SMA® Multi-Functional Resins

Product Bulletin

TABLE OF CONTENTS

INTRODUCTION .......................................................................................................................... 4CRAY VALLEY’S STYRENE MALEIC ANHYDRIDE RESINS ... .............................................5-6TYPICAL PHYSICAL PROPERTIES OF STYRENE MALEIC ANHYDRIDE RESINS ...... ...7-11REACTIONS OF STYRENE MALEIC ANHYDRIDE RESINS ............................................. 12-13SAFETY, HANDLING & STORAGE INFORMATION ............................................................... 14SUPPLEMENTAL STYRENE MALEIC ANHYDRIDE LITERATURE ........................................ 15

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INTRODUCTION

SMA® multifunctional resins are a family of low molecular weight resins which include styrene/maleic anhydride,amic acids, imides, copolymer base resins, partial esters of the base resins and aqueous ammonia salt solutions ofthe base resins and ester resins.

SMA® resins are used in diverse applications such as paper sizing, powder coating, pigment dispersions, inks, overprint varnishes, leather retanning, microelectronics fabrication and processing, carpet/textile cleaners and floorcare products.

SMA® resins can function as polymeric surfactants in dispersing and emulsifying applications, as high functionalitycross-linking agents or as chemical intermediates in the production of specialty polymers.

SMA® resins are well known for their high functionality, high thermal properties, low viscosities of high solids, andas their salts, aqueous solutions, low color, and low VOC content.

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CH CH2 CH CH

C CO Ox n

x = 1-4,6,8 n = 8-12

SMA Base Resins

O

CH CH2 H C CH

C CO OO

+

Styrene

Maleic Anhydride

Cray Valley’s Styrene Maleic Anhydride Resins

CH CH2 CH CH

C CO Ox n

x = 1-4, n = 8-12

SMA Base Resins

O

CH CH2 CH CH CH CH

CCOO O

C C

OR OH

O Oy z nx

x = 1-4, y = 0.20-0.35, z = 0.65-0.80 n = 8-12SMA Ester Resins

ROH

Base ResinsSMA® 1000, SMA® 2000 and SMA® 3000 resinsare unmodified styrene/maleic anhydride copolymerswith styrene/maleic anhydride ratios of 1/1, 2/1 and 3/1, respectively. SMA® EF-30, EF-40, EF-60 and EF-80 are 3/1, 4/1, 6/1 and 8/1 styrene/maleic anhydridecopolymers which are manufactured for uniformreactivity and certified for extremely high purity. SMA®

1000, 2000, 3000 and EF-30are available in flake(F) or powder (P) form, while SMA® EF-40, EF-60

and EF-80 are available only as flake. SMA® baseresins are characterized by high glass transitiontemperatures and softening points, high thermalstability, extremely low VOC content, high meltviscosities, high solubility in a number of organicsolvents and the ability to form low viscosity aqueousalkali salt solutions at basic pH. The anhydridefunctionality in SMA® base resins is much less reactivetowards atmospheric moisture up-take and hydrolysisthan is a typical non-polymeric anhydride.

Ester ResinsSMA® ester resins are prepared by partialesterification of SMA® base resins. The ester resinscontain a combination of anhydride and mono-ester/mono carboxylic acid functionality. There are fivecommercial grades of SMA® ester resins: SMA®

1440, 17352, 2625, 3840 and 31890. SMA® 17352and 2625 are available in flake or powder form, whileSMA® 1440, 3840 and 31890 are available only inflake form. The ester resins differ by the base resin

used to prepare the ester, the structure of the esterifyingalcohol and extent of esterification. The SMA® esterresins exhibit many of the desirable characteristicsshown by the SMA® base resin. In addition, the SMA®

ester resins exhibit generally low melt viscosities,reactivity typical of the carboxylic acid functionality,improved solubility in many organic solvents and refinedpolymeric surfactant properties, including generallybetter compatibility with other polymeric and non-polymeric surfactants.

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Product Appearance pH % Solids Viscosity @ 25 oC, cps Mw SMA® 1000MA Clear light golden solution 6.8 35 500 5,500

SMA® Resin Aqueous Ammonia Salt SolutionsSMA® 1000, 2000, 3000, 4000, 1440, 2625 and17352 are available as hydrolyzed (H) grades, whichare aqueous solutions of the SMA® resin ammonia salts.This form of SMA® resin is particularly well suited foruse in preparing water-based formulations. SMA® Hgrade products are true solutions, with high clarity andexcellent freeze/thaw stabilities. They are stable atbasic pH (>8), and, in general, exhibit lower solutionviscosities at higher pH. SMA® H grade products areinfinitely miscible in water, and are stable in thepresence of many other polymeric and non-polymericsurfactants.

