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M-Cure Products - Reactive Modifiers
for Epoxy/Amine Cure Systems
TABLE OF CONTENTS
INTRODUCTION .................................................................................................. 3
PRODUCT BULLETINS
M-Cure 100 ...................................................................................................... 4
M-Cure 200 ...................................................................................................... 5
M-Cure 201 ...................................................................................................... 6
M-Cure 202 ...................................................................................................... 7
M-Cure 203 ...................................................................................................... 8
M-Cure 204 ...................................................................................................... 9
M-Cure 300 .................................................................................................... 10
M-Cure 400 .................................................................................................... 11
FORMULATING ACRYLATE MODIFIED
EPOXY/AMINE COATINGS ............................................................................. 12
PERFORMANCE DATA ................................................................................ 13-19
SELECTION OF AMINE CURING AGENTS FOR
ACRYLATE MODIFIED EPOXY FORMULATING ................................... 20-26
CHEMICAL RESISTANCE FOR ACRYLATE MODIFIED
EPOXY/AMINE COATINGS ........................................................................ 27-33
ACRYLATE ESTERS AS REACTIVE MODIFIERS
FOR AMBIENT CURE WATERBORNE EPOXY COATINGS .................. 34-39
SAFETY, HANDLING AND STORAGE INFORMATION ......................... 40-41
2
INTRODUCTION
Amine curing of acrylate monomers is a direct addition chemistry that allows rapid
polymerization of virtually zero VOC systems at temperatures below 50Ā°F. This type
of technology is referred to as Michael Addition chemistry. Acrylate monomers, when
used in two-part epoxy/amine formulations, offer a number of significant advantages
such as:
ā? 100% Solids formulating
ā? Viscosity reduction of conventional epoxies
ā? Fast ambient and low temperature cure
ā? Reduced amine blush
ā? A wide range of formulating latitude
ā? Improved wetting characteristics
Sartomer offers proprietary monomer and oligomer blends designated as
"M-CureĀ® Products" which are designed specifically for use in Michael Addition
reactions. These products have been used in applications such as adhesives,
industrial coatings, industrial flooring, polymer concrete for repair and restoration,
marine primers and coatings, and traffic paint to enhance cure and performance
properties.
This bulletin discusses Michael Addition chemistry and the use of M-CureĀ®
Products in this type of reaction. Each M-CureĀ® Product is described in an
individual data sheet to allow ease of physical and chemical property analysis. The
product selection is dependent on the method of application, desired pot life,
physical properties and curing conditions for the formulator's specific application.
Proper selection of M-CureĀ® products and amine curing agents is the key to
achieving optimum performance. Product performance data is also presented to
allow comparison and differentiation of the M-CureĀ® Products.
3
Ā®
M-CURE 100
AROMATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 100
M-CureĀ® 100 is an aromatic acrylate monomer
TYPICAL PHYSICAL AND
designed to reduce the viscosity of amine cured
CHEMICAL PROPERTIES
epoxy coatings without significantly affecting
coating hardness and chemical resistance, or
significantly reducing reactivity. M-CureĀ® 100 Appearance Clear liquid
also has excellent wetting properties. Inhibitor, ppm 995 MEHQ
Color, APHA (G=Gardner scale) 100
Viscosity, cps. 140 @ 25C
PRODUCT HIGHLIGHTS Equivalent weight 257-267
Use level, wt. % = 10-40 Density, lbs/gal. 8.70
Viscosity reduction
Excellent wetting characteristics
Low odor
Extends pot life
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Flexibility
Adhesion
Low shrinkage
Hardness & abrasion resistance
Heat resistance
Impact strength
SUGGESTED APPLICATIONS
Adhesives
Concrete coatings
Floor grouts coatings
Polymer concrete
4
Ā®
M-CURE 200
AROMATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 200
M-CureĀ® 200 is an aromatic monomer with moder-
TYPICAL PHYSICAL AND
ate dilution efficiency. As a modifier, M-CureĀ® 200
CHEMICAL PROPERTIES
will maintain chemical resistance, hardness and
moisture resistance. M-CureĀ® 200 is recommended
for applications requiring moderate cure rates and Appearance Clear liquid
Inhibitor, ppm. 500 MEHQ, 65 HQ
abrasion resistance.
Color, APHA (G=Gardner scale) 50
Density, lbs./gal. 9.4
PRODUCT HIGHLIGHTS Viscosity, cps. 331 @ 25C
Use level, wt. % = 10-40 Equivalent weight 130-140
Aromatic
Good cold temperature cure
Low odor
Extends pot life
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Low shrinkage
Hardness
Heat resistance
Abrasion resistance
Impact strength
SUGGESTED APPLICATIONS
Floor coatings
Encapsulants
Grouts
Mortars
Potting compounds
5
Ā®
M-CURE 201
ALIPHATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 201
M-CureĀ® 201 is an aliphatic acrylate monomer that
TYPICAL PHYSICAL AND
gives excellent viscosity reduction and light fast-
CHEMICAL PROPERTIES
ness. M-CureĀ® 201 also exhibits good cold tem-
perature cure properties.
Appearance Clear liquid
Inhibitor, ppm. 85 MEHQ, 70 HQ
Color, APHA (G=Gardner scale) 20
Density, lbs./gal. 8.9
Viscosity, cps. 11 @ 25C
PRODUCT HIGHLIGHTS
Equivalent weight 95-105
Use level, wt. % = 10-40
Good cold temperature cure
Viscosity reduction
PERFORMANCE PROPERTIES
Weatherability
Chemical resistance
Hardness
Heat Resistance
Abrasion resistance
Water resistance
SUGGESTED APPLICATIONS
Self-leveling coatings
Grouts
Adhesives
6
Ā®
M-CURE 202
ALIPHATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 202
M-CureĀ® 202 is an aliphatic oligomer that has excellent
TYPICAL PHYSICAL AND
pigment wetting properties. M-CureĀ® 202 offers
CHEMICAL PROPERTIES
moderate viscosity reduction moderate flexibility.
M-CureĀ® 202 is recommended as a reactive pigment and
Appearance Clear liquid
filler for wetting and oligomer dispersion.
Inhibitor, ppm. 2589 MEHQ
Color, APHA (G=Gardner scale) 2G
Density, lbs./gal. 8.6
Viscosity, cps. 700 @ 25C
PRODUCT HIGHLIGHTS Equivalent weight 205-215
Use level, wt. % = 5-20
Excellent pigment wetting characteristics
Moderate viscosity reduction
Reactive wetting agent
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Flexibility
Adhesion
Low shrinkage
Hardness & abrasion resistance
Heat resistance
SUGGESTED APPLICATIONS
Grouts
Coatings
Adhesives
Sealants
7
M-CUREĀ® 203
AROMATIC URETHANE ACRYLATE MODIFIER
FOR EPOXY/AMINE SYTEMS
DESCRIPTION
M-CureĀ® 203
M-CureĀ® 203 is an aromatic urethane acrylate designed TYPICAL PHYSICAL AND
to improve the flexibility and toughness of epoxy/amine CHEMICAL PROPERTIES
cured coatings. Cured epoxy coatings containing
M-CureĀ® 203 will have improved elongation proper-
Appearance Clear liquid
ties, moderate tensile strength, and improved abra-
Inhibitor, ppm <400
sion properties. Color, APHA (G=Gardner scale) 60
Density, lbs./gal. 8.7
PRODUCT HIGHLIGHTS Viscosity, cps. 370 @ 60C
Equivalent weight 420-430
Use level, wt. % = 10-40
Aromatic
Improves elongation
Extends pot life
Produces soft, low modulus coatings
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Flexibility
Adhesion
Low shrinkage
Hardness
Heat resistance
Impact strength
SUGGESTED APPLICATIONS
Adhesives
Floor & Rebar coatings
Sealants
8
Ā®
M-CURE 204
METALLIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION M-CureĀ® 204
M-CureĀ® 204 is metallic acrylate designed to
TYPICAL PHYSICAL AND
improve the hardness and abrasion resistance of
CHEMICAL PROPERTIES
epoxy/amine cured coatings. M-CureĀ® 204 is a
solid, white powder that can be dispersed in the Appearance White powder
epoxy resin using standard equipment such as a Density, lbs./gal. 13.9
Equivalent weight 90-110
cowles blade mixer.
