wash fastness ----------------------------------------------------------72

xi

3.5.1.1 Test procedure -------------------------------------------------73

3.5.2 Light fastness ----------------------------------------------------------73

4. RESULTS AND DISCUSSION ------------------------------------------------74

4.1 Synthesis of mono- and bis-reactive 2,3-epoxy and 3-chloro-2-

hydroxy propyl derivatives ---------------------------------------------------75

4.2 Applications --------------------------------------------------------------------77

4.2.1 Pretreatment with cationic fixing agents ---------------------------78

4.2.1.1 Effect of temperature and time on the cationisation of

cotton fabrics --------------------------------------------------78

4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide

(ow cationic agent) concentrations on the cationisation

of cotton fabrics -----------------------------------------------81

4.2.2 Dyeing of untreated and pretreated cotton fabrics with

direct dyes --------------------------------------------------------------84

4.2.2.1 Effect of dyeing temperature --------------------------------84

4.2.2.2 Effect of dyeing time -----------------------------------------87

4.2.2.3 Effect of dye concentration ----------------------------------89

4.2.2.4 Effect of cationic agent concentration ----------------------91

Shades of direct dyes on untreated (C) and pretreated

(C-1, C-2 and C-3; 2% owf) cotton fabrics ----------------97


reactive dyes -----------------------------------------------------------99

xii

4.2.3.1 Effect of dyeing temperature --------------------------------99

4.2.3.2 Effect of dyeing time ----------------------------------------102

4.2.3.3 Effect of dye concentration --------------------------------104

4.2.3.4 Effect of cationic agent concentration --------------------106

4.2.3.5 Effect of alkali (anhydrous Na2CO3) ----------------------108

Shades of reactive dyes on untreated (C) and

pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics -114


acid dyes --------------------------------------------------------------117

Shades of acid dyes on wool, untreated (C) and pretreated

(C-1, C-2 and C-3; 2% owf) cotton fabrics -----------------------121

4.2.5 Aftertreatment of direct dyes with a bis-reactive cationic

fixing agent -----------------------------------------------------------122

4.2.5.1 Effect of pH on the aftertreatment of direct dyeings ----122

4.2.5.2 Effect of cationic agent concentration on the

aftertreatment of direct dyeings ---------------------------126

Shade change of direct dyeings by aftertreatment

with a bis-reactive derivative (30b) -----------------------127

5. CONCLUSIONS -----------------------------------------------------------------128

REFERENCES ----------------------------------------------------------------------132

VITA -----------------------------------------------------------------------------------144

xiii

Appendix A

Colour strength (K/S) curves of untreated (C) and pretreated (C-1,

C-2 and C-3) cotton fabrics dyed with direct dyes (Table 25) ---------146

Appendix B

Colour strength (K/S) curves of untreated cotton fabrics dyed with

direct dyes by conventional method (Table 26) --------------------------150

Appendix C


C-2 and C-3) cotton fabrics dyed with reactive dyes in the absence

of salt and alkali (Table 32) -------------------------------------------------152

Appendix D


C-2 and C-3) cotton fabrics dyed with reactive dyes in the presence

of alkali (Table 33) -----------------------------------------------------------157

Appendix E

Colour strength (K/S) curves of untreated cotton fabrics dyed

with reactive dyes by conventional method (Table 34) -----------------161

Appendix F

Colour strength (K/S) curves of wool, untreated (C) and pretreated

(C-1, C-2 and C-3) cotton fabrics dyed with acid dyes -----------------163

Appendix G

Publications----------------------------------------------------165

xiv

Page

Table 1 General classification of surfactants ---------------------------------8

Table 2 Properties of acid dyes with cationic cotton using no salt

at pH 7 ------------------------------------------------------------------26

Table 3 Fastness properties of direct, reactive and acid dyes with

nylon, conventional cotton and cationised cotton ----------------30

Table 4 Fastness properties of acid dye on cotton cationised with

different quaternary salts ---------------------------------------------31

Table 5 Fastness properties of direct dyes on untreated and treated

cotton fabrics -----------------------------------------------------------34

Table 6 Fastness properties of direct dyes on untreated (C) and

pretreated cotton fabrics with mono (C-1) and bis-reactive

(C-2) cationic agents --------------------------------------------------37

Table 7 Fastness properties of direct dyes on untreated and treated

(poly epichlorohydrin-dimethylamine) cotton ---------------------41

Table 8 Colour strength and fastness properties of 1:2 metal complex

acid dyes on untreated and pretreated cotton (PT) ----------------43

LLIISSTT OOFF TTAABBLLEESS

xv

Table 9 Fastness properties of acid dyes on cotton -------------------------45

Table 10 Fastness properties of direct dyes on cotton aftertreated with

cationic fixing agents / syntan ---------------------------------------46

Table 11 Fastness properties of direct dyeings aftertreated with

Fixogene CXF and Matexil FC-ER under neutral and

alkaline conditions ----------------------------------------------------47

Table 12 Pretreatment conditions ----------------------------------------------65

Table 13 Dyeing conditions with direct dyes ---------------------------------68

Table 14 Dyeing conditions with reactive dyes ------------------------------69

Table 15 Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b

and 31a-b ---------------------------------------------------------------76

Table 16 λ max. values of the dyes ---------------------------------------------77

Table 17 Effect of temperature on the chlorine content of

cationised fabric -------------------------------------------------------79

Table 18 Effect of pretreatment time on the chlorine content of

cationised fabric ------------------------------------------------------80

Table 19 Effect of cationic agent concentration on the chlorine

content of cationised fabric ------------------------------------------81

Table 20 Effect of NaOH concentration on the chlorine


Table 21 % Reflectance (at λ max. 510 nm) and the colour strength

(K/S) values of untreated (C) and pretreated (C-1, C-2 and

xvi

C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange

26 (2% owf) under different temperature conditions -------------85



C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26

(2% owf) at 100 oC for different time periods ---------------------88



C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26

at 100 oC for 30 minutes using different dye concentrations ----90


(K/S) values of cotton fabrics pretreated with different conc.

of cationic agents (C-1, C-2 and C-3) and dyed with C.I.

Direct Orange 26 (2% owf) at 100 oC for 30 minutes ------------92

Table 25 Colour strength (K/S) and fastness properties of direct dyes

(2% owf) on untreated (C) and pretreated (C-1, C-2 and

C-3; 2% owf) cotton fabrics -----------------------------------------94

Table 26 Colour strength (K/S) and fastness properties of untreated

cotton fabrics dyed with direct dyes (2% owf) by

conventional method --------------------------------------------------96



xvii

C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange

13 (2% owf) at different temperature conditions ----------------100



C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange

13 (2% owf) at 80 oC for different time periods -----------------103



C-3; 2% owf) cotton fabrics dyed with different conc. of C.I.

Reactive Orange 13 at 80 oC for 30 minutes -------------------105


(K/S) values of cotton fabrics pretreated with different conc.

of cationic agents (C-1, C-2 and C-3) and dyed with C.I.

Reactive Orange 13 (2% owf) at 80 oC for 30 minutes ---------107


(K/S) values of pretreated cotton fabrics (C-1, C-2 and C-3;

2% owf) dyed with C.I. Reactive Orange 13 (2% owf) at 80

oC for 30 minutes using different amounts of alkali ------------109

Table 32 Colour strength (K/S) and fastness properties of reactive dyes

(2% owf) on untreated (C) and pretreated (C-1, C-2 and C-3;

2% owf) cotton fabrics in the absence of salt and alkali --------111

Table 33 Colour strength (K/S) and fastness properties of reactive

xviii

dyes (2% owf) on pretreated (C-1, C-2 and C-3; 2% owf)

cotton fabrics in the presence of alkali (anhydrous Na2CO3;

20g/L) -----------------------------------------------------------------112

Table 34 Colour strength (K/S) and fastness properties of reactive

dyes (2% owf) on untreated cotton fabrics dyed by

conventional method ------------------------------------------------113



C-3; 2% owf) cotton fabrics dyed with different concentrations

of C.I. Acid Yellow 23 at 100 oC for 60 minutes ----------------118

Table 36 Colour strength and wash fastness properties of acid dyes on

wool, untreated (C) and pretreated (C-1, C-2 and C-3;

2% owf) cotton fabrics ----------------------------------------------120

Table 37 Colorimetric data for untreated and aftertreated direct

dyeings before wash fastness testing ------------------------------123

Table 38 Wash fastness data for untreated and aftertreated direct

dyeings ----------------------------------------------------------------124

Table 39 Colorimetric data for untreated and aftertreated direct

dyeings after wash fastness testing --------------------------------125

xix

Page

Figure 1 Classification of auxiliaries --------------------------------------------7

Figure 2 Fixing agents showing various degrees of functionality ---------10

Figure 3 Modes of reaction of the various fixing agents --------------------11

Figure 4 General scheme for the synthesis of bis-reactive 2,3-epoxy /

3-chloro-2-hydroxy propyl derivatives of quaternary

ammonium chloride ---------------------------------------------------15

Figure 5 General scheme for the synthesis of mono-reactive 2,3-epoxy /

3-chloro-2-hydroxy propyl derivatives of quaternary

ammonium chloride ---------------------------------------------------16

Figure 6 Modification of cotton with N-methylolacrylamide --------------24

Figure 7 Reaction of epoxypropyl derivatives with cellulose --------------27

Figure 8 Reaction of halohydroxy propyl derivatives with cellulose -----28

Figure 9 Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy

propyl derivatives of quaternary ammonium chloride -----------53

Figure 10 Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy

propyl derivatives of quaternary ammonium chloride -----------54

LLIISSTT OOFF FFIIGGUURREESS

xx

Figure 11 Dyeing profile of untreated cotton fabric with direct dyes ------66

Figure 12 Dyeing profile of untreated cotton fabric with reactive dyes ----67

Figure 13 Dyeing profile of untreated and pretreated cotton fabrics with

acid dyes ----------------------------------------------------------------70

Figure 14 Aftertreatment of direct dyed cotton fabrics with cationic

fixing agent (30b) -----------------------------------------------------71

Figure 15 Effect of temperature on the chlorine content of cationised

fabric --------------------------------------------------------------------79

Figure 16 Effect of pretreatment time on the chlorine content of


Figure 17 Effect of cationic agent concentration on the chlorine


Figure 18 Effect of NaOH concentration on the chlorine content of


Figure 19 Effect of temperature on the colour strength (K/S) of

untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)

cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) -------86

Figure 20 Effect of dyeing time on the colour strength (K/S) of


cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) ------89

Figure 21 Effect of dye conc. on the colour strength (K/S) of untreated

(C) and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics

xxi

dyed with C.I. Direct Orange 26 ------------------------------------91

Figure 22 Effect of cationic agent concentration on the colour strength

(K/S) of pretreated cotton fabrics (C-1, C-2 and C-3) dyed

with C.I. Direct Orange 26 (2% owf) -------------------------------93

Figure 23 Colour strength (K/S) values of untreated (C) and pretreated

(C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I.

Direct Orange 26 ------------------------------------------------------95

Figure 24 Effect of temperature on the colour strength (K/S) values of


cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --101

Figure 25 Effect of dyeing time on the colour strength (K/S) of


cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --104

Figure 26 Effect of dye conc. on the colour strength (K/S) of


cotton fabrics dyed with C.I. Reactive Orange 13 ---------------106

Figure 27 Effect of cationic agent concentration on the colour

strength (K/S) of pretreated (C-1, C-2 and C-3) cotton

fabrics dyed with C.I. Reactive Orange 13 (2% owf) -----------108

xxii

Figure 28 Effect of alkali conc. on the colour strength (K/S) of

pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed

with C.I. Reactive Orange 13 (2% owf) --------------------------110

Figure 29 Effect of dye conc. on the colour strength (K/S) of untreated

(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton

fabrics dyed with C.I. Acid Yellow 23 ---------------------------119

xxiii

AATCC Review American Association of Textile Chemists and

Colorists Review

Adv. Color. Sci. Tech. Advances in Colour Science and Technology

Am. Dyestuff Rep. American Dyestuff Reporter

C Untreated cotton fabric

C-1 Cotton pretreated with compound 30a

C-2 Cotton pretreated with compound 30b

C-3 Cotton pretreated with compound 28c

Chem. Abs. Chemical Abstract

Color. Technol. Coloration Technology

Conc. Concentration

Conf. Conference

Dyeings dyed textile fibres

J.A.O.C.S. Journal of the American Oil Chemists' Society

J.S.D.C. Journal of the Society of Dyers and Colourists

K/S Colour strength

LLIISSTT OOFF SSYYMMBBOOLLSS //

AABBBBRREEVVIIAATTIIOONNSS

xxiv

owf of weight of fibre

Rev. Prog. Color. Review of Progress in Coloration

SAWTRI. South African Wool Textile Research Institute,

Tech. Rep. Technical Report

Temp. Temperature

Text. Chem. Colorist Textile Chemist and Colorist

Text. Res. J. Textile Research Journal

λ max. Absorbance at the wavelength of maximum

absorption

IINNTTRROODDUUCCTTIIOONN

1

Chapter 1

IINNTTRROODDUUCCTTIIOONN

1.1 DYES AND DYEING

Dyes are intensely coloured substances used for the coloration of

various substrates including paper, leather, fur, hair, foods, drugs, plastics and

textile materials. They are retained in these substrates by physical adsorption,

salt or metal complex formation or by the formation of covalent chemical

bonds [1].

Until the middle of nineteenth century all dyes were natural products,

extracted in most cases from a variety of plants, but also from a few animal

sources. Plant sources include roots, stems, leaves, flowers and fruits while

animal sources include certain dried insects. At present practically all dyes are

coloured organic chemicals synthesised from products of the petro-chemical

and coal-tar industries [2].

2

Dyeing is a process of colouring textile fibres and other materials so that

colouring matter becomes an integral part of the material rather than a surface

coating. The mechanism of dyeing must differ with the nature of the material,

that is, whether it is protein, cellulose or some synthetic substance [3]. The

appropriate dye class for the fibre must be used along with specific dyeing

conditions in order to gain an optimum result [4].

1.2 CLASSIFICATION OF DYES

Dyes are usually classified in two ways [5]:

1. According to the chemical constitution of the dye molecules e.g. azo

dyes, triphenylmethane dyes, stilbene dyes, anthraquinoid dyes etc. or

2. According to the method of application of the dye e.g. direct dyes, acid

dyes, reactive dyes, disperse dyes, vat dyes, sulphur dyes, mordant

dyes, metal complex dyes, basic dyes and azoic dyes.

Dyes are organic molecules and can also be classified as [5]:

1. Anionic dyes-------- in which the colour is caused by the anionic part of

the dye molecule e.g. direct, reactive and acid dyes

2. Cationic dyes------- in which the colour is caused by the cationic part of

the dye molecule e.g. basic dyes

3. Non-ionic dyes----- in which the colour is caused by the whole dye

molecule e.g. disperse dyes

3

1.3 ANIONIC DYES

Textile fibres may be dyed with anionic dyes including direct dyes, acid

dyes and reactive dyes or with cationic dyes. The term anionic dyes is intended

to mean dyes in which coloured ion is anionic in character containing sulphonic

or carboxylic groups. These dyes have long been known for the dyeing of

natural fibres such as wool and cotton as acid and direct dyes [6]. Amongst

anionic dyes, direct and reactive dyes are the most popular dye classes used for

the dyeing of cellulosic fibres which comprise over 40% of world textile

consumption.

1.3.1 DIRECT DYES

All direct dyes are substantive to cellulosic fibres. Substantivity means

the affinity of the dye with the fibre to which it is applied. The substantivity of

direct dyes for cotton is due to the linear and planar structure of the dye

molecules, which enables close alignment with chains of cellulose molecules

resulting in significant hydrogen bonding. However, the wet fastness properties

of direct dyes are inadequate for many end uses and these dyes have been

replaced to a great extent by reactive dyes which have better wet fastness and

exceptional brightness in many hues but the prime advantages of direct dyes

are ease of application, wide range of shade and economy compared with dyes

of higher fastness (reactive, sulphur or vat) [7]. There are still many

applications in the textile industry for goods dyed with direct dyes, particularly

4

where a high standard of wet fastness is not required. The development of

specialised crosslinking aftertreating agents for use with selected direct dyes of

high light fastness has enabled direct dyes to compete more effectively with

reactive dyes in meeting severe wet fastness requirements. In fact, direct dyes

are second only to sulphur dyes in their textile usage worldwide with vat and

fibre reactive dyes well behind [8].

1.3.2 REACTIVE DYES

Reactive dyes are regarded as being substantive as well as reactive to the

textile fibres. These dyes are also widely used for the dyeing of cellulosic fibres

because of their wide shade range and excellent wet fastness which arises from

a covalent bond formed between dye and the fibre. However, reactive dyeing

process requires high salt and alkali concentrations, even then the dyeing

process results in strongly coloured effluents. The fundamental problem of

reactive dyeing is that the reaction of reactive dye with water (hydrolysis)

competes with the formation of the desired covalent bond between the dye and

textile substrates (fixation reaction) and up to 40% of the reactive dye may

hydrolyse in the dyeing process. As this hydrolysed dye cannot react with the

fibre it should be washed off thoroughly in order to achieve the desired

superior wet fastness of the reactive dyeing. This involves expensive washing

off procedures and the treatment of the effluents. Thus, reactive dyes have both

economic and environmental drawbacks [9,10].

5

1.3.3 ACID DYES

Acid dyes, which are primarily used for the dyeing of nitrogenous fibres

such as wool, silk and nylon, are also anionic in nature. The relatively non-

linear structure of these acid dyes does not facilitate close alignment with the

molecular chains in cellulose, which in turn prevents hydrogen bonding.

Therefore, these dyes are not substantive to cellulosic fibres. However,

cationised cellulosic fibres can be dyed with acid dyes of both the non-

metallised and pre-metallised types. This increase in substantivity is due to the

interaction of anionic sulphonic groups in the dye molecules with the cationic

groups in the modified cellulose [11].

Generally, the dyed cellulosic fibres have a fastness to washing that does

not meet the requirements of today's consumers. This is particularly the case

not only for many direct dyes but to a lesser extent for reactive dyes also [12].

1.4 THE NEED FOR AUXILIARIES

The practice of dyeing has recently led to increased requirements in

terms of quality of dyeings and profitability of the dyeing process. There is

hardly a dyeing or printing process of commercial importance that can be

adequately operated by the use of dyes and water alone. Practically every

colorant–substrate system requires the use of additional products known as

auxiliaries.

An auxiliary has been defined [13] as:

6

"A chemical or formulated chemical product which enables a processing

operation in preparation, dyeing, printing or finishing to be carried out more

effectively or which is essential if a given effect is to be obtained."

The selection of dyes and dyeing auxiliaries is a crucial factor in

optimising dyeing processes. Different auxiliaries improve the application

characteristics and performance in terms of penetration, levelling, fixation and

shade deepening to provide brilliant intense dyeings.

The class of auxiliaries which is used to improve the retention of dye by

the fibre is traditionally called fixing agents. These chemicals function by

forming a dye-fixing agent complex of large molecular size and reduced

aqueous solubility and therefore higher wet fastness [14].

1.5 CLASSIFICATION OF AUXILIARIES

It is much harder to device a classification system for auxiliaries than it

is for dyes. The broadest classification of auxiliaries is achieved simply by

dividing them into non-surfactants and surfactants. Non-surfactants include

simple electrolytes, acids and bases, both inorganic and organic whereas

surfactants are defined [13] as:

"An agent, soluble or dispersible in a liquid, which reduces the surface

tension of the liquid"

7

Figure 1 Classification of auxiliaries

1.5.1 CLASSIFICATION OF SURFACTANTS

Surfactants owe their properties to their molecular structure, which

contains both hydrophobic and hydrophilic parts. The surfactants used as

textile auxiliaries can be divided into four major groups (Table 1) depending

on the type and distribution of the polar forces [15].

Auxiliaries

Non-surfactants Surfactants

Simple electrolytes

Acids and bases, both inorganic and organic

Anionic surfactants

Non-ionic surfactants

Amphoteric surfactants

Cationic surfactants

8

Table 1 General classification of surfactants

Class of surfactant Degree of ionic charge on the

_____________________________________________

hydrophobe hydrophile (associated ion)

Anionic surfactants Weakly negative Strongly positive

Cationic surfactants Weakly positive Strongly negative

Non-ionic surfactants Uncharged Uncharged

Amphoteric surfactants These possess balanced negative and positive charges, one or

other of which dominates in solution depending on pH

1.6 PRETREATMENTS AND AFTERTREATMENTS FOR

ANIONIC DYES

The use of pretreatments or aftertreatments to improve the fastness

properties of dyeings has a long and prolific history. Notable improvements in

the wet fastness properties of anionic dyes can be brought about by

pretreatment or aftertreatment of textile fibres [16].

Three main approaches which were adopted for the pretreatment of

cellulose fibres include:

1. Vinyl grafting

2. Reaction with cationic molecules

3. Application of cationic polymers

Different aftertreatment processes include:

1. Diazotization and development

2. Metal salt treatments

9

3. Formaldehyde treatment

4. Cationic fixing agents

5. Crosslinking agents and resin treatments

Amongst various pretreatment and aftertreatment systems cationic fixing

agents are most widely used.

1.6.1 CATIONIC FIXING AGENTS

Cationic fixing agents were initially applied as aftertreatments to the

dyed textile fibres to improve their wet fastness properties [17,18]. However,

the improved fastness was related only to non-detergent agencies. Later on, this

limitation of mono-functional cationic fixing agents has been overcome by the

development of polyfunctional crosslinking fixing agents which carry reactant

groups capable of forming more permanent bonds with other suitable groups in

the dye or fibre [19,20]. The basic mechanism of multifunctional fixing agents

has been well described by Robinson [21] as shown in Figure 2 and 3.

During 1980's there was a great revival of interest in the techniques for

enhancing the dyeability of cellulosic fibres with reactive or direct dyes by

pretreatment with a great variety of cationic products usually based on

nitrogen. This modification of cellulosic fibres with cationic agents resulted in

increased substantivity of anionic dyes for cellulosic fibres by introducing new

cationic sites. Lewis and Lei reviewed numerous chemicals that can be used to

provide cationic charges to cotton fibres [22]. Pretreatment of cellulosic fibres

10

with cationic agents has been reported to enhance the uptake of anionic dyes

and facilitate the fixation of reactive dyes in the absence of either salt or alkali

[23,24]. The cationised fibre not only has improved substantivity for direct and

reactive dyes, but could also be dyed with acid dyes [11].

