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.
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
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
C
C
CH
CH2
x
O
O
CH
CH
C
C
O
O
n
O
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
C O
CH
n
CH2
x
O
O
C
C
CH
CH
y
CH
O
O
x = 1-4, n = 8-12
CH
C
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
5
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
6
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
7
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
8
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
o
Temperature C
o
Temperature C
Properties of SMA® Resin Aqueous Ammonia Salt Solutions
Aqueous Viscosity vs. pH
Aqueous Viscosity vs. % Solids
55
2000
50
1800
45
1600
o
Viscosity (cP) at 30 C
40
1200
SMA 3000
o
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
7
8
9
10
pH of 15% Solids Aqueous Ammoniacal Solutions
400
200
0
0
10
20
30
40
50
60
Wt. % Solids
9
11
Thermal Stability of SMA Resins (TGA in Air)
10
Solubility of SMA® Resins in Common Solvents at 30°C
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
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).
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 180ºC 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 (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
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 material’s 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 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
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: [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 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