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synopsis
INSTITUTE OF CHEMICAL TECHNOLOGY (University under Section -3 of the UGC Act 1956)
Maharashtra Govt’s Elite Status and Centre of Excellence Matunga, Mumbai – 400019
A SYNOPSIS OF THE THESIS TO BE SUBMITTED TO
THE INSTITUTE OF CHEMICAL TECHNOLOGY/UNIVERSITY OF MUMBAI
FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY (SCIENCE) IN
CHEMISTRY
TITLE OF THESIS : Synthetic Reactions & Applications of Chemically Recycled Products from Polyester Waste
NAME OF CANDIDATE : Mr. Rikhil Vinodkumar Shah
NAME AND DESIGNATION : Prof. S. R. Shukla OF RESEARCH GUIDE Professor of Technology of Dyeing & Printing PLACE OF RESEARCH WORK : Dept. of Fibres & Textile Processing Technology Institute of Chemical Technology, Matunga, Mumbai-400019 DATE OF ADMISSION : 15th December, 2009 REGISTRATION NUMBER AND DATE : 11Chy4052, 21/09/2010 DATE OF SUBMISSION OF : 6th May, 2013
SYNOPSIS SIGNATURE OF RESEARCH GUIDE SIGNATURE OF CANDIDATE
(Prof. S. R. Shukla) (Rikhil V. Shah)
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
Introduction:
Ever since the first industrial scale production of synthetic polymers took place in
the 1940s, their production, consumption and waste generation rate of the plastic solid
waste has considerably increased.
Poly (ethylene terephthalate) (PET) is one of the versatile engineering plastics
showing excellent thermal and mechanical properties. It is non-toxic, semi-crystalline,
thermoplastic polyester with high strength and crystal clear transparency. Although its
main application is in the apparel sector, large quantities are also consumed in the
manufacture of X-ray films and food packaging, especially in production of soft-drink
bottles. The post-consumer PET product waste does not create a direct hazard; however,
its substantial volume fraction in solid waste streams coupled with its high resistance to
the atmospheric and biological degradation is the main threat to the environment.1 Since
it is not appropriate to dispose off waste PET on land-fill sites, alternative methods of
recycling, including physical and chemical ones, have been developed.
Chemical recycling appears to be the only alternative that is sustainable.2 PET
possesses ester groups, which can be cleaved by some reagents, such as water
(hydrolysis), 3, 4 alcohols (alcoholysis), 1, 3 glycols (glycolysis), 5, 6 and amines
(aminolysis). 7, 8 Great attention has been paid to chemical recycling of PET waste
leading to recovery of the monomeric products that can be further used in the synthesis of
chemicals or intermediates of interest. 9
In the present work, PET soft drink bottle waste was depolymerized using
different routes and the products obtained were subjected to various chemical reactions to
get useful chemicals.
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
The work done is summarized as follows:
1. Phase transfer catalyzed alkaline hydrolysis of PET Waste
Reaction parameters: PET Waste (1mol); Aq. NaOH (3 mol); TBAB (3% w/w); Time (3h);
Temp (80°C).
Poly(ethylene terephthalate) (PET) waste bottle flakes were hydrolyzed under
atmospheric pressure by aqueous solution of NaOH at temperature below 80°C using
phase transfer catalyst (PTC). Hydrolysis of PET bottle waste was carried out having
particle size >6mm using tetra butyl ammonium bromide (TBAB) as PTC and non polar
solvents like 1,4-dioxane, xylene, etc. have been used to accelerate the rate of reaction.
One of the monomers terephthalic acid (TPA) has been produced with excellent yield (88
%) using PTC in alkaline hydrolysis of PET waste. The reaction conditions were mild as
compared to those reported in the literature.
a. Aminolysis of PET Waste
b. Using N-(2-aminoethyl) ethanolamine3
O
O O
O CH2
H2C
PET Waste
n
H2N
HN
OH O
NH
HN
HO
O
HN
NH
OHCatalystRef lux
BHAETA
Reaction parameters: PET Waste (1mol); AEEA (4 mol); Catalyst (0.5% w/w); Time (4h)
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
The aminolysis of PET bottle waste was successfully carried out under atmospheric
pressure in the excess of N-(2-Aminoethyl) ethanolamine (AEEA). The aminolysis with
1:4 PET: amine ratio, 0.5% w/w sodium acetate catalyst under reflux for 5 h gave pure
bis (-(2-hydroxyethyl amino) ethyl) terephthalamide (BHAETA) with about 72 % yield.
It has application as chain extender in polyurethane industry.
c. Using propanol amines
Reaction parameters: PET Waste (1mol); Amine (5 mol); Catalyst (0.5% w/w); Time (5h)
Aminolytic depolymerization of post consumer poly (ethylene terephthalate) (PET)
bottle waste with 2-amino-2-methyl-1-propanol, 1-amino-2-propanol and 3-amino-1-
propanol under atmospheric condition was investigated in the presence of sodium acetate
O
O
O
O
n
PET Waste
O
NH
OH
O
HNHO
O
NH
OH
O
HN
OH
O
NH
OH
O
HN
HO
BHPTA BHIPTA BHAMPTA
HONH2 HO
NH2
HO NH2
3-amino-1-propanol 1-amino-2-propanol2-amino-2-methyl-1-propanol
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
as catalyst. The virtual products obtained in pure form were respectively bis (1-hydroxy-
2-methylpropan-2-yl) terephthalamide (BHMPTA), bis (2- hydroxypropyl)
terephthalamide (BHIPTA) and bis-(3-hydroxy propyl) terephthalamide (BHPTA). The
products BHIPTA (82%) and BHPTA (80%) were obtained in pure forms with good
yields with reaction time of 5 h.