Amines [25], quaternary ammonium [26], phosphonium [27] and

tertiary sulphonium [28] compounds can be used as dye fixing agents. By far

the most important type of cationic fixing agents used in textile processing is

quaternary ammonium salt.

Figure 2 Fixing agents showing various degrees of functionality

+

+

+

+

Monofunctional type

Bifunctional type

Trifunctional type

Tetrafunctional type

11

Figure 3 Modes of reaction of the various fixing agents

1.6.1.1 QUATERNARY AMMONIUM SALTS

Quaternary ammonium salts have widespread applications in different

fields and are used as surfactants [29], phase transfer catalysts [30,31],

solvents, drugs, herbicides [32], antimicrobials [33-35] and disinfectants [36].

Being surfactants these compounds are used as softeners for textile and paper

(H+)

(OH -)

3OS-D o+ -

3OS-D o

HO

HO

O

HO

O

O

Monofunctional type

Bifunctional type

Trifunctional type

Tetrafunctional type

Cellulose 3OS-D

3OS-D o

+ -

+ -

+ -

12

products, as emulsifiers [37,38], as washing agents for textile materials dyed or

printed with cationic dyes [39] and as fixing agents for cellulose-containing

materials dyed with anionic dyes [40,41]. The positive charge in these

compounds imparts antistatic properties to wool, cotton and other cellulosic

fibres as well as certain synthetic fibres [38,42].

Amongst the manifold applications, one of the primary functions of

these compounds is their use as cationic fixing agents. Different quaternary

ammonium salts [40,43,44] have been applied to the fibres either as

pretreatment or aftertreatment to improve the wet fastness properties of anionic

dyes. These include monomeric or polymeric quaternary ammonium salts

having different reactive groups. The most commonly used quaternary

ammonium salts are:

1. dialkyl azetidinium chloride (1)

2. epoxy / halohydroxy propyl derivatives (2, 3)

3. mono- and bis-reactive haloheterocyclic derivatives (4)

4. poly-epichlorohydrin dialkyl derivatives (5)

The anions in these fixing agents are usually chloride or bromide.

N+

OHR1

R2

-Cl

O

N+

R1

R2R3

X-

N+

R1

R2R3OH

Cl

X-

1 2 3

13

N

N

N

Cl

R NHN

+ R2R1

R3

X-

O

N+

R2

R1HX

-n

4 5

Many of the attempts to fix quaternary ammonium salts to cellulose via

ether linkage have included the use of epoxy / halohydroxy propyl derivatives

[45,46]. Amongst these derivatives, 2,3-epoxypropyl trimethyl ammonium

chloride [47,48] and 3-chloro-2-hydroxy propyl trimethyl ammonium chloride

[49] have been reported to improve the dye exhaustion and fastness properties

but the results left scope for further work.

Mono- and bis-reactive haloheterocyclic derivatives usually based on

cyanuric chloride have also been reported to improve the wet fastness

properties of anionic dyes [50]. However, the reactivity of mono-reactive

haloheterocyclic derivatives to the textile fibres is low and these compounds

are also expensive. So the practical utility of these compounds is low.

Polymeric cationic agents have also been reported in this regard. These

compounds usually show poor penetration and distribution of dyes [22]

resulting in poor light fastness properties of the dyed textile fibres as compared

to fabrics pretreated with lower molecular weight compounds.

14

1.7 PROBLEMS ENCOUNTERED WITH THE FIXING AGENTS

Although a variety of fixing agents have been used to improve the

fastness properties of anionic dyes but to date none has achieved significant

commercial success. All these treatments enhanced the uptake of the dye yet

there are practical drawbacks to all these treatments including hue changes,

poor penetration into the fibre [51] and light fastness limitations [22]. These

areas require further investigations and there is still a need for novel dyeing

processes that improve properties in respect of application and fastness

properties of the dyeings.

1.8 PLAN OF WORK

Although mono-reactive epoxy / halohydroxy propyl derivatives

improved the wet fastness properties of anionic dyes but to the best of our

knowledge, no significant work has been done on bis-reactive epoxy /

halohydroxy propyl derivatives or mono-reactive epoxy / halohydroxy propyl

derivatives of quaternary ammonium salts containing some other reactive

groups.

Keeping this in view and due to our interest in the synthesis of cationic

fixing agents, this research is proposed that pertains to the synthesis of new bis-

reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary

ammonium chloride (Figure 4). We expect that these compounds will bind to

the fibre more permanently and provide more cationic dye sites for anionic

15

dyes, thus showing a higher affinity and reactivity with the fibre than the

mono-reactive epoxy / halohydroxy propyl derivatives. This will not only

enhance the uptake of the dye but also improve the general fastness properties.

In addition, mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl

derivatives containing cyano and carboxylic groups will also be synthesised

(Figure 5). It is expected that these additional groups may further enhance the

exhaustion and fixation ability of these compounds by forming a linkage with

the fibre and /or the dye.

N

R

R (CH2)nN

R

R

Cl-

O

N+

R

R

(CH2)n

N+R

R

O

Cl-

O

Cl

O

ClConc. HCl

Cl-

N+ R

R(CH2)n N

+R

R

OHOH

ClCl

Cl-

Figure 4 General scheme for the synthesis of bis-reactive 2,3-epoxy / 3-

chloro-2-hydroxy propyl derivatives of quaternary ammonium

chloride

16

N

R

R

(CH2)n

X

N+

R

R

(CH2)nX

O

Cl-

N+

R

R

(CH2)n

XOH

ClCl

-

O

Cl

O

ClConc. HCl

Figure 5 General scheme for the synthesis of mono-reactive 2,3-epoxy / 3-

chloro-2-hydroxy propyl derivatives of quaternary ammonium

chloride

Reaction parameters for the synthesis of these compounds will be

optimised. The newly synthesised compounds will be purified by different

purification techniques and the purified compounds will be characterised using

different spectroscopic techniques.

These newly synthesised mono- and bis-reactive quaternary ammonium

compounds will be used as pretreatments and aftertreatments to the cotton

fabrics dyed with anionic dyes (direct, reactive and acid dyes). The colour

strength (K/S) values and fastness properties of the dyeings will be determined

and the effect of fixation on shade change and fastness properties will be

evaluated.

LLIITTEERRAATTUURREE

RREEVVIIEEWW

18

Chapter 2

LLIITTEERRAATTUURREE RREEVVIIEEWW

2.1 GENERAL DEVELOPMENT

Most early dyeing processes used naturally occurring coloured

compounds e.g. dye woods [52], which had no significant affinity for cotton

and silk. These processes required a metal salt mordant before dyeing and after

dyeing, fixation with tannin.

The major growth and establishment of the synthetic dye industry was

initiated with the discovery of Congo Red, the first direct dye for cotton,

in1884 [53]. Although some early direct dyeings were claimed to be fast to

soaping [54] it was soon appreciated that fastness to light and wet treatments

left much to be desired.

From 1930 onwards, complexing of direct dyes, present on the fibre,

with aqueous solutions of cationic fixing agents began to be fully exploited.

The importance and use of these agents was greatly extended by the

19

development of products rising from the condensation of cyanamide (6) or

similar compounds with formaldehyde. These resin fixatives [55] of which

Fibrofix (7) was a classical example [56], could be applied by a simple,

finishing technique to cellulosic fibres dyed or printed with direct dyes. This

resin fixative class was rapidly extended to provide a large number of agents

based on the condensation products of formaldehyde with cyanamide

derivatives [57], which were suitable for aftertreatment of direct dyes on

cellulose fibres. Later on, the reaction products of cyanamide or cyanamide

derivatives with monofunctional or polyfunctional amines and the condensates

of these amines with formaldehyde or N-methylol derivatives were used as an

aftertreatment to improve the wet fastness properties of anionic dyes on

cellulose fibres [58,59]. Other relevant developments in this area have been

reviewed in detail [60].

NH2 C N

NH2

NH

NH

N

CN

+

n

nX-

6 7

Extensive research work has shown that formaldehyde based resin

finished products release formaldehyde into the atmosphere directly or during

processing, handling, garment manufacturing and subsequent wearing of

20

textiles due to the hydrolysis of unreacted or partially crosslinked N-methylol

derivatives present on the fibre. Direct release of formaldehyde into the

working environment causes severe irritation to eyes, nasal passages and

respiratory tract while an unreacted or partially crosslinked resin causes an

allergenic response of the skin upon continuous handling of textiles [61]. For

reasons of these health problems associated with formaldehyde, there was an

increasing demand for non-formaldehyde fixing agents. It has also been

reported that formaldehyde containing fixing agents for direct dyeing could be

substituted by nitrogen containing non-formaldehyde fixatives without

sacrificing the performance properties of the finished goods. Selection of

suitable non-formaldehyde fixatives could actually produce better products

than using the formaldehyde fixative [8]. Nitrogenous-based dye fixing agents

have also been reported to improve overall fastness properties, without

affecting the tone and depth of shades of reactive dyes on cotton substrates.

The results indicated that commercial non-formaldehyde and formaldehyde-

based dye fixing agents could be replaced by laboratory developed

nitrogenous-based dye fixing agents [62].

After the discovery of reactive dyes, dyeing with reactive dyes became

the most versatile method for the coloration of cellulosic fabrics. These dyes

were used instead of aftertreated direct dyes but they have both economic and

environmental drawbacks because of high salt usage and insufficient fixation

caused by hydrolysis leading to pollution of the effluent [9]. However, if an

21

aftertreatment is given prior to the rinsing stage, hydrolysed dye also gets fixed

showing improved wet fastness. Therefore, aftertreatment still remained an

extremely useful way of improving the wet fastness properties of a deep dyeing

that failed to meet the necessary standards.

Developments taking place during the recent decade have enabled direct

dyes to compete with reactive dyes in the field of severe wet fastness

requirements. The production, in the 1960’s, of polyfunctional cross-linking

fixing agents [19,20,63,64] capable of reacting with both dye and fibre was a

significant development. These agents were used to aftertreat dyes on

cellulosic, polyamide and wool fibres.

The use of anionic dyes (acid, direct and reactive dyes) and cationic

fixing agents is widespread in dyeing processes. Many studies have been

devoted to improve the fastness properties of anionic dyes by pretreating or

aftertreating the fibres with amines or reactive cationic agents. Most of these

studies have used monomeric or polymeric quaternary ammonium salts having

different reactive groups. These include dialkyl azetidinium chloride,

epoxypropyl / halohydroxy propyl trialkyl derivatives of ammonium chloride,

mono- and bis-reactive haloheterocyclic compounds and poly-epichlorohydrin

dimethylamine derivatives.

The mechanisms of dyeing cotton textiles pretreated with quaternary

compounds of mono-reactive epoxypropyl type and mono- and bis-reactive

chlorotriazine type were studied. The high reactivity and better thermal

22

stability of chlorotriazine type agents than epoxypropyl type agents made them

suitable for pad-batch or exhaust applications rather than the more costly pad-

bake process and gave effective enhancement of reactive dye uptake [51]. Later

on, it was found that the pretreatment of cotton fabric with bis-reactive cationic

agent promoted higher extents of dye exhaustion and fixation than that with

mono-reactive cationic agent [50]. The low substantivity and poor thermal

stability of mono-reactive epoxypropyl agents made them unsuitable for

exhaust application and was also responsible for the poor dye penetration due

to significant migration of agent during the thermal reaction step of pad-bake

process leading to non-uniform distribution of cationic dye sites on the fibre

[51]. The reactivity of cotton with such type of compounds has been studied

under a variety of conditions [48,65,66] but no best procedure has yet been

established. Recent work has shown that cotton cationised through a pad-batch

process gave excellent dye penetration indicating the uniform distribution of

cationic dye sites through this process. Thus, a pad-batch process seems to be

good for achieving high yields of cationically modified cotton with uniform

distribution of dye sites [67]. The pad-batch dyeing technique has now become

an important dyeing method for its simplicity, low consumption of energy and

water, and excellent reproducibility [68].

Recently, a new method based on the sol-gel process has proved to be an

effective way to improve the wash fastness of direct dyes on cotton without

essential loss of properties such as handle and strength of the fabric [69]. This

23

process involves the fixation of dyes through hydrogen bonding, van der Waal's

forces and covalent bonding. It was also found that a sol prepared from an

epoxy containing precursor exhibited the best results as a fixing agent on dyed

cotton [70].

2.2 MONOMERIC QUATERNARY AMMONIUM SALTS

The use of cationic agents in the form of primary, secondary, tertiary

and quaternary amine residues has been known since 1926 [25,26].

Pretreatment of cotton fabrics with Katamin AB (alkylbenzyldimethyl

ammonium chloride; 8) has been reported to increase the uptake of reactive

dyes and reduce the amount of dye and alkali required for dyeing [71].

N+

CH3

CH3

RCl

-

OH NH

O

CH2

8 9

To investigate systematically the effect of attaching a variety of amines

to the cellulose fibre, cotton was modified by pretreatment with N-

methylolacrylamide (9; Allied Colloids) to introduce pendant-activated double

bond (Figure 6). By introducing amino residues at these new sites good colour

yield and high fixation values of reactive dyes were achieved at pH 5-7 in the

absence of electrolyte but light fastness was lowered. Cellulose modified with

24

only N-methylolacrylamide (9) also gave high colour yields with dyes

containing pendant aliphatic amino residues in the presence of electrolyte under

alkaline conditions [23].

Cell OH + OH NH

O

CH2O NH

O

CH2Cell OH2o

+ZnCl2 / 150 C

Figure 6 Modification of cotton with N-methylolacrylamide

Recently, a new fibre-reactive quaternary compound containing an

acrylamide residue was synthesised and applied to cotton fabrics using a pad–

bake process. It was found that the treated fibre could be dyed with reactive

dyes without the addition of salt or alkali. The reactive dyes were almost

completely exhausted and showed a high degree of covalent bonding with the

pretreated cellulose [72]. A fibre-reactive chitosan derivative, O-

acrylamidomethyl-N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan

chloride, was used for the modification of cotton. Dyeing of this modified fibre

with direct and reactive dyes gave higher colour yields and better wash fastness

properties without the addition of salt but reduced the light fastness as

compared to the untreated cotton [73]. Cationic starch had also been used for

the modification of cotton fabrics. Dyeing of this modified fibre with reactive

dyes using a continuous dyeing method gave improved dye fixation and level

25

dyeing without the presence of salt compared with untreated cotton. The

dyeings also showed good wash and rub fastness [74].

2.2.1 AZETIDINIUM CHLORIDE

An investigation of the direct dyeing of cotton cationised with 1,1-

dimethyl-3-hydroxy azetidinium chloride (10), 1,1-diethyl-3-hydroxy

azetidinium chloride (11) or Sandene 8425 (aliphatic polyamine derivative;

Clariant) showed improved dye absorption and firmness of colour in the

absence of salt in a neutral medium [41,75]. The above-modified fibre also

enhanced the exhaustion and fixation of acid (Table 2) [11] and reactive dyes

[76] on cotton in the absence of salt in a neutral medium. The effect of alkali

pretreatment followed by 1,1-dimethyl-3-hydroxyazetidinium chloride

(DMAC) treatment on the dyeability of cotton yarn with reactive dyes has been

reported to produce a much stronger colour yield than by DMAC treatment

without alkali pretreatment [77].

N+CH3

CH3

OHCl-

N

+H5C2

H5C2

OHCl-

10 11

26

Table 2 Properties of acid dyes with cationic cotton using no salt at pH 7

K/S Fastness properties

_____________ ____________________________

Washinga

After After _________________

Dye Treatmentb wash DMFc A C W Light

C.I. Acid I 3.62 0.95 4 4 3-4 4

Red 73 II 9.34 4.02 2-3 2 2 6

III 1.04 0.39 2-3 4 3-4 5-6

C.I. Acid I 2.51 0.50 2-3 2 2-3 2-3

Orange 7 II 6.18 0.98 2 2-3 2-3 6

III 1.05 0.35 2 4-5 4-5 3

C.I. Acid I 1.23 0.35 2 3-4 2 5

Yellow 36 II 3.25 0.37 2 4 3 4-5

III 0.64 0.21 3 3-4 4-5 4

C.I. Acid I 3.87 2.03 2 3-4 2 5

Green 12 II 7.14 4.76 4 4 3 5

III 1.95 0.41 2 4 3 6

C.I. Acid I 2.72 2.66 3-4 2-3 2-3 6

Red 183 II 12.14 5.88 4 4-5 4 6

III 2.51 0.43 3 4-5 4-5 6

C.I. Acid I 4.63 3.20 2 4 2-3 6

Red 214 II 12.51 7.55 3-4 3-4 3-4 6

III 3.25 0.68 2 2 3 6

a. A, change in colour; C, staining on cotton; W, staining on wool

b. I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3-

hydroxy azetidinium chloride (DEA-AC)

c. DMF, dimethylformamide

27

2.2.2 EPOXY AND HALOHYDROXY PROPYL DERIVATIVES

Several patents have covered the preparation of epoxy and halohydroxy

propyl derivatives of ammonium chloride [78-82]. Many attempts have been

made to fix epoxy and halohydroxy propyl derivatives to cellulose via an ether

linkage. Epoxypropyl derivatives of ammonium chloride react with cellulose

under alkaline conditions to form ethers (Figure 7).

O

N+

R3R2

R1Cl

-

Cell OH N+

R1

R2 R3 OH

OCell

Cl-

OH-

+

Figure 7 Reaction of epoxypropyl derivatives with cellulose

However, when halohydroxy propyl derivatives have been used for the

cationisation of cellulosic fabrics under alkaline conditions, an epoxide ring is

first formed in the cationising agent by the action of alkali and it then reacts

with the hydroxyl group of cellulose under alkaline conditions (Figure 8).

Alkali is required both for the formation of epoxide ring and for its reaction

with cellulose. Thus, both epoxy and halohydroxy propyl derivatives have the

same reactive group.

28

N+

R1

R2 R3 OH

Cl

Cl-

O

N+

R3R2

R1 Cl-

OH-

O

N+

R3R2

R1 Cl-

Cell OH N+

R1

R2 R3 OH

OCell

Cl-

OH-

+

Figure 8 Reaction of halohydroxy propyl derivatives with cellulose

The first product of this type was Glytac A (Protex; 12), which reacted

with cellulose via the epoxy group at alkaline pH [83]. The use of 2,3-

epoxypropyl trimethylammonium chloride (12) as pretreatment, a simultaneous

treatment or an aftertreatment increased the fixation and fastness properties

(except rubbing fastness) of direct dyes on cotton textiles. It has been observed

that a pretreatment generally produced better results than an aftertreatment. An

increase in the number of solubilising groups on the direct dye molecules

generally resulted in a deterioration of the rubbing fastness of pretreated fabrics

and an improvement in case of aftertreated fabrics [84]. This treatment has also

been reported to increase the fixation of various reactive dyes on cotton but

reduced the fastness properties of dyed fabrics [85].

A comparative study of the reactive dyeing of unmodified cotton and

cotton cationised with compound (12) with dyes having four different reactive

groups showed that cationic cotton gave the same colorfastness as the

unmodified cotton, but usually with higher colour yields [47]. Cotton modified

29

with this agent through a cold pad-batch process has been reported to show

excellent colour yields and fastness properties for a number of direct

(Crompton & Knowles), reactive and acid dyes (Dystar), without the use of

electrolytes or multiple rinses, which are normally employed in cotton dyeing

(Table 3) [67].

O

N+

CH3

CH3CH3

Cl-

N+

R1

R2R3OH

Cl

Cl-

12 13

R1 = R2 = R3 = CH3, C2H5, C3H7, C5H11

3-chloro-2-hydroxypropyltrialkyl derivatives of ammonium chloride

(13) were synthesised through the reaction of various trialkylamines with

epichlorohydrin and were used for the cationisation of cellulosic fibres under

alkaline conditions. Cationised fibres showed slightly better light fastness than

those on nylon or wool dyed with the same acid dye (Ciba) but their wash

fastness decreased with increasing length of hydrocarbon chain (Table 4). The

cationised fibres also showed excellent antimicrobial activity in spite of the

small amount of cationic agent introduced into the fibre. It was also found that

antimicrobial activity increased with the increase in the hydrocarbon chain

[86].

30

Table 3 Fastness properties of direct, reactive and acid dyes with nylon,

conventional cotton and cationised cotton

Colour fastness

_______________________

Change Light

Dye Cotton fabric K/S in colour Staining a fastnessb

Conventional cotton and cationised cotton

C.I. Direct Blue 78 Untreated 8.67 2 2-3 5

Cationic 13.99 4-5 4 5

C.I. Direct Blue 86 Untreated 8.76 1 2-3 5

Cationic 44.74 5 4-5 5

C.I. Direct Red 80 Untreated 14.16 2 2 3-4

Cationic 20.11 4-5 5 4-5

C.I. Direct Yellow 106 Untreated 10.29 3 3-4 5

Cationic 14.46 5 5 5

C.I. Reactive Blue 21 Untreated 15.08 4-5 5 5

Cationic 53.34 4 5 4-5

C.I. Reactive Blue 203 Untreated 16.37 4-5 4-5 5

Cationic 24.24 4-5 4-5 4-5

C.I. Reactive Red 239 Untreated 8.24 5 4-5 4-5

Cationic 12.40 5 4-5 4-5

C.I. Reactive Orange107 Untreated 6.91 4-5 5 5

Cationic 18.24 4 5 4-5

Nylon and cationised cotton

C.I. Acid Black 172 Nylon 4-5 4-5 5

Cationic cotton 2-3 4-5 5

C.I. Acid Blue 221 Nylon 4-5 4-5 5

Cationic cotton 3-4 4-5 4-5

C.I. Acid Red 260 Nylon 5 4-5 5


C.I. Acid Yellow 79 Nylon 4-5 4-5 5


a. Staining of nylon fabric during laundering and staining on cotton

b. 20h

31

Table 4 Fastness properties of acid dye on cotton cationised with different

quaternary salts

Wash fastness

___________________

Cationic Change Light

Dye Substrate agenta in colour Staining fastness

C.I. Acid Cotton CMAC 4-5 3 4-5

Red 127 CEAC 4 3 4-5

CPAC 3 2-3 4-5

CP5AC 3 2-3 4-5

CDTAC 1-2 2 4-5

Nylon - 4-5 2-3 4

Wool - 4-5 2-3 4

a. CMAC, 3-chloro-2-hydroxypropyltrimethyl ammonium chloride; CEAC, 3-chloro-2-

hydroxypropyltriethyl ammonium chloride; CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium

chloride; CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride; CDTAC, 3-chloro-2-

hydroxypropyldimethyltetradecyl ammonium chloride

The dyeing behavior of cotton, cationised with 3-chloro-2-

hydroxypropyl trimethyl ammonium chloride (14; Fisher Scientific), with

direct dyes was investigated. Findings revealed that cationised cotton could be

dyed without salt and required less rinsing to remove unfixed dye than cotton

dyed by conventional methods [49]. Dyeing of this cationised cotton with

fibre-reactive dyes showed deeper shades. Moreover, nonlinear colour

behaviour occurred with cationised cotton at lower concentrations than with

unmodified cotton, suggesting that predicting shades on cationised cotton

requires caution [87]. Significant differences in dyeing rates and dye uptake of

acid dyes on this cationic cotton were observed over untreated cotton. Fastness

32

to laundering and light was greatly improved for cationic cotton over untreated

cotton, but remained somewhat lower than the values for nylon [88].

