Product Bulletin. SMA Multi-Functional Resins

Transcription

1 Product Bulletin SMA Multi-Functional Resins

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3 TABLE OF CONTENTS INTRODUCTION... 4 CRAY VALLEY S STYRENE MALEIC ANHYDRIDE RESINS PROPERTIES OF STYRENE MALEIC ANHYDRIDE RESINS REACTIONS OF STYRENE MALEIC ANHYDRIDE RESINS SAFETY, HANDLING & STORAGE INFORMATION SUPPLEMENTAL STYRENE MALEIC ANHYDRIDE LITERATURE... 15

4 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. 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

5 Cray Valley s Styrene Maleic Anhydride Resins Base Resins SMA 1000, SMA 2000, SMA 2021, SMA 3000 and SMA 3024 resins are unmodified styrene/ maleic anhydride copolymers with 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 anhydride copolymers which are manufactured for uniform reactivity 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 base resins are characterized by high glass transition temperatures and softening points, high thermal stability, extremely low VOC content, high melt viscosities, high solubility in a number of organic solvents and the ability to form low viscosity aqueous alkali salt solutions at basic ph. The anhydride functionality in SMA base resins is much less reactive towards atmospheric moisture up-take and hydrolysis than is a typical non-polymeric anhydride. CH CH 2 HC CH Styrene + O C C O O Maleic Anhydride CH CH 2 CH CH x O C C O O x = 1-4,6,8 n = 8-12 SMA Base Resins n Ester Resins SMA ester resins are prepared by partial esterification of SMA base resins. The ester resins contain a combination of anhydride and mono-ester/ mono carboxylic acid functionality. There are five commercial grades of SMA ester resins: SMA 1440, 17352, 2625, 3840 and SMA and 2625 are available in flake or powder form, while SMA 1440, 3840 and are available only in flake form. The ester resins differ by the base resin used to prepare the ester, the structure of the esterifying alcohol and extent of esterification. The SMA ester resins exhibit many of the desirable characteristics shown 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 refined polymeric surfactant properties, including generally better compatibility with other polymeric and nonpolymeric surfactants. CH CH 2 CH CH x n O C C O O x = 1-4, n = 8-12 SMA Base Resins ROH O O O C C CH CH 2 CH CH CH CH x y z n O C C O OR OH x = 1-4, y = , z = n = 8-12 SMA Ester Resins 5

6 SMA Resin Aqueous Ammonia Salt Solutions SMA 1000, 2000, 2021, 3000, 3024, 4000, 1440, 2625 and are available as hydrolyzed (H) grades, which are aqueous solutions of the SMA resin ammonia salts. This form of SMA resin is particularly well suited for use in preparing water-based formulations. SMA H grade products are true solutions, with high clarity and excellent freeze/thaw stabilities. They are stable at basic ph (>8), and, in general, exhibit lower solution viscosities at higher ph. SMA H grade products are infinitely miscible in water, and are stable in the presence of many other polymeric and non-polymeric surfactants. SMA Resin Aqueous Sodium Salt Solutions SMA 1000, 2021, 3000 and 4000HNa are available as hydrolyzed HNa or HK grades, which are aqueous solutions of the SMA resin sodium or potassium salts. These forms of SMA resins are particularly well suited for use in preparing water-based formulations. SMA HNa and HK grades are true solutions, with high clarity and excellent freeze/thaw stabilities. They are stable at basic ph (>10), and, in general, exhibit lower solution viscosities at higher ph. SMA HNa and HK grades are infinitely miscible in water, and are stable in the presence of many other polymeric and nonpolymeric surfactants. Properties of SMA 1000 Amic Acid Product Appearance ph % Solids 25 o C, cps M w SMA 1000MA Clear light golden solution ,500 SMA 1000 Amic Acid SMA 1000MA is a low molecular weight styrenemaleic anhydride amic acid resin which exhibits a unique combination of properties. This product is supplied as a high solids, low viscosity water solution with a neutral ph, low ionic character and very low VOC content. It functions as a very efficient polymeric surfactant in variety of applications, including forming stable, low-tarnish metallic pigment dispersions and inks. SMA Imides SMA Imide Resins are low molecular weight copolymers of styrene and dimethylaminopropylamine (DMAPA) maleimide. These products have a high level of tertiary amine functionality, have high thermal stability, low VOC content and form high solids solutions in organic solvents or, as their cationic salts, in water. SMA Imide Resins can function as polyimide or polyamine additives, serving as a crosslinking agent, curing catalyst or surface modifying agent. Typical use areas include alkali resistant coatings, adhesives and polymer modification. SMA Imide Resins easily form cationic salts which can perform a variety of functions in water-based applications, serving as a cationic dispersants or emulsifying agents or as a flocculating or coagulating agent. Typical use areas include paper manufacture and surface sizing, pigment dispersions, inks, overprint varnishes and water treatment. 6

