Sma Multi Functional Resins (Europe)

7/23/2019 Sma Multi Functional Resins (Europe)

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SMA Multi-Functional Resins

Product Bulletin


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TABLE OF CONTENTS

INTRODUCTION .......................................................................................................................... 4

CRAY VALLEYS 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


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INTRODUCTION

SMAmultifunctional 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.

SMAresins 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.

SMAresins 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.

SMAresins 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.


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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 O

O

+

Styrene

Maleic Anhydride

Cray Valleys 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

CC

OO O

C C

OR OH

O Oy z nx

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

SMA Ester Resins

ROH

Base Resins

SMA1000, SMA2000 and SMA3000 resins

are unmodified styrene/maleic anhydride copolymers

with styrene/maleic anhydride ratios of 1/1, 2/1 and 3/

1, respectively. SMAEF-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 SMAEF-40, EF-60

and EF-80 are available only as flake. SMAbase

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 SMAbase resins is much less reactive

towards atmospheric moisture up-take and hydrolysis

than is a typical non-polymeric anhydride.

Ester Resins

SMA ester resins are prepared by partial

esterification of SMAbase resins. The ester resins

contain a combination of anhydride and mono-ester/

mono carboxylic acid functionality. There are five

commercial grades of SMAester resins: SMA

1440, 17352, 2625, 3840 and 31890. SMA17352

and 2625 are available in flake or powder form, while

SMA1440, 3840 and 31890 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 SMAester

resins exhibit many of the desirable characteristics

shown by the SMAbase 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 non-

polymeric surfactants.


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Product Appearance pH % Solids Viscosity @ 25oC, cps Mw

SMA

1000MA Clear light golden solution 6.8 35 500 5,500

SMAResin Aqueous Ammonia Salt Solutions

SMA1000, 2000, 3000, 4000, 1440, 2625 and

17352 are available as hydrolyzed (H) grades, which

are aqueous solutions of the SMAresin ammonia salts.

This form of SMAresin is particularly well suited for

use in preparing water-based formulations. SMAH

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. SMAH grade products are

infinitely miscible in water, and are stable in the

presence of many other polymeric and non-polymeric

surfactants.

SMAResin Aqueous Sodium Salt Solutions

SMA1000, 3000 and 4000HNa are available as

hydrolyzed HNa or HK grades, which are aqueous

solutions of the SMAresin sodium or potassium salts.

These forms of SMAresins 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. SMAHNa and HK

grades are infinitely miscible in water, and are stable in

the presence of many other polymeric and non-

polymeric surfactants.

Properties of SMA1000 Amic Acid

SMA1000 Amic Acid

SMA1000MA is a low molecular weight styrene-

maleic 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 andinks.

SMAImides

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. SMAImide 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. SMAImide Resins easily form

cationic salts which can perform a variety of functionsin 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.


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Product Mw MnMelt Viscosity @

200oC (poise)

Acid value mg

KOH/g sampleTg (

oC)

SMA1440 7,000 2,900 ~ 300 165-205 60

SMA17352 7,000 2,900 ~10,000 255-285 125

SMA2625 9,000 3,100 ~1,000 200-240 110

SMA3840 10,500 4,100 ~ 50 95-120 75

SMA31890 17,000 5,500 ~15 100-120 45

Properties of Styrene Maleic Anhydride Resins

Properties of SMABase Resins and Ester

Resins

SMAresins exhibit various physical properties which

are important in determining which resin to use.