PRODUCT HIGHLIGHTS
Use level, wt. % = 1-10
Metallic acrylate
Improves metal adhesion
Gloss reducer
Low skin irritation
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Flexibility
Adhesion
Low shrinkage
Hardness
Heat resistance
Abrasion resistance
Impact strength
SUGGESTED APPLICATIONS
Floor coatings
Self leveling coatings
Traffic striping
9
M-CURE Ā® 300
ALIPHATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 300
M-CureĀ® 300 is an aliphatic acrylate monomer
TYPICAL PHYSICAL AND
designed for applications requiring fast cure rate,
CHEMICAL PROPERTIES
excellent chemical resistance and good heat dis-
tortion properties. M-CureĀ® 300 also offers very
good cold temperature curing without amine Appearance Clear liquid
Inhibitor, ppm. 235 MEHQ, 30 HQ
blush.
Color, APHA (G=Gardner scale) 35
Density, lbs./gal. 9.1
PRODUCT HIGHLIGHTS Viscosity, cps. 100 @ 25C
Use level, wt. % = 10-40 Equivalent weight 111-121
Fast cure response
Good heat distortion resistance
Good low temperature cure
Offer excellent lightfastness
PERFORMANCE PROPERTIES
Weatherability
Chemical & water resistance
Adhesion
Low shrinkage
Hardness
Heat resistance
Abrasion resistance
Impact resistance
SUGGESTED APPLICATIONS
Floor coatings
Self-leveling coatings
Traffic striping
10
Ā®
M-CURE 400
ALIPHATIC ACRYLATE MODIFIER FOR EPOXY/AMINE SYSTEMS
DESCRIPTION
M-CureĀ® 400
M-CureĀ® 400 is an aliphatic acrylate monomer TYPICAL PHYSICAL AND
that is designed for applications where CHEMICAL PROPERTIES
extremely fast cure rates are required, particularly
at cold temperatures. Due to the extremely fast Appearance Clear liquid
reactivity at room temperatures, pot life is Inhibitor, ppm. 290 MEHQ, 20 HQ
Color, APHA (G=Gardner scale) 60
dramatically reduced.
Density 9.5
PRODUCT HIGHLIGHTS Viscosity, cps. 180 @ 25C
Equivalent weight 80-90
Use level, wt. % = 10-40
Excellent cure response
Good cold temperature cure
Minimizes tack-free time
PERFORMANCE PROPERTIES
Weatherability
Chemical resistance
Adhesion
Hardness
Heat resistance
Abrasion resistance
Water resistance
SUGGESTED APPLICATIONS
Rapid set coatings
Floor coatings
Adhesives
Traffic striping
11
Formulating Acrylate Modified Epoxy/Amine Coatings
Acrylate monomers possess highly reactive C=C double ality and molecular weight. The calculations for
bonds which can react with primary and secondary determining the stoichiometric amount of curing agent
amine curing agents to form a crosslinked thermoset needed to react with all epoxy and acrylate reactive
polymer. They can also be combined with a Bis A, Bis sites in the epoxy/amine cure system is presented.
F or epoxy novalac resin and other additives and fillers
in the resin side (Part A) of a two-part epoxy/amine
cure system. As with all two-part systems, the acrylate/ Stoichiometric Calculations
epoxy blend of Part A should be packaged separately
and not come in contact with the amine hardener (Part Weight Equivalent Weight
B) until application. Formulation (Parts) (Eq. Wt.)
A DGEBA* 70 190
M-CureĀ® 201
B 20 99
Acrylate monomers are also good diluents that allow
M-CureĀ® 100
C 10 262
formulators to develop high solids or 100% solids
Total 100 grams
systems without significantly reducing reactivity hard-
ness or chemical resistance. Equivalent Weight of Formulation =
Total Weight of Resin Blend
Acrylate modified epoxy systems can be formulated
for both ambient and sub-ambient curing as well as
Wt. A Wt. B Wt. C
elevated temperature curing. The application of heat + +
will significantly reduce formulation viscosity and pot Eq. Wt. A Eq. Wt. B Eq. Wt. C
life.
70/190 + 20/99 + 10/262 = .609
Acrylate modified systems can be cured with aliphatic Eq. Wt Formulation = 100 = 164.3
amines, amidoamines and cycloaliphatic amines. The 0.609
preferred curing agent for acrylate monomers is ali-
Calculating Stoichiometric Amount of Amine
phatic amines or blends of aliphatic and cycloaliphatic
needed to react with Formulation
amines.
Eq. Wt of Amine = molecular weight of amine
Proper selection of acrylate monomers and curing number of amine hydrogens
agents is the key to achieving optimum performance in
=
120 = 24
hardness development, tensile properties, reactivity
5
and viscosity reduction. Blends of aliphatic and cy- Stoichiometric amount = Eq. Wt. of amine x 100
cloaliphatic amines such as Ancamine 1608 and 2143 needed (phr) Eq. Wt. of formulation
at a 20/80 ratio give very good performance properties
= 24 x 100 = 14.6 phr
without amine blush. The graphs on pages 13 through
164.3
19 are provided to aid in the acrylate monomer selec- needed to react
tion process. The choice of monomer and curing agent with formulation
is dependent on the method of application, desired pot
Final Formulation Parts
life, physical properties, and curing conditions.
DGEBA 70.0
M-CureĀ® 201 20.0
Optimum performance is achieved when a stoichio- M-CureĀ® 100 10.0
metric amount or slightly less is used. A stoichiometric Amine 14.6
amount of amine is calculated from the epoxide equiva-
lent weight (EEW) and the acrylate equivalent weight * DGEBA is diglycidyl ether bisphenol A.
(AEW). The acrylate equivalent weight is a measure of
C=C double bond content based on acrylate function-
12
Viscosity Reduction
(using Diglycidyl Ether of Bis A (DGEBA) with
EEW=190)
Effect of Diluent on Viscosity on DGEBA
10000
Viscosity (cps @ 25C)
M-Cure 100
M-Cure 200
M-Cure 201
M-Cure 202
1000 M-Cure 203
M-Cure 300
M-Cure 400
100
0 10 20 40
Wt % Diluent
Room Temperature Reactivity
Gel Time of 50 gra m mass; @ 77Ā°F
Formulation: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) at stoichiometric
amount
Effects of Diluent on Gel Time
Room Temperature
70
60
Gel Time (min)
50
40
30
20
10
0
D GEBA M -Cure M-Cure M-Cure M -Cure M-Cure M-Cure M -Cure
20 3 100 202 20 0 300 201 40 0
Diluent
13
Room Temperatur e Reactivity
Fo rmu la tion : 8 0% DG E BA , 2 0 % D ilue nt, An cam in e 2 1 43 /An cam in e1 60 8 (8 0 /2 0 blen d ) at sto ichi o metric amo u nt
Effects of Diluent on Cure Time
1/8" Thick Specimens Room Temperature
350
Tack Free Set Time (min)
300
250
200
150
100
50
0
DGEB A M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure
203 10 0 202 200 300 2 01 400
Dilu ent
Thin-Film Room Temperature Reactivity
Formulation: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) at stoichiometric amount
Effects of Diluent on Cure Time
15 mil Films Room Temperature
Tack Free Set Time (min)
350
300
250
200
150
100
50
0
DGEBA M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure
203 100 202 200 300 201 400
Diluent
14
Cold Temperature Thin Film Reactivity
Formulation: 80% DGEBA, 20% Diluent, Ancamine 2143 Ancamine 1608 (80/20 blend) at stoichometric amount
/
Cure Conditions: 35F Environment; 15 mil film thickness
Effects of Diluent on Thin Film Cure Time
Tack Free Set Time (min)
1600
1400
1200
1000
800
600
400
200
0
DGEBA M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure
203 100 202 200 300 201 400
Diluent
Hardness Development
Formulation: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) stoichiometric amount
Cure Conditions: Room Temperature, 1/8 inch film thickness
Effects of Diluent on Hardness
Development
90
DGEBA
80
Shore D Hardness
M-Cure 100
70
M-Cure 200
60 M-Cure 201
50 M-Cure 202
40 M-Cure 203
30 M-Cure 300
M-Cure 400
20
10
0
0 3 6 12 24
Hours after Cure (hours)
ASTMD D2240-86 Samples cured 7 days at room temperature
15
Hardness Development
Formulation: 80% DGEBA, 20% M-Cure 300, Amine Curing Agent (stoichiometric amount)
Cure Condi tions: Room Temperature, 1/4 inch film thickness
Effects of Amine Hardener on
Hardness Development
100 Ancamine 1618
Shore D Hardness
Ancamine 1608
80
1618/1608
60 9:1 ratio
1618/1608
40 7:3 Ratio
1618/1608
20 5:5 ratio
0
0 24 48 168
Hours
ASTM D2240-86 Samples cure
7 days at room temperature
Tensile Strength
Formula tion: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) at stoichiometric amount
15 mil film thickne ss
Effect of Diluen t on Tensile Strength
