Product Bulletin - Cray Valley

1 Product Bulletin SMA Multi-Functional Resins TABLE OF CONTENTS. INTRODUCTION .. 4. CRAY Valley 'S STYRENE MALEIC ANHYDRIDE RESINS ..5-6. TYPICAL PHYSICAL PROPERTIES OF STYRENE MALEIC ANHYDRIDE RESINS ..7-11. REACTIONS OF STYRENE MALEIC ANHYDRIDE RESINS .. 12-13. SAFETY, HANDLING & STORAGE INFORMATION .. 14. SUPPLEMENTAL STYRENE MALEIC ANHYDRIDE LITERATURE .. 15. 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 of the base resins and ester resins. SMA resins are used in diverse applications such as paper sizing, powder coating, pigment dispersions, inks, over print varnishes, leather retanning, microelectronics fabrication and processing, carpet/textile cleaners and floor care products. SMA resins can function as polymeric surfactants in dispersing and emulsifying applications, as high functionality cross-linking agents or as chemical intermediates in the production of specialty polymers.

2 SMA resins are well known for their high functionality, high thermal properties, low viscosities of high solids, and as their salts, aqueous solutions, low color, and low VOC content. 4. Cray Valley 's Styrene Maleic Anhydride Resins Base Resins and EF-80 are available only as flake. SMA base SMA 1000, SMA 2000 and SMA 3000 resins resins are characterized by high glass transition are unmodified styrene/maleic anhydride copolymers temperatures and softening points, high thermal with styrene/maleic anhydride ratios of 1/1, 2/1 and 3/ stability, extremely low VOC content, high melt 1, respectively. SMA EF-30, EF-40, EF-60 and EF- viscosities, high solubility in a number of organic 80 are 3/1, 4/1, 6/1 and 8/1 styrene/maleic anhydride solvents and the ability to form low viscosity aqueous copolymers which are manufactured for uniform alkali salt solutions at basic pH. The anhydride reactivity and certified for extremely high purity.

3 SMA functionality in SMA base resins is much less reactive 1000, 2000, 3000 and EF-30are available in flake towards atmospheric moisture up-take and hydrolysis (F) or powder (P) form, while SMA EF-40, EF-60 than is a typical non-polymeric anhydride. CH CH2 HC CH CH CH2 CH CH. + x n O C C O O C C O. O O. Maleic Anhydride x = 1-4,6,8 n = 8-12. Styrene SMA Base Resins Ester Resins used to prepare the ester, the structure of the esterifying SMA ester resins are prepared by partial alcohol and extent of esterification. The SMA ester esterification of SMA base resins. The ester resins resins exhibit many of the desirable characteristics contain a combination of anhydride and mono-ester/ shown by the SMA base resin. In addition, the SMA . mono carboxylic acid functionality. There are five ester resins exhibit generally low melt viscosities, commercial grades of SMA ester resins: SMA reactivity typical of the carboxylic acid functionality, 1440, 17352, 2625, 3840 and 31890.

4 SMA 17352 improved solubility in many organic solvents and refined and 2625 are available in flake or powder form, while polymeric surfactant properties, including generally SMA 1440, 3840 and 31890 are available only in better compatibility with other polymeric and non- flake form. The ester resins differ by the base resin polymeric surfactants. O O O. C C. ROH. CH CH2 CH CH CH CH2 CH CH CH CH. x n x y z n O C C O O C C O. O OR OH. x = 1-4, n = 8-12 x = 1-4, y = , z = n = 8-12. SMA Base Resins SMA Ester Resins 5. SMA Resin Aqueous Ammonia Salt Solutions SMA Resin Aqueous Sodium Salt Solutions SMA 1000, 2000, 3000, 4000, 1440, 2625 and SMA 1000, 3000 and 4000 HNa are available as 17352 are available as hydrolyzed (H) grades, which hydrolyzed HNa or HK grades, which are aqueous are aqueous solutions of the SMA resin ammonia salts. solutions of the SMA resin sodium or potassium salts. This form of SMA resin is particularly well suited for These forms of SMA resins are particularly well suited use in preparing water-based formulations.

5 SMA H for use in preparing water-based formulations. SMA . grade products are true solutions, with high clarity and HNa and HK grades are true solutions, with high excellent freeze/thaw stabilities. They are stable at clarity and excellent freeze/thaw stabilities. They are basic pH (>8), and, in general, exhibit lower solution stable at basic pH (>10), and, in general, exhibit lower viscosities at higher pH. SMA H grade products are solution viscosities at higher pH. SMA HNa and HK. infinitely miscible in water, and are stable in the grades are infinitely miscible in water, and are stable in presence of many other polymeric and non-polymeric the presence of many other polymeric and non- surfactants. polymeric surfactants. Properties of SMA 1000 Amic Acid Product Appearance pH % Solids Viscosity @ 25 oC, cps Mw SMA 1000MA Clear light golden solution 35 500 5,500. SMA 1000 Amic Acid level of tertiary amine functionality, have high thermal SMA 1000MA is a low molecular weight styrene- stability, low VOC content and form high solids maleic anhydride amic acid resin which exhibits a solutions in organic solvents or, as their cationic salts, unique combination of properties.