Properties of SMA

Resins

Properties of SMAEsters

Properties of SMAResins and Ester Aqueous Base Solutions

Resin Grade Solids Content (wt%) pH Viscosity (cPs at 30oC) Gardner Color

SMA1000H 35.5-39.5 8.5 - 9.5 200-1,200


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SMA

Resins - Applications Guide

Application/Market Property Recommended Product Relevant Brochures

General Brochure General properties 3100

Cutting SMAInto Water 4951

Overprint Varnishes, Ink Heat Resistance 1000, 17352, 2000 4958

Adhesion To Polymer Films 1440, 31890

Viscosity Stability 2625, 3000 4955Powder 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

Viscosity(cP)at30oC

SMA 3000

SMA 2625

SMA 17352

SMA 2000

SMA 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

Viscosity(cP)at30oC SMA 3000

SMA 2625

SMA 2000

SMA 1440

SMA 17352

SMA 1000

Melt Viscosities of SMA Ester Resins

10

100

1000

10000

100000

140 160 180 200 220

TemperatureoC

Viscosity(poise)

SMA 17352

SMA 2625

SMA 1440

SMA 3840

Melt Viscosities of SMA Base Resins

100

1000

10000

100000

150 170 190 210 230

TemperatureoC

Viscosity

(poise)

SMA 1000

SMA 2000SMA EF30

SMA EF40


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Thermal Stability of SMA Resins (TGA in Air)


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Solubility of SMAResins in Common Solvents at 30C

SMA Resin 1000 1440 17352 2000 2625 3000 3840 EF40

Aliphatic

Cyclohexane I I I I I I I I

n-Hexane I I I I I I I I

n-Heptane I I I I I I I I

Aromatic

Toluene I I I I I PS S PS

Xylene I I I I I PS S I

Alcohols

Methanol I PS PS I PS I PS I

Ethanol,190 pf I PS I I I I PS I

Ethanol, 200 pf I S PS I PS I PS I

1-Propanol I PS PS I PS I PS I

2-Propanol I PS I I I I PS I

Ketones

Acetone VS VS VS VS VS VS VS VS

2-Butanone VS VS VS VS VS VS VS VS

4-Methyl-2-pentanone VS VS VS VS VS VS VS VS

Ethers

Tetrahydrofuran VS VS VS VS VS VS VS VS

1,4-Dioxane VS VS VS VS VS VS VS S

Others

Ethyl Acetate VS VS VS VS VS VS VS VS

Propyl Acetate VS VS VS VS VS VS VS VSDimethylforamide VS VS VS VS VS VS VS VS

Ethoxyethanol I S S I S I S PS

Ethylene glycol I I I I I I I I

Propylene glycol I PS I I I I I I

Propylene carbonate S S S S S S I S

Key g/100ml

I 75


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Reactions of SMAResins

Substitution

The pendant aromatic groups in SMA1000, 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 (SMA1000,

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

200C 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

SMA1000 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 SMAresins, a non-

reacting diluent and the desired amine. Typical reaction

conditions are 150 to 180C 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 SMAresins 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 toprepare water-soluble salts.

While a number of grades of SMAammonia salt

solutions (H grade), sodium salt solutions (HNa grade)

and potassium salt solutions (HK) are commercially

offered, SMAresin solutions can also be prepared

from the solid resins. For example, SMAresins 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 SMAResin 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.


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SMA

Resin

Grade

Parts of 28%

Ammonium

Hydroxide/100 Parts

Resin*

Suggested Reaction

Temperature (C)

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 SMAHydrolysisFormulations are based on acid numbers in Table 1,

with 15% excess ammonia and giving a product in the

pH range 8.5-9.5.


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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 materials 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 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 (1-877-871-2729) or our

web site (www.crayvalleyus.com).

Cray Valley offers these additional documents dis-

cussing our SMAresins to aid in formulating.

Solubilizing SMAs

SMAin Epoxy Hybrid Powder Coatings

SMAEpoxy Powder Coatings

SMAPigment Dispersions

SMA Ink Post Add Brochure

SMASolvent Brochure

Surface Sizing with SMAs


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Corporate Headquarters

Cray Valley USA, LLC

468 Thomas Jones Way, Suite 100

Exton, PA 19341

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

E-mail: [email protected]

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's

control. The listed properties are illustrative only, and not product specificati ons. Cray Valley Company disclaims any liability in connection with the use of the information,

Sma Multi Functional Resins (Europe)

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