SMA® Resin Aqueous Sodium Salt SolutionsSMA® 1000, 3000 and 4000HNa are available ashydrolyzed HNa or HK grades, which are aqueoussolutions of the SMA® resin sodium or potassium salts.These forms of SMA® resins are particularly well suitedfor use in preparing water-based formulations. SMA®

HNa and HK grades are true solutions, with highclarity and excellent freeze/thaw stabilities. They arestable at basic pH (>10), and, in general, exhibit lowersolution viscosities at higher pH. SMA® HNa and HKgrades are infinitely miscible in water, and are stable inthe presence of many other polymeric and non-polymeric surfactants.

Properties of SMA® 1000 Amic Acid

SMA® 1000 Amic AcidSMA® 1000MA is a low molecular weight styrene-maleic anhydride amic acid resin which exhibits aunique combination of properties. This product issupplied as a high solids, low viscosity water solutionwith a neutral pH, low ionic character and very lowVOC content. It functions as a very efficient polymericsurfactant in variety of applications, including formingstable, low-tarnish metallic pigment dispersions andinks.

SMA® ImidesSMA® Imide Resins are low molecular weightcopolymers of styrene and dimethylaminopropylamine(DMAPA) maleimide. These products have a high

level of tertiary amine functionality, have high thermalstability, low VOC content and form high solidssolutions in organic solvents or, as their cationic salts,in water. SMA® Imide Resins can function as polyimideor polyamine additives, serving as a crosslinking agent,curing catalyst or surface modifying agent. Typical useareas include alkali resistant coatings, adhesives andpolymer modification. SMA® Imide Resins easily formcationic salts which can perform a variety of functionsin water-based applications, serving as a cationicdispersants or emulsifying agents or as a flocculatingor coagulating agent. Typical use areas include papermanufacture and surface sizing, pigment dispersions,inks, overprint varnishes and water treatment.

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Product Mw Mn Melt Viscosity @

200oC (poise) Acid value mg KOH/g sample Tg (oC)

SMA® 1440 7,000 2,900 ~ 300 165-205 60 SMA® 17352 7,000 2,900 ~10,000 255-285 125 SMA® 2625 9,000 3,100 ~1,000 200-240 110 SMA® 3840 10,500 4,100 ~ 50 95-120 75 SMA® 31890 17,000 5,500 ~15 100-120 45

Properties of Styrene Maleic Anhydride Resins

Properties of SMA® Base Resins and EsterResins

SMA® resins exhibit various physical properties whichare important in determining which resin to use.

Properties of SMA® Resins

Properties of SMA® Esters

Properties of SMA® Resins and Ester Aqueous Base Solutions

Resin Grade Solids Content (wt%) pH Viscosity (cPs at 30oC) Gardner Color SMA® 1000H 35.5-39.5 8.5 - 9.5 200-1,200 <2 SMA® 1440H 31.0 – 36.5 8.0 – 9.5 5,000 – 15,000 <5 SMA® 2000H 20.0 – 24.0 8.5 – 9.5 As measured <2 SMA® 3000H 13.0 – 15.0 8.0 - 9.5 < 500 <2 SMA® 2625H 18.5 – 20.0 8.0 – 9.5 As measured <3 SMA® 17352H 24.0 – 26.0 8.0 – 9.5 As measured <3 SMA® 1000HNa 39 – 41.0 8.0 - 11.0 < 500 As measured SMA® 3000HK 29.0 – 31.0 8.0 –11.0 <5,000 As measured SMA® 4000 HNa 19.0 – 21.0 8.0 –11.0 < 500 As measured

Properties of SMA® Imides

Product Amine Index (meq/gram) Tg (oC) 5% Mass Loss Temp (oC) 10% Mass Loss (oC) SMA® 1000 I 3.15 85 317 344 SMA® 2000 I 2.5 88 301 336 SMA® 3000 I 2.15 90 294 328 SMA® 4000 I 1.75 90 303 334

Product SM A® Ratio M w M n M elt Viscosity (Poise) @ 200oC

Acid value mg KOH/g sample Tg (oC)

SMA® 1000 1:1 5,000 2,100 ~60,000 465-495 155 SMA® 2000 2:1 7,500 2,700 ~6,000 335-375 135 SMA® 3000 2:1 7,500 2,700 ~6,000 330-380 135 SMA® EF-30 3:1 9,500 3,050 ~3,000 275-285 125 SMA® EF-40 4:1 11,000 3,600 ~750 195-235 115 SMA® EF-60 6:1 11,500 5,500 ~70 141-171 106 SMA® EF-80 8:1 14,400 7,500 ~100 105-135 104