6 This Product is in water. SMA Imide Resins can function as polyimide supplied as a high solids, low viscosity water solution or polyamine additives, serving as a crosslinking agent, with a neutral pH, low ionic character and very low curing catalyst or surface modifying agent. Typical use VOC content. It functions as a very efficient polymeric areas include alkali resistant coatings, adhesives and surfactant in variety of applications, including forming polymer modification. SMA Imide Resins easily form stable, low-tarnish metallic pigment dispersions and cationic salts which can perform a variety of functions inks. in water-based applications, serving as a cationic dispersants or emulsifying agents or as a flocculating SMA Imides or coagulating agent. Typical use areas include paper SMA Imide Resins are low molecular weight manufacture and surface sizing, pigment dispersions, copolymers of styrene and dimethylaminopropylamine inks, overprint varnishes and water treatment.

7 (DMAPA) maleimide. These products have a high 6. Properties of Styrene Maleic Anhydride Resins Properties of SMA Base Resins and Ester SMA resins exhibit various physical properties which Resins are important in determining which resin to use. Properties of SMA Resins M elt Viscosity Acid value mg Product SM A Ratio Mw Mn Tg ( oC). (Poise) @ 200 oC KOH/g sample SM A 1000 1:1 5,000 2,100 ~60,000 465-495 155. SM A 2000 2:1 7,500 2,700 ~6,000 335-375 135. SM A 3000 2:1 7,500 2,700 ~6,000 330-380 135. SM A EF-30 3:1 9,500 3,050 ~3,000 275-285 125. SM A EF-40 4:1 11,000 3,600 ~750 195-235 115. SM A EF-60 6:1 11,500 5,500 ~70 141-171 106. SM A EF-80 8:1 14,400 7,500 ~100 105-135 104. Properties of SMA Esters Melt Viscosity @ Acid value mg Product Mw Mn Tg (oC). 200oC (poise) KOH/g sample 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.

8 SMA 31890 17,000 5,500 ~15 100-120 45. Properties of SMA Resins and Ester Aqueous Base Solutions Resin Grade Solids Content (wt%) pH Viscosity (cPs at 30oC) Gardner Color SMA 1000H - 200-1,200 <2. SMA 1440H 5,000 15,000 <5. SMA 2000H As measured <2. SMA 3000H - < 500 <2. SMA 2625H As measured <3. SMA 17352H As measured <3. SMA 1000 HNa 39 - < 500 As measured SMA 3000HK <5,000 As measured SMA 4000 HNa < 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 85 317 344. SMA 2000 I 88 301 336. SMA 3000 I 90 294 328. SMA 4000 I 90 303 334. 7. 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.

9 Paper making, Surface Sizing Water Resistance 3000, 2625 1530. Paper Making Wet End, Stability in Cationic Systems 1000I, 2000I, 3000I. Paper Coatings for Ink Jet Waterborne Ink, Paint Pigment Dispersion Stability, Color 1440H, 17352H 4952. Dispersion Development, Low Viscosity Cationic Systems 1000I, 2000I, 3000I, 4000I 4957, 4953. Carbon Black 1440, 17352 4953. Metallics 1000MA 4950. Solvent Borne Ink, Paint Dispersion Stability, Color 3840, 17352 4966. Pigment Dispersion Development, Low Viscosity Latex gloves flame Stability of divalent ion 1000, 17352. retardant/antioxidant dispersant containing fillers (calcium, magnesium). Emulsion Polymerization Particle size control and 1000, 2000, 17352. stability, heat resistance Carpet Treatment/Shampoos Stain/water resistance 1000, 2000, 17352 4965. Wax/Floor Polish Coating Leveling 2625, 17352. Printed Wiring Boards Improved Dielectric Properties, EF30, EF40, EF60, EF80. Heat resistance Wax Emulsions Hydrophobicity, Particle size 1000, 2000, 3000 4964.

10 Control and stability Leather Tanning Divalent cation stability 1000 4960, 4961. 8. Melt Viscosities Melt Viscosities of SMA Base Resins Melt Viscosities of SMA Ester Resins 100000 100000. Viscosity (poise). Viscosity (poise). 10000 SMA 17352. 10000 SMA 1000. SMA 2625. SMA 2000 1000. SMA EF30 SMA 1440. 1000 SMA EF40 100 SMA 3840. 10. 100. 140 160 180 200 220. 150 170 190 210 230. o o Temperature C Temperature C. Properties of SMA Resin Aqueous Ammonia Salt Solutions Aqueous Viscosity vs. pH. Aqueous Viscosity vs. % Solids 55. 2000. 50. 1800. 45. 1600 40. 35. Viscosity (cP) at 30 C. o 1400 SMA 3000. SMA 2625. 30 SMA 17352. SMA 2000. 1200 SMA 1000. Viscosity (cP) at 30 C. SMA 3000 25. o SMA 2625. SMA 2000. 1000 SMA 1440 20. SMA 17352. SMA 1000. 15. 800. 10. 600. 5. 6 7 8 9 10 11. pH of 15% Solids Aqueous Ammoniacal Solutions 400. 200. 0. 0 10 20 30 40 50 60. Wt. % Solids 9. Thermal Stability of SMA Resins (TGA in Air). 10. Solubility of SMA Resins in Common Solvents at 30 C.