7 Properties of Styrene Maleic Anhydride Resins Properties of SMA Base Resins and Ester Resins SMA resins exhibit various physical properties which are important in determining which resin to use. Properties of SMA Resins Product SMA Ratio M w M n Melt Viscosity Acid value mg 200 o C KOH/g sample Tg ( o C) SMA :1 5,000 2,100 ~60, SMA :1 7,500 2,700 ~6, SMA :1 21,000 12, SMA :1 9,500 3,050 ~3, SMA EF-30 3:1 9,500 3,050 ~3, SMA :1 24,000 10,000 ~15, SMA EF-40 4:1 11,000 3,600 ~ SMA EF-60 6:1 11,500 5,500 ~ SMA EF-80 8:1 14,400 7,500 ~ Properties of SMA Esters Product M w M n Melt Acid value mg 200 o C (poise) KOH/g sample Tg ( o C) SMA ,000 2,900 ~ SMA ,000 2,900 ~10, SMA ,000 3,100 ~1, SMA ,500 4,100 ~ SMA ,000 5,500 ~ Properties of SMA Resins and Ester Aqueous Base Solutions Resin Grade Solids Content (wt%) ph Viscosity (cps at 30 o C) Gardner Color SMA 1000H ,200 <2 SMA 1440H ,000 15,000 <5 SMA 2000H As measured <2 SMA 2021H < SMA 3000H < 500 <2 SMA 3024H < SMA 2625H As measured <3 SMA 17352H As measured <3 SMA 1000HNa < 500 As measured SMA 2021HNa < SMA 3000HK <5,000 As measured SMA 4000 HNa < 500 As measured Properties of SMA Imides Product Amine Index (meq/gram) Tg ( o C) 5% Mass Loss Temp ( o C) 10% Mass Loss ( o C) SMA 1000 I SMA 2000 I SMA 3000 I SMA 4000 I

8 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, Adhesion To Polymer Films 1440, Viscosity Stability 2625, Powder Coatings Matting Agent 3000, 2625, 3840 Paper making, Surface Sizing Water Resistance 3000, 2625, Paper Making Wet End, Stability in Cationic Systems 1000I, 2000I, 3000I Paper Coatings for Ink Jet Waterborne Ink, Paint Pigment Dispersion Dispersion Stability, Color 1440H, 17352H 4952 Development, Low Viscosity Cationic Systems 1000I, 2000I, 3000I, 4000I 4957, 4953 Carbon Black 1440, Metallics 1000MA 4950 Solvent Borne Ink, Paint Dispersion Stability, Color 3840, Pigment Dispersion Development, Low Viscosity Latex gloves flame Stability of divalent ion 1000, retardant/antioxidant dispersant containing fillers (calcium, magnesium) Emulsion Polymerization Particle size control and 1000, 2000, stability, heat resistance Carpet Treatment/Shampoos Stain/water resistance 1000, 2000, Wax/Floor Polish Coating Leveling 2625, Printed Wiring Boards Improved Dielectric Properties, EF30, EF40, EF60, EF80 Heat resistance Wax Emulsions Hydrophobicity, Particle size 1000, 2000, control and stability Leather Tanning Divalent cation stability 1000HNa, 2021HNa 4960,

9 Melt Viscosities Melt Viscosities of SMA Base Resins Melt Viscosities of SMA Ester Resins Viscosity (poise) SMA 1000 SMA 2000 SMA EF30 SMA EF40 Viscosity (poise) SMA SMA 2625 SMA 1440 SMA Temperature o C Temperature o C Properties of SMA Resin Aqueous Ammonia Salt Solutions Aqueous Viscosity vs. % Solids Aqueous Viscosity vs. ph Viscosity (cp) at 30 o C SMA 3000 SMA 2625 SMA 2000 SMA 1440 SMA SMA 1000 Viscosity (cp) at 30 o C SMA 3000 SMA 2625 SMA SMA 2000 SMA ph of 15% Solids Aqueous Ammoniacal Solutions Wt. % Solids 9

10 Thermal Stability of SMA Resins (TGA in Air) 10

11 Solubility of SMA Resins in Common Solvents at 30 C SMA Resin EF40 Aliphatic Cyclohexane I I I I I I I I I I n-hexane I I I I I I I I I I n-heptane I I I I I I I I I I Aromatic Toluene I I I I I I PS PS S PS Xylene I I I I I I PS PS S I Alcohols Methanol I PS PS I I PS I I PS I Ethanol,190 pf I PS I I I I I I PS I Ethanol, 200 pf I S PS I I PS I I PS I 1-Propanol I PS PS I I PS I I PS I 2-Propanol I PS I I I I I I PS I Ketones Acetone VS VS VS VS VS VS VS VS VS VS 2-Butanone VS VS VS VS VS VS VS VS VS VS 4-Methyl-2-pentanone VS VS VS VS VS VS VS VS VS VS Ethers Tetrahydrofuran VS VS VS VS VS VS VS VS VS VS 1,4-Dioxane VS VS VS VS VS VS VS VS VS S Others Ethyl Acetate VS VS VS VS VS VS VS VS VS VS Propyl Acetate VS VS VS VS VS VS VS VS VS VS Dimethylforamide VS VS VS VS VS VS VS VS VS VS Ethoxyethanol I S S I I S I I S PS Ethylene glycol I I I I I I I I I I Propylene glycol I PS I I I I I I I I Propylene carbonate S S S S S S S S I S Key g/100ml I <1 PS 1-15 S VS >75 11