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SMA® Resins - Applications Guide Application/Market Property Recommended Product Relevant Brochures General Brochure General properties 3100 Cutting SMA® Into Water 4951 Overprint Varnishes, Ink Heat Resistance 1000, 17352, 2000 4958 Adhesion To Polymer Films 1440, 31890 Viscosity Stability 2625, 3000 4955 Powder Coatings Matting Agent 3000, 2625, 3840 Paper making, Surface Sizing Water Resistance 3000, 2625 1530 Paper Making – Wet End, Paper Coatings for Ink Jet

Stability in Cationic Systems 1000I, 2000I, 3000I

Waterborne Ink, Paint Pigment Dispersion

Dispersion Stability, Color Development, Low Viscosity

1440H, 17352H 4952

Cationic Systems 1000I, 2000I, 3000I, 4000I 4957, 4953 Carbon Black 1440, 17352 4953 Metallics 1000MA 4950 Solvent Borne Ink, Paint Pigment Dispersion

Dispersion Stability, Color Development, Low Viscosity

3840, 17352 4966

Latex gloves – flame retardant/antioxidant dispersant

Stability of divalent ion containing fillers (calcium, magnesium)

1000, 17352

Emulsion Polymerization Particle size control and stability, heat resistance

1000, 2000, 17352

Carpet Treatment/Shampoos Stain/water resistance 1000, 2000, 17352 4965 Wax/Floor Polish Coating Leveling 2625, 17352 Printed Wiring Boards Improved Dielectric Properties,

Heat resistance EF30, EF40, EF60, EF80

Wax Emulsions Hydrophobicity, Particle size control and stability

1000, 2000, 3000 4964

Leather Tanning Divalent cation stability 1000 4960, 4961

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Melt Viscosities

Aqueous Viscosity vs. pH

5

10

15

20

25

30

35

40

45

50

55

6 7 8 9 10 11

pH of 15% Solids Aqueous Ammoniacal Solutions

Vis

cosi

ty (c

P) a

t 30

o C

SMA 3000SMA 2625SMA 17352SMA 2000SMA 1000

Properties of SMA® Resin Aqueous Ammonia Salt Solutions

Aqueous Viscosity vs. % Solids

0

200

400

600

800

1000

1200

1400

1600

1800

2000

0 10 20 30 40 50 60

Wt. % Solids

Vis

cosi

ty (c

P) a

t 30 o

C SMA 3000SMA 2625SMA 2000SMA 1440SMA 17352SMA 1000

Melt Viscosities of SMA Ester Resins

10

100

1000

10000

100000

140 160 180 200 220

Temperature oC

Vis

cosi

ty (p

oise

)

SMA 17352SMA 2625SMA 1440SMA 3840

Melt Viscosities of SMA Base Resins

100

1000

10000

100000

150 170 190 210 230

Temperature oC

Vis

cosi

ty (p

oise

)

SMA 1000SMA 2000SMA EF30SMA EF40

10

Thermal Stability of SMA Resins (TGA in Air)

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Solubility of SMA® Resins in Common Solvents at 30°C

SMA® Resin 1000 1440 17352 2000 2625 3000 3840 EF40AliphaticCyclohexane I I I I I I I In-Hexane I I I I I I I In-Heptane I I I I I I I I

AromaticToluene I I I I I PS S PSXylene I I I I I PS S I

AlcoholsMethanol I PS PS I PS I PS IEthanol,190 pf I PS I I I I PS IEthanol, 200 pf I S PS I PS I PS I1-Propanol I PS PS I PS I PS I2-Propanol I PS I I I I PS I

KetonesAcetone VS VS VS VS VS VS VS VS2-Butanone VS VS VS VS VS VS VS VS4-Methyl-2-pentanone VS VS VS VS VS VS VS VS

EthersTetrahydrofuran VS VS VS VS VS VS VS VS1,4-Dioxane VS VS VS VS VS VS VS S

OthersEthyl Acetate VS VS VS VS VS VS VS VSPropyl Acetate VS VS VS VS VS VS VS VSDimethylforamide VS VS VS VS VS VS VS VSEthoxyethanol I S S I S I S PSEthylene glycol I I I I I I I IPropylene glycol I PS I I I I I IPropylene carbonate S S S S S S I S

Key g/100mlI <1PS 1-15S 15-50VS >75

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Reactions of SMA® Resins

SubstitutionThe pendant aromatic groups in SMA® 1000, 2000,3000, EF-30, EF-40, EF-60 and EF-80 resins willundergo substitution reactions typical of aromaticsystems. Sulfonation can be conducted in commercialreactors by reaction of the base resin and sulfur trioxide(or other suitable sulfonation reagent) in an inert solvent(typically a halogenated solvent). The number ofaromatic groups sulfonated can be controlled, in part,by reaction conditions. The resultant sodium orpotassium sulfonates have surface active properties andhave applications such as dispersants for oil drillingproducts.