7000
6000
Tensile Strength (psi)
5000
4000
3000
2000
1000
0
DGEBA M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure
400 200 300 201 202 100 203
Diluent
ASTM D-882 Sample cure 7 days at room te mpe rature
16
Elongation @ Break
Formula tion: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 ble nd) at stoichiometric
amount 15 mil film thickness
Effect of Diluent on Break Elongation
8
Elongation to Break (%)
7
6
5
4
3
2
1
0
DGEBA M-Cure 400 M-Cure 201 M-Cure 200 M-Cure 300 M-Cure 202
Diluent
ASTM D-882 Samples cure 7 days at room temperature
Elongation @ Break
Formula tion: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) at stoichiom etric
amount 15 mil film thickness
Effect of Diluent on Break Elongation
120
Elongation to Break (%)
100
80
60
40
20
0
DGEBA 20% M-Cure 203 20% M-Cure 100 40% M-Cure 203
Diluent
ASTM D-882 Sa mples cure 7 days at room temperature
17
Tensile Modulus
Formulation: 80% DGEBA, 20% Diluent, Ancamine 2143/Ancamine 1608 (80/20 blend) at stoichiometric
amount 15 mil film thickness
Effect of Diluent on Tensile Modulus at 0.1% Elongation
250000
Tensile Strength (ksi)
200000
150000
100000
50000
0
DGEBA M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure M-Cure
400 200 300 201 202 100 203
Diluent
ASTM D-882 Samples cure 7 days at room temperature
Room Temperature Reactivity
Formulation: 80% Diluent, Anca mine 2143/Ancam ine 1608 (80/20 blend) at stoichiome tric am ount Gel Tim e =
50 gram massCure Tim e = tack fre e set time 15 mil film
Acrylate Mono mer vs. Glycidyl Ether
1 400 Cure Ti me (35 F)
1 200
Cure Response (min)
1 000
800
600 Cure Ti me (35 F)
Cure Ti me (77 F)
400
Cure Ti me (77 F)
200
Gel Ti me (77 F) Gel Ti me (77 F)
0
1 ,4 BGDE (EEW-1 27) M-Cu re 20 0 (AEW- 13 5)
18
Room Temperature Reactivity
Formulation:80% DGEBF, 20% Diluent, Ancamine 2353/Ancamide 1608 (80/20 blend) at stoichiometric amount
Acrylate Monomer vs. Glycidyl Ether
70
60
50
Gel Time (min)
40
30
20
10
0
20% Acrylate Monomer 10% Acrylate 20% C12-C14 GE
M-Cure 400 10% C12-C14 GE
Room Te mperature Reactivity
Fo rmu la tion :80 % D GE BF, 2 0% Dilu en t, A n camine 23 5 3/A nc amide 16 0 8 (80 /20 b lend ) a t stoich iometric am ou n t
Ac ryla te Mo nome r vs. Glyc idyl Ether
70
60
Gel Time (min)
50
40
30
20
10
0
20% Ac rylate M o nomer 10 % Acrylate 20% C1 2-C1 4 GE
M-Cure 400 1 0% C 12 -C1 4 G E
19
SELECTION OF AMINE CURING AGENTS FOR ACRYLATE MODIFIED EPOXY FORMULATING
Introduction Chemistry
Low viscosity, high molecular weight acrylate mono- Acrylate modified epoxy formulations, when cured,
mers and oligomers contain highly reactive C=C double form highly crosslinked thermoset polymer networks.
bonds that provide reactive sites for amine curing Acrylate modified epoxy coatings can be polymerized
agents. The proper selection of amine curing agent, with a variety of curing agents including polyamines
combined with an acrylate monomer or acrylate oligo- and cycloaliphatic amines. Aliphatic amines are gener-
mer modified Bis-A, Bis-F, or novalac epoxy resin, in ally the preferred curing agent. Amines react with
two-part ambient cured coatings can result in the acrylates by a Michael Addition polymerization reac-
following properties: tion as shown.
ā? Viscosity reduction without a loss in reactivity Reaction of acrylate and amine curing agent.
Low temperature curing (down to 0oC )
ā?
ā?
R-NH + CH = CH R-NH- CH - CH
ā? Improved substrate wetting 2 2 2 2
ā? Reduced amine blush
C= O C=O
ā? Fast cure response
ā? Reduced exotherm during cure O-R O-R
ā? Rapid development of hardness
Amine - Acrylate Adduct
ā? Low odor in both liquid and cured states
A variety of amine curing agents are commercially The Michael Addition reaction of an acrylate with a
available to meet the performance requirements of a primary amine is very rapid. Aliphatic amines such as
diethylenetriamine(DETA), triethylenetetraamine
broad range of epoxy/amine cure coating markets. In
(TETA) and m-xylene diamine (MXDA) are excellent
the industrial floor coating market, cycloaliphatic amines
curing agents for this reaction.
are typically used for their excellent hardness develop-
ment and chemical resistance. In the fast-setting Various substituent groups (R) impart certain types of
adhesive and coatings market, such as traffic marking, physical properties and characteristics. For instance,
aromatic substituent groups promote chemical
aliphatic amines are used for their high reactivity. In
resistance, thermal resistance and hardness. Aliphatic
the general purpose, lower cost coatings and adhesives
alkane groups promote light fastness, chemical and
markets, such as grouts and/or high build floor top-
moisture resistance. Either structure provides chemical
pings, amidoamines can be used due to lower reactivity resistance particularly to bases and alkane solvents.
and lower exotherm upon cure. The substituent (R) group can also contain other
reactive groups such as hydroxyls or additional C =C
double bonds.
A number of commercial amine curing agents have
been screened for compatibility and reactivity in two-
Formulating
component acrylate monomer/oligomer modified ep- Acrylate monomers, hereafter referred to as M-CureĀ®
oxy systems to identify those which yield optimum resins, are blended with the epoxy resin and other
performance. additives and fillers in the resin portion of the coating.
The M-CureĀ® resins are compatible with all conven-
tional epoxy resins (i.e. Bis A, Bis F, Novolac Epoxy).
Obviously, the amine curing agents evaluated in this
As with all two-part coating formulations, the acrylate/
paper represent only a small portion of the numerous epoxy resin blend should not come in contact with the
curing agents that are commercially available today. hardener until application.
The amines that are selected for evaluation represent
High solids systems can be formulated with minimum
good starting point recommendations, although the
solvent for viscosity reduction. Acrylate monomers
formulator is certainly not limited to them. The intent
are also good diluents that allow formulators to de-
of this work is to determine trends in formulated
velop 100% solids systems without significantly re-
product performance with the use of different types of
ducing reactivity, hardness or chemical resistance.
amine curatives.
20
In general, modification of an epoxy/amine formula-
Acrylate modified epoxy systems can be formulated for
tion with the M-CureĀ® resins results in a reduction in
both ambient and subambient curing, as well as elevated
the gel time or working time of the formulation but
temperature (baked systems) curing. The application
gives significantly faster thin film cure times. The
of heat will significantly reduce formulation viscosity
general trend exhibited in Table 2 is that the M-CureĀ®
and accelerate curing.
resins react much faster with aliphatic curing agents
than with cycloaliphatics and amidoamines.
Proper selection of acrylate monomer and curing agent
is the key to achieving optimum performance. The
Table 3 shows a summary of results for hardness
selection of monomer and curing agent is dependent on
development and tensile properties for these formula-
the method of application, desired pot life, physical
tions. Hardness is developed much faster with ali-
properties and curing conditions (i.e., temperature).
phatic amines than with cycloaliphatics and
Ultimate reactivity and hardness development are
amidoamines. Amidoamines are extremely slow in
achieved when aliphatic amines or blends of cy-
developing hardness using the M-CureĀ® resins. The
cloaliphatic and aliphatic amines are used as the curing
tensile properties shown in Table 3 suggest that tensile
agents. For amine curing agents, a stoichiometric
strength and elongation may be a function of the base
amount or slightly less is used to insure optimum
amine chemistry but the tensile modulus is a function
performance.
of the amine-reactivity with the M-CureĀ® 201.