N+

CH3

CH3

CH3OH

Cl

Cl-

14

The printing properties of cationised cotton that had been pretreated

with compound (12) were examined and cationisation was found to be very

effective in reducing fixation (steaming) times and washing off processes, and

in increasing colour yield and wet fastness properties for a number of reactive

[89] and direct dyes [90]. Printing on this cationic cotton with acid dyes could

be carried out at neutral pH because of the presence of cationic charges on the

fibers at all pH values, avoiding the need for a pH regulator in the print paste

and for neutralisation during washing. This technique did not need an intensive

washing procedure, and thus appeared to be a more environmentally friendly

printing process [91]. The effect of cationisation on the quality of ink-jet

printing on cotton fabrics was also investigated. Ink-jet printing with reactive

dyes [92] and reactive inks [93] on cationised cotton was found to have good

potential as a cost-effective and more environmentally friendly printing method

using less dye, less thickener and less alkali without relinquishing outline

sharpness.

33

Epoxy and halohydroxy propyl derivatives of diallylamine (15 and 16)

have also been reported in this regard. Different epoxy and halohydroxy propyl

derivatives of diallylamine were synthesised and applied to cotton fabrics

before dyeing or during dyeing. Cotton fabrics treated with these agents

showed improved fastness properties for a number of direct dyes (Table 5)

[45].

O

N+

CH3

CH2CH2

X-

N+

CH3

OH

Cl

CH2CH2

X-

15 16

X = OSO3CH3, OSO3C2H5, SO3C6H4CH3-

The effect of cationisation on the performance of cotton finishes has also

been investigated. Cationisation of cotton with 2,3-epoxypropyl trimethyl

ammonium chloride (12) [94] and 3-chloro-2-hydroxypropyl trimethyl

ammonium chloride (14) [95] has been reported not to affect adversely the

finishes. However, the alkali required for the process improved the wrinkle

recovery angles of the treated fabrics.

34

Table 5 Fastness properties of direct dyes on untreated and treated cotton

fabrics

ISO C2S Wash fastness

________________________

Cationic Cotton Change Staining

Dye agenta fabric in colour on cotton

C.I. Direct Red 80 I Without 4 2

With 5 3-4

C.I. Direct Blue 71 I Without 4 2

With 5 5

C.I. Direct Violet 66 I Without 4-5 4

With 5 5

C.I. Direct Green 26 I Without 4-5 3-4

With 5 5

a. I, N- (3-chloro-2-hydroxypropyl)-N-methyl-N, N-diallyl ammonium p-toluenesulphonate

2.2.3 MONO- AND BIS-REACTIVE HALOHETEROCYCLIC

DERIVATIVES

Mono- and bis-reactive haloheterocyclic compounds having

monochlorotriazine as the reactive group have also been used for the

cationisation of cellulose. Although these treatments enhanced the uptake of

dye, there are practical drawbacks to all these treatments, including hue

changes, poor penetration into the fibre [51] and light fastness limitations [22].

Monofunctional cationic agents of monochlorotriazine type (17) were

evaluated on cotton yarn in the production of differential dyeing effects. Yarn

pretreated with these cationic agents showed better uptake of acid and direct

35

dyes than does untreated yarn [96]. The stoichiometry of interaction of both

acid and direct dyes with cotton modified with a reactive cationic agent (18)

was examined. The results showed that the presence of the cationic sites

enhanced the amount of dye taken up by diffuse adsorption [97].

N

N

N

NH NHN

+H5C2

R

C2H5

Cl

X-

17

Cl-

N

N

N

NH NHN

+

C2H5

Cl

H5C2

18

Recent developments revealed that cotton fabrics pretreated with mono-

and bis-reactive cationic agents (19 and 20) showed fairly high degrees of

exhaustion and fixation of direct dyes under neutral conditions in the absence

of salt. Improved fastness was achieved for this modified fibre when compared

with untreated samples. Results also indicated that cotton pretreated with the

36

bis-reactive cationic agent showed higher degrees of dye exhaustion and

fixation relative to cotton pretreated with mono-reactive agent (Table 6) [50].

I-

N

N

N

NH NHN

+

C2H5

Cl

H5C2 C2H5

19

NHNH

N

N

N

N

N

N

Cl Cl

NHNH

N+

N+ C2H5

C2H5H5C2C2H5

H5C2

H5C2

I-

I-

20

Reactive cationic agents, phenylmonochlorotriazinyl and epoxypropyl,

were used for cotton pretreatment using a pad–dry–curing technique. The

dyeability of cationised cotton fabrics using CI Acid Red 1 was found to be

dependent on the cationic agent concentration and the appropriate mixture used

[98]. More complex multifunctional structures (21 and 22) have also been

evaluated by exhaust applications and these gave effective enhancement of dye

uptake [99,100].

37

Table 6 Fastness properties of direct dyes on untreated (C) and pretreated

cotton fabrics with mono- (C-1) and bis-reactive (C-2) cationic

agents

Wash fastnessa

__________________________

Cotton Change Light

Dye fabricb F (%) in colour SC SW fastness

C.I. Direct Yellow 50 C - 3-4 3-4 3 4-5

C-1 32 4 4 4 5

C-2 75 4-5 4-5 4-5 4-5

C.I. Direct Orange 61 C 3 3-4 3 3-4 4-5

C-1 45 4 4 4 4-5

C-2 83 4-5 4-5 4-5 4-5

C.I. Direct Blue 71 C 1 3 2 1-2 4

C-1 28 4 4 3-4 4

C-2 68 4 4 4 2

C.I. Direct Green 26 C 2 3-4 3 3 4

C-1 29 4-5 4-5 4-5 3-4

C-2 58 4-5 4-5 4-5 2

a. SC, staining on cotton; SW, staining on wool

b. C-1, Cotton cationised with monochlorotriazine mono-reactive cationic agent; C-2, Cotton

cationised with bischlorotriazine bis-reactive cationic agent

NHNH

N

N

N

N

N

N

Cl Cl

NHNH

N+

N+CH3

CH3CH3 CH3 CH3

CH3

--Cl Cl

21

38

NH

N

N

N

NH

N

N

N

ClCl

NHNH OHOH

N+

N+

CH3

CH3

CH3

CH3

CH3

CH3

Cl-Cl

-

22

2.3 POLYMERIC QUATERNARY AMMONIUM SALTS

Many cationic polymers have been applied to cellulose with a view to

enhance the uptake of anionic dyes and it is considerably more difficult in these

instances to interpret the precise mechanism of the interactions involved, apart

from the obvious participation of electrostatic forces between the dye anions

and the basic groups (often quaternary nitrogen atoms) in the polymer.

Polyamide-epichlorohydrin resin (Hercosett 125; Hercules Powder

Corpn.), having azetidinium cation (23) as the reactive group, was applied to

cotton with a view to produce a modified fibre suitable for the absorption and

fixation of reactive dyes at neutral pH in the absence of salt. Selected highly

reactive dyes gave good colour yield and fixation but lower fixation values

were obtained when dyes of low reactivity were applied to the pretreated cotton

[101].

39

N+

OHCl-

23

A comparative study of the reactive dyeing of cellulosic fibres modified

with Hercosett 125, 1,1-dimethyl-3-hydroxyazetidinium chloride (10) or Glytac

A (12) revealed that fixation of reactive dyes, even under neutral or slightly

acidic conditions, was attributed to the presence of highly nucleophilic

secondary, tertiary or quaternary amino groups. Light fastness of the fibres

pretreated with polymeric compound was poor because of poor penetration and

distribution of dyes. However, pretreatment with lower molecular weight

compound resulted in improved light fastness [22]. It was thought that better

fixation of both high and low reactivity dyes might be achieved by introducing

more highly nucleophilic sites into the cotton. Incorporation of thiourea and

ethylenediamine into the polymer Hercosett 125, during the application process

has beneficial effects on the results obtained. Thiourea addition inhibits the

crosslinking of the resin, leaving more nucleophilic NH groups as sites for dye

reaction [102]. Ethylenediamine promotes crosslinking of the resin but itself

provides extra NH groups as dye reactive sites [103].

Pretreatment of cotton with a cationic / nucleophilic polymer facilitates

the dyeing of cotton with a variety of reactive dyes in the absence of salt and

alkali at neutral pH [104]. The dyeings thus produced were level and of

40

comparable depths to those obtained using the appropriate standard methods.

Pretreated dyeings showed excellent wash fastness but reduction in light

fastness. This pretreatment has also reduced the time and water required for

dyeing, thus becoming a more environmentally friendly method for the reactive

dyeing of cotton [10].

Derivatives of poly-epichlorohydrin, instead of epichlorohydrin were

prepared and used as new cationic agents. Polyepichlorohydrin-dimethylamine

derivative (24) was applied to cotton under alkaline conditions by the

exhaustion method. Pretreatment of cotton with this agent not only reduced the

amount of salt needed, but also increased the exhaustion efficiency and

perspiration fastness of direct dyes (BAY; Table 7) [105].

O

N+

CH3

CH3HCl

-n

24

41

Table 7 Fastness properties of direct dyes on untreated and treated (poly

epichlorohydrin-dimethylamine) cotton

Wash fastness

________________________

Cotton Change Staining Light

Dye fabric K/S in colour on cotton fastness

C.I. Direct Blue 78 Untreated 14.02 3-4 3 4

Treated 14.26 3 3 3-4

C.I. Direct Orange 39 Untreated 11.58 3-4 3-4 4

Treated 11.90 3 3 3-4

C.I. Direct Blue 86 Untreated 6.06 3-4 4-5 4

Treated 11.74 2-3 4-5 3-4

A commercial cationic fixing agent, Solfix E (modified quaternary

polyamine derivative; Ciba) was used to pretreat cotton prior to dyeing with six

commercial direct dyes in the presence of electrolyte. Pretreatment enhanced

the colour strength but wash fastness was similar to their untreated counterparts

[106]. Pretreated fabrics also gave improved printability with pigment and

anionic dyes. The prints obtained on cationised cotton showed better overall

fastness properties than prints obtained on untreated cotton [107]. Three

commercial cationic fixing agents, namely Matexil FC-PN (a phenol

formaldehyde ammonium chloride condensate; ICI), Matexil FC-ER (poly

diallyldimethyl ammonium chloride; 25, ICI) and Solfix E (Ciba), originally

marketed as aftertreating agents for direct dyes, were used as pretreatments for

cotton modification. Pretreatment was found to increase the colour strength of

42

the dyeings when dyeing had been carried out without electrolyte. However,

when electrolyte was used, the pretreated samples exhibited generally lower

colour strength than the standard dyeings. The wash fastness of the dyeings

almost remained unaffected by pretreatment while light fastness was slightly

lowered [108].

The study of the effect of different pretreatment agents on the uptake of

1:2 metal complex acid dyes by samples of cotton / polyamide fabrics showed

excellent dye uptake by the pretreated samples compared with the untreated

samples. The pretreatment using Matexil FC-ER (25, ICI) or a development

cationic fixing agent gave the most uniform results [109]. Modification of

cotton with a polymeric quaternary ammonium compound of 4-vinyl pyridine

(26) has enabled the dyeing of cotton fibre with 1:2 metal complex acid dyes

without salt at neutral or slightly acidic pH values. Pretreated dyeings displayed

high colour strength, good to very good wash fastness and excellent light

fastness (Table 8) [110].

N+

CH3 CH3

Cl-

n

NN+

CH3

Cl-

n n

25 26

43

Table 8 Colour strength and fastness properties of 1:2 metal complex acid

dyes on untreated and pretreated cotton (PT)

Wash fastness

_______________________

Cotton Change Staining Light

Dye fabrica K/S in colour on cotton fastness

C.I. Acid Yellow 137 Untreated 2.1 - - -

PT 14.4 5 5 7

C.I. Acid Red 182 Untreated 1.8 - - -

PT 18.0 5 5 6

C.I. Acid Black 107 Untreated 2.3 - - -

PT 15.8 4-5 5 7

C.I. Acid Orange 144 Untreated 1.5 - - -

PT 12.3 4-5 5 6

C.I. Acid Blue 284 Untreated 1.9 - - -

PT 16.1 4-5 5 6

C.I. Acid Brown 384 Untreated 0.8 - - -

PT 15.7 4 5 6

C.I. Acid Violet 90 Untreated 1.4 - - -

PT 16.3 4 5 6

C.I. Acid Blue 193 Untreated 1.7 - - -

PT 13.8 4 5 7

a. PT, cotton pretreated with poly (4-vinyl-N-ethylpyridine) quaternised polymer

Homopolymer or copolymers of alkyl diallylamine with epichlorohydrin

have also been reported to improve the wet fastness properties of anionic dyes

on textile fibres [12,111]. Aftertreatment with copolymers of mono and

diallylamine enhanced the colour fastness of reactive dyes on cellulosic fabrics

[112,113].

44

Aftertreatment of the dyeings produced on cellulosic fibres, pretreated

with fixing agent 25 and Fixogene CXF (copolymer of dimethylamine and

epichlorohydrin; 27, ICI), with cationic polymers enhanced the light and wash

fastness of acid (Table 9) [114] and reactive dyes [44]. The subsequent

application of syntan (synthetic tanning agent) to the aftertreated dyeings

enhanced the effectiveness of commercial cationic fixing agents, Matexil FC-

ER (25) and Fixogene CXF (27), in improving the wash fastness of three

commercial direct dyes (Ciba- Geigy) on cotton but the effect of syntan was

both dye and fixing agent specific (Table 10) [115]. It has also been examined

that wash fastness was noticeably better when these fixing agents were applied

under alkaline conditions (Table 11) [116].

N(CH3)2

OH

+ Cl-

n

27

45

Table 9 Fastness properties of acid dyes on cotton

Pretreatmenta Aftertreatmentb Wash fastness

___________ ____________ __________________________

Staining

Cotton Mate- Mate- Shade ________________ Light

Sample rial % rial % change C W N K/S fastness

C.I. Acid Green 106

1C - - - - - - 0.9 -

1.1 PT1 2 - - 3/3-4 4-5/5 - - 5.60 6-7

1.2 PT1 2 AT1 2 3-4/4 5 - - 5.78 -

1.3 PT1 2 AT2 2 3-4 5 - - 5.80 -

1.4 PT1 2 AT3 2 4/4-5 5 - - 5.73 -

1.5 PT2 2 - - 2/2-3 4-5/5 - - 6.05 -

1.6 PT2 2 AT1 2 3-4 5 - - 6.01 -

1.7 PT2 2 AT2 2 2-3/3 5 - - 6.06 -

1.8 PT2 2 AT3 2 4-5 5 - - 5.97 -

C.I. Acid Red 315

2C.1 - - - - - - - - 1.96 -

2.1.1 PTI 2 - - 3 2-3 4 3/3-4 9.89 5

2.1.2 PTI 2 AT1 2 3-4 3 4-5 3-4/4 - -

2.1.3 PTI 2 AT3 2 4 3/3-4 4-5 4 - -

2.1.4 PT2 2 - - 2-3 2-3 3-4/4 3/3-4 10.93 -

2.1.5 PT2 2 AT1 2 3-4 3 4 3-4 - -

2.1.6 PT2 2 AT3 2 4 3-4 4-5 4 - -

C.I. Acid Yellow 235

2C.2 - - - - - - - - 2.17 -

2.2.1 PT1 2 - - 3 4-5 3-4 4/4-5 7.23 6-7

2.2.2 PT1 2 AT1 2 3-4 4-5 4/4-5 4-5 - -

2.2.3 PT1 2 AT3 2 3-4/4 5 4-5 4-5 - -

2.2.4 PT2 2 - - 2/2-3 4-5 3/3-4 4 6.54 -

2.2.5 PT2 2 AT1 2 3-4/4 4-5 4 4-5 - -

2.2.6 PT2 2 AT3 2 4 5 4-5 4-5 - -

a. PT1, Matexil FC-ER; PT2, Fixogene CXF;

b. AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, Copolymer of diallyldimethyl ammonium and

diallyl-2-hydroxy-3-chloropropyl ammonium chloride

46

Table 10 Fastness properties of direct dyes on cotton aftertreated with

cationic fixing agents / syntan

K/S Wash fastnessa

______________ _________________

Before After

Dye Aftertreatmentsb wash wash S C V

C.I. Direct NIL 14.84 11.13 4 1 1-2

Red 89 4% M FC-ER 14.21 12.75 4-5 2-3 3

4% M FC-ER / 2% F AXF 13.77 13.34 4-5 2-3 3

4% F CXF 14.74 12.72 4-5 1-2 2

4% F CXF / 2% F AXF 14.45 13.26 4-5 2 2-3

C.I. Direct NIL 10.98 8.01 3 1 1-2

Yellow 106 4% M FC-ER 10.49 9.94 4 2-3 3

4% M FC-ER / 2% F AXF 10.31 10.11 4 3 3-4

4% F CXF 10.36 8.81 4 1-2 2

4% F CXF / 2% F AXF 10.65 8.73 4 1-2 2

C.I. Direct NIL 17.06 12.42 3 1 1-2

Blue 85 4% M FC-ER 17.06 16.94 4-5 2-3 3

4% M FC-ER / 2% F AXF 16.81 16.14 4-5 2-3 3

4% F CXF 16.08 15.79 4-5 1-2 2

4% F CXF / 2% F AXF 16.81 15.96 4-5 2 2

a. S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscose

b. M, Matexil; F, Fixogene

47

Table 11 Fastness properties of direct dyeings aftertreated with Fixogene

CXF and Matexil FC-ER under neutral and alkaline conditions

Colour fastness

__________________

Staininga

Shade __________

Dye pH Cationic agent K/S change C V

C.I. Direct Red 89 - NIL 14.84 4 1 1-2

7 4% Fixogene CXF 14.74 4-5 1-2 2

11 4% Fixogene CXF 14.64 4-5 2 2-3

- NIL 14.84 4 1 1-2

7 4% Matexil FC-ER 14.21 4-5 2-3 3

11 4% Matexil FC-ER 13.18 4-5 3 3

C.I. Direct Yellow 106 - NIL 10.98 3 1 1-2

7 4% Fixogene CXF 10.36 4 1-2 2

11 4% Fixogene CXF 10.57 4 2-3 3

- NIL 10.98 3 1 1-2

7 4% Matexil FC-ER 10.49 4 2-3 3

11 4% Matexil FC-ER 10.57 4 3-4 4

C.I. Direct Blue 85 - NIL 17.06 3 1 1-2

7 4% Fixogene CXF 16.08 4-5 1-2 2

11 4% Fixogene CXF 16.68 4-5 2 3

- NIL 17.06 3 1 1-2

7 4% Matexil FC-ER 17.06 4-5 2-3 3

11 4% Matexil FC-ER 17.40 4-5 3 4

a. C, Cotton; V, Viscose

A new fibre modification technique based on a cationic acrylic

copolymer (polymer pL) has been established. Pretreatment of cotton with this

polymer increased both the substantivity and reactivity of the fibre towards

reactive dyes, even under neutral or acidic conditions [117]. Recently, poly

48

(vinylamine chloride) has been investigated as a pretreatment for the salt-free

dyeing of cotton with reactive dyes. Dye fixation was found to be much higher

than by conventional dyeing without pretreatment, even in the presence of a

large amount of salt. Dyed cotton pretreated with poly (vinylamine chloride)

showed excellent wash fastness and good rub fastness [118].

Grafting reactions with cellulose by free radical polymerisation have

been explored for many years but the development of modified cotton fibres

with enhanced dyeability via this route has attracted particular interest recently.

The direct dyeing properties of cotton grafted with 2-vinylpyridine and then

quaternised with alkyl bromides or epichlorohydrin were studied under various

dyeing conditions. The results indicated that grafting with 2-vinylpyridine

increased the dye exhaustion markedly and quaternised grafted specimens

showed a further increase in exhaustion of dyes [119]. The modification and

bleaching of cotton was carried out in a single bath by graft polymerisation of

the cationic monomer, methacrylolaminopropyltrimethyl ammonium chloride.

This modified bleached cotton enhanced the colour strength of reactive dye in

the absence of salt. However, the bleaching performance in the presence of

modifying agent was slightly reduced [120].

EEXXPPEERRIIMMEENNTTAALL

WWOORRKK

50

Chapter 3

EEXXPPEERRIIMMEENNTTAALL WWOORRKK

3.1 GENERAL INFORMATION

N,N,N',N'-tetraethylmethylenediamine was synthesised in the laboratory

by the reported method [121]. Clarke's method [122] was used for the synthesis

of N,N-dimethylglycine hydrochloride while 3-dimethylaminopropionic acid

hydrochloride was prepared by the acidic hydrolysis of 3-

dimethylaminopropionitrile [123]. These hydrochlorides were converted to free

amino acids by Galat's method [124]. Other chemicals and solvents were

obtained from Merck, BDH or Acros and were used after purification through

distillation. Progress of the reactions was monitored by performing chemical

tests and TLC of the reaction mixture. The products were purified through

various methods and vacuum dried before performing spectroscopic analysis.

Purity of the products was checked by thin layer chromatography using

precoated silica gel plates (Merck 60F254). Elemental analysis was performed

51

on Carto Erba MOD-1106 elemental analyser. The structures of the quaternary

ammonium salts were charaterised using IR and 1H–NMR spectroscopy. IR

spectra were recorded on a Thermo Nicolet IR 200 spectrometer. 1H–NMR

spectra were recorded in MeOH-d4 solution on a Bruker DPX-400 instrument

at 400 MHz. Chemical shifts are reported in ppm using TMS as an internal

standard. Mass spectra were recorded on a Jeol SX-102 instrument.

Scoured and bleached cotton fabric was used for dyeing. Commercial

samples of C.I. Direct Orange 26, C.I. Direct Red 31, C.I. Direct Black 22, C.I.

