Product Bulletin

SMA Multi-Functional Resins

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

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.

Cray Valleys Styrene Maleic Anhydride Resins

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.

Base Resins
SMA 1000, SMA 2000 and SMA 3000 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 EF80 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

CH

CH2

HC
O

CH

CH

CH2

x
O

CH

CH

Maleic Anhydride
x = 1-4,6,8

Styrene

n = 8-12

SMA Base Resins

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.

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

O
ROH
CH

CH2

x
O

CH

CH

C O

CH

CH2

CH

CH

CH
O

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

CH

z
n
C O

OR

OH

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

SMA Base Resins

SMA Ester Resins

SMA Resin Aqueous Ammonia Salt Solutions

SMA 1000, 2000, 3000, 4000, 1440, 2625 and
17352 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, 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
SMA 1000MA

Appearance
Clear light golden solution

pH
6.8

% Solids
35

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.

Viscosity @ 25 oC, cps

500

Mw
5,500

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.

SMA Imides
SMA Imide Resins are low molecular weight
copolymers of styrene and dimethylaminopropylamine
(DMAPA) maleimide. These products have a high

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
SM A
SM A
SM A
SM A
SM A
SM A
SM A

1000
2000
3000
EF-30
EF-40
EF-60
EF-80

SM A Ratio
1:1
2:1
2:1
3:1
4:1
6:1
8:1

Mw

Mn

5,000
7,500
7,500
9,500
11,000
11,500
14,400

2,100
2,700
2,700
3,050
3,600
5,500
7,500

M elt Viscosity
(Poise) @ 200 oC
~60,000
~6,000
~6,000
~3,000
~750
~70
~100

Acid value mg
KOH/g sample
465-495
335-375
330-380
275-285
195-235
141-171
105-135

Tg ( oC)
155
135
135
125
115
106
104

Properties of SMA Esters

Product
SMA 1440
SMA 17352
SMA 2625
SMA 3840
SMA 31890

Mw

Mn

7,000
7,000
9,000
10,500
17,000

2,900
2,900
3,100
4,100
5,500

Melt Viscosity @
200oC (poise)
~ 300
~10,000
~1,000
~ 50
~15

Acid value mg
KOH/g sample
165-205
255-285
200-240
95-120
100-120

Tg (oC)
60
125
110
75
45

Properties of SMA Resins and Ester Aqueous Base Solutions

Resin Grade
SMA 1000H
SMA 1440H
SMA 2000H
SMA 3000H
SMA 2625H
SMA 17352H
SMA 1000HNa
SMA 3000HK
SMA 4000 HNa

Solids Content (wt%)

35.5-39.5
31.0 36.5
20.0 24.0
13.0 15.0
18.5 20.0
24.0 26.0
39 41.0
29.0 31.0
19.0 21.0

pH
8.5 - 9.5
8.0 9.5
8.5 9.5
8.0 - 9.5
8.0 9.5
8.0 9.5
8.0 - 11.0
8.0 11.0
8.0 11.0

Viscosity (cPs at 30oC)

200-1,200
5,000 15,000
As measured
< 500
As measured
As measured
< 500
<5,000
< 500

Gardner Color
<2
<5
<2
<2
<3
<3
As measured
As measured
As measured

Properties of SMA Imides

Product
SMA 1000 I
SMA 2000 I
SMA 3000 I
SMA 4000 I

Amine Index (meq/gram)

3.15
2.5
2.15
1.75

Tg (oC)
85
88
90
90

5% Mass Loss Temp (oC)

317
301
294
303

10% Mass Loss (oC)

344
336
328
334

SMA Resins - Applications Guide

Application/Market
General Brochure
Cutting SMA Into Water
Overprint Varnishes, Ink

Powder Coatings
Paper making, Surface Sizing
Paper Making Wet End,
Paper Coatings for Ink Jet
Waterborne Ink, Paint Pigment
Dispersion

Solvent Borne Ink, Paint

Pigment Dispersion
Latex gloves flame
retardant/antioxidant dispersant
Emulsion Polymerization
Carpet Treatment/Shampoos
Wax/Floor Polish
Printed Wiring Boards
Wax Emulsions
Leather Tanning

Property
General properties

Recommended Product

Heat Resistance
Adhesion To Polymer Films
Viscosity Stability
Matting Agent
Water Resistance
Stability in Cationic Systems