Ancamine 1856 and Epicure 3370 yield very high
A stoichiometric amount of amine is calculated from
tensile strengths. Ancamine 1618 and Ancamine 2143
the epoxide equivalent weight (EEW) and the acrylate
yield the highest elongations. The aliphatics show
monomer equivalent weight (AEW). For guidance on
much higher tensile modulus values than the
calculation of the stoichiometric amount of amine
cycloaliphatics and amidoamines.
please refer to Figure 1 in the section of this brochure
titled āFormulating Acrylate Modified Epoxy/Amine
For the second study one amine curing agent from each
Coatingsā? on page 12.
of three classes was selected for evaluation with all of
the M-CureĀ® resins. The formulation described above
Refer to Table 1 for a list of the commercially available
was used. The selected amines were as follows:
curing agents included in the testing.
Cycloaliphatic - Epicure 3370
Discussion of Results
Aliphatic - Ancamine 1638
The initial screening involved modification of a conven-
Amidoamine - Ancamine 2386
tional Bis A epoxy with M-CureĀ® 201 and curing with
the appropriate amount of curing agent. The basic
Table 4 shows a summary of results for the mix
formulation is as follows:
viscosity and cure performance of these formulations.
M-CureĀ® 201, M-CureĀ® 300 and M-CureĀ® 400 for-
Part A Parts by Wt.
mulations exhibit the lowest viscosity due to the low
DGEBA 80
viscosity of the resin and the higher loading of amine
M-CureĀ® 201 20
required for full conversion.
Part B
The gel times and cure times reported in Table 4
Amine Curing Agent SA*
indicate that a broad range of cure performance can be
achieved by varying the combination of M-CureĀ® resin
* stoichiometric amount as calculated
and curing agent. If the formulator is using an aliphatic
amine, M-CureĀ® 100 and M-CureĀ® 203 can be used
Table 2 shows a summary of results for the mix viscos-
to extend gel time but still give fast cure times. If the
ity and cure performance of these formulations.
application requires a cycloaliphatic or amidoamine,
In general, cycloaliphatics and amidoamines exhibit
the formulator would be better off using a more
lower viscosities than aliphatics. However, Ancamine
reactive M-Cure resin like M-CureĀ® 201 or M-CureĀ®
1638 gives good viscosity reduction.
400 in order to get the optimum performance.
21
The tensile properties of a specific formulation can be
Table 5 shows a summary of results for the hardness
varied depending on the combination of amine curing
development and tensile properties for these formula-
agent and M-CureĀ® resin. If the formulator is using an
tions. The results indicate that excellent hardness devel-
aliphatic amine like Ancamine 1638, high tensile strength
opment can be achieved (>80 Shore D in 2 hrs.) using
and modulus can be achieved using the slower reacting
Ancamine 1638 in combination with any of the
M-CureĀ® resins like M-CureĀ® 100, M-CureĀ® 202 and
M-CureĀ® resins. Using the cycloaliphatic amine Epi-
M-CureĀ® 203. However, if the application requires a
cure 3370, it takes 8-9 hours for systems modified with
cycloaliphatic or amidoamine, M-CureĀ® 200, M-CureĀ®
M-CureĀ® 200, M-CureĀ® 201, M-CureĀ® 202 and M-
300 and M-CureĀ® 400 would be required to maintain
CureĀ® 400 to reach 80 Shore D. When the amidoamine
good physical properties.
is used, there is little effect on hardness development.
22
Table 1. Commercially Available Curing Agents
Supplier Base Amine AHEW
Cycloaliphatics
Ancamine 1618 Air Products IPDA 113
Ancamine 2143 Air Products MDCHA 115
Ancamine 2280 Air Products MDCHA 110
Epicure 3370 Shell IPDA 72
Epicure 3382 Shell IPDA 118
Aliphatics
Ancamine 1638 Air Products DETA 31
Ancamine 1856 Air Products B13DMA 73
Epicure 3282 Shell DETA 38
Amidoamines
Ancamine 500 Air Products TOFA 90
Ancamine 2386 Air Products Mixture
Epicure 3055 Shell TOFA 90
Epicure 3072 Shell Miixture 65
Table 2. Summary of M-Cure 201 Modified Epoxy Viscosity & Cure Performance Data......
Aliphatic Mix Viscosity Gel Time Tack-Free Cure Time
@ 25o C (cps)
Amines phr 50 gm mass (mins) 15 mil film (hrs)
Epicure 3282 24.0 2,960 6 1.33
Ancamine 1638 19.6 870 3 0.92
Ancamine 1856 46.2 1,700 8 1.125
Tack-Free Cure Time
Cycloaliphatic Mix Viscosity Gel Time
@ 25o C (cps)
Amines phr 50 gm mass (mins) 15 mil film (hrs)
Ancamine 1618 71.5 820 53 9.0
Ancamine 2143 72.7 985 60 10.0
Ancamine 2280 69.6 960 74 12.0
Epicure 3370 45.5 320 25 4.0
Epicure 3382 74.6 680 39 6.5
Mix Viscosity Gel Time Tack-Free Cure Time
@ 25o C (cps)
Amidoamines phr 50 gm mass (mins) 15 mil film (hrs)
Epicure 3055 56.9 770 480 >24.0
Ancamide 500 56.9 730 390 18.0
Ancamide 2386 58.9 884 240 15.0
Epicure 3072 41.1 1,374 40 8.0
23
Table 3. Summary of M-Cure 201 Modified Epoxy Hardness and Tensile Property Data
Shore āDā? Hardness Development Tensile Properties
1/8ā? thickness; 77o F 15 mil films; 7 days @ 77 o F
Aliphatic Amines 1 2 3 6 24 72 Tensile Elongation Tensile
hr hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
Epicure 3282 (24.0 phr) 28 58 80 87 87 88 3,930 2.1 261,804
Ancamine 1638 (19.6 phr) 83 83 84 86 87 88 5,720 3.2 248,626
Ancamine 1856 (46.2 phr) 77 79 80 87 87 88 6,885 4.3 227,129
Shore āDā? Hardness Development Tensile Properties
1/8ā? thickness; 77 o F 15 mil films; 7 days @ 77o F
Cycloaliphatic Amines 3 6 12 18 24 72 Tensile Elongation Tensile
hrs hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
Ancamine 1618 (71.5 phr) 0 0 12 26 35 70 4,953 12.7 143,000
Ancamine 2143 (72.7 phr) 0 0 10 28 42 76 5,713 8.9 146,000
Ancamine 2280 (69.6 phr) 0 0 0 0 21 72 2,439 47.0 50,000
Epicure 3370 (45.5 phr) 20 70 78 81 83 86 8,572 6.1 195,000
Epicure 3382 (74.6 phr) 0 0 32 44 72 80 2,765 39.0 81,000
Shore āDā? Hardness Development Tensile Properties
1/8ā? thickness; 77o F 15 mil films; 7 days @ 77o F
Amidoamines 3 6 12 24 72 168 Tensile Elongation Tensile
hrs hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
Epicure 3055 (56.9 phr) 0 10 20 25 40 55 3,703 4.1 115,420
Ancamide 500 (58.9 phr) 0 10 20 25 45 52 2,792 4.2 110,277
Ancamide 2386 (41.1 phr) 0 10 20 30 53 61 2,779 5.6 99,905
Epicure 3072 (46.2 phr) 10 30 45 64 81 85 4,155 4.4 177,861
24
Table 4. Summary of M-Cure Modified Epoxy Viscosity and Cure Performance Data
Ancamine Mix Viscosity @ Gel Time Tack-Free Cure Time
25o C (cps) 15 mils @ 25o C (hrs)
1638 phr 50 gm mass (mins)
DGEBA 16.8 1,800 15 3.08
M-Cure 100 15.8 2,500 20 2.00
M-Cure 200 18.0 2,000 3 1.75
M-Cure 201 19.6 500 6 2.25
M-Cure 202 16.4 1,700 12 2.45
M-Cure 203 14.9 2,500 15 3.25
M-Cure 300 18.7 1,000 7 2.68
M-Cure 400 20.7 NT 2 1.33
C12-C14 GE 15.5 400 24 5.00+
Epicure Mix Viscosity @ Gel Time Tack-Free Cure Time
25o C (cps) 15 mils @ 25o C (hrs)
3370 phr 50 gm mass (mins)
DGEBA 39.4 2,465 31 5.0
M-Cure 100 37.1 1,280 36 6.0
M-Cure 200 42.6 1,320 16 4.0
M-Cure 201 46.2 520 17 4.0
M-Cure 202 38.5 1,680 25 5.0
M-Cure 203 35.0 2,320 40 6.5
M-Cure 300 44.1 1,040 19 4.5
M-Cure 400 48.7 960 9 3.0
C12-C14 GE 36.6 440 43 9.0
Ancamide Mix Viscosity @ Gel Time Tack-Free Cure Time
25o C (cps) 15 mils @ 25o C (hrs)