Reactive Orange 13, C.I. Reactive Red 45, C.I. Reactive Blue 5, C.I. Acid

Yellow 23 and C.I. Acid Black 234 were generously supplied by Sandal

Dyestuff Industries Limited, Pakistan and were used without further

purification. All other chemicals used were of laboratory reagent grade. The

absorption maximum (λ max. values) of dyes were measured using UV-1700

Pharmaspec UV-Visible spectrophotometer. Dyeing of cotton samples was

carried out in ATLAS D 400 IR Infrared laboratory dyeing machine. Datacolor

SF 650X Spectraflash was used for colorimetric analysis of the dyed samples

and WASHTEC-P ST 13 8TY was used for the washing of the dyed samples.

Colorfastness to light of the dyed textile fabrics was determined using ATLAS

Ci 3000+ Xenon Weather-Ometer. Grey scales were used for assessing change

in colour and staining of adjacent fabrics.

52

3.2 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY /

3-CHLORO-2-HYDROXY PROPYL DERIVATIVES OF

QUATERNARY AMMONIUM CHLORIDE

Eight mono-reactive (Figure 9) and four bis-reactive (Figure 10) 2,3-

epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium

chloride have been synthesised by reacting epichlorohydrin with suitable

tertiary amines and diamines. Mono-reactive derivatives also contain cyano and

carboxylic groups in addition to 2,3-epoxy / 3-chloro-2-hydroxy propyl groups.

Reaction parameters such as time and temperature have been optimised for the

synthesis of these compounds.

53

N

CH3

CH3

(CH2)n

X

N+

CH3

CH3

(CH2)n

X

H

O

Cl

N+

CH3

CH3

(CH2)n

XO

N+

CH3

CH3

(CH2)n

XOH

Cl

Cl-

Cl-

Cl-

O

Cl30-50 C

Conc. HCl

20 Co

OH2

30-50 C

OH2

o o

28 29

X = CN, COOH

n = 1, 2

Figure 9 Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy

propyl derivatives of quaternary ammonium chloride

28a n = 1, X = CN 29a n = 1, X = CN

28b n = 1, X = COOH 29b n = 1, X = COOH

28c n = 2, X = CN 29c n = 2, X = CN

28d n = 2, X = COOH 29d n = 2, X = COOH

54

N(CH2)n

N

R

R

R

R

N+

(CH2)nN

+

R

R

R

RH HConc. HCl

20 C

O

Cl30-50 C

OH2

30-50 C

OH2

O

Cl

N+

(CH2)nN+

R

RR

RO

O

N+

(CH2)nN+

R

RR

R OH

Cl

OH

Cl

Cl-

Cl-

Cl-

Cl-

Cl-

Cl-

o

oo

30 31

R = CH3, C2H5

n = 1, 2

Figure 10 Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl

derivatives of quaternary ammonium chloride

30a n = 1, R = C2H5 31a n = 1, R = C2H5

30b n = 2, R = CH3 31b n = 2, R = CH3

55

3.2.1 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONO-

AND BIS-REACTIVE 2,3-EPOXYPROPYL DERIVATIVES: (28a-d and

30a-b)

Amine (1.0 mmol) was added dropwise to a mixture of epichlorohydrin

(1.0 mmol) and water (10 ml) over a period of 1 hour with constant stirring and

maintaining the temperature between 30-50 oC. The resulting mixture was

stirred at this temperature for 8-10 hours. After the completion of reaction,

water and unreacted reactants were distilled off under reduced pressure and the

crude product was purified by extraction with chloroform or ether to obtain a

yellow to brown viscous product. Due to its high moisture sensitivity, product

was kept in vacuum desiccator for drying. Same procedure was followed for

the synthesis of compounds 30a-b except that the mole ratio of diamine to

epichlorohydrin was 1: 2 respectively.

The products were identified by performing specific chemical tests for

epoxy group [125], tertiary amines [126] and quaternary ammonium salts

[127].

N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride

(28a)

N+

CH3

CH3

O

CN

Cl-

56

Pale yellow viscous liquid, IR: 2970, 2230, 1478, 1260, 910 cm–1, 1H-

NMR (MeOH-d4): δ 4.40 (2H, s, CH2-CN), δ 3.45 (1H, dd, J=3.1,16.5 Hz,

CH2-N), δ 3.33 (6H, s, CH3), δ 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23

(1H, m, epoxy CH), δ 2.75 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.49 (1H, dd,

J=3.3,4.9 Hz, epoxy CH2), MS m/z: 141 [M+], 126 [M+-CH3], HRMS calcd. for

C7H13ClN2O: 176.6439; found: 176.6454, Anal. calcd. for C7H13ClN2O: C,

47.59; H, 7.41; N, 15.85; found: C, 47.55; H, 7.40; N, 15.80.

N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride

(28b)

N+

CH3

CH3

O

O

OH

Cl-

Pale yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395,

1262, 937 cm–1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.20 (2H, s,

CH2-COOH), δ 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), δ 3.31 (6H, s, CH3), δ

3.26 (1H, dd, J=4.4,16.4 Hz, CH2-N), δ 3.22 (1H, m, epoxy CH), δ 2.77 (1H,

dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.50 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS

m/z: 160 [M+], 145 [M+-CH3], HRMS calcd. for: C7H14ClNO3: 195.6440;

found: 195.6457, Anal. calcd. for C7H14ClNO3: C, 42.97; H, 7.21; N, 7.15;

found: C, 42.94; H, 7.17; N, 7.19.

57

N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride

(28c)

N+

CH3

CH3

O CN

Cl-

Yellow viscous liquid, IR: 2960, 2248, 1482, 1257, 920 cm–1, 1H-NMR

(MeOH-d4): δ 3.65 (2H, t, J=7.0 Hz, CH2), δ 3.45 (1H, dd, J=3.1,16.5 Hz, CH2-

N), δ 3.33 (6H, s, CH3), δ 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23 (1H, m,

epoxy CH), δ 2.82 (2H, t, J=6.9 Hz, CH2-CN), δ 2.75 (1H, dd, J=4.2,4.9 Hz,

epoxy CH2), δ 2.49 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 155 [M+], 140

[M+-CH3], HRMS calcd. for: C8H15ClN2O: 190.6705; found: 190.6722, Anal.

calcd. for C8H15ClN2O: C, 50.39; H, 7.92; N, 14.69; found: C, 50.36; H, 7.90;

N, 14.72.

N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride

(28d)

N+

CH3

CH3

O

O

OH

Cl-

Yellow viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1271,

965 cm-1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 3.53 (2H, t, J=7.0

Hz, CH2), δ 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), δ 3.31 (6H, s, CH3), δ 3.26

58

(1H, dd, J=4.4,16.4 Hz, CH2-N), δ 3.22 (1H, m, epoxy CH), δ 2.77 (1H, dd,

J=4.2,4.9 Hz, epoxy CH2), δ 2.67 (2H, t, J=7.2 Hz, CH2–COOH), δ 2.50 (1H,

dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 174 [M+], 159 [M+-CH3], HRMS calcd.

for: C8H16ClNO3: 209.6705; found: 209.6721, Anal. calcd. for C8H16ClNO3: C,

45.82; H, 7.69; N, 6.68; found: C, 45.85; H, 7.69; N, 6.64.

Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]

(30a)

N+

N+

C2H5

H5C2

C2H5H5C2

O

O

Cl-

Cl-

Pale yellow viscous liquid, IR: 2987, 2960, 1472, 1269, 900 cm–1, 1H-

NMR (MeOH-d4): δ 5.20 (2H, s, N+-CH2-N+), δ 3.45 (2H, dd, J=3.1,16.5 Hz,

CH2-N), δ 3.29 (8H, q, J=7.0 Hz, CH2-CH3), δ 3.26 (2H, dd, J=4.4,16.5 Hz,

CH2-N), δ 3.23 (2H, m, epoxy CH), δ 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2),

δ 2.49 (2H, dd, J=3.3,4.9 Hz, epoxy CH2), δ 1.25 (12H, t, J=7.0 Hz, CH3), MS

m/z: 272 [M+], 243 [M+-C2H5], 215 [M+-2,3-epoxypropyl], HRMS calcd. for:

C15H32Cl2N2O2: 343.3328; found: 343.3361, Anal. calcd. for C15H32Cl2N2O2:

C, 52.47; H, 9.39; N, 8.15; found: C, 52.50; H, 9.39; N, 8.10.

59

Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride]

(30b)

Cl-

Cl-N

+

CH3

CH3ON

+

CH3

CH3

O

Reddish-brown viscous liquid, IR: 3010, 2958, 1470, 1272, 920 cm–1,

1H-NMR (MeOH-d4): δ 3.72 (4H, s, CH2), δ 3.45 (2H, dd, J=3.1,16.5 Hz, CH2-

N), δ 3.33 (12H, s, CH3), δ 3.26 (2H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23 (2H,

m, epoxy CH), δ 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.49 (2H, dd,

J=3.3,4.9 Hz, epoxy CH2), MS m/z: 230 [M+], 215 [M+-CH3], 173 [M+-2,3-

epoxypropyl], HRMS calcd. for: C12H26Cl2N2O2: 301.2530; found: 301.2557,

Anal. calcd. for C12H26Cl2N2O2: C, 47.84; H, 8.69; N, 9.29; found: C, 47.79; H,

8.65; N, 9.26.

3.2.2 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONO-

AND BIS-REACTIVE 3-CHLORO-2-HYDROXYPROPYL

DERIVATIVES: (29a-d and 31a-b)

Conc. HCl (1.0 mmol) was added to the aqueous solution of amine (1.0

mmol) over a period of 1 hour under slow stirring and maintaining the

temperature below 20 oC. After complete addition of HCl, reaction mixture was

stirred for half an hour at this temperature and showed a neutral pH. Then

60

epichlorohydrin was added slowly to the above reaction mixture with

continuous stirring. The temperature was raised to 30-50 oC and the reaction

mixture was stirred at this temperature for 8-10 hours. After the completion of

reaction, water and unreacted reactants were distilled off under reduced

pressure and the crude product was purified by extraction with chloroform or

ether to obtain a clear to yellow viscous product. Due to its high moisture

sensitivity, product was kept in vacuum desiccator for drying. Same procedure

was followed for the synthesis of 31a-b except that the mole ratio of diamine to

Conc. HCl and epichlorohydrin was 1: 2: 2 respectively.

The products were identified by performing specific chemical tests for

epoxy group [125], tertiary amines [126] and quaternary ammonium salts

[127].

N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium

chloride (29a)

N+

CH3

CH3OH

Cl CN

Cl-

Pale yellow viscous liquid, IR: 3252, 2970, 2230, 1478, 1100, 735 cm–1,

1H-NMR (MeOH-d4): δ 4.40 (2H, s, CH2-CN), δ 4.37 (1H, brs, OH), δ 4.18

(1H, m, CH), δ 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd, J=3.1,16.5

Hz, CH2), δ 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (6H, s, CH3), δ 3.27

61

(1H, dd, J=4.3,16.5 Hz, CH2), MS m/z: 177.5 [M+], 162.5 [M+-CH3], 128 [M+-

CH2Cl], HRMS calcd. for: C7H14Cl2N2O: 213.1049; found: 213.1065, Anal.

calcd. for C7H14Cl2N2O: C, 39.45; H, 6.62; N, 13.14; found C, 39.42; H, 6.60;

N, 13.10.

N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium

chloride (29b)

N+

CH3

CH3OH

Cl

O

OH

Cl-

Yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395, 1060,

742 cm-1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.38 (1H, brs,

OH), δ 4.20 (2H, s, CH2-COOH), δ 4.18 (1H, m, CH), δ 3.63 (1H, dd,

J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd, J=3.1,16.4 Hz, CH2), δ 3.42 (1H, dd,

J=4.7,6.0 Hz, CH2-Cl), δ 3.31 (6H, s, CH3), δ 3.27 (1H, dd, J=4.4,16.4 Hz,

CH2), MS m/z: 196.5 [M+], 181.5 [M+-CH3], 147 [M+-CH2Cl], HRMS calcd.

for: C7H15Cl2NO3: 232.1049; found: 232.1062, Anal. calcd. for C7H15Cl2NO3:

C, 36.22; H, 6.51; N, 6.03; found: C, 36.18; H, 6.50; N, 6.07.

62

N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium

chloride (29c)

N+

CH3

CH3OH

ClC

N

Cl -

Yellowish-brown viscous liquid, IR: 3240, 2960, 2248, 1482, 1100, 735

cm–1, 1H-NMR (MeOH-d4): δ 4.37 (1H, brs, OH), δ 4.18 (1H, m, CH), δ 3.65

(2H, t, J=7.0 Hz, CH2), δ 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd,

J=3.1,16.5 Hz, CH2), δ 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (6H, s,

CH3), δ 3.27 (1H, dd, J=4.3,16.5 Hz, CH2), δ 2.82 (2H, t, J=6.9 Hz, CH2-CN),

MS m/z: 191.5 [M+], 176.5 [M+-CH3], 142 [M+-CH2Cl], HRMS calcd. for:

C8H16Cl2N2O: 227.1314; found: 227.1329, Anal. calcd. for C8H16Cl2N2O: C,

42.30; H, 7.09; N, 12.33; found: C, 42.27; H, 7.05; N, 12.30.

N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium

chloride (29d)

N+

CH3

CH3OH

Cl O

OH

Cl-

Clear viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1070, 740

cm–1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.38 (1H, brs, OH), δ

4.18 (1H, m, CH), δ 3.63 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd,

63

J=3.1,16.4 Hz, CH2), δ 3.53 (2H, t, J=7.0 Hz, CH2), δ 3.42 (1H, dd, J=4.7,6.0

Hz, CH2-Cl), δ 3.31 (6H, s, CH3), δ 3.27 (1H, dd, J=4.4,16.4 Hz, CH2), δ 2.67

(2H, t, J=7.2 Hz, CH2–COOH), MS m/z: 210.5 [M+], 195.5 [M+-CH3], 161

[M+-CH2Cl], HRMS calcd. for: C8H17Cl2NO3: 246.1315; found: 246.1330,

Anal. calcd. for C8H17Cl2NO3: C, 39.03; H, 6.96; N, 5.69; found: C, 39.01; H,

6.90; N, 5.65.

Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-diethylammonium

chloride] (31a)

N+

N+

C2H5

H5C2

C2H5H5C2

OH

Cl

OH

Cl

Cl-

Cl-

Pale yellow viscous liquid, IR: 3220, 2987, 2960, 1472, 1095, 740 cm–1,

1H-NMR (MeOH-d4): δ 5.20 (2H, s, N+-CH2-N+), δ 4.37 (2H, brs, OH), δ 4.18

(2H, m, CH), δ 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (2H, dd, J=3.1,16.5

Hz, CH2), δ 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.29 (8H, q, J=7.0 Hz,

CH2), δ 3.27 (2H, dd, J=4.4,16.5 Hz, CH2), δ 1.25 (12H, t, J=7.0 Hz, CH3), MS

m/z: 345 [M+], 316 [M+-C2H5], 295.5 [M+-CH2Cl], HRMS calcd. for:

C15H34Cl4N2O2: 416.2547; found: 416.2579, Anal. calcd. for C15H34Cl4N2O2:

C, 43.28; H, 8.23; N, 6.72; found: C, 43.25; H, 8.19; N, 6.75.

64

Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium

chloride] (31b)

Cl-

Cl -

N+

CH3

CH3

OH

Cl

N+

CH3

CH3

OH

Cl

Clear viscous liquid, IR: 3224, 3010, 2958, 1470, 1100, 742 cm–1, 1H-

NMR (MeOH-d4): δ 4.37 (2H, brs, OH), δ 4.18 (2H, m, CH), δ 3.72 (4H, s,

CH2), δ 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (2H, dd, J=3.1,16.5 Hz,

CH2), δ 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (12H, s, CH3), δ 3.27 (2H,

dd, J=4.4,16.5 Hz, CH2), MS m/z: 303 [M+], 288 [M+-CH3], 253.5 [M+-CH2Cl],

HRMS calcd. for: C12H28Cl4N2O2: 374.1749; found: 374.1775, Anal. calcd. for

C12H28Cl4N2O2: C, 38.51; H, 7.54; N, 7.48; found: C, 38.55; H, 7.51; N, 7.52.

3.3 APPLICATIONS

The synthesised compounds were applied to cotton fabrics as

pretreatments and optimum conditions for the cationisation of cotton fabric

with these compounds have been determined. Dyeing properties of these

pretreated fabrics with direct, reactive and acid dyes have also been

investigated. These compounds were also applied to the dyed cotton fabrics as

aftertreatments and the effect of different pH conditions and concentration on

the effectiveness of these compounds as fixing agents has been studied.

65

Since both epoxy and halohydroxy propyl derivatives of quaternary

ammonium salts react with cellulose under alkaline conditions and have the

same reactive group as shown in Figure 7 and 8 therefore, epoxy derivatives

have been applied to the cotton fabrics as pretreatments and aftertreatments and

their effects on the colour strength (K/S) and fastness properties of dyed fabrics

have been evaluated.

3.3.1 APPLICATION OF CATIONIC FIXING AGENTS AS

PRETREATMENT

3.3.1.1 Pretreatment of cotton fabrics

Cotton fabrics were pretreated with compounds 30a, 30b and 28c using

the exhaust method (Table 12). Pretreatment was carried out in a laboratory

dyeing machine at a liquor ratio of 25:1. Afterwards, the fabrics were rinsed in

tap water and then neutralised with 2% CH3COOH for 5 minutes at 40o C.

Neutralised fabrics were again rinsed in tap water and dried at room

temperature.

Table 12 Pretreatment conditions

Pretreatment Temperature Time Conc. of NaOH Conc. of cationic

method (oC) (min.) (% ow cationic agent) agenta (% owf)

1. 40-100 30 30 2

2. 80 20-50 30 2

3. 80 30 30 2-10

4. 80 30 10-40 2

a. 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride]

66

3.3.2 DYEING CONDITIONS FOR UNTREATED COTTON FABRICS

3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by

conventional method

Untreated cotton fabrics were dyed with direct dyes in a laboratory

dyeing machine at a liquor ratio of 25:1 using 15-30g/L of sodium chloride

under neutral conditions. Dyeing was started at 30 oC and temperature of the

dye bath was raised to 100 oC over 20 minutes. Dyeing was continued at this

temperature for a further 50 minutes. Dye bath was then cooled and discarded

(Figure 11). Dyed fabrics were rinsed thoroughly in tap water and dried at

room temperature.

Figure 11 Dyeing profile of untreated cotton fabric with direct dyes

3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes by

conventional method

Untreated cotton fabrics were dyed with reactive dyes in a laboratory

dyeing machine according to the dyeing profile shown in Figure 12. Dyed

samples were rinsed in tap water, then rinsed in hot water at 60 oC for 5

15-30 g/L NaCl

30 oC

25: 1

100 oC50 min.

Rinsing

67

minutes and again rinsed in tap water. Dyed samples were squeezed and dried

at room temperature.

Figure 12 Dyeing profile of untreated cotton fabric with reactive dyes

3.3.2.3 Dyeing of wool fabrics with acid dyes

Wool fabrics were dyed with acid dyes (2% owf) at a liquor ratio of

30:1. The pH of the bath was adjusted to 3 with acetic acid prior to adding the

fabric. The bath was then heated to 100 oC in 25 minutes and held at this

temperature for 1 hour. The bath was then cooled and discarded. The fabric

was rinsed in tap water and dried.

3.3.3 DYEING CONDITIONS FOR PRETREATED COTTON FABRICS

3.3.3.1 Dyeing of pretreated cotton fabrics with direct dyes

Pretreated cotton fabrics were dyed with direct dyes in the absence of

salt in a laboratory dyeing machine at a liquor ratio of 25:1 under neutral

conditions (Table 13). Dye bath was then cooled and dyed fabrics were rinsed

20g/ L Na2CO3

60 g/ L NaCl

25: 1

45 min. 80 oC

30 oC

Rinsing

68

thoroughly in tap water and dried at room temperature. The effect of

temperature, time, dye concentration and fixing agent concentration on the

dyeing behaviour of pretreated cotton fabrics has been investigated. For

comparison, untreated cotton fabrics were also dyed under the same conditions.

Table 13 Dyeing conditions with direct dyes

Dyeing Temperature Time Conc. of dyea Conc. of cationic agentb method (oC) (min.) (% owf) (% owf)

1. 60-100 30 2 2

2. 100 20-50 2 2

3. 100 30 2-6 2

4. 100 30 2 1-4

a. C. I. Direct Orange 26

b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N-

(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)-

N,N-dimethylammonium chloride

3.3.3.2 Dyeing of pretreated cotton fabrics with reactive dyes

Pretreated cotton fabrics were dyed with reactive dyes in a laboratory

dyeing machine at a liquor ratio of 25:1 (Table 14). Dye bath was then cooled

and dyed fabrics were rinsed thoroughly in tap water and dried at room

temperature. The effect of dyeing conditions on the pretreated fabrics has been

investigated in detail. For comparison, untreated cotton fabrics were also dyed

with reactive dyes under the same conditions.

69

Table 14 Dyeing conditions with reactive dyes

Dyeing Temperature Time Na2CO3 Conc. of dyea Conc. of cationic method (oC) (min.) (g/L) (% owf) agentb (% owf)

1. 60-100 30 - 2 2

2. 80 15-45 - 2 2

3. 80 30 - 2-6 2

4. 80 30 - 2 1-4

5. 80 30 10-20 2 2

a. C. I. Reactive Orange 13

b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N-

(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)-

N,N-dimethylammonium chloride

3.3.3.3 Dyeing of untreated and pretreated cotton fabrics with acid dyes

Untreated and pretreated (2% owf) cotton fabrics were dyed with acid

dyes (1-4% owf) in a laboratory dyeing machine according to the dyeing

profile shown in Figure 13. Dyed samples were then rinsed in tap water,

squeezed and dried at room temperature.

70

Dye 1-4% owf

pH Neutral

Liquor ratio 30:1

Figure 13 Dyeing profile of untreated and pretreated cotton fabrics with acid

dyes

3.3.4 APPLICATION OF CATIONIC FIXING AGENTS AS AN

AFTERTREATMENT

A bis-reactive derivative of quaternary ammonium salt (Compound 30b)

was applied to cotton fabrics dyed with direct dyes. The effect of different pH

conditions and concentration on the effectiveness of this cationic fixing agent

has been investigated.

3.3.4.1 Dyeing with direct dyes

Cotton fabrics were dyed with direct dyes (2% owf) in a laboratory

dyeing machine at a liquor ratio of 25:1 using 15g/L of sodium chloride.