12 Reactions of SMA Resins Substitution The pendant aromatic groups in SMA 1000, 2000, 3000, EF-30, EF-40, EF-60 and EF-80 resins will undergo substitution reactions typical of aromatic systems. Sulfonation can be conducted in commercial reactors by reaction of the base resin and sulfur trioxide (or other suitable sulfonation reagent) in an inert solvent (typically a halogenated solvent). The number of aromatic groups sulfonated can be controlled, in part, by reaction conditions. The resultant sodium or potassium sulfonates have surface active properties and have applications such as dispersants for oil drilling products. Esterification Alcohols will react with base resins (SMA 1000, 2000, 3000, EF-30, EF-40, EF-60 or EF-80) to form monoesters by ring opening of the anhydride groups. Esterification can be performed in commercial reactors by charging the base resin and appropriate alcohol to the reactor and heating with agitation under inert atmosphere. Typical reaction conditions are 160 to 200ºC for 30 to 90 minutes. For esterification greater than 50%, or formation of diester groups, water must be removed and a catalyst is generally needed to increase reaction rate. A number of functional groups including halogen, amine and unsaturated groups have been introduced by means of esterification of base resins with appropriate functionalized alcohols. Reactants with hydroxyl functionality greater than 1 will cross-link SMA base resins. For example, primary diols, such as 1, 4-butanediol, will react with SMA 1000 resin at room temperature, in 1 to 3 days (the reaction will take place faster at elevated temperatures). Imidization Amines will react with base resins and with partial ester resins to form amides. Imidization can be performed in commercial reactors using the SMA resins, a nonreacting diluent and the desired amine. Typical reaction conditions are 150 to 180ºC for 2 to 3 hours. Water that is formed during the reaction must be removed to affect complete imidization. The resultant styrene/n-substituted maleimide polymers generally have higher thermal stability and higher melting ranges. Solubilizing In Water Strong or weak bases will react with the anhydride or carboxylic acid functionality of SMA resins to form water-soluble salts. Ammoniacal solutions containing styrene/ammonium maleate polymers are readily prepared with ammonium hydroxide. Solutions of styrene/sodium maleate polymers are produced when aqueous sodium hydroxide is used. Amines, such as morpholine or triethanolamine, can also be used to prepare water-soluble salts. While a number of grades of SMA ammonia salt solutions (H grade), sodium salt solutions (HNa grade) and potassium salt solutions (HK) are commercially offered, SMA resin solutions can also be prepared from the solid resins. For example, SMA resins are readily soluble in aqueous ammonia. Solids content can be varied over a wide range. Solution viscosities are influenced by the styrene to maleic anhydride ratio, the alcohol employed to prepare the partial ester and the degree of esterification. Ammoniacal solution viscosities increase with an increase in the styrene to maleic anhydride ratio. A general procedure for preparing 15% solutions is as follows (Please refer to our technical bulletin Solubilizing SMA Resin for a more detailed procedure.): - Charge vessel with water and add SMA resins while maintaining vigorous agitation. - Slowly add ammonium hydroxide; a slight exotherm will occur. - Heat to suggested reaction temperature and maintain temperature and agitation until solution is complete. 12

13 Process Variables for SMA Hydrolysis Formulations are based on acid numbers in Table 1, with 15% excess ammonia and giving a product in the ph range SMA Resin Grade Parts of 28% Ammonium Hydroxide/100 Parts Resin* Suggested Reaction Temperature (ºC)

14 Safety, Handling & Storage Information TOXICOLOGY AND SAFE USE INFORMATION Materials in this document can cause eye and skin irritation. Handle in accordance with good industrial hygiene practices, and wear protective equipment to prevent exposure of these product to the eyes, skin and respiratory tract. Consult the material s MSDS before using any chemical in this bulletin. 14

15 Supplemental Sytrene Maleic Anhydride Literature Technical literature including starting formulations, technical papers, product bulletins, and material safety data sheets are available to optimize the use of Cray Valley's products. Literature can be obtained through Cray Valley's customer service group ( ) or our web site ( Solubilizing SMA s SMA in Epoxy Hybrid Powder Coatings SMA Epoxy Powder Coatings SMA Pigment Dispersions SMA Ink Post Add Brochure SMA Solvent Brochure Surface Sizing with SMA s Cray Valley offers these additional documents discussing our SMA resins to aid in formulating. 15

16 Corporate Headquarters Cray Valley USA, LLC 468 Thomas Jones Way, Suite 100 Exton, PA Tel: 877-US1-CRAY ( ) For contact information worldwide, please refer to Cray Valley's web site at: 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's control. 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 /10