2386 phr 50 gm mass (mins)
DGEBA 50.3 2,600 225 8.5
M-Cure 100 47.3 1,600 450 15.0
M-Cure 200 54.0 1,850 320 9.5
M-Cure 201 58.8 840 415 11.5
M-Cure 202 49.1 2,000 370 12.0
M-Cure 203 44.6 2,600 430 14.0
M-Cure 300 56.17 1,400 305 9.0
M-Cure 400 62.2 1,600 118 7.5
C12-C14 GE 46.7 600 > 500 > 16.0
25
Table 5. Summary of M-Cure Modified Epoxy Hardness and Tensile Properties Data
Shore āDā? Hardness Development Tensile Properties
1/8ā? thickness; 77o F 15 mil films; 7 days @ 77o F
Ancamine 1 2 3 6 24 72 Tensile Elongation Tensile
1638 hr hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
DGEBA 78 82 82 83 83 84 NT NT NT
M-Cure 100 82 83 83 83 83 83 4,888 2.3 201,372
M-Cure 200 84 83 83 83 83 83 6,139 2.9 211,626
M-Cure 201 82 82 82 83 83 83 5,591 2.6 148,000
M-Cure 202 82 83 85 85 86 86 7,463 4.1 199,340
M-Cure 203 82 83 85 85 85 85 6,124 3.6 191,340
M-Cure 300 85 86 86 86 87 88 5,862 2.8 195,388
M-Cure 400 85 86 86 87 88 88 3,987 1.3 290,493
C12-C14 GE 79 82 82 83 83 83 3,252 2.6 160,100
Shore āDā? Hardness Development Tensile Properties
1/8ā? thickness; 77o F 15 mil films;7 days @ 77o F
Epicure 3 6 9 12 24 72 Tensile Elongation Tensile
3370 hrs hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
DGEBA 60 84 85 87 87 NT 6,896 1.2 289,000
M-Cure 100 10 59 73 82 84 NT 5,794 4.3 176,120
M-Cure 200 46 80 85 85 85 NT 6,636 4.0 206,623
M-Cure 201 45 70 80 84 87 NT 6,159 4.8 174,150
M-Cure 202 32 74 84 84 84 NT 6,890 5.5 174,169
M-Cure 203 10 49 74 78 82 NT 5,459 5.6 156,119
M-Cure 300 33 76 74 85 86 NT 6,429 4.2 186,141
M-Cure 400 56 78 84 86 86 NT 6,231 3.6 217,225
C12-C14 GE 60 84 85 87 87 NT 3,557 4.3 109,497
Shore "D" Hardness Development Tensile Propertes
1/8" thickness; 77Ā° F 15 mil films; 7 days @ 77Ā° F
Ancamide 3 6 12 24 72 168 Tensile Elongation Tensile
2386 hrs hrs hrs hrs hrs hrs Strength (psi) (%) Modulus (psi)
DGEBA 0 0 25 65 78 83 5,464 2.7 210,187
M-Cure 100 0 0 0 25 50 80 2,669 7.4 100,744
M-Cure 200 0 0 10 40 52 81 4,088 4.2 129,502
M-Cure 201 0 0 0 15 37 81 2,373 6.7 87,856
M-Cure 202 0 0 10 44 59 80 2,877 4.7 105,758
M-Cure 203 0 0 0 20 52 78 2,295 5.5 79,412
M-Cure 300 0 0 10 40 55 78 3,167 3.5 131,398
M-Cure 400 0 0 15 48 59 79 2,884 2.4 130,137
C12-C14 GE 0 0 0 18 43 76 2,032 5.3 56,990
26
CHEMICAL RESISTANCE FOR ACRYLATE MODIFIED EPOXY/AMINE COATINGS
Reaction of Acrylate and Amine Curing Agent
Introduction
ā?
Low viscosity, high molecular weight acrylate mono- R-NH2 + CH2 = CH R-NH- CH2 - CH2
mers and oligomers contain highly reactive C=C double
C= O C=O
bonds that provide reactive sites for amine curing
agents. The proper selection of amine curing agent O-R O-R
combined with an acrylate monomer/oligomer modi- Amine - Acrylate Adduct
fied Bis-A, Bis-F, or novalac epoxy resin in two-part,
ambient cured coatings can result in 100% solids The Michael Addition reaction of an acrylate with
systems which exhibit excellent chemical resistance. primary amines is very rapid. Aliphatic amines such as
diethylenetriamine (DETA), triethylenetetraamine
A variety of amine curing agents are commercially (TETA) and m-xylene diamine (MXDA) are excellent
available to meet the chemical resistance requirements curing agents for this reaction.
for the protective coatings market. Cycloaliphatic
amines are commonly used in the industrial floor Formulating
coatings market due to their excellent hardness devel- Acrylate monomers, specifically M-CureĀ® resins, are
opment and chemical resistance but tend to be slow blended with the epoxy resin and other additives and
curing. Aliphatic amines exhibit very high reactivity fillers in the resin portion of the coating. The M-Cure Ā®
for faster cure and good mechanical properties and resins are compatible with all conventional epoxy resins
also provide good moisture and solvent resistance. (i.e., Bis A, Bis F, Novolac Epoxy). As with all two-
They can be used for fast-drying, metal primer appli- part coating formulations, the acrylate/epoxy resin
cations or maintenance coatings but their use is limited blend should not come in contact with the hardener
due to amine blush characteristics. until application.
A number of commercial amine curing agents have High solids systems can be formulated with minimum
been screened for compatibility and reactivity in two- solvent for viscosity reduction. Acrylate monomers are
component acrylate monomer/oligomer modified ep- also good diluents that allow formulators to develop
oxy systems to identify those which yield optimum 100% solids systems without significantly reducing the
performance in terms of chemical resistance. chemical resistance.
Obviously, the amine curing agents evaluated in this Acrylate modified epoxy systems can be formulated for
bulletin represent only a small portion of the numerous both ambient and sub-ambient curing as well as el-
curing agents that are commercially available today. evated temperatures (baked systems). The application
The amines that are selected for evaluation represent of heat will significantly reduce formulation viscosity
good starting point recommendations, although the and accelerate curing.
formulator is certainly not limited to them. The intent
of this work is to determine trends in chemical resis- Proper selection of acrylate monomer and curing agent
tance with the use of different types of amine curatives. is the key to achieving optimum chemical resistance.
The selection of monomer and curing agent is depen-
Chemistry dent on the method of application, desired pot life,
Acrylate modified epoxy coatings when cured form physical properties and curing conditions (i.e., tem-
highly crosslinked thermoset polymer networks. Acry- perature). The best chemical resistance is achieved
late modified epoxy coatings can be polymerized with when aliphatic amines or blends of cycloaliphatic and
a variety of curing agents including polyamines and aliphatic amines are used as the curing agent. For amine
cycloaliphatic amines. Aliphatic amines are generally the curing agents, a stoichiometric amount or slightly less
preferred curing agent. Amines react with acrylates by a is used to insure optimum performance.
Michael Addition polymerization reaction as shown.
27
Table 3 shows a summary of results for chemical
A stoichiometric amount of amine is calculated from
resistance of these formulations. All of the M-CureĀ®
the epoxide equivalent weight (EEW) and the acrylate
resins when cured with the aliphatic amine (Ancamine
monomer equivalent weight (AEW). For guidance on
1638) except M-CureĀ® 202 and M-CureĀ® 203 exhib-
calculation of the stoichiometric amount of amine
ited good solvent resistance. M-CureĀ® 200 and M-
please refer to the section of the brochure titled
CureĀ® 400 offer the best resistance to glacial acetic
"Formulating Acrylate Modified Epoxy/Amine
acid when cured with this amine.
Coatings" on page 12. The list of commercially avail-
able curing agents were included in the initial testing
All of the resins except for M-CureĀ® 200 and M-
and are listed in Table 1.