Dyeing was started at 30 oC and then temperature was raised to 100 oC over 20

minutes. Dyeing was continued at this temperature for a further 50 minutes.

100 oC

60 min.

30 oC Rinsing

71

Dye bath was then cooled to 70 oC and discarded. Dyed fabrics were rinsed

thoroughly and dried at room temperature.

3.3.4.2 Aftertreatment with cationic fixing agent (30b)

2% and 4% (owf) of bis-reactive cationic agent (30b) was applied to the

dyed fabrics (2% owf) in a laboratory dyeing machine at a liquor ratio of 25:1.

The cationic agent was applied both at pH 7 and pH 11. The method used is

given in Figure 14.

A Dyed cotton fabric (2% owf)

Cationic fixing agent (2% or 4% owf)

Either pH 7 or pH 11 using 1% NaOH soln.

Liquor ratio 25:1

Figure 14 Aftertreatment of direct dyed cotton fabrics with cationic fixing

agent (30b)

3.4 COLOUR MEASUREMENT

The reflectance values and the corresponding CIE L*, a*, b*, C* and ho

colour coordinates of the samples were measured using Datacolor SF 650X

40 oC

30 minutes

A

72

Spectraflash attached to a personal computer under illuminant D65 using a 10o

standard observer. From the reflectance values at the λ max. of the dyeings (R),

the colour strength (K/S) values of the samples were calculated using Kubelka-

Munk equation (Eqn. 1).

3.5 FASTNESS TESTING

Colour fastness is the fundamental requirement of dyed textile materials.

It is defined [128] as "Resistance to the change in colour of the dyed textile

material when subjected to a particular set of conditions." Colour fastness is

usually assessed with respect to change in colour of the fabric in the test and

with respect to staining of adjacent fabrics.

3.5.1 WASH FASTNESS

Wash fastness of the dyeings was determined according to standard ISO

methods [129]. Samples were subjected to ISO 105: C06/C2S wash test (60

oC).

2R

(1 – R) 2 K/S = Eqn. 1

73

3.5.1.1 Test procedure

The composite specimen (fabric under test stitched with adjacent fabric)

along with 25 steel balls was placed in each container and necessary amount of

detergent solution, previously heated to 60 ± 2 oC, was added to give a liquor

ratio of 50:1. The specimen was run at this temperature for 30 minutes. The

composite specimen was removed, rinsed twice for a period of 1 minute in

separate 100 ml portions of water at 40 oC. The specimen was squeezed,

unstitched and dried at room temperature. After drying, samples were visually

assessed for shade change and staining on adjacent fabric using grey scale. The

grey scale ranges from 5 for no shade change (or no stain on adjacent fiber)

down to 1 for a severe shade change (or staining) with half points in between.

3.5.2 LIGHT FASTNESS

Colour fastness to light of the dyeings was tested according to AATCC

test method 16-2003 [130]. The dyed samples were exposed to xenon arc using

AATCC Blue Wool Light Fastness Standards as a reference. The

colourfastness to light of the specimens was evaluated by comparison of the

colour change of the exposed portion to the masked portion of the test

specimen or unexposed original material using grey scale for colour change.

RREESSUULLTTSS AANNDD

DDIISSCCUUSSSSIIOONN

75

Chapter 4

RREESSUULLTTSS AANNDD DDIISSCCUUSSSSIIOONN

4.1 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY

AND 3-CHLORO-2-HYDROXY PROPYL DERIVATIVES

It has been found that below 30 oC either little or no product is formed

even after stirring for long hours. High temperature was avoided due to the

cleavage of epoxy ring of epichlorohydrin and the synthesised products. In

addition high temperature may lead to the polymerisation of product. A

temperature range of 30–50 oC was found to be most suitable to get the

products using stoichiometric ratio of reactants. Reaction conditions and yields

of these compounds are given in Table 15. Reactions were monitored by

performing specific chemical tests for epoxy group [125], tertiary amines [126]

and quaternary ammonium salts [127]. Epoxy compounds (28a-d and 30a-b)

gave negative test for tertiary amines and positive test for quaternary amines

whereas halohydroxy compounds (29a-d and 31a-b) showed positive test for

76

quaternary amines and negative test for tertiary amines and epoxy group. The

IR and 1H–NMR data, which have been given in experimental section, also

confirmed the identity of the compounds.

Table 15 Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b and 31a-b

Salt Reaction conditions Yield (%) Salt Reaction conditions Yield (%)

28a 30 oC, 9 hrs. 57 29a 40-50 oC, 8 hrs. 59

28b 40-50 oC, 8 hrs. 72 29b 40-50 oC, 8 hrs. 69

28c 30 oC, 9 hrs. 75 29c 40-50 oC, 8 hrs. 78

28d 40 oC, 8 hrs. 65 29d 40 oC, 7 hrs. 73

30a 40-50 oC, 10 hrs. 53 31a 40-50 oC, 10 hrs. 40

30b 40-50 oC, 9 hrs. 86 31b 30-40 oC, 8 hrs. 84

Solubility of these compounds has been checked in different solvents.

All the compounds were soluble in methanol, DMSO and water while they

were insoluble in ether and chloroform. Purity of these compounds has been

checked by thin layer chromatography using precoated silica gel plates (Merck

60F254) and following the method of Bluhm and Li [131]. It has further been

verified by elemental analysis and results of elemental analysis have been

given in experimental section.

The products obtained were in the form of viscous liquid due to their

hygroscopic nature. However under anhydrous conditions using chloroform as

a solvent, products were obtained as white crystalline solid. These crystalline

products again turned into viscous liquid on exposure to air/ atmosphere after a

77

short while. Therefore, the products were dried before elemental analysis by

keeping in vacuum desiccator for several days.

4.2 APPLICATIONS

The synthesised quaternary ammonium chlorides have been applied to

the cotton fabrics as pretreatments and aftertreatments and promising results

have been obtained. The absorption maximum (λ max.) values of the dyes

(used in this work) in aqueous solution were measured by UV-Visible

Spectrophotometer and the λ max. values of the cotton fabrics dyed with these

dyes were measured by datacolor. The λ max. values of the dyes in aqueous

solution and on the dyed fabrics are given in Table 16.

Table 16 λ max. values of dyes

λ max. (nm) λ max. (nm) λ max. (nm)

Dye in water of fabrics dyed under of fabrics dyed under

neutral conditions alkaline conditions

C. I. Direct Orange 26 507 510 -

C. I. Direct Red 31 524 540 -

C. I. Direct Black 22 658 630 -

C. I. Reactive Orange 13 492 500 500

C. I. Reactive Red 45 520 520 540

C. I. Reactive Blue 5 598 600 610

C. I. Acid Yellow 23 416 400 -

C. I. Acid Black 234 608 610 -

78

4.2.1 PRETREATMENT WITH CATIONIC FIXING AGENTS

Cotton fabrics were cationised by pretreatment with mono-reactive

(compound 28c) and bis-reactive derivatives (compound 30a and 30b) under

alkaline conditions using the exhaust method. A bis-reactive derivative,

compound 30b was used to determine the optimum conditions for the

pretreatment of cotton fabrics. The amount of cationic agent (compound 30b)

introduced into the cotton fabric was evaluated from the chlorine content of the

fabric. The chlorine content of the cationised fabrics under different

pretreatment conditions have been given in Table 17-20 and graphically

represented in Figure 15-18.

4.2.1.1 Effect of temperature and time on the cationisation of cotton

fabrics

As shown in Table 17, chlorine content of the fabric increased with the

increase in temperature up to 80 oC and then decreased rapidly. From Table 18,

it can also be observed that chlorine content of the fabric increased with time

up to 30 minutes and then decreases rapidly. The decrease in chlorine content

may be due to the partial hydrolysis of the cationic agent that occurs at high

temperature prior to its reaction with cellulose. Therefore, further study of the

pretreatment conditions was carried out at 80o C for 30 minutes.

79

Table 17 Effect of temperature on the chlorine

content of cationised fabric

Temperature Chlorine content

(oC) of the fabric (%)

40 0.2838

60 0.2950

80 0.3308

100 0.2662

0

0.1

0.2

0.3

0.4

0 20 40 60 80 100 120

Temp. (oC)

Chl

orin

e co

nten

t (%

)

Figure 15 Effect of temperature on the chlorine content of cationised cotton

fabric [Cationisation conditions: Compound 30b; 2% (owf), NaOH

30% (ow cationic agent), Liquor ratio 25:1, Time 30 min.]

80

Table 18 Effect of pretreatment time on the

chlorine content of cationised fabric

Time Chlorine content

(min.) of the fabric (%)

20 0.2844

30 0.3308

40 0.2917

50 0.2623

0

0.1

0.2

0.3

0.4

0 10 20 30 40 50 60

Time (min.)

Chl

orin

e co

nten

t (%

)

Figure 16 Effect of pretreatment time on the chlorine content of cationised

cotton fabric [Cationisation conditions: Compound 30b; 2% (owf),

NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC]

81

4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide (ow cationic

agent) concentrations on the cationisation of cotton fabrics

The effect of cationic agent concentration (based on the weight of the

fabric) and sodium hydroxide concentration (based on the weight of cationic

agent) on the chlorine content of the cationised fabric has also been

investigated. It was found that chlorine content of the fabric increases with the

increase in the conc. of the cationic agent (Table 19). However, the rate of

increase of chlorine content decreases with the increase in the conc. of the

cationic agent above 2% (owf).

Table 19 Effect of cationic agent concentration on

the chlorine content of cationised fabric

Conc. of cationic agent Chlorine content

(% owf) of the fabric (%)

2 0.3308

4 0.3459

6 0.3678

8 0.3806

10 0.3986

From Table 20, it can also be seen that chlorine content of the fabric

increases with the increase in the conc. of sodium hydroxide up to 30% (ow

cationic agent). A further increase in the conc. of sodium hydroxide decreases

82

the chlorine content of the fabric suggesting that a conc. of 30% (ow cationic

agent) was sufficient for the fixation of cationic agent with the fabric.

Table 20 Effect of NaOH concentration on the

chlorine content of cationised fabric

Conc. of NaOH Chlorine content

(% ow cationic agent) of the fabric (%)

10 0.2741

20 0.2844

30 0.3308

40 0.2940

The use of high concentration of alkali or the fixing agent increases the

rate of hydrolysis of the cationic agent which in turn decreases the chlorine

content of the fabric. Thus, cationic agent 2% (owf) and sodium hydroxide

30% (ow cationic agent) were chosen as optimum conditions for the

pretreatment of cotton fabrics. The effect of cationic agent and NaOH

concentration on the chlorine content of cationised cotton fabric has been

graphically represented in Figure 17 and 18.

Under the above mentioned conditions, cotton fabrics were cationised

by pretreatment with bis-reactive derivatives 30a (C-1) and 30b (C-2). A

mono-reactive derivative, 28c was also used for the cationisation of cotton

fabrics under the same conditions (C-3). This compound contains cyano group,

hydrolysis of which might take place during pretreatment.

83

0

0.1

0.2

0.3

0.4

0.5

0 2 4 6 8 10 12

Conc. of cationic agent (% owf)

Chl

orin

e co

nten

t (%

)

Figure 17 Effect of cationic agent concentration on the chlorine content of

cationised cotton fabric [Cationisation conditions: Compound 30b;

NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC,

Time 30 min.]

0

0.1

0.2

0.3

0.4

0 10 20 30 40 50

Conc. of NaOH (% ow cationic agent)

Chl

orin

e co

nten

t (%

)

Figure 18 Effect of NaOH conc. on the chlorine content of cationised cotton

fabric [Cationisation conditions: Compound 30b; 2% (owf), Temp.

80 oC, Time 30 min., Liquor ratio 25:1]

84

4.2.2 DYEING OF UNTREATED AND PRETREATED COTTON

FABRICS WITH DIRECT DYES

Untreated cotton fabric (C) and cotton fabrics pretreated with compound

30a (C-1), 30b (C-2) and 28c (C-3) were dyed with direct dyes in the absence

of salt under neutral conditions (Table 13). The effect of pretreatment on the

direct dyeing properties of cotton fabrics was studied in detail. This study was

carried out with C.I. Direct Orange 26 (λ max. 510 nm). The % Reflectance

values (%R) of the dyeings were measured using datacolor. From the

reflectance values at the λ max. of the dyeings (R), the colour strength (K/S)

values of the dyed fabrics were calculated using Kubelka-Munk equation (See

Eqn.1 on page 72).

4.2.2.1 Effect of dyeing temperature

The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton

fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt

under neutral conditions at different temperature conditions. The % Reflectance

values (%R) of the dyeings were measured and from the reflectance values at

the λ max. of the dyeings (R), the colour strength (K/S) values of the dyed

fabrics were calculated and are given in Table 21.

85

Table 21 % Reflectance (at λ max. 510 nm) and the colour strength (K/S)

values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)

cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) under

different temperature conditions

Temperature Cotton % Reflectance at Reflectance Colour strength

(oC) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

60 C 8.22 0.0822 5.12

C-1 4.85 0.0485 9.33

C-2 3.94 0.0394 11.71

C-3 3.66 0.0366 12.67

70 C 7.25 0.0725 5.93

C-1 4.29 0.0424 10.67

C-2 3.49 0.0349 13.34

C-3 3.35 0.0335 13.94

80 C 6.13 0.0613 7.18

C-1 3.86 0.0386 11.97

C-2 3.05 0.0305 15.40

C-3 3.13 0.0313 14.99

90 C 5.21 0.0521 8.62

C-1 3.34 0.0334 13.98

C-2 2.78 0.0278 16.99

C-3 2.91 0.0291 16.19

100 C 4.56 0.0456 9.98

C-1 3.00 0.0300 15.68

C-2 2.49 0.0249 19.09

C-3 2.68 0.0268 17.67

a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-

diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-

N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-

epoxypropyl)-N,N-dimethylammonium chloride

86

The dyeing behaviour of untreated cotton (C) and cotton cationised with

30a (C-1), 30b (C-2) and 28c (C-3) with direct dyes has shown that an increase

in temperature is accompanied by an increase in the colour strength (K/S) of

the dyeings (Figure 19).

0

5

10

15

20

25

50 60 70 80 90 100 110

Temp. (oC)

K/S

K/S CK/S C-1K/S C-2K/S C-3

Figure 19 Effect of temperature on the colour strength (K/S) of untreated

(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed

with C.I. Direct Orange 26 (2% owf)

This may be due to the increase in the disaggregation of the dye

molecules and /or increase in the rate of dye penetration into the fibre. During

the normal dyeing process of untreated cotton fabric, an equilibrium is

established between the dye in the fibre and dye in the solution. However,

during the dyeing of cationised cotton, this equilibrium is shifted towards

87

cationic cotton due to increased dye uptake as a result of interaction between

the dye anions and cations in the fibre. The cationised cotton fabrics C-1 and

C-2 would have higher content of cationic dye sites relative to C-3 due to their

bis-reactive and bis-cationic nature. However, C-1 showed lower colour

strength than C-2 and C-3 because of the steric hindrance of the cationic agent

with the dye molecules. In other words, increase in the length of hydrocarbon

chain attached to the ammonium group decreased the colour strength of the

dyeings. Generally, higher content of the cationic dye sites in the fibre results

in greater dye exhaustion and fixation, thus enhancing the colour strength of

the dyeings.

4.2.2.2 Effect of dyeing time


fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt

under neutral conditions at 100 oC for different time periods. The %

Reflectance values (%R) of the dyeings were measured and from the


values of the dyed fabrics were calculated and are given in Table 22.

88



cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) at 100 oC

for different time periods

Dyeing time Cotton % Reflectance at Reflectance Colour strength

(min.) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

20 C 5.38 0.0538 8.32

C-1 3.99 0.0399 11.55

C-2 3.12 0.0312 15.04

C-3 3.37 0.0337 13.85

30 C 4.56 0.0456 9.98

C-1 3.00 0.0300 15.68

C-2 2.49 0.0249 19.09

C-3 2.68 0.0268 17.67

40 C 4.02 0.0402 11.45

C-1 3.36 0.0336 13.89

C-2 2.78 0.0278 16.99

C-3 2.74 0.0274 17.26

50 C 3.83 0.0383 12.07

C-1 3.72 0.0372 12.45

C-2 3.14 0.0314 14.93

C-3 2.81 0.0281 16.80





An increase in dyeing time also results in an increase in the colour

strength (K/S) of the dyeings (Figure 20). Results revealed that a dyeing time

of 30 minutes was sufficient to achieve the maximum colour strength for

cationised cotton fabrics (C-1, C-2 and C-3). A further increase in dyeing time

89

resulted in a decrease in the colour strength of cationised fabrics in all cases.

This may be due to the deterioration of the fixing agent-fibre bonds and / or

dye-fixing agent complex on prolonged heating.

0

5

10

15

20

25

0 10 20 30 40 50 60

Time (min.)

K/S


Figure 20 Effect of dyeing time on the colour strength (K/S) of untreated (C)

and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed

with C.I. Direct Orange 26 (2% owf)

4.2.2.3 Effect of dye concentration


fabrics were dyed with different concentrations (2-6% owf) of C.I. Direct

Orange 26 in the absence of salt under neutral conditions at a temperature of

100 oC for 30 minutes. The % Reflectance values (%R) of the dyeings were

measured and from the reflectance values at the λ max. of the dyeings (R), the

colour strength (K/S) values of the dyed fabrics were calculated and are given

in Table 23.

90



cotton fabrics dyed with C.I. Direct Orange 26 at 100 oC for 30

minutes using different dye concentrations

Dye conc. Cotton % Reflectance at Reflectance Colour strength

(% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

2 C 4.56 0.0456 9.98

C-1 3.00 0.0300 15.68

C-2 2.49 0.0249 19.09

C-3 2.68 0.0268 17.67

3 C 4.23 0.0423 10.84

C-1 2.98 0.0298 15.79

C-2 2.46 0.0246 19.33

C-3 2.57 0.0257 18.46

4 C 3.90 0.0390 11.84

C-1 2.94 0.0294 16.02

C-2 2.42 0.0242 19.67

C-3 2.47 0.0247 19.25

5 C 3.53 0.0353 13.18

C-1 2.61 0.0261 18.17

C-2 2.37 0.0237 20.10

C-3 2.19 0.0219 21.84

6 C 3.20 0.0320 14.64

C-1 2.31 0.0231 20.65

C-2 2.18 0.0218 21.94

C-3 1.97 0.0197 24.39





91

From Figure 21, it is clear that an increase in the dye concentration

increases the colour strength for both the untreated (C) and pretreated fabrics

(C-1, C-2 and C-3). This may be due to the excess of dye anions in the dye

solution at higher conc. which form hydrogen bonds with the fabric in addition

to those having electrostatic interactions with the cationic dye sites of the

pretreated fabrics.

0

5

10

15

20

25

30

0 1 2 3 4 5 6 7

Dye conc. (% owf)

K/S


Figure 21 Effect of dye conc. on the colour strength (K/S) of untreated (C)

and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics dyed with

C.I. Direct Orange 26

4.2.2.4 Effect of cationic agent concentration

The cotton fabrics pretreated with different concentrations of compound

30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Direct Orange 26 (2%

owf) in the absence of salt under neutral conditions at a temperature of 100 oC

92

for 30 minutes. The % Reflectance values (%R) of the dyeings were measured

and from the reflectance values at the λ max. of the dyeings (R), the colour

strength (K/S) values of the dyed fabrics were calculated and are given in

Table 24.


values of cotton fabrics pretreated with different conc. of cationic

agents (C-1, C-2 and C-3) and dyed with C.I. Direct Orange 26

(2% owf) at 100 oC for 30 minutes

Cationic agent Cotton % Reflectance at Reflectance Colour strength

conc. (% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

1 C-1 3.59 0.0359 12.94

C-2 3.56 0.0356 13.06

C-3 3.03 0.0303 15.51

2 C-1 3.00 0.0300 15.68

C-2 2.49 0.0249 19.09

C-3 2.68 0.0268 17.67

3 C-1 3.11 0.0311 15.09

C-2 2.78 0.0278 16.99

C-3 2.77 0.0277 17.06

4 C-1 3.22 0.0322 14.54

C-2 3.17 0.0317 14.78

C-3 2.87 0.0287 16.43

a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium

chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-

dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-


93

The effect of cationic agent concentration on the uptake of direct dyes is

shown in Figure 22. The results indicated that an increase in the concentration

of cationic agent above 2% owf causes a decrease in the colour strength of the

pretreated dyeings. This may be due to the partial hydrolysis of the cationic

agent that occurs at higher concentrations under alkaline conditions during the

pretreatment step, resulting in a decrease in the cationic dye sites in the fibre

which in turn decreased the colour strength of the dyeings.

0

5

10

15

20

25

0 1 2 3 4 5

Conc. of cationic agent (% owf)

K/S

K/S C-1K/S C-2K/S C-3

Figure 22 Effect of cationic agent concentration on the colour strength (K/S)

of pretreated cotton fabrics (C-1, C-2 and C-3) dyed with C.I.

Direct Orange 26 (2% owf)

On the basis of the results obtained, untreated (C) and pretreated (C-1,

C-2 and C-3; 2% owf) cotton fabrics were dyed with three direct dyes (2%

owf) in the absence of salt at neutral pH. The colour strength and fastness

properties of these dyeings are given in Table 25. The results indicated that

94

pretreated fabrics C-1, C-2 and C-3 have higher colour strength (K/S) values

than the untreated fabrics (Figure 23). The wash fastness properties of

pretreated fabrics were comparable or slightly better than the untreated fabrics

but with higher colour strength. However, pretreatment has caused a slight

decrease in the light fastness of the pretreated dyeings. This is common with

such treatments [16].

Table 25 Colour strength (K/S) and fastness properties of direct dyes (2%

owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)

cotton fabrics

Wash fastness

_________________

Shade Staining Light

Dye Cotton fabrica K/S change on cotton fastness

C.I. Direct Orange 26 C 9.98 3-4 3-4 4-5

C-1 15.68 3 3-4 4

C-2 19.09 3-4 4 4

C-3 17.67 3 3 3-4

C.I. Direct Red 31 C 8.94 2-3 4 3-4

C-1 14.58 2-3 3-4 3

C-2 15.83 3 3 3

C-3 15.68 1-2 2-3 3

C.I. Direct Black 22 C 12.56 4 3-4 5

C-1 13.67 3 4 5

C-2 14.96 3-4 3-4 5

C-3 14.64 3 3 4-5





95

The effect of additional group in mono-reactive cationic agent (28c) has

also been investigated. The presence of additional group enhanced the colour

strength of the dyeings (C-3) as a result of the interaction with other suitable

groups in the dye molecules. Since these interactions still relies on electrostatic

forces therefore, the wash fastness properties of the dyeings were inferior to the

fabrics pretreated with bis-reactive cationic agents (C-1 and C-2).