d. Application of microwave irradiation for aminolytic depolymerization
Microwave heating was studied for aminolytic depolymerization of PET waste using
1-amino-2-propanol and 3-amino-1-propanol. The same optimized reaction parameters of
conventional heating were used by varying time of reaction up to 9 min. Decrease in the
time of reaction from 5 h to 7 min was achieved on using microwave irradiation as a
heating source with yields comparable to the conventional method.
e. Synthesis of bis-oxazoline and bis-oxazine
Bis-oxazolines and bis-oxazines have been used as chain extenders and cross-linkers in
polymers. BHIPTA and BHPTA were subjected to cyclization at ambient temperature
condition to obtain respectively 1,4-bis (5-methyl-4,5-dihydrooxazol-2-yl) benzene
(PBIOXA) and 1, 4-bis (5, 6-dihydro-4H-1, 3-oxazin-2-yl) benzene (PBOXA). Thus it is
possible to synthesize useful chemicals from PET waste
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
O
O
O
O
n
PET Waste
O
NH
OH
O
HNHO
O
NH
OH
O
HN
OH
BHPTA BHIPTA
HONH2HO NH2
3-amino-1-propanol 1-amino-2-propanol
N
O O
N N
O O
N
PBOXAPBIOXA
SOCl2 SOCl2
Reaction parameters: BHPTA (1mol); SOCl2 (4 mol); Time (16 h); Temp (27°C)
2. Synthesis of heterocyclic derivatives from PET waste and evaluation of their
antibacterial activity
The literature shows that compounds bearing 1,3,4-oxadiazole/thiadiazole and 1,2,4-
triazole derivatives possess wide variety of biological activitiy. The present study deals
with the prearation of terephthalic dihydrazide (TPHD) from PET waste via aminolysis
using hydrazine hydrate. The TPHD was further subjected to chemical reactions to obtain
various heterocycles. All synthesized compounds were characterized and evaluated for
the anti bacterial activity. Activity of each compound was compared with ciprofloxacin
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
and sulphametoxazol and found to show moderate activity as compared to these
standards.
O
O
HN NH2
NHH2N
Ar
N
C
X
O
HN
NH
X
NH
Ar
O
NH
HN
X
NH
Ar
NN
X X
NN
NH
NH
ArAr
NN
N N
NN
HXXH
Ar Ar
TPHD
Conc.H2SO4 2N NaOH
Ethanol/ 3 h
2(a-d) 3(a-d)
3. Acidic ionic liquid catalyzed synthesis of 2-oxazolines from β-hydroxyamides
2-oxazolines are widely found in natural products with a different range of biological
activities in catalysis and as synthetic intermediates. Also bis-oxazolines and different
chiral oxazolines have been widely used as auxillaries and ligands in asymmetric
synthesis. We have developed novel acidic ionic liquid and used for synthesis of 2-
oxazolines from β-hydroxyamides. The products were obtained in good yields for variety
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
of substrates. Efficient reaction protocol was developed and ionic liquid was recyclable
up to 3 cycles.
R NH
O
R N
O[SO3H-pBIM][HSO4]
90 oC
1a-i, R = Ar' 3a-i, R = Ar'
OH
Reaction parameters: β-hydroxy amide (2 mmol); IL (1 ml); Time (3h); Temp (90°C)
4. Phosphine free copper oxide catalyzed sonogashira coupling reaction
I H+CuO/ Ethanol amine
90οC
AryIodide Phenyl Acetylene Coupling productWithout any additivephoshane free
Reaction parameters: Aryl Iodide (1.2 mmol); Phenyl Acetylene (1 mmol); CuO (15% w/w);
Ethanol Amine (2 ml); Time (5h); Temp (90°C)
A new, efficient and inexpensive system has been developed to catalyze sonogashira
cross coupling reaction between aryl iodides and terminal alkynes. We have employed
CuO as catalyst using ethanolamine as ligand, base and solvent. The reaction conditions
were mild as compared to those reported in literature and products obtained were in good
to excellent yields.
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India
References:
1. Karayannidis, G. P. ; Achilias, D. S. Macromol Mater Eng 2007, 292, 128.
2. Karayannidis, G. P. ; Achilias, D. S. Water, Air and Soil pollution :Focus 2004, 4, 385
3. Paszun, D.; Spychaj, T. Ind Eng Chem Res 1997, 36, 1373.
4. Kosmidis, V. A.; Achilias, D. S.; Karayannidis, G. P. Macromol Mater Eng 2001, 286,
640.
5. Shukla, S. R.; Kulkarni, K. S. J Appl Polym Sci 2002, 85, 1765.
6. Shukla, S. R.; Harad, A. M. J Appl Polym Sci 2005, 97, 513.
7. Shukla, S. R.; Harad, A. M. Polym Degrad Stab 2006, 91, 1850.
8. Soni, R. K.; Dutt, K.; Jain, A.; Soam, S.; Singh S. J Appl Polym Sci 2009, 113, 1090.
9. Shukla, S. R.; Palekar, V. P.; Pingale, N. D. Color Tech 2010, 126, 55.
©Rikhil Shah, Institute of Chemical Technology (ICT), Mumbai, India