CureĀ® 203 exhibit less than 1% weight gain in water
using the cycloaliphatic amine (Epicure 3370). Sol-
Discussion of Results
vent resistance for M-CureĀ® 200, M-CureĀ® 201, M-
The initial screening involved modification of a con-
CureĀ® 300 and M-CureĀ® 400 modified formulations
ventional Bis A epoxy with M-CureĀ® 201 and curing
is improved over the unmodified formulations using
with the appropriate amount of curing agent. The basic
Epicure 3370. However, glacial acetic acid resistance
formulation is as follows: (top of following page)
is poorer for the M-CureĀ® 201, M-CureĀ® 300 and
M-CureĀ® 400 modified formulations. Since the for-
Part A Parts by Wt.
mulations with Epicure 3370 showed the best perfor-
DGEBA 80
mance for a cycloaliphatic amine, they were tested in
M-CureĀ® 201 20
a number of different chemicals. These results are
shown in Table 4 . For the most part, the same trends
Part B
Amine Curing Agent SA* hold true. The higher acrylate functionality, lower
equivalent weight resins (i.e., M-CureĀ® 200, 201,
* stoichiometric amount as calculated
300, 400) exhibit the best solvent resistance (i.e.,
heptane, xylene, ethanol) but poorer acid resistance
(i.e., acetic, hydrochloric, sulfuric).
Table 2 shows a summary of results for the chemical
resistance exhibited by these formulations. The chemi-
The third study of this bulletin involved the blending of
cals chosen are water, toluene and a 10% solution of
an aliphatic amine curing agent with a cycloaliphatic
glacial acetic acid. Chemical resistance is measured by
curing agent to achieve the benefit of high crosslink
determining the weight gain of a specified sample after
density (good chemical resistance) without a high
immersion in the test chemical over time. Table 2
degree of blushing. An 80/20 percent by weight blend
indicates that the aliphatic amines provide the best
of Ancamine 2143 cycloaliphatic amine and Ancamine
overall chemical resistance. Ancamine 1638 provides
1608 aliphatic amine was selected as the curing agent.
the best water resistance and solvent resistance of all
Formulations consisting of 80 parts by weight DGEBA
the curing agents tested. Ancamine 1856 exhibited the
epoxy resin and 20 parts by weight M-CureĀ® resin
best resistance to glacial acetic acid. Epicure 3370
cured with a stoichiometric amount of the aforemen-
contains MXDA ( an aliphatic amine) and thus yields
tioned blended curing agent were evaluated for weight
a higher crosslink density and the best chemical resis-
gain in water, toluene and 10% glacial acetic acid.
tance.
These results are shown in Table 4. These results show
significant improvement in chemical resistance over
Based on this data, Ancamine 1638 and Epicure 3370
the straight cycloaliphatic curing agent with a signifi-
were selected for further evaluation with all of the M-
cant reduction in the amine blush observed when the
CureĀ® resins. The same formulation was used except
straight aliphatic amine was used.
that 20 parts of M-CureĀ® 201 was replaced by the
other M-CureĀ® resins and the amount of amine was
adjusted accordingly.
28
The final study involved a comparison of a typical pre- Table 6 shows the chemical resistance data for these
diluted epoxy formulation where the DGEBA has been formulations. Replacement of the monoepoxide diluent
modified with 20 pbw of a monoepoxide (C12-C14 by M-CureĀ® 400 results in improved water and 50%
GE) versus a formulation where half of the monoepoxide NaOH caustic resistance and a very significant im-
is replaced by M-CureĀ® 400. The formulations are as provement in the solvent resistance. Therefore, it has
follows: been demonstrated that by using the M-CureĀ® resin in
combination with a conventional epoxy diluent you can
Formulation A B
achieve the benefit of viscosity reduction, improve
cure speed and still maintain good chemical resistance
Part A
characteristics.
DGEBA Epoxy Resin 80 80
C12-C14 Epoxy Modifier 20 10
M-CureĀ® 400 ā? 10
Part B
Epicure 3370 Curing Agent 35 43
Mix Viscosity @ 25Ā°C (cps) 440 600
Gel Time, 50 gm mass (mins) 43 15
Tack-free Cure Time, 15 mils (hrs) 9.0 2.0
29
Table 1. Commercially Available Curing Agents
Supplier Base Amine AHEW
Cycloaliphatics
Ancamine 1618 Air Products IPDA 113
Ancamine 2143 Air Products MDCHA 115
Ancamine 2280 Air Products MDCHA 110
Epicure 3370 Shell IPDA 72
Epicure 3382 Shell IPDA 118
Aliphatics
Ancamine 1638 Air Products DETA 31
Ancamine 1856 Air Products B13DMA 73
Epicure 3282 Shell DETA 38
Table 2. Summary of M-Cure 201 Modified Epoxy Chemical Resistance Data
% Wt. Gain after Immersion
Water Toluene 10% Acetic Acid
Aliphatic 24 hr 7 day 28 day 24 hr 7 day 28 day 24 hr 7 day 28 day
Amine
Epicure 3282 0.11 0.44 0.70 2.00 3.94 5.31 2.14 5.21 9.00
(24.0 phr)
Ancamine 1638 0.08 0.25 0.52 0.03 0.20 0.27 0.89 4.59 8.14
(19.6 phr)
Ancamine 1856 0.12 0.40 0.82 0.20 0.72 3.21 0.41 1.49 2.41
(46.2 phr)
% Wt. Gain after Immersion
Water Toluene 10% Acetic Acid
Cycloaliphatic 24 hr 7 day 28 day 24 hr 7 day 28 day 24 hr 7 day 28 day
Amine
Ancamine 1618 NA 0.682 1.380 NA 2.390 D NA 2.580 5.750
(71.5 phr)
Ancamine 2143 NA 0.494 1.080 NA 1.400 D NA 6.460 15.800
(72.7 phr)
Ancamine 2280 NA 0.615 1.220 NA 2.950 D NA 3.030 7.200
(69.6 phr)
Epicure 3370 NA 0.304 0.650 NA 5.630 D NA 2.000 5.000
(45.5 phr)
Epicure 3382 NA 0.480 0.960 NA 8.000 D NA 1.130 3.200
(74.6 phr)
30
Table 3. Summary of M-Cure Modified Epoxy Chemical Resistance Data
% Wt. Gain after Immersion
Water Toluene 10% Acetic Acid
Ancamine 1638 24 hr 7 day 28 day 24 hr 7 day 28 day 24 hr 7 day 28 day
DGEBA 0.065 0.195 0.420 0.049 0.064 0.082 0.226 0.484 0.933
M-Cure 100 0.062 0.202 0.440 0.068 0.097 0.408 0.676 1.506 3.077
M-Cure 200 0.106 0.246 0.350 0.033 0.050 0.099 0.418 0.890 1.392
M-Cure 201 0.060 0.189 0.430 0.045 0.070 0.143 0.861 2.036 4.513
M-Cure 202 0.093 0.269 0.570 3.467 4.628 6.347 2.822 3.970 5.914
M-Cure 203 0.193 0.388 0.650 7.345 8.827 11.149 2.454 5.205 5.712
M-Cure 300 0.081 0.210 0.460 0.046 0.066 0.165 0.708 1.696 3.296
M-Cure 400 0.104 0.226 0.380 0.039 0.113 0.142 0.562 1.204 1.984
C12-C14 GE 0.013 0.133 0.370 1.741 7.924 22.442 1.575 3.211 4.817
% Wt. Gain after Immersion
Water Xylene 10% Acetic Acid
Epicure 3370 24 hr 7 day 28 day 24 hr 7 day 28 day 24 hr 7 day 28 day
DGEBA 0.080 0.120 0.450 2.00 5.560 9.230 1.490 3.350 5.300
M-Cure 100 0.220 0.530 0.980 1.160 5.330 10.810 1.210 2.700 4.920
M-Cure 200 0.220 0.580 1.050 1.050 3.640 6.720 2.210 5.330 9.820
M-Cure 201 0.180 0.470 0.840 0.610 2.930 5.900 2.090 5.100 12.540
M-Cure 202 0.130 0.330 0.660 1.380 5.690 11.020 0.930 2.030 3.440
M-Cure 203 0.270 1.200 3.320 0.710 4.670 10.150 0.970 2.250 4.050
M-Cure 300 0.190 0.220 0.880 0.570 3.220 6.420 2.700 6.420 12.600
M-Cure 400 0.160 0.410 0.700 0.090 1.080 2.500 3.080 8.810 17.620
C12-C14 GE 0.230 0.530 0.970 9.920 22.440 31.450 1.090 2.520 4.390
31
Table 4. Summary of M-Cure Modified Epoxy Chemical Resistance Data for Epicure 3370 Formulations
Chemical Resistance (% Weight Gain after Immersion)