0

5

10

15

20

25

0 1 2 3 4 5 6

Dye conc. (% owf)

K/S


Figure 23 Colour strength (K/S) values of untreated (C) and pretreated (C-1,

C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange

26

A comparison of the direct dyeing of pretreated cotton fabrics (C-1, C-2

and C-3; 2% owf) (Table 25) with untreated cotton fabrics dyed by

conventional method (Table 26) has indicated that pretreated fabrics showed

slightly lower colour strength as compared to the untreated cotton fabrics dyed

96

by conventional method. However, the wash fastness results of pretreated

fabrics were comparable or better than those of untreated fabrics. The colour

strength values of the pretreated fabrics could be enhanced by increasing the

dye conc. as shown in Figure 21.

Table 26 Colour strength (K/S) and fastness properties of untreated cotton

fabrics dyed with direct dyes (2% owf) by conventional method

Wash fastness

________________________________ Light

Dye K/S Shade change Staining on cotton fastness

C.I. Direct Orange 26 23.04 3-4 3 4-5

C.I. Direct Red 31 16.31 2 3 4

C.I. Direct Black 22 18.77 3-4 3-4 5

The above findings revealed that cationised cotton fabrics could be dyed

with direct dyes without salt and require less dyeing time as compared to the

cotton fabrics dyed by conventional methods. Thus, high salt concentrations

can be avoided in the direct dyeing of cotton fabrics which leads to the

pollution of the effluents. Pretreatment of cotton fabrics with cationic fixing

agents has shown good colour strength and comparable wash fastness

properties without adversely affecting the light fastness of the dyeings. In short,

the bis-reactive agents have proved to be more effective than the mono-reactive

agent. Amongst bis-reactive derivatives, the compound with lower steric

hindrance has shown superior results.

97

SSHHAADDEESS OOFF DDIIRREECCTT DDYYEESS OONN UUNNTTRREEAATTEEDD ((CC)) AANNDD

PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN

FFAABBRRIICCSS

C.I. DIRECT ORANGE 26

Untreated cotton (C)

(With salt) (Without salt)

Pretreated cotton

C-1 C-2 C-3

C.I. DIRECT RED 31



Pretreated cotton

C-1 C-2 C-3

98

C.I. DIRECT BLACK 22



Pretreated cotton

C-1 C-2 C-3

99


FABRICS WITH REACTIVE DYES


30a (C-1), 30b (C-2) and 28c (C-3) were dyed with reactive dyes in the

absence of salt and alkali (Table 14). The effect of pretreatment on the reactive

dyeing properties of cotton fabrics was studied in detail. This study was carried

out with C.I. Reactive Orange 13 (λ max. 500 nm). The % Reflectance values

(%R) of the dyeings were measured using datacolor. From the reflectance

values at the λ max. of the dyeings (R), the colour strength (K/S) values of the

dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on

page 72).

4.2.3.1 Effect of dyeing temperature


fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt

and alkali at different temperature conditions. The % Reflectance values (%R)

of the dyeings were measured and from the reflectance values at the λ max. of

the dyeings (R), the colour strength (K/S) values of the dyed fabrics were

calculated and are given in Table 27.

100



cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at

different temperature conditions

Temperature Cotton % Reflectance at Reflectance Colour strength

(oC) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

60 C 51.79 0.5179 0.2243

C-1 44.97 0.4497 0.3367

C-2 28.57 0.2857 0.8929

C-3 17.05 0.1705 2.0178

70 C 52.38 0.5238 0.2164

C-1 43.65 0.4365 0.3637

C-2 27.04 0.2704 0.9843

C-3 16.51 0.1651 2.1110

80 C 53.58 0.5358 0.2010

C-1 42.87 0.4287 0.3806

C-2 26.10 0.2610 1.0462

C-3 16.03 0.1603 2.1993

90 C 54.06 0.5406 0.1951

C-1 42.89 0.4289 0.3802

C-2 26.39 0.2639 1.0266

C-3 17.48 0.1748 1.9478

100 C 54.53 0.5453 0.1895

C-1 42.92 0.4292 0.3795

C-2 26.49 0.2649 1.0199

C-3 19.15 0.1915 1.7067





101

The dyeing behaviour of untreated (C) and pretreated (C-1, C-2 and C-

3) cotton fabrics with reactive dyes has shown that colour strength values of

pretreated cotton fabrics (C-1, C-2 and C-3) increase with the increase in

temperature up to 80 oC and then decrease whereas in case of untreated cotton

fabrics (C) colour strength values gradually decrease with the increase in

temperature (Figure 24).

0

0.5

1

1.5

2

2.5

50 60 70 80 90 100 110

Temp. (oC)

K/S


Figure 24 Effect of temperature on colour strength (K/S) values of untreated

(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed

with C.I. Reactive Orange 13 (2% owf)

The increase in colour strength with temperature in case of pretreated

fabrics results from the greater exhaustion and fixation of reactive dyes due to

the cationic sites present in the fibre while the deterioration of the dye

molecules in case of untreated fabrics and the breaking of fixing agent-fibre

102

bonds or dye-fixing agent complex in case of pretreated fabrics at high

temperature results in a decrease in the colour strength of the dyeings.

However, pretreated fabrics showed higher colour strength values as compared

to the untreated fabrics at all temperatures in all cases due to the greater affinity

of cationic fabrics with the anionic dye molecules. Superior results were

obtained when dyeing was carried out with cotton fabric pretreated with

compound 28c (C-3). This may be the result of interaction between the dye

molecules and the additional group in compound 28c.

4.2.3.2 Effect of dyeing time


fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt

and alkali at 80 oC for different time periods. The % Reflectance values (%R)

of the dyeings were measured and from the reflectance values at the λ max. of

the dyeings (R), the colour strength (K/S) values of the dyed fabrics were

calculated and are given in Table 28.

103



cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at 80

oC for different time periods

Time Cotton % Reflectance at Reflectance Colour strength

(min.) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

15 C 54.44 0.5444 0.1906

C-1 43.53 0.4353 0.3662

C-2 28.37 0.2837 0.9042

C-3 17.19 0.1719 1.9946

30 C 53.58 0.5358 0.2010

C-1 42.87 0.4287 0.3806

C-2 26.10 0.2610 1.0462

C-3 16.03 0.1603 2.1993

45 C 51.56 0.5156 0.2275

C-1 46.53 0.4653 0.3072

C-2 29.32 0.2932 0.8519

C-3 18.01 0.1801 1.8662





Results indicated that the colour strength (K/S) values of pretreated

fabrics (C-1, C-2 and C-3) decrease with the increase in dyeing time above 30

minutes which may be the result of deterioration of dye-fixing agent complex

and/or fixing agent-fibre bonds on prolonged heating at high temperature.

However, the colour strength (K/S) values of untreated cotton fabrics (C)

gradually increase with the increase in dyeing time (Figure 25).

104

0

0.5

1

1.5

2

2.5

0 15 30 45 60

Time (min.)

K/S


Figure 25 Effect of dyeing time on the colour strength (K/S) of untreated (C)


with C.I. Reactive Orange 13 (2% owf)

4.2.3.3 Effect of dye concentration


fabrics were dyed with different concentrations (2-6% owf) of C.I. Reactive

Orange 13 in the absence of salt and alkali at a temperature of 80 oC for 30

minutes. The % Reflectance values (%R) of the dyeings were measured and

from the reflectance values at the λ max. of the dyeings (R), the colour strength

(K/S) values of the dyed fabrics were calculated and are given in Table 29.

105



cotton fabrics dyed with different conc. of C.I. Reactive Orange 13

at 80 oC for 30 minutes



2 C 53.58 0.5358 0.2010

C-1 42.87 0.4287 0.3806

C-2 26.10 0.2610 1.0462

C-3 16.03 0.1603 2.1993

3 C 51.27 0.5127 0.2315

C-1 38.32 0.3832 0.4964

C-2 25.99 0.2599 1.0537

C-3 15.92 0.1592 2.2203

4 C 50.26 0.5026 0.2461

C-1 37.81 0.3781 0.5114

C-2 25.55 0.2555 1.0846

C-3 15.62 0.1562 2.2791

5 C 49.96 0.4996 0.2506

C-1 35.12 0.3512 0.5992

C-2 20.89 0.2089 1.4979

C-3 13.87 0.1387 2.6742

6 C 49.70 0.4970 0.2545

C-1 33.07 0.3307 0.6772

C-2 17.97 0.1797 1.8722

C-3 12.57 0.1257 3.0405





106

From Figure 26, it is clear that increase in the concentration of the dye

resulted in an increase in the colour strength values of the untreated (C) and

pretreated (C-1, C-2 and C-3) cotton fabrics. This may be due to the excess of

dye anions in the dye solution at higher concentrations which interact with the

fabric in addition to those having electrostatic interactions with the cationic dye

sites of the pretreated fabrics.

0

0.5

1

1.5

2

2.5

3

3.5

0 1 2 3 4 5 6 7

Dye conc. (% owf)

K/S




with C.I. Reactive Orange 13

4.2.3.4 Effect of cationic agent concentration

The cotton fabrics pretreated with different concentrations of compound

30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Reactive Orange 13

(2% owf) in the absence of salt and alkali at a temperature of 80 oC for 30

107

minutes. The % Reflectance values (%R) of the dyeings were measured and

from the reflectance values at the λ max. of the dyeings (R), the colour strength

(K/S) values of the dyed fabrics were calculated and are given in Table 30.


values of cotton fabrics pretreated with different conc. of cationic

agents (C-1, C-2 and C-3) and dyed with C.I. Reactive Orange 13

(2% owf) at 80 oC for 30 minutes

Cationic agent Cotton % Reflectance at Reflectance Colour strength

conc. (% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

1 C-1 49.23 0.4923 0.2617

C-2 34.88 0.3488 0.6078

C-3 24.86 0.2486 1.1355

2 C-1 42.87 0.4287 0.3806

C-2 26.10 0.2610 1.0462

C-3 16.03 0.1603 2.1993

3 C-1 43.57 0.4357 0.3654

C-2 26.88 0.2688 0.9945

C-3 17.40 0.1740 1.9605

4 C-1 43.88 0.4388 0.3588

C-2 27.12 0.2712 0.9792

C-3 18.84 0.1884 1.7481





The effect of cationic agent concentration on the uptake of reactive dyes

indicated that an increase in the concentration of cationic agent above 2% (owf)

108

causes a decrease in the colour strength of the pretreated dyeings (Figure 27).

This may be due to the partial hydrolysis of the cationic agent that occurs at

higher concentrations under alkaline conditions during the pretreatment step,

resulting in a decrease in the cationic dye sites in the fibre which in turn

decreased the colour strength of the dyeings.

0

0.5

1

1.5

2

2.5

0 1 2 3 4 5

Cationic agent conc. (% owf)

K/S


Figure 27 Effect of cationic agent concentration on the colour strength (K/S)

of pretreated (C-1, C-2 and C-3) cotton fabrics dyed with C.I.

Reactive Orange 13 (2% owf)

4.2.3.5 Effect of alkali (anhydrous Na2CO3)

The effect of alkali on the reactive dyeing properties of pretreated

fabrics was investigated. The pretreated cotton fabrics (C-1, C-2 and C-3; 2%

owf) were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt

but in the presence of alkali at a temperature of 80 oC for 30 minutes. The %

Reflectance values (%R) of the dyeings were measured and from the

109


values of the dyed fabrics were calculated and are given in Table 31.


values of pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf)

dyed with C.I. Reactive Orange 13 (2% owf) at 80o C for 30

minutes using different amounts of alkali

Amount of Cotton % Reflectance at Reflectance Colour strength

alkali (g/L) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R

NIL C-1 42.87 0.4287 0.3806

C-2 26.10 0.2610 1.0462

C-3 16.03 0.1603 2.1993

10g/L C-1 23.74 0.2374 1.2248

C-2 20.56 0.2056 1.5347

C-3 13.08 0.1308 2.8880

20g/L C-1 12.58 0.1258 3.0374

C-2 12.40 0.1240 3.0942

C-3 12.28 0.1228 3.1330





The pretreated cotton fabrics (C-1, C-2 and C-3) have shown more

pronounced results when the dyeing was carried out in the presence of alkali

(Figure 28). The use of anhydrous sodium carbonate in the reactive dyeing of

pretreated fabrics enhanced the colour strength of the dyeings even in the

110

absence of salt as a result of fixation of the dye with the fibre under alkaline

conditions.

0

0.5

1

1.5

2

2.5

3

3.5

NIL 10g/L 20g/L

Amount of alkali (Na2CO3 anhydrous)

K/S


Figure 28 Effect of alkali (Na2CO3) on the colour strength (K/S) of pretreated

(C -1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive

Orange 13 (2% owf)

As shown in Figure 28, colour strength values increase with the

increase in the concentration of alkali. It is also clear that at higher alkali

concentration, colour strength values of the pretreated fabrics (C-1, C-2 and C-

3) were independent of the cationic agent used. This indicates that the cationic

agents used for the pretreatment of cotton fabrics have exhausted the dyes on to

the fabric due to the interaction between cationic agents and anionic dye

molecules and then fixation is brought about under alkaline conditions. Thus,

the exhaustion of reactive dyes onto cotton fabrics can be obtained by the

111

pretreatment of cotton fabrics with cationic fixing agents instead of using high

salt concentrations which is usually required for reactive dyeing.

Using the above mentioned dyeing conditions, untreated (C) and

pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with three

reactive dyes (2% owf) in the absence of salt and alkali (Table 32).

Table 32 Colour strength (K/S) and fastness properties of reactive dyes (2

% owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2%

owf) cotton fabrics in the absence of salt and alkali

Wash fastness

________________



C.I. Reactive Orange 13 C 0.2010 2-3 5 5

C-1 0.3806 2 5 4

C-2 1.0462 1 5 3-4

C-3 2.1993 1 4-5 3

C.I. Reactive Red 45 C 0.0820 2 5 5

C-1 0.1455 1-2 5 3-4

C-2 0.5602 1 5 3-4

C-3 0.7816 1 5 3

C.I. Reactive Blue 5 C 0.079 3 5 5

C-1 0.2838 4 5 4

C-2 0.7353 4-5 4-5 4

C-3 1.39 2-3 4-5 3-4





112

Dyeing of pretreated fabrics (C-1, C-2 and C-3; 2% owf) was also

carried out without salt but in the presence of alkali (anhydrous Na2CO3;

20g/L) at the same time. The colour strength and fastness properties of these

dyeings are given in Table 33.


% owf) on pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics

in the presence of alkali (anhydrous Na2CO3; 20g/L)

Wash fastness

________________



C.I. Reactive Orange 13 C-1 3.23 2-3 5 5

C-2 3.09 3-4 5 5

C-3 3.13 4 5 4-5

C.I. Reactive Red 45 C-1 1.09 2-3 5 4-5

C-2 1.16 4 5 4-5

C-3 1.14 2-3 5 4

C.I. Reactive Blue 5 C-1 3.82 3 5 4-5

C-2 4.71 4 5 4-5

C-3 5.25 4-5 5 4





A comparative study of the reactive dyeing of pretreated cotton fabrics

in the presence of alkali (Table 33) and untreated fabrics dyed by conventional

113

method (Table 34) revealed that cationic cotton showed lower colour strength

but similar wash fastness results as compared to untreated fabrics dyed by

conventional method.


% owf) on untreated cotton fabrics dyed by conventional method

Wash fastness

________________


Dye Cotton fabric K/S change on cotton fastness

C. I. Reactive Orange 13 Untreated 9.86 3-4 5 5

C. I. Reactive Red 45 Untreated 5.02 3-4 5 5

C. I. Reactive Blue 5 Untreated 12.14 4-5 5 5

The overall results indicate that pretreated fabrics C-1, C-2 and C-3

could be dyed with reactive dyes in the absence of salt and alkali. Reactive

dyeing of pretreated cotton fabrics without salt and alkali gave higher colour

strength and comparable wash fastness properties relative to the corresponding

untreated fabrics (Table 32). Although the use of alkali has further enhanced

the colour strength values of pretreated dyeings (Table 33) yet the results were

lower than the fabrics dyed by conventional method. On the contrary, the wash

fastness results of the pretreated dyeings were similar to the untreated

conventional dyeings. Thus, high electrolyte concentration can be avoided by

the pretreatment of cotton fabrics with cationic fixing agents. The presence of

some suitable groups in the cationic agents may further improve the results.

114

SSHHAADDEESS OOFF RREEAACCTTIIVVEE DDYYEESS OONN UUNNTTRREEAATTEEDD ((CC)) AANNDD

PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN

FFAABBRRIICCSS

C.I. REACTIVE ORANGE 13


(With salt and alkali) (Without salt and alkali)

Pretreated cotton

With alkali Without salt and alkali

C-1

C-2

C-3

115

C.I. REACTIVE RED 45



Pretreated cotton


C-1

C-2

C-3

116

C.I. REACTIVE BLUE 5



Pretreated cotton


C-1

C-2

C-3

117


FABRICS WITH ACID DYES


30a (C-1), 30b (C-2) and 28c (C-3) were dyed with acid dyes (1-4% owf)

under neutral conditions (Figure 13). The effect of pretreatment on the dyeing

properties of cotton fabrics with acid dyes was studied. This study was carried

out with C.I. Acid Yellow 23 (λ max. 400 nm). The % Reflectance values

(%R) of the dyeings were measured using datacolor and from the reflectance

values at the λ max. of the dyeings (R), the colour strength (K/S) values of the

dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on

page 72) and are given in Table 35.

118



cotton fabrics dyed with different concentrations of C.I. Acid

Yellow 23 at 100 oC for 60 minutes



1 C 53.36 0.5336 0.2038

C-1 51.88 0.5188 0.2231

C-2 51.73 0.5173 0.2252

C-3 42.66 0.4266 0.3853

2 C 52.46 0.5246 0.2154

C-1 47.57 0.4757 0.2889

C-2 47.28 0.4728 0.2939

C-3 33.41 0.3341 0.6636

3 C 52.34 0.5234 0.2169

C-1 46.83 0.4683 0.3018

C-2 44.74 0.4474 0.3412

C-3 29.16 0.2916 0.8604

4 C 51.99 0.5199 0.2216

C-1 45.12 0.4512 0.3337

C-2 42.09 0.4209 0.3983

C-3 25.57 0.2557 1.0832





From Figure 29, it can be observed that colour strength increased with

increase in dye concentration applied to the cationised fabrics whereas in case

of untreated fabric colour strength was very low because acid dyes have low

119

affinity for cellulose. It was also observed that colour strength (K/S) of the

cotton fabric modified with compound 28c (C-3) was higher as compared to the

other pretreated fabrics (C-1 and C-2) suggesting that additional group in

compound 28c has also developed some interactions with the dye molecules.

0

0.2

0.4

0.6

0.8

1

1.2

0 1 2 3 4 5

Conc. of dye (% owf)

K/S




with C.I. Acid Yellow 23

The colour strength and wash fastness results of acid dyeings (2% owf)

(Table 36) revealed that cationic cotton could be dyed with acid dyes.

Although the colour strength (K/S) values of cationic cotton were lower than

that of wool dyed with the same acid dye however, the wash fastness results of

acid dyes on cationic cotton were comparable to those on wool dyed with the

same acid dye except the colour change of pretreated cotton fabrics dyed with

120

C.I. Acid Black 234. On the contrary, the colour change of untreated and

pretreated cotton fabrics dyed with C.I. Acid Yellow 23 was better than that on

wool dyed with the same acid dye. This difference of colour change during

wash fastness testing indicated that C.I. Acid Yellow 23 was more firmly

attached to the cationised cotton fibre as compared to C.I. Acid Black 234. This

behaviour of acid dyes seems to be dependant on the structure of dyes.

Table 36 Colour strength (K/S) and wash fastness properties of acid dyes

on wool, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)

cotton fabrics

Wash fastness

___________________________

Staining

Shade ____________ Light

Dye Fabrica K/S change Cotton Wool fastness

C.I. Acid C 0.21 2 4 4-5 4-5

Yellow 23 C-1 0.28 4 3-4 4-5 4

C-2 0.29 2 3-4 4-5 4

C-3 0.66 2 4 4-5 4

Wool 30.45 1 4-5 4-5 4

C.I. Acid C 1.65 1 4-5 4-5 5

Black 234 C-1 4.01 1 4 4 4

C-2 4.85 1 4 4 4-5

C-3 6.57 1 3-4 4 4-5

Wool 39.65 4-5 3 4 5





121

SSHHAADDEESS OOFF AACCIIDD DDYYEESS OONN WWOOOOLL,, UUNNTTRREEAATTEEDD ((CC))

AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN

FFAABBRRIICCSS

C.I. ACID YELLOW 23

Wool Untreated cotton (C)

Pretreated cotton

C-1 C-2 C-3

C.I. ACID BLACK 234

Wool Untreated cotton (C)

Pretreated cotton

C-1 C-2 C-3

122

4.2.5 AFTERTREATMENT OF DIRECT DYES WITH A BIS-

REACTIVE CATIONIC FIXING AGENT

Cotton fabrics dyed with direct dyes (2% owf) were aftertreated with a

bis-reactive cationic agent compound 30b under neutral and alkaline

conditions. The % Reflectance (%R) values and the colour coordinates of the

dyeings before and after wash fastness test were measured using datacolor.

From the reflectance values at the λ max. of the dyeings (R), the colour

strength (K/S) values of the dyed fabrics were calculated and are given in

Table 37 and 39.

4.2.5.1 Effect of pH on the aftertreatment of direct dyeings

Visual comparison of untreated and aftertreated dyeings have revealed a

slight change in colour of the dyeings aftertreated with cationic fixing agent.

This is usually encountered with such treatments [16]. The extent of this colour

change imparted by aftertreatment at pH 7 varied only slightly than by

aftertreatment at pH 11. This visual assessment was supported by colorimetric

data obtained for untreated and aftertreated dyeings (Table 37).

The results of Table 37 show a decrease in the colour strength (K/S) of

the aftertreated dyeings indicating their low wet fastness due to the bleeding of

some dye during warm (40 oC) aqueous aftertreatment process. However, this

decrease in colour strength (K/S) was found to be dependant on the pH of the

aftertreatment. Results indicated that colour strength (K/S) values of

aftertreated dyeings were higher at pH 11 than at pH 7.