EsterificationAlcohols will react with base resins (SMA® 1000,2000, 3000, EF-30, EF-40, EF-60 or EF-80) to formmonoesters by ring opening of the anhydride groups.Esterification can be performed in commercial reactorsby charging the base resin and appropriate alcohol tothe reactor and heating with agitation under inertatmosphere. Typical reaction conditions are 160 to200ºC for 30 to 90 minutes. For esterification greaterthan 50%, or formation of diester groups, water mustbe removed and a catalyst is generally needed toincrease reaction rate. A number of functional groupsincluding halogen, amine and unsaturated groups havebeen introduced by means of esterification of baseresins with appropriate functionalized alcohols.Reactants with hydroxyl functionality greater than 1will cross-link SMA® base resins. For example,primary diols, such as 1, 4-butanediol, will react withSMA® 1000 resin at room temperature, in 1 to 3 days(the reaction will take place faster at elevatedtemperatures).

ImidizationAmines will react with base resins and with partial esterresins to form amides. Imidization can be performedin commercial reactors using the SMA® resins, a non-reacting diluent and the desired amine. Typical reactionconditions are 150 to 180ºC for 2 to 3 hours.

Water that is formed during the reaction must beremoved to affect complete imidization. The resultantstyrene/N-substituted maleimide polymers generallyhave higher thermal stability and higher melting ranges.

Solubilizing In WaterStrong or weak bases will react with the anhydride orcarboxylic acid functionality of SMA® resins to formwater-soluble salts. Ammoniacal solutions containingstyrene/ammonium maleate polymers are readilyprepared with ammonium hydroxide. Solutions ofstyrene/sodium maleate polymers are produced whenaqueous sodium hydroxide is used. Amines, such asmorpholine or triethanolamine, can also be used toprepare water-soluble salts.

While a number of grades of SMA® ammonia saltsolutions (H grade), sodium salt solutions (HNa grade)and potassium salt solutions (HK) are commerciallyoffered, SMA® resin solutions can also be preparedfrom the solid resins. For example, SMA® resins arereadily soluble in aqueous ammonia. Solids contentcan be varied over a wide range. Solution viscositiesare influenced by the styrene to maleic anhydride ratio,the alcohol employed to prepare the partial ester andthe degree of esterification. Ammoniacal solutionviscosities increase with an increase in the styrene tomaleic anhydride ratio.

A general procedure for preparing 15% solutions is asfollows (Please refer to our technical bulletin“Solubilizing SMA® Resin” for a more detailedprocedure.):

- Charge vessel with water and add SMA®

resins while maintaining vigorous agitation.

- Slowly add ammonium hydroxide; a slightexotherm will occur.

- Heat to suggested reaction temperature andmaintain temperature and agitation untilsolution is complete.

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SMA Resin Grade

Parts of 28% Ammonium

Hydroxide/100 Parts Resin*

Suggested Reaction Temperature (ºC)

1000 60 75-85

2000 44 75-85

3000 34 75-85

1440 23 50-60

17352 34 70-80

2625 27 70-80

Process Variables for SMA® HydrolysisFormulations are based on acid numbers in Table 1,with 15% excess ammonia and giving a product in thepH range 8.5-9.5.

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TOXICOLOGY AND SAFE USEINFORMATION

Materials in this document can cause eye and skinirritation. Handle in accordance with good industrial

hygiene practices, and wear protective equipment toprevent exposure of these product to the eyes, skinand respiratory tract. Consult the material’s MSDSbefore using any chemical in this bulletin.

Safety, Handling & Storage Information

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Supplemental Sytrene Maleic Anhydride Literature

Technical literature including starting formulations,technical papers, product bulletins, and material safetydata sheets are available to optimize the use of CrayValley's products.

Literature can be obtained through Cray Valley'scustomer service group (1-877-871-2729) or ourweb site (www.crayvalleyus.com).

Cray Valley offers these additional documents dis-cussing our SMA® resins to aid in formulating.

Solubilizing SMA’sSMA® in Epoxy Hybrid Powder CoatingsSMA® Epoxy Powder CoatingsSMA® Pigment DispersionsSMA® Ink Post Add BrochureSMA® Solvent BrochureSurface Sizing with SMA’s

3100 01/10

Corporate Headquarters

Cray Valley USA, LLC468 Thomas Jones Way, Suite 100

Exton, PA 19341

Tel: 877-US1-CRAY (877-871-2729)

E-mail: TechSupport@crayvalleyus.com

For contact information worldwide, please refer to Cray Valley's web site at:http://www.crayvalley.com

The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond Cray Valley Company'scontrol. The listed properties are illustrative only, and not product specifications. Cray Valley Company disclaims any liability in connection with the use of the information,

and does not warrant against infringement by reason of the use of its products in combination with other material or in any process.