M-Cure 100 M-Cure 200 M-Cure 201 M-Cure 202 M-Cure 203 M-Cure 300 M-Cure 400 DGEBA
Water
24 hrs 0.22 0.22 0.18 0.13 0.27 0.19 0.16 0.15
7 days 0.53 0.58 0.47 0.33 0.32 0.32 0.41 0.32
28 days 0.98 1.05 0.84 0.66 1.20 0.88 0.70 0.45
Solvents
Heptane
24 hrs 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00
7 days 0.03 0.02 0.03 0.02 0.01 0.03 0.02 0.02
28 days 0.06 0.04 0.08 0.04 0.03 0.09 0.06 0.06
Xylene
24 hrs 1.06 1.05 0.61 1.38 0.71 0.57 0.09 2.00
7 days 5.33 3.64 2.93 5.69 4.67 3.22 1.08 5.56
28 days 10.81 6.72 5.90 11.02 10.15 6.42 2.50 9.23
Ethanol
24 hrs 2.16 2.21 2.54 2.22 9.19 1.45 1.74 2.73
7 days 5.18 5.18 6.22 5.21 14.33 3.08 4.29 6.62
28 days 9.34 9.46 11.74 9.16 21.79 7.41 8.25 10.60
Acids
10% HCI
24 hrs 0.38 0.44 0.70 0.27 0.31 0.55 0.81 0.25
7 days 0.88 1.17 2.25 0.68 0.77 1.73 2.67 0.60
28 days 1.37 1.89 4.19 1.05 1.18 3.03 5.29 0.94
10% Acetic
24 hrs 1.21 2.21 2.09 0.93 0.97 2.70 3.08 1.49
7 days 2.70 5.33 5.10 2.03 2.25 6.42 8.81 3.35
28 days 4.92 9.82 12.54 3.44 4.05 12.60 17.62 5.30
10% Sulfuric
24 hrs. 0.17 0.59 0.50 0.41 0.51 1.11 1.42 0.41
7 days 1.18 3.32 7.50 1.11 1.41 4.18 7.05 0.91
28 days 2.13 6.19 15.20 1.77 2.23 8.30 14.90 1.24
Bases
5% NaCI
24 hrs 0.15 0.23 0.16 0.12 0.19 0.14 0.15 0.12
7 days 0.48 0.65 0.49 0.39 0.59 0.42 0.49 0.37
28 days 0.76 1.05 0.39 0.61 0.91 0.65 0.79 0.68
50% NaOH
24 hrs 0.12 0.09 0.14 0.05 0.09 0.18 0.10 0.05
7 days 0.24 0.20 0.23 0.13 0.15 0.47 0.26 0.16
28 days 0.77 1.02 0.96 0.48 0.61 1.08 1.50 0.73
32
Table 5. Chemical Resistance Data for M-Cure Modified Epoxy Formulations
(80/20 Blend of Ancamine 2143 / Ancamine 1608)
% Wt. Gain After Immersion
Water Toluene 10% Acetic Acid
Modifier 24 hr 7 day 28 day 24 hr 7 day 28 day 24 hr 7 day 28 day
DGEBA 0.080 0.270 0.560 0.110 1.470 2.270 1.340 3.970 6.660
M-Cure 100 0.120 0.310 0.950 0.240 2.260 7.450 0.390 0.910 1.950
M-Cure 200 0.100 0.270 0.830 0.250 0.930 2.390 0.550 1.170 2.650
M-Cure 201 0.100 0.270 0.740 0.060 0.380 1.310 0.550 1.150 2.600
M-Cure 202 0.140 0.310 1.070 0.560 2.110 5.350 0.560 1.200 2.540
M-Cure 203 0.170 0.390 1.070 1.560 4.750 10.260 0.660 1.420 2.990
M-Cure 300 0.160 0.380 1.240 0.600 0.990 1.650 2.060 5.370 10.720
M-Cure 400 0.090 0.260 0.8200 0.020 0.140 0.690 0.630 1.520 3.590
Table 6. Chemical Resistance for M-Cure 400 Modified Pre-Diluted Epoxy /
Epicure 3370 Formulations
Formulation A Formulation B
(20% C12-C14 GE) (10% C12-C14GE) GE)
Water
24 hrs 0.23 0.17
7 days 0.53 0.22
28 days 0.97 0.79
Heptane
24 hrs 0.05 0.01
7 days 0.49 0.04
28 days 1.11 0.07
Xylene
24 hrs 9.92 0.30
7 days 31.45 3.33
28 days 42.44 9.10
50% NaOH
24 hrs 0.21 0.09
7 days 0.35 0.20
28 days 1.17 0.66
33
ACRYLATE ESTERS AS REACTIVE MODIFIERS FOR AMBIENT CURE
WATERBORNE EPOXY COATINGS
curatives used in the waterborne epoxy market also
INTRODUCTION
contain solvents for similar reasons, as well as for
Ever since the technology was developed in the mid-
1970ās by W. McWhorter1, acrylate ester monomers viscosity reduction. Therefore, a very low VOC or
100% solvent-free waterborne system is difficult to
and oligomers have found increasing use as reactive
diluents and modifiers for two-component amine-cured achieve with current technology.
epoxy coatings. In these systems, the acrylate ester
effectively reduces formulation viscosity but also re- Moreover, waterborne epoxy resin dispersion technol-
acts rapidly with the polyamine curative through a ogy despite evolving rapidly in recent years toward
Michael Addition polymerization reaction. By varying higher performance still does not offer the perfor-
the acrylate ester functionality in the coating, the mance of high solids or solvent-based systems. In
formulator can vary the resulting crosslink density of terms of coating surface properties such as mar resis-
the polymeric network formed. Also, by varying the tance, abrasion resistance and gloss; or coating integrity
acrylate ester type and molecular weight, a broad range (i.e. hardness, chemical resistance and corrosion resis-
of performance properties such as flexibility, abrasion tance), waterborne epoxy systems have still fallen
resistance, adhesion and substrate wetting characteris- short. Another problem associated with waterborne
tics can be achieved2. epoxies is their poor adhesion to difficult substrates
such as oily metals or plastics.
The benefit that arises from acrylate modification is the
In this paper we have studied the effect of acrylate ester
ability to formulate low VOC systems with improved
monomer or oligomer addition to the waterborne
ambient and low temperature curing performance. The
epoxy resin dispersion in a formulated coating. The
addition of low molecular weight epoxy resin modifi-
properties studied were those required by a typical high
ers (i.e., mono- and poly glycidyl ethers) to a high
gloss, light-duty industrial maintenance coating. These
solids formulation typically results in a loss of drying or
properties include coating VOCās, cure performance
performance properties. However, by using acrylate
and film characteristics. The authors have also studied
ester modifiers, cure time is accelerated while main-
the effect of acrylate ester concentration, acrylate ester
taining coating integrity. Some of the applications
functionality and type, and acrylate ester molecular
where this technology is utilized include the traffic
weight. The objective of this work was to determine
striping, industrial flooring, industrial protective coat-
the feasibility of acrylate ester modification of water-
ing, and rapid-setting structural adhesive markets.
borne epoxy coatings to enhance their performance
while maintaining low VOC and fast dry. The work
Another method for achieving a low VOC, two-com-
presented is preliminary and additional work is needed
ponent, ambient-cure epoxy system is by using
to validate the findings.
waterborne epoxy resin dispersions. Waterborne ep-
oxies have shown significant growth in the coatings
Experiment
market due to their faster dry times and improved
The materials used in the study are listed in Table 1.
safety and handling compared to their solvent-borne
They are all commercial products and are described
counterparts. Aqueous two-pack systems are often
only by generic description and equivalent weight.
used for maintenance coatings where solvent vapor is
Most of these materials are proprietary mixtures and
a problem such as hospitals, schools and poorly venti-
therefore cannot be referred to by specific chemical
lated areas3. However, the majority of commercially
name. Four basic formulations were tested with differ-
available waterborne epoxy resin dispersions used in
ent acrylate esters. The basic formulations are listed in
the coatings industry contain 5-20 parts by weight of a
Table 2 and will be referred to from this point on as
non-reactive, volatile solvent to 1) improve the aque-
Systems A, B, C and D, respectively. These formula-
ous dispersion freeze-thaw stability and 2) aid in
tions vary in non-volatile content from 55% to 64 %.