123

Table 37 Colorimetric data for untreated and aftertreated direct dyeings

before wash fastness testing

Aftertreatment

Dye pH conc. (% owf) L* a* b* C* ho K/S

C.I. Direct 0 49.54 60.40 51.78 79.55 40.61 23.04

Orange 26 7 2 50.93 59.69 52.82 79.70 41.51 21.53

4 50.65 60.11 52.88 80.06 41.34 22.15

11 2 49.81 61.39 51.97 80.43 40.25 22.70

4 50.07 61.09 51.56 79.94 40.16 21.84

C.I. Direct 0 34.80 46.97 0.73 46.98 0.89 16.31

Red 31 7 2 34.59 45.34 1.04 45.35 1.31 15.30

4 34.78 45.69 1.01 45.71 1.27 15.46

11 2 34.65 45.86 1.42 45.89 1.77 15.79

4 34.91 46.12 1.43 46.14 1.78 15.62

C.I. Direct 0 19.69 -1.55 -1.86 2.42 230.17 18.77

Black 22 7 2 19.90 -0.67 -2.28 2.38 253.74 17.39

4 19.34 -0.41 -2.33 2.36 260.06 18.09

11 2 19.45 -1.05 -2.04 2.30 242.87 18.54

4 19.55 -1.02 -1.99 2.23 242.84 18.31

The wash fastness results of untreated and aftertreated dyeings

are shown in Table 38, from which it is apparent, that aftertreatment either

under neutral or alkaline conditions improved the wash fastness of the dyeings.

However, wash fastness imparted by aftertreatment at pH 11 was superior to

that imparted by aftertreatment at pH 7. These findings are also supported by

the colorimetric data of untreated and aftertreated dyeings after wash fastness

testing (Table 39).

124

Table 38 Wash fastness data for untreated and aftertreated direct dyeings

Wash fastness ______________________________________

Staining

Aftertreatment Shade ________________________

Dye pH conc. (% owf) change Cotton Viscose

C.I. Direct Orange 26 0 3-4 3 3-4

7 2 4 3-4 4

4 3 4 4

11 2 4-5 4 4-5

4 4-5 4 4-5

C.I. Direct Red 31 0 2 3 3-4

7 2 3 3-4 4

4 2-3 3 3-4

11 2 3 4 4-5

4 3 4 4-5

C.I. Direct Black 22 0 3-4 3-4 4

7 2 4 4 4-5

4 4-5 4 4

11 2 4-5 4-5 4-5

4 4-5 4 4-5

125

Table 39 Colorimetric data for untreated and aftertreated direct dyeings

after wash fastness testing

Aftertreatment

Dye pH conc. (% owf) L* a* b* C* ho K/S

C.I. Direct 0 51.79 59.65 50.61 78.23 40.31 18.85

Orange 26 7 2 50.73 59.64 51.16 78.58 40.62 20.56

4 50.33 58.94 49.95 77.26 40.28 19.93

11 2 50.61 61.11 51.10 79.66 39.90 20.84

4 50.49 61.11 50.74 79.43 39.71 20.75

C.I. Direct 0 39.83 48.45 -2.17 48.50 357.43 11.45

Red 31 7 2 36.69 45.95 -0.93 45.96 358.83 12.26

4 38.25 46.11 -1.59 46.14 358.02 11.71

11 2 37.33 46.23 -1.58 46.26 358.04 12.49

4 37.69 46.64 -1.58 46.67 358.06 12.42

C.I. Direct 0 21.99 -2.31 -2.43 3.35 226.50 16.13

Black 22 7 2 20.79 -1.19 -2.43 2.71 243.89 16.68

4 20.57 -1.17 -2.43 2.70 244.24 16.99

11 2 19.18 -0.87 -2.18 2.35 248.13 18.39

4 19.86 -0.86 -2.55 2.69 251.36 17.88

A comparison of the colour strength (K/S) values of untreated and

aftertreated dyeings after wash fastness testing clearly indicates that dyeings

aftertreated under alkaline conditions have higher K/S values than the untreated

and aftertreated dyeings under neutral conditions. This can be explained on the

basis of reactive nature of cationic fixing agent being used as an aftertreatment.

Under neutral conditions, cationic fixing agent interacts electrostatically with

the anionic dye molecules forming a large complex of reduced aqueous

solubility within the dyed substrate. While under alkaline conditions, cationic

126

fixing agent not only interacts electrostatically with the anionic dye molecules

but also forms a covalent linkage with the hydroxy groups of cellulose as

shown in Figure 7, explaining the observed higher wash fastness.

4.2.5.2 Effect of cationic agent concentration on the aftertreatment of

direct dyeings

The effect of cationic agent concentration on the aftertreated dyeings has

also been investigated. Colorimetric data before wash fastness testing (Table

37) has shown that an increase in the concentration of cationic agent increases

the colour strength of the aftertreated dyeings under neutral conditions.

However under alkaline conditions, an increase in the concentration of cationic

agent causes a decrease in the colour strength of the aftertreated dyeings. This

is believed to be due to the partial hydrolysis of the cationic fixing agent that

occurs at higher concentrations prior to its reaction with cellulose.

127

SSHHAADDEE CCHHAANNGGEE OOFF DDIIRREECCTT DDYYEEIINNGGSS BBYY

AAFFTTEERRTTRREEAATTMMEENNTT WWIITTHH AA BBIISS--RREEAACCTTIIVVEE

DDEERRIIVVAATTIIVVEE ((3300bb))

C.I. Direct C.I. Direct C.I. Direct Orange 26 Red 31 Black 22

Untreated dyeings

Aftertreatment 2%

at pH 7

4%

Aftertreatment 2%

at pH 11

4%

CCOONNCCLLUUSSIIOONNSS

129

Chapter 5

CCOONNCCLLUUSSIIOONNSS

Eight mono-reactive and four bis-reactive 2,3-epoxy / 3-chloro-2-

hydroxy propyl derivatives of quaternary ammonium chloride were synthesised

and evaluated as cationic fixing agents for improving the colour strength (K/S)

and fastness properties of anionic dyes on cellulosic fabrics. The structures of

the synthesised compounds were characterised using IR and 1H-NMR

spectroscopy. Optimum conditions for the fixation of these cationic agents to

the cotton fabrics were determined from the chlorine content of the fabric using

compound 30b.

It was found that pretreatment with cationic fixing agents (30a, 30b,

28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive and

acid) dyes under neutral conditions in the absence of salt. Higher colour

strength (K/S) and good wash fastness properties were obtained with the

pretreated fabrics as compared to the untreated fabrics dyed with the same

130

direct and reactive dyes. The results showed that increase in the length of

hydrocarbon chain attached to the quaternary nitrogen in bis-reactive

derivatives decreased the colour strength of the dyeings but their wash fastness

remained unaffected. It was interesting to note that colour strength of the

dyeings pretreated with a mono-reactive derivative (28c) was comparable (in

case of direct dyes) or superior (in case of reactive and acid dyes) to the fabrics

pretreated with bis-reactive derivatives (30a and 30b). On the contrary, the

wash fastness of the dyeings pretreated with a mono-reactive derivative

(compound 28c) was comparable (in case of reactive dyes) or inferior (in case

of direct dyes) to the dyeings pretreated with bis-reactive agents (compound

30a and 30b). These findings suggest that an additional group in the cationic

agent may enhance the colour strength of the dyeings due to its interaction with

the dye or the fibre but the wash fastness of the dyeings was related to its

reactivity. Bis-reactive derivatives showed better wash fastness because of their

greater fixation to the fabrics as compared to the mono-reactive derivatives.

In comparison with conventional dyeings with direct and reactive dyes,

pretreated fabrics required less dyeing time and showed similar wash fastness

but slightly lower colour strength (K/S) values. Results also indicated that

pretreated cotton fabrics could also be dyed with acid dyes which otherwise

have little substantivity towards cotton. However, the colour strength and wash

fastness comparable to acid-dyed wool was not obtained. It was also found that

light fastness of the dyeings was lowered by pretreatment.

131

Aftertreatment of direct dyeings with a bis-reactive derivative (30b)

improved the colour strength and wash fastness properties under neutral and

alkaline conditions. However, aftertreatment under alkaline conditions

produced dyeings with better wash fastness than by aftertreatment under

neutral conditions.

It could be concluded that pretreatment with cationic fixing agents has

become an environmentally friendly and energy saving process for the direct

and reactive dyeing of cotton fabrics by reducing the amount of salt & alkali

and time taken for dyeing. Aftertreatment with cationic agents has slightly

changed the colour of the direct dyeings but has beneficial effects on the wash

fastness results.

RREEFFEERREENNCCEESS

133

RR EEFF EERR EENN CC EESS

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144

VVIITTAA Saima Sharif was born on January 02, 1975 in Lahore, Pakistan. She

received Bachelor of Science degree from the University of Punjab in 1994. In

1996, she joined the Department of Chemistry, Government College Lahore

and received Master of Science degree in 1997. In March 1999, she was

appointed as a Lecturer in Chemistry at Govt. Islamia Degree College for

Women, Hafizabad. Since then she has been working as a Lecturer.

She enrolled in the University of Education, Lahore in 2003 and started

her studies towards the Doctor of Philosophy degree under the supervision of

Dr. Saeed Ahmad/ Chairman, Department of Chemistry, University of Science

and Technology, Bannu-NWFP, Pakistan.

Publications

♦ Role of quaternary ammonium salts in improving the fastness

properties of anionic dyes on cellulose fibres, Saima Sharif, Saeed

Ahmad and Mian Muhammad Izhar-ul-Haq, Coloration Technology,

2007, 123(1), 8-17. (U.K) (Review article)

♦ Synthesis and spectroscopic characterisation of epoxy / halohydroxy

propyl derivatives of quaternary ammonium salts, Saima Sharif,

145

Saeed Ahmad and Mian Muhammad Izhar-ul-Haq, Chinese Journal

of Chemistry. (Accepted)

♦ Aftertreatment of direct dyes on cotton with a bis-reactive cationic

fixing agent, Saima Sharif, Saeed Ahmad, Mian Muhammad Izhar-ul-

Haq, Muhammad Naeem Khan and Muhammad Fauz-ul-Azeem,

(Submitted)

♦ Effect of cationic fixing agents on the direct dyeing properties of

cotton fabrics. (Submitted)

146

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Role of quaternary ammonium salts inimproving the fastness properties ofanionic dyes on cellulose fibres

Saima Sharif,a,b Saeed Ahmadb,* and Mian MuhammadIzhar-ul-Haqa

aDivision of Science and Technology, University of Education, Township Campus, CollegeRoad, Township, Lahore-54770, Pakistan

bApplied Chemistry Research Centre, PCSIR Laboratories Complex, Ferozepur Road,

Lahore-54600, Pakistan

Email: [email protected]

The object of this study was to review the developments taking place during 1990–2005 regarding theuse of quaternary ammonium salts as dye fixing agents for improving the fastness properties of anionicdyes on cellulose fibres. As far as fastness properties are concerned, this review is restricted only tofastness to light, washing and water treatments.

IntroductionThe practice of dyeing has recently led to increased

requirements in terms of quality of dyeings and

profitability of the dyeing process. There is still a need for

novel dyeing processes that improve properties, in respect

of application and fastness properties of the dyeings.

Cellulose fibres can be dyed with direct and reactive

dyes. The affinity of direct dyes for cotton is due to the

linear and planar structure of the dye molecules, which

enables close alignment with chains of cellulose

molecules resulting in significant hydrogen bonding.

Generally, the dyed cellulosic fibres have a fastness to

washing that does not meet the requirements of today’s

consumers. This is particularly the case not only for

many direct dyes but to a lesser extent for reactive dyes

also [1]. Although direct dyes possess inadequate wet

fastness properties they are still widely used for their

ease of application, comparatively low cost and wide

range of shades [2]. Acid dyes, which are primarily used

for the dyeing of nitrogenous fibres such as wool, silk and

nylon, are also anionic in nature. The relatively nonlinear

structure of these acid dyes does not facilitate close

alignment with the molecular chains in cellulose, which

in turn prevents hydrogen bonding. Therefore, these dyes

are not substantive to cellulosic fibres. However,

cationised cellulosic fibres can be dyed with acid dyes of

both the non-metallised and premetallised types. This

increase in substantivity is due to the interaction of

anionic sulphonic groups in the dye molecules with the

cationic groups in the modified cellulose [3].

Notable improvements in the wet fastness properties of

anionic dyes can be brought about by pretreatment or

aftertreatment of textile fibres. The use of pretreatments

or aftertreatments to improve the fastness properties of

dyeings has a long and prolific history. Various

pretreatment and aftertreatment systems have been

developed but at the moment most widely used are

cationic fixing agents. These chemicals function by

forming a complex of high molecular weight and low

aqueous solubility and therefore high wet fastness [4].

Amines [5], quaternary ammonium [6], phosphonium

[7] and tertiary sulphonium compounds [8] can be used

as dye fixing agents. By far the most important type of

cationic fixing agents used in textile processing is

quaternary ammonium salt. Different quaternary

ammonium salts [9,10] have been applied to the fibres

either as pretreatment or aftertreatment to improve the

fastness properties of anionic dyes.

There has been significant new developments in this

area with respect to developing commercially feasible

fixing agents in the last one and half decade. These new

developments during the period from 1990 to 2005 form

the subject matter of this review article. As far as the

fastness properties are concerned, this review is restricted

only to fastness to light, washing and water treatments.

General developmentMost early dyeing processes used naturally occurring

coloured compounds, e.g. dye woods [11], which had no

significant affinity for cotton and silk. These processes

required a metal salt mordant before dyeing and after

dyeing, fixation with tannin.

The major growth and establishment of the synthetic

dye industry was initiated with the discovery of Congo

Red, the first direct dye for cotton, in 1884 [12]. Although

some early direct dyeings were claimed to be fast to

soaping [13] it was soon appreciated that fastness to light

and wet treatments left much to be desired.

From 1930 onwards, complexing of direct dyes, present

on the fibre, with aqueous solutions of cationic fixing

agents began to be fully exploited. The importance and

use of these agents was greatly extended by the

development of products rising from the condensation of

cyanamide (1) or similar compounds with formaldehyde.

These resin fixatives [14] of which Fibrofix (2) was a

doi: 10.1111/j.1478-4408.2006.00053.x

8 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17

classical example [15], could be applied by a simple,

finishing technique to cellulosic fibres dyed or printed

with direct dyes. This resin fixative class was rapidly

extended to provide a large number of agents based on

the condensation products of formaldehyde with

cyanamide derivatives [16], which were suitable for

aftertreatment of direct dyes on cellulose fibres. Later on,

the reaction products of cyanamide or cyanamide

derivatives with monofunctional or polyfunctional amines

and the condensates of these amines with formaldehyde

or N-methylol derivatives were used as an aftertreatment

to improve the wet fastness properties of anionic dyes on

cellulose fibres [17,18]. Other relevant developments in

this area have already been reviewed in detail [19].

Extensive research work has shown that formaldehyde-

based resin finished products release formaldehyde into

the atmosphere directly or during processing, handling,

garment manufacturing and subsequent wearing of

textiles due to the hydrolysis of unreacted or partially

crosslinked N-methylol derivatives present on the fibre.

Direct release of formaldehyde into the working

environment causes severe irritation to eyes, nasal

passages and respiratory tract while an unreacted or

partially crosslinked resin causes an allergenic response

of the skin upon continuous handling of textiles [20]. For

reasons of these health problems associated with

formaldehyde, there was an increasing demand for

non-formaldehyde fixing agents. It has also been reported

that formaldehyde containing fixing agents for direct

dyeing could be substituted by nitrogen containing

non-formaldehyde fixatives without sacrificing the

performance properties of the finished goods. Selection of

suitable non-formaldehyde fixatives could actually

produce better products than using the formaldehyde

fixative [21]. Nitrogenous-based dye fixing agents have

also been reported to improve overall fastness properties,

without affecting the tone and depth of shades of reactive

dyes on cotton substrates. The results indicated that

commercial non-formaldehyde and formaldehyde-based

dye-fixing agents could be replaced by laboratory

developed nitrogenous-based dye fixing agents [22].

After the discovery of reactive dyes, dyeing with reactive

dyes became the most versatile method for the coloration

of cellulosic fabrics. These dyes were used instead of

aftertreated direct dyes. However, the fundamental

problem of reactive dyeing is that the reaction of reactive

dye with water (hydrolysis) competes with the formation of

the desired covalent bond between the dye and textile

substrates (fixation reaction). As the hydrolysed dye cannot

react with the fibre it should be washed off thoroughly in

order to achieve the desired superior wet fastness of the

reactive dyeing. This involves expensive washing off

procedures and the treatment of the effluent. Thus, reactive

dyes have both economic and environmental drawbacks

because of high salt usage and insufficient fixation caused

by hydrolysis leading to pollution of the effluent [23].

However, if an aftertreatment is given prior to the rinsing

stage, hydrolysed dye also gets fixed showing improved

wet fastness. Therefore, aftertreatment still remained an

extremely useful way of improving the wet fastness

properties of a deep dyeing that failed to meet the

necessary standards.

Developments taking place during the recent decade

have enabled direct dyes to compete with reactive dyes in

the field of severe wet fastness requirements. The

production, in the 1960s, of polyfunctional crosslinking

fixing agents [24,25] capable of reacting with both dye

and fibre was a significant development. These agents

were used to after-treat dyes on cellulosic, polyamide and

wool fibres.

During 1980s there was a great revival of interest in the

techniques for enhancing the dyeability of cellulosic fibres

with reactive or direct dyes by pretreatment with a great

variety of cationic products usually based on nitrogen.

This modification of cellulosic fibres with cationic agents

resulted in increased substantivity of anionic dyes for

cellulosic fibres by introducing new cationic sites. Lewis

and Lei reviewed numerous chemicals that can be used to

provide cationic charges to cotton fibres [26]. Pretreatment

of cellulosic fibres with cationic agents has been reported

to enhance the uptake of anionic dyes and facilitate the

fixation of reactive dyes in the absence of either salt or

alkali [27,28]. The cationised fibre not only has improved

substantivity for direct and reactive dyes, but could also

be dyed with acid dyes [3].

The use of anionic dyes (acid, direct and reactive dyes)

and cationic fixing agents is widespread in dyeing

processes. Many studies have been devoted to improve the

fastness properties of anionic dyes by pretreating or

aftertreating the fibres with amines or reactive cationic

agents. Most of these studies have used monomeric or

polymeric quaternary ammonium salts having different

reactive groups. These include dialkyl azetidinium

chloride, epoxypropyl/halo-hydroxypropyl trialkyl

derivatives of ammonium chloride, mono- and bis-reactive

haloheterocyclic compounds and poly-epichlorohydrin

dimethylamine derivatives.

The mechanisms of dyeing cotton textiles pretreated

with quaternary compounds of epoxypropyl type and

mono- and bis-reactive chlorotriazine type were studied.

The high reactivity and better thermal stability of

chlorotriazine type agents than epoxypropyl type agents

made them suitable for pad–batch or exhaust applications

rather than the more costly pad–bake process and gave

effective enhancement of reactive dye uptake [29]. Later

on, it was found that the pretreatment of cotton fabric with

bis-reactive cationic agent promoted higher extents of dye

exhaustion and fixation than that with mono-reactive

cationic agent [30]. The presence of heterocyclic ring and

imino groups in the chloroazine type agents contributes

towards the higher substantivity of these agents for

cellulose substrates than the epoxypropyl type agents. The

low substantivity and poor thermal stability of

H2N C N1

NH2

HNN

Xn

NHCNn

2

Sharif et al. Role of quaternary ammonium salts

ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 9

epoxypropyl agents made them unsuitable for exhaust

application and was also responsible for the poor dye

penetration due to significant migration of agent during the

thermal reaction step of pad–bake process leading to non-

uniform distribution of cationic dye sites on the fibre [29].

The reactivity of cotton with such types of compounds has

been studied under a variety of conditions [9,31,32] but no

best procedure has yet been established. Recent work has

shown that cotton cationised through a pad–batch process

gave excellent dye penetration indicating the uniform

distribution of cationic dye sites through this process.

Thus, a pad–batch process seems to be good for achieving

high yields of cationically modified cotton with uniform

distribution of dye sites [33]. The pad–batch dyeing

technique has now become an important dyeing method

for its simplicity, low consumption of energy and water,

and excellent reproducibility [34].

Monomeric quaternary ammonium saltsThe use of cationic agents in the form of primary,

secondary, tertiary and quaternary amino residues has

been known since 1926 [5,6]. To investigate systematically

the effect of attaching a variety of amines to the cellulose

fibre, cotton was modified by pretreatment with N-

methylolacrylamide (3; Allied Colloids) to introduce a

pendant-activated double bond (Scheme 1). By introducing

amino residues at these new sites good colour yield and

high fixation values of reactive dyes were achieved at pH

5–7 in the absence of electrolyte but light fastness was

lowered. Cellulose modified with only N-methyl-

olacrylamide also gave high colour yields with dyes

containing pendant aliphatic amino residues in the

presence of electrolyte under alkaline conditions [27].

Recently, a new fibre-reactive quaternary compound

containing an acrylamide residue was synthesised and

applied to cotton fabrics using a pad–bake process. It was

found that the treated fibre could be dyed with reactive

dyes without the addition of salt or alkali. The reactive

dyes were almost completely exhausted and showed a

high degree of covalent bonding with the pretreated

cellulose [35]. Cationic starch had also been used for the

modification of cotton fabrics. Dyeing of this modified

fibre with reactive dyes using a continuous dyeing method

gave improved dye fixation and level dyeing without the

presence of salt compared with untreated cotton. The

dyeings also showed good wash and rub fastness [36].

Azetidinium chloride

An investigation of the direct dyeing of cotton cationised

with 1,1-dimethyl-3-hydroxy azetidinium chloride (4),

1,1-diethyl-3-hydroxy azetidinium chloride (5) or

Sandene 8425 (aliphatic polyamine derivative; Clariant)

showed improved dye absorption and firmness of colour

in the absence of salt in a neutral medium [37,38]. The

above-modified fibre also enhanced the exhaustion and

fixation of acid (Table 1) [3] and reactive dyes [39] on

cotton in the absence of salt in a neutral medium. The

effect of alkali pretreatment followed by 1,1-dimethyl-3-

hydroxyazetidinium chloride (DMAC) treatment on the

dyeability of cotton yarn with reactive dyes has been

reported to produce a much stronger colour yield than by

DMAC treatment without alkali pretreatment [40].