1000, 17352, 2000

1440, 31890
2625, 3000
3000, 2625, 3840
3000, 2625
1000I, 2000I, 3000I

Dispersion Stability, Color

Development, Low Viscosity
Cationic Systems
Carbon Black
Metallics
Dispersion Stability, Color
Development, Low Viscosity
Stability of divalent ion
containing fillers (calcium,
magnesium)
Particle size control and
stability, heat resistance
Stain/water resistance
Coating Leveling
Improved Dielectric Properties,
Heat resistance
Hydrophobicity, Particle size
control and stability
Divalent cation stability

1440H, 17352H

1000I, 2000I, 3000I, 4000I

1440, 17352
1000MA
3840, 17352

Relevant Brochures
3100
4951
4958
4955
1530
4952
4957, 4953
4953
4950
4966

1000, 17352
1000, 2000, 17352
1000, 2000, 17352
2625, 17352
EF30, EF40, EF60, EF80

4965

1000, 2000, 3000

4964

1000

4960, 4961

Melt Viscosities
Melt Viscosities of SMA Base Resins

Melt Viscosities of SMA Ester Resins

10000

Viscosity (poise)

Viscosity (poise)

100000

SMA 1000
SMA 2000
SMA EF30
SMA EF40

1000

100000
SMA
SMA
SMA
SMA

10000
1000
100

17352
2625
1440
3840

10

100
150

170

190

210

140

230

160

180

200

220

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

Viscosity (cP) at 30 C

40

1200
SMA 3000

Viscosity (cP) at 30 C

1400

35

SMA 3000
SMA 2625
SMA 17352

30

SMA 2000
SMA 1000

25

SMA 2625
SMA 2000
1000

20

SMA 1440
SMA 17352
SMA 1000

15

800
10

600
5
6

10

pH of 15% Solids Aqueous Ammoniacal Solutions

400

200

0
0

10

20

30

40

50

60

Wt. % Solids

11

Thermal Stability of SMA Resins (TGA in Air)

10

Solubility of SMA Resins in Common Solvents at 30C

SMA Resin
Aliphatic
Cyclohexane
n-Hexane
n-Heptane

1000

1440

17352

2000

2625

3000

3840

EF40

I
I
I

I
I
I

I
I
I

I
I
I

I
I
I

I
I
I

I
I
I

I
I
I

Aromatic
Toluene
Xylene

I
I

I
I

I
I

I
I

I
I

PS
PS

S
S

PS
I

Alcohols
Methanol
Ethanol,190 pf
Ethanol, 200 pf
1-Propanol
2-Propanol

I
I
I
I
I

PS
PS
S
PS
PS

PS
I
PS
PS
I

I
I
I
I
I

PS
I
PS
PS
I

I
I
I
I
I

PS
PS
PS
PS
PS

I
I
I
I
I

Ketones
Acetone
2-Butanone
4-Methyl-2-pentanone

VS
VS
VS

VS
VS
VS

VS
VS
VS

VS
VS
VS

VS
VS
VS

VS
VS
VS

VS
VS
VS

VS
VS
VS

Ethers
Tetrahydrofuran
1,4-Dioxane

VS
VS

VS
VS

VS
VS

VS
VS

VS
VS

VS
VS

VS
VS

VS
S

Others
Ethyl Acetate
Propyl Acetate
Dimethylforamide
Ethoxyethanol
Ethylene glycol
Propylene glycol
Propylene carbonate

VS
VS
VS
I
I
I
S

VS
VS
VS
S
I
PS
S

VS
VS
VS
S
I
I
S

VS
VS
VS
I
I
I
S

VS
VS
VS
S
I
I
S

VS
VS
VS
I
I
I
S

VS
VS
VS
S
I
I
I

VS
VS
VS
PS
I
I
S

Key
I
PS
S
VS

g/100ml
<1
1-15
15-50
>75

11

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.

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.

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
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
SMA 1000 resin at room temperature, in 1 to 3 days
(the reaction will take place faster at elevated
temperatures).

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.):

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 180C for 2 to 3 hours.

12

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.

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 8.5-9.5.
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

13

Safety, Handling & Storage Information

hygiene practices, and wear protective equipment to

prevent exposure of these product to the eyes, skin
and respiratory tract. Consult the materials MSDS
before using any chemical in this bulletin.

TOXICOLOGY AND SAFE USE

INFORMATION
Materials in this document can cause eye and skin
irritation. Handle in accordance with good industrial

14

Supplemental Sytrene Maleic Anhydride Literature

Solubilizing SMAs
SMA in Epoxy Hybrid Powder Coatings
SMA Epoxy Powder Coatings
SMA Pigment Dispersions
SMA Ink Post Add Brochure
SMA Solvent Brochure
Surface Sizing with SMAs

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 discussing our SMA resins to aid in formulating.

15

CorporateHeadquarters
Cray Valley USA, LLC
468 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'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.

3100 01/10