Post on 17-Feb-2018
7/23/2019 Sma Multi Functional Resins (Europe)
1/16
SMA Multi-Functional Resins
Product Bulletin
7/23/2019 Sma Multi Functional Resins (Europe)
2/16
7/23/2019 Sma Multi Functional Resins (Europe)
3/16
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
7/23/2019 Sma Multi Functional Resins (Europe)
4/164
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.
7/23/2019 Sma Multi Functional Resins (Europe)
5/165
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.
7/23/2019 Sma Multi Functional Resins (Europe)
6/166
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.
7/23/2019 Sma Multi Functional Resins (Europe)
7/167
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
7/23/2019 Sma Multi Functional Resins (Europe)
8/168
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
7/23/2019 Sma Multi Functional Resins (Europe)
9/169
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
7/23/2019 Sma Multi Functional Resins (Europe)
10/1610
Thermal Stability of SMA Resins (TGA in Air)
7/23/2019 Sma Multi Functional Resins (Europe)
11/1611
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
7/23/2019 Sma Multi Functional Resins (Europe)
12/1612
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.
7/23/2019 Sma Multi Functional Resins (Europe)
13/1613
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.
7/23/2019 Sma Multi Functional Resins (Europe)
14/1614
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
7/23/2019 Sma Multi Functional Resins (Europe)
15/16
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 (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
7/23/2019 Sma Multi Functional Resins (Europe)
16/16
Corporate Headquarters
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 specificati ons. Cray Valley Company disclaims any liability in connection with the use of the information,