Epoxy and halohydroxy propyl derivatives

Several patents have covered the preparation of epoxy

and halohydroxy propyl derivatives of ammonium

chloride [41–45]. Many attempts have been made to fix

epoxy and halohydroxy propyl derivatives to cellulose via

an ether linkage. Epoxypropyl derivatives of ammonium

chloride react with cellulose under alkaline conditions

to form ethers (Scheme 2). However, when

halohydroxypropyl derivatives have been used for the

cationisation of cellulosic fabrics under alkaline

conditions, an epoxide ring is first formed in the

cationising agent by the action of alkali and it then reacts

with the hydroxyl group of cellulose under alkaline

conditions (Scheme 3). Alkali is required both for the

formation of epoxide ring and for its reaction with

cellulose. Thus, both epoxy and halohydroxy propyl

derivatives have the same reactive group.

The first product of this type was Glytac A (Protex; 6),

which reacted with cellulose via the glycidyl group at

alkaline pH [46]. 3-Chloro-2-hydroxypropyltrialkyl

derivatives of ammonium chloride (7) were synthesised

through the reaction of various trialkylamines with

epichlorohydrin and were used for the cationisation of

cellulosic fibres under alkaline conditions. Cationised

fibres showed slightly better light fastness than those on

nylon or wool dyed with the same acid dye (Ciba) but

their wash fastness decreased with increasing length

of hydrocarbon chain (Table 2) [47]. The use of

2,3-epoxypropyltrimethyl ammonium chloride (6) as

pretreatment, a simultaneous treatment or an

aftertreatment increased the fixation and fastness

properties (except rubbing fastness) of direct dyes on

cotton textiles. It has been observed that a pretreatment

generally produced better results than an aftertreatment.

An increase in the number of solubilising groups on the

HO NH

O

CH2

3

Cell OH HO NH

O

CH2 O NH

OCH2Cell H2OZnCl2 / 150 °C

Scheme 1

MeN

MeOH

4

Cl

EtN

EtOH

5

Cl



direct dye molecules generally resulted in a deterioration

of the rubbing fastness of pretreated fabrics and an

improvement in the case of aftertreated fabrics [48]. This

treatment has also been reported to increase the fixation

of various reactive dyes on cotton but reduced the

fastness properties of dyed fabrics [49]. A comparative

study of the reactive dyeing of unmodified cotton and

cotton cationised with compound 6 with dyes having four

different reactive groups showed that cationic cotton gave

the same colour fastness as the unmodified cotton, but

usually with higher colour yields [50]. Cotton modified

with this agent through a cold pad–batch process has

been reported to show excellent colour yields and

fastness properties for a number of direct (Crompton &

Knowles), reactive and acid dyes (Dystar), without the

use of electrolytes or multiple rinses, which are normally

employed in cotton dyeing (Table 3) [32,33].

Table 1 Properties of acid dyes with cationic cotton using no salt at pH 7

Dye Treatmentb

K/S Fastness properties

After wash After DMFc

Washinga

LightA C W

CI Acid Red 73 I 3.62 0.95 4 4 3–4 4II 9.34 4.02 2–3 2 2 6III 1.04 0.39 2–3 4 3–4 5–6

CI Acid Orange 7 I 2.51 0.50 2–3 2 2–3 2–3II 6.18 0.98 2 2–3 2–3 6III 1.05 0.35 2 4–5 4–5 3

CI Acid Yellow 36 I 1.23 0.35 2 3–4 2 5II 3.25 0.37 2 4 3 4–5III 0.64 0.21 3 3–4 4–5 4

CI Acid Green 12 I 3.87 2.03 2 3–4 2 5II 7.14 4.76 4 4 3 5III 1.95 0.41 2 4 3 6

CI Acid Red 183 I 2.72 2.66 3–4 2–3 2–3 6II 12.14 5.88 4 4–5 4 6III 2.51 0.43 3 4–5 4–5 6

CI Acid Red 214 I 4.63 3.20 2 4 2–3 6II 12.51 7.55 3–4 3–4 3–4 6III 3.25 0.68 2 2 3 6

a A, change in colour; C, staining on cotton; W, staining on woolb I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3-hydroxy azetidinium chloride (DEA-AC)c DMF, dimethyl formamide

R1

NR2

R3 OCell OH

OH R1

NR2 R3

OH

OCell

ClCl

Scheme 2

R1

NR2

R3 OCell OH

OH R1

NR2 R3

OH

OCell

R1

NR2

R3 O

OHR1

NR2 R3

OH

Cl

Cl

ClCl

Cl

Scheme 3

ON

Me

MeMe

6

Cl

ClOH

NR1

R2

R3

C2H5

C3H7

CH3

C5H11

R1 = R2 = R3 =

7

Cl

Table 2 Fastness properties of acid dye on cotton cationisedwith different quaternary salts

Dye SubstrateCationicagenta

Wash fastness

Lightfastness

Changein colour Staining

CI AcidRed 127

Cotton CMAC 4–5 3 4–5CEAC 4 3 4–5CPAC 3 2–3 4–5CP5AC 3 2–3 4–5CDTAC 1–2 2 4–5

Nylon 4–5 2–3 4Wool 4–5 2–3 4

a CMAC, 3-chloro-2-hydroxypropyltrimethyl ammonium chloride;CEAC, 3-chloro-2-hydroxypropyltriethyl ammonium chloride;CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium chloride;CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride;CDTAC, 3-chloro-2-hydroxypropyldimethyltetradecyl ammonium chloride



The dyeing behaviour of cotton, cationised with

3-chloro-2-hydroxypropyltrimethyl ammonium chloride

(8; Fisher Scientific), with direct dyes was investigated.

Findings revealed that cationised cotton could be dyed

without salt and required less rinsing to remove unfixed

dye than cotton dyed by conventional methods [51].

Dyeing of this cationised cotton with fibre-reactive dyes

showed deeper shades. Moreover, nonlinear colour

behaviour occurred with cationised cotton at lower

concentrations than with unmodified cotton, suggesting

that predicting shades on cationised cotton requires

caution [52]. Significant differences in dyeing rates and

dye uptake of acid dyes on this cationic cotton were

observed over untreated cotton. Fastness to laundering

and light was greatly improved for cationic cotton over

untreated cotton, but remained somewhat lower than the

values for nylon [53].

The printing properties of cationised cotton that had

been pretreated with compound 6 were found to be

very effective in reducing fixation (steaming) times and

washing off processes, and in increasing colour yield

and wet fastness properties for a number of reactive

[54] and direct dyes [55]. Printing on cationic cotton

with acid dyes could be carried out at neutral pH

because of the presence of cationic charges on the fibres

at all pH values, avoiding the need for a pH regulator

in the print paste and for neutralisation during washing.

This technique did not need an intensive washing

procedure, and thus appeared to be a more

environmentally friendly printing process [56]. The

effect of cationisation on the quality of ink-jet printing

on cotton fabrics was also investigated. Ink-jet printing

with reactive dyes or reactive inks on cationised cotton

was found to have good potential as a cost-effective and

more environmentally friendly printing method using

less dye, less thickener and less alkali without

relinquishing outline sharpness [57,58].

Epoxy and halohydroxy propyl derivatives of

diallylamine (9 and 10) have also been reported in this

regard. Cotton pretreated with these agents showed

improved fastness properties for a number of direct dyes

(Table 4) [59].

Table 3 Fastness properties of direct reactive, and acid dyes with nylon, conventional cotton and cationised cotton

Dye Cotton fabric K/S

Colour fastness

Light fastnessbChange in colour Staininga

Conventional cotton and cationised cottonCI Direct Blue 78 Untreated 8.67 2 2–5 5

Cationic 13.99 4–5 4 5CI Direct Blue 86 Untreated 8.76 1 2–5 5

Cationic 44.74 5 4–5 5CI Direct Red 80 Untreated 14.16 2 2 3–5

Cationic 20.11 4–5 5 4–5CI Direct Yellow 106 Untreated 10.29 3 3–5 5

Cationic 14.46 5 5 5CI Reactive Blue 21 Untreated 15.08 4–5 5 5

Cationic 53.34 4 5 4–5CI Reactive Blue 203 Untreated 16.37 4–5 4–5 5

Cationic 24.24 4–5 4–5 4–5CI Reactive Red 239 Untreated 8.24 5 4–5 4–5

Cationic 12.40 5 4–5 4–5CI Reactive Orange 107 Untreated 6.91 4–5 5 5

Cationic 18.24 4 5 4–5Nylon and cationised cottonCI Acid Black 172 Nylon 4–5 4–5 5

Cationic cotton 2–5 4–5 5CI Acid Blue 221 Nylon 4–5 4–5 5

Cationic cotton 3–5 4–5 4–5CI Acid Red 260 Nylon 5 4–5 5

Cationic cotton 3–5 3–5 5CI Acid Yellow 79 Nylon 4–5 4–5 5

Cationic cotton 4–5 4–5 5

a Staining of nylon fabric during laundering, and staining on cottonb 20 h

Cl

OH

NMe

Me Me

8

Cl

ON

CH3

CH2

CH2

Cl

OH

N

CH3

CH2

CH2

OSO3CH3 OSO3C2H5 SO3C6H4CH3=

9 10

X

X

X



Mono- and bis-reactive haloheterocyclic derivatives

Mono- and bis-reactive haloheterocyclic compounds

having monochlorotriazine as the reactive group have

also been used for the cationisation of cellulose. Although

these treatments enhanced the uptake of dye, there are

practical drawbacks to all these treatments, including hue

changes, poor penetration into the fibre [29] and light

fastness limitations [26].

Monofunctional cationic agents of monochlorotriazine

type (11) were evaluated on cotton yarn in the

production of differential dyeing effects. Yarn pretreated

with these cationic agents show better uptake of acid and

direct dyes than does untreated yarn [60]. The

stoichiometry of interaction of both acid and direct dyes

with cotton modified with a reactive cationic agent (12)

was examined. The results showed that the presence of

the cationic sites enhanced the amount of dye taken up

by diffuse adsorption [61]. Recent developments revealed

that cotton fabrics pretreated with mono- and bis-reactive

cationic agents (13 and 14) showed fairly high degrees of

exhaustion and fixation of direct dyes under neutral

conditions in the absence of salt. Improved fastness was

also achieved for this modified fibre when compared

with untreated samples. Results also indicated that

cotton pretreated with the bis-reactive cationic agent

showed higher degrees of dye exhaustion and fixation

relative to cotton pretreated with mono-reactive agent

(Table 5) [30].

Reactive cationic agents, phenylmonochlorotriazinyl

and epoxypropyl, were used for cotton pretreatment using

a pad–dry–curing technique. The dyeability of cationised

cotton fabrics using CI Acid Red 1 was found to be

dependent on the cationic agent concentration and the

appropriate mixture used [62]. More complex

multifunctional structures (15) have also been evaluated

by exhaust applications and these gave effective

enhancement of dye uptake [63].

Polymeric quaternary ammonium saltsMany cationic polymers have been applied to cellulose

with a view to enhance the uptake of anionic dyes and

it is considerably more difficult in these instances

Table 4 Fastness properties of direct dyes on untreated andtreated cotton fabrics

DyeCationicagenta

Cottonfabric

ISO C2S wash fastness

Changein colour

Stainingon cotton

CI Direct Red 80 I Without 4 2With 5 3–4

CI Direct Blue 71 I Without 4 2With 5 5

CI Direct Violet 66 I Without 4–5 4With 5 5

CI Direct Green 26 I Without 4–5 3–4With 5 5

a I, N-(3-chloro-2-hydroxypropyl)-N-methyl-N,N-diallyl ammoniump-toluenesulphonate

NH

N

N

N

Cl

NH

NEt

Et

R

11X

N

N

N

Cl

NH

NH

N

Et

Et

12

Cl

NH

N

N

N

Cl

NH

NEt

Et

Et

13I

N

NN

NN

N

NHHN

Cl Cl

HN

N EtEtEt

HN

NEt EtEt

14

II

Table 5 Fastness properties of direct dyes on untreated (C) andpretreated cotton fabrics with mono- (C-1) and bis-reactive (C-2)cationic agents

DyeCottonfabricb F (%)

Wash fastnessa

Lightfastness

Changein colour SC SW

CI DirectYellow 50

C 3–4 3–4 3 4–5C-1 32 4 4 4 5C-2 75 4–5 4–5 4–5 4–5

CI DirectOrange 61

C 3 3–4 3 3–4 4–5C-1 45 4 4 4 4–5C-2 83 4–5 4–5 4–5 4–5

CI DirectBlue 71

C 1 3 2 1–2 4C-1 28 4 4 3–4 4C-2 68 4 4 4 2

CI DirectGreen 26

C 2 3–4 3 3 4C-1 29 4–5 4–5 4–5 3–4C-2 58 4–5 4–5 4–5 2

a SC, staining on cotton; SW, staining on woolb C-1, cotton cationised with monochlorotriazine mono-reactive cationicagent; C-2, cotton cationised with bischlorotriazine bis-reactive cationicagent

N

NN

NN

N

NHHN

Cl Cl

HN

N MeMeMe

HN

N MeMeMe 15

CI CI



to interpret the precise mechanism of the interactions

involved, apart from the obvious participation of

electrostatic forces between the dye anions and the basic

groups (often quaternary nitrogen atoms) in the polymer.

Polyamide-epichlorohydrin resin (Hercosett 125;

Hercules Powder Corpn), having azetidinium cation

(16) as the reactive group, was applied to cotton with a

view to producing a modified fibre suitable for the

absorption and fixation of reactive dyes at neutral pH in

the absence of salt. Selected highly reactive dyes gave

good colour yield and fixation but lower fixation values

were obtained when dyes of low reactivity were applied

to the pretreated cotton [64]. It was thought that better

fixation of both high and low reactivity dyes might be

achieved by introducing more highly nucleophilic sites

into the cotton. Incorporation of thiourea and

ethylenediamine into the polymer during the application

process has beneficial effects on the results obtained.

Thiourea addition inhibits the crosslinking of the resin,

leaving more nucleophilic NH groups as sites for dye

reaction [65]. Ethylenediamine promotes crosslinking of

the resin but itself provides extra NH groups as dye

reactive sites [66].

Derivatives of poly-epichlorohydrin, instead of

epichlorohydrin were prepared and used as new cationic

agents. Poly-epichlorohydrin dimethylamine derivative

(17) was applied to cotton under alkaline conditions by

the exhaustion method. Pretreatment of cotton with this

agent not only reduced the amount of salt needed, but

also increased the exhaustion efficiency and perspiration

fastness of direct dyes (BAY; Table 6) [2].

A commercial cationic fixing agent, Solfix E (modified

quaternary polyamine derivative; Ciba) was used to

pretreat cotton prior to dyeing with six commercial direct

dyes in the presence of electrolyte. Pretreatment

enhanced the colour strength but wash fastness was

similar to their untreated counterparts [67]. Pretreated

fabrics also gave improved printability with pigment and

anionic dyes. The prints obtained on cationised cotton

showed better overall fastness properties than prints

obtained on untreated cotton [68]. Three commercial

cationic fixing agents, namely Matexil FC-PN (a phenol

formaldehyde ammonium chloride condensate, ICI),

Matexil FC-ER (poly diallyldimethyl ammonium chloride;

18, ICI) and Solfix E (Ciba), originally marketed as

aftertreating agents for direct dyes, were used as

pretreatments for cotton modification. Pretreatment was

found to increase the colour strength of the dyeings when

dyeing had been carried out without electrolyte.

However, when electrolyte was used, the pretreated

samples exhibited generally lower colour strength than

the standard dyeings. The wash fastness of the dyeings

almost remained unaffected by pretreatment while light

fastness was slightly lowered [69]. The study of the effect

of different pretreatment agents on the uptake of 1:2

metal complex acid dyes by samples of cotton/polyamide

fabrics showed excellent dye uptake by the pretreated

samples compared with the untreated samples. The

pretreatment using Matexil FC-ER (18, ICI) or a

development cationic fixing agent gave the most uniform

results [70]. Homopolymer or copolymers of alkyl

diallylamine with epichlorohydrin have also been

reported to improve the wet fastness properties of anionic

dyes on textile fibres [1].

Aftertreatment of the dyeings produced on cellulosic

fibres, pretreated with fixing agent 18 and Fixogene CXF

(copolymer of dimethylamine and epichlorohydrin; 19,

ICI), with cationic polymers enhanced the light and wash

fastness of acid (Table 7) [71] and reactive dyes [72]. The

subsequent application of syntan (synthetic tanning

agent) to the aftertreated dyeings enhanced the

effectiveness of commercial cationic fixing agents 18 and

Fixogene CXF, in improving the wash fastness of three

commercial direct dyes (Ciba-Geigy) on cotton but the

effect of syntan was both dye and fixing agent specific

(Table 8) [4]. It has also been examined that wash

fastness was noticeably better when these fixing agents

were applied under alkaline conditions (Table 9) [73].

A new fibre modification technique based on a cationic

acrylic copolymer (polymer pL) has been established.

Pretreatment of cotton with this polymer increased both

the substantivity and reactivity of the fibre towards

reactive dyes, even under neutral or acidic conditions [74].

Recently, poly(vinylamine chloride) has been investigated

Table 6 Fastness properties of direct dyes on untreated andtreated (poly-epichlorohydrin dimethylamine) cotton

DyeCottonfabric K/S

Wash fastness

Lightfastness

Changein colour

Stainingon cotton

CI DirectBlue 78

Untreated 14.02 3–5 3 4Treated 14.26 3 3 3–5

CI DirectOrange 39

Untreated 11.58 3–5 3–5 4Treated 11.90 3 3 3–5

CI DirectBlue 86

Untreated 6.06 3–5 4–5 4Treated 11.74 2–5 4–5 3–5

NOH

16

CI

O

NH

MeMe

n

17

CI

NMe Me

n

18

CI

N(CH3)2OH

n

19

CI



as a pretreatment for the salt-free dyeing of cotton with

reactive dyes. Dye fixation was found to be much higher

than by conventional dyeing without pretreatment, even in

the presence of a large amount of salt. Dyed cotton

pretreated with poly(vinylamine chloride) showed

excellent wash fastness and good rub fastness [75].

ConclusionDifferent quaternary ammonium salts have been applied

to the cellulosic fibres either as pretreatment or

aftertreatment to improve the fastness properties of

anionic dyes on cellulosic fibres. These treatments

Table 8 Fastness properties of direct dyes on cotton aftertreated with cationic fixing agents/syntan

Dye Aftertreatmentsb

K/S Wash fastnessa

Before wash After wash S C V

CI Direct Red 89 Nil 14.84 11.13 4 1 1–24% M FC-ER 14.21 12.75 4–5 2–3 34% M FC-ER/2% F AXF 13.77 13.34 4–5 2–3 34% F CXF 14.74 12.72 4–5 1–2 24% F CXF/2% F AXF 14.45 13.26 4–5 2 2–3

CI Direct Yellow 106 Nil 10.98 8.01 3 1 1–24% M FC-ER 10.49 9.94 4 2–3 34% M FC-ER/2% F AXF 10.31 10.11 4 3 3–44% F CXF 10.36 8.81 4 1–2 24% F CXF/2% F AXF 10.65 8.73 4 1–2 2

CI Direct Blue 85 Nil 17.06 12.42 3 1 1–24% M FC-ER 17.06 16.94 4–5 2–3 34% M FC-ER/2% F AXF 16.81 16.14 4–5 2–3 34% F CXF 16.08 15.79 4–5 1–2 24% F CXF/2% F AXF 16.81 15.96 4–5 2 2

a S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscoseb M, Matexil; F, Fixogene

Table 7 Fastness properties of acid dyes on cotton

Cottonsample

Pretreatmenta Aftertreatmentb Wash fastness

LightfastnessMaterial % Material %

Shadechange

Staining

C W N K/S

CI Acid Green 1061C 0.91.1 PT1 2 3 4–5 5.60 671.2 PT1 2 AT1 2 3–4 5 5.781.2 PT1 2 AT2 2 3–4 5 5.801.4 PT1 2 AT3 2 4 5 5.731.5 PT2 2 2 4–5 6.051.6 PT2 2 AT1 2 3–4 5 6.011.7 PT2 2 AT2 2 2–3 5 6.061.8 PT2 2 AT3 2 4–5 5 5.97

CI Acid Red 3152C.1 1.962.1.1 PTI 2 3 2–3 4 3 9.89 52.1.2 PTI 2 AT1 2 3–4 3 4–5 3–42.1.3 PTI 2 AT3 2 4 3 4–5 42.1.4 PT2 2 2–3 2–3 3–4 3 10.932.1.5 PT2 2 AT1 2 3–4 3 4 3–42.1.6 PT2 2 AT3 2 4 3–4 4–5 4

CI Acid Yellow 2352C.2 2.172.2.1 PT1 2 3 4–5 3–4 4 7.23 672.2.2 PT1 2 AT1 2 3–4 4–5 4 4–52.2.3 PT1 2 AT3 2 3–4 5 4–5 4–52.2.4 PT2 2 2 4–5 3 4 6.542.2.5 PT2 2 AT1 2 3–4 4–5 4 4–52.2.6 PT2 2 AT3 2 4 5 4–5 4–5

a PT1, Matexil FC-ER; PT2, Fixogene CXFb AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, copolymer of diallyldimethylammonium and diallyl-2-hydroxy-3-chloropropyl ammonium chloride



enhanced the exhaustion, fixation and wet fastness

properties of anionic dyes on cellulose fibres.

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Table 9 Fastness properties of direct dyeings aftertreated with Fixogene CXF and Matexil FC-ER under neutral and alkaline conditions

Dye pH Cationic agent K/S

Colour fastness

Shade change

Staininga

C V

CI Direct Red 89 Nil 14.84 4 1 1–27 4% Fixogene CXF 14.74 4–5 1–2 2

11 4% Fixogene CXF 14.64 4–5 2 2–3Nil 14.84 4 1 1–2

7 4% Matexil FC-ER 14.21 4–5 2–3 311 4% Matexil FC-ER 13.18 4–5 3 3

CI Direct Yellow 106 Nil 10.98 3 1 1–27 4% Fixogene CXF 10.36 4 1–2 2

11 4% Fixogene CXF 10.57 4 2–3 3Nil 10.98 3 1 1–2

7 4% Matexil FC-ER 10.49 4 2–3 311 4% Matexil FC-ER 10.57 4 3–4 4

CI Direct Blue 85 Nil 17.06 3 1 1–27 4% Fixogene CXF 16.08 4–5 1–2 2

11 4% Fixogene CXF 16.68 4–5 2 3Nil 17.06 3 1 1–2

7 4% Matexil FC-ER 17.06 4–5 2–3 311 4% Matexil FC-ER 17.40 4–5 3 4

a C, cotton; V, viscose



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