coalescing the resin to improve its film forming proper-
The acrylate ester modifier is added at 10 parts by
ties. In addition, the majority of commercial polyamine weight of Part A (Note* - studies were conducted at 5
34
Table 1. Summary of Experimental Materials
PRODUCT DESCRIPTION EQUIVALENT WEIGHT
Epoxy Dispersions
#1 1001 Semi-solid Bis A Epoxy Waterborne Dispersion* 500
#2 1002 Solid Bis A Epoxy Waterborne Dispersion 680
Acrylate Ester Modifiers
M-Cure 100 Aromatic Monofunctional Acrylate Monomer Mixture 262
M-Cure 201 Aliphatic Difunctional Acrylate Monomer Mixture 100
M-Cure 202 Aliphatic Difunctional Epoxy Acrylate Blend 210
M-Cure 203 Aromatic Difunctional Epoxy Urethane Acrylate Blend 425
M-Cure 300 Aliphatic Trifunctional Acrylate Monomer Mixture 116
Amine Curing Agents
#1 Solvent-borne Polyamidoamine adduct 324
#2 Polyamide 133
#3 Propoxylated Aliphatic Amine 81
* contains 5 - 20% solvent
Table 2. Experimental Formulations Tested
FORMULATION A B C D
Part A
Epoxy Dispersion #1 (w/solvent) 90 --- 90 ---
Epoxy Dispersion #2 (w/o solvent) --- 90 --- 90
Acrylate Ester 10 10 10 10
DI Water 5 5 5 5
Part B
Polyamidoamine Curing Agent #1 (36-64) (29-59) --- ---
50/50 Blend of Polyamide Curing Agent #2/ --- --- (11-20) (9-18)
Propoxylated Aliphatic Amine #3
DI Water 5 5 5
Non-Volatile Content (% by wt.) 55-57 58-60 60-62 62-64
Part A: Part B Mix Ratio (by volume) 1.4:1-2.4:1 1.5:1-2.8:1 3.7:1-5.9:1 4.0:1-6.6:1
and 20 parts by weight but 10 parts gave the best All coating specimens were prepared by the drawdown
results). Five parts by weight of deionized water was method using various wire wound rods. The films were
added to both Part A and Part B to reduce viscosity prepared with care so that dry film coating thickness
further and to compatibilize the components. was uniform (3 - 5 mil range). Coatings were pre-
pared on mill finished aluminum, cold-rolled steel and
Viscosity measurements were made using a Brookfield phosphate treated steel, depending on the test being
RVT viscosmeter at 25oC with the appropriate spindle/ performed.
velocity combinations. Viscosities were measured on
Part A alone and after mixing Part A and Part B. Tack-free cure times were determined by applying
nominal pressure on the film surface with the gloved
Gel times were determined by adding a 50 gm mass of tip of the index finger and pulling back away from the
the epoxy/acrylate ester/amine formulation to a tri- film. The tack-free cure time is the point at which
pour polypropylene beaker containing a wooden ap- there is no transfer of coating and no film deforma-
plicator stick. The gel time reported is the time elapsed tion.
from mixing to the time the applicator stick no longer
moves freely.
35
Figure 1
Abrasion resistance was measured using a Taber
Abrader following ASTM D4060. CS-17 wheels and
500 gram weights were used. Weight loss was mea- Acrylate Ester Modification Effect on
sured after 1000 cycles. Viscosity
35000
Solvent resistance was measured by the MEK double
Viscosity @77 F (cps)
30000
rub method. This method involves saturation of a pa- 25000 None
20000 100
per towel with MEK solvent and wiping across the 201
15000
202
surface of the film back and forth with nominal pres- 10000
203
5000
300
sure. One wipe back and forth constitutes one double 0
#1 #2
rub. Waterborne Epoxy Dispersion
Humidity resistance was measured by placing coated
panels in a Q-U-V Accelerated Weathering Tester us-
ing the 40oC condensation cycle only. Humidity resis-
Cure Performance
tance was determined by observing the film appear-
Figures 2 and 3 show that acrylate ester modification of
ance before and after exposure for blistering, clarity
waterborne epoxy dispersions generally result in a re-
and gloss retention. Blistering was rated on a 0-3 scale
duction of gel time, but have no significant effect on
with 0 - No Blistering;
tack-free cure time. The lower equivalent weight acry-
late ester modifiers M-CureĀ® 201 and M-CureĀ® 300
1 - Slight Blistering; 2 - Moderate Blistering and 3 -
exhibit a reduction in gel time or pot life for all the
Severe Blistering. Gloss at 60Ā° was measured using a
systems due to their high reactivity. Acrylate esters in
Micro Tri-Glossmeter from Byk-Gardner. Gloss Re-
general exhibit a shorter gel time with the conventional
tention was calculated by dividing gloss readings at
solvent-based polyamidoamine curing agent # 1 used in
specified time intervals by the gloss reading at time
the formulations of systems A and B than those with the
zero.
solvent-free polyamide/alkoxylated aliphatic amine blend
(Curing Agents # 2 & 3, respectively) used in the
DISCUSSION OF RESULTS
formulations of systems C and D. In addition, formula-
tions of systems A and C containing the lower molecular
Viscosity Reduction
weight epoxy resin exhibit a shorter gel time than those
Figure 1 shows that acrylate modification of a water-
of the higher solids formulations of systems B and D
borne epoxy dispersion resulted in viscosity reduction
which are based on the higher molecular weight epoxy.
for both the conventional coating resin (Epoxy Dis-
Formulations modified with acrylate ester M-CureĀ®
persion #1) and the higher molecular weight, solvent-
203 exhibit a long gel time and pot life (up to 24 hrs) but
free resin (Epoxy Dispersion #2) after thorough mix-
still cured in a thin film similar to the other formulations.
ing. However, viscosity reduction appeared to be de-
pendent on acrylate ester type and solvency charac-
The tack-free cure time is reduced slightly with the more
teristics. The aliphatic acrylate esters M-CureĀ® 201
reactive acrylate esters M-CureĀ® 201 and M-CureĀ®
and M-CureĀ® 300 are not good solvents for the high
300 in systems A and B, but not as much as expected.
molecular weight epoxy resins and therefore exhib-
However, in most of the formulations the tack-free cure
ited higher viscosities. The higher molecular weight
time is slightly extended. The drying process of the
acrylate esters M-CureĀ® 100, M-CureĀ® 202 and M-
coating still requires removal of water from the film and
CureĀ® 203 exhibit better compatibility with the epoxy
as the film cures more rapidly with acrylate ester modi-
dispersion and resulted in lower viscosity.
fication, the water is more difficult to remove which
results in the appearance of an uncured film surface.
36
The formulations of systems C and D using the
Figure 2
polymide/alkoxylated amine curing exhibited higher
hardness than the polyamidoamine cured formula-
Acrylate Ester Modification Effect on
tions. The solvent-free formulations of system D
Gel Time
exhibited the highest hardness.
8
7
6
The solvent resistance observed in the systems tested
Gel Time @77F
None
50 gms (hrs)
5 100
after 24 hours was only slightly improved by acrylate
201
4
202
3
ester modification. However, solvent resistance after
203
2
300
7 days was significantly improved. For systems A and
1
0
C, based on the lower molecular weight epoxy, the
System A System B System C System D
formulations modified with acrylate ester M-CureĀ®
100, M-CureĀ® 202 and M-CureĀ® 300 exhibit the best
solvent resistance. System B and D based on the
solvent-free higher molecular weight epoxy exhibit
Figure 3
better overall solvent resistance. Systems C and D
formulations cured with the polyamide/alkoxylated
Acrylate Ester Modification Effect on
aliphatic amine blend exhibit good solvent resistance
Cure Time
and the formulations modified with the aliphatic
5
trifunctional acrylate ester M-CureĀ® 300 exhibit ex-
4.5
Tack-Free Cure Time @77F
4
cellent solvent resistance (>100 MEK double rubs
None
3.5
15 mil Film (hrs)
100
3
after 7 days).
201
2.5
202
2
203
1.5
1 300
The abrasion resistance was only tested for formula-
0.5
0
System A System B System C System D
tions of systems A and B, which were cured with the
conventional solvent-based polyamidoamine curative.
The results indicate that abrasion resistance is im-
proved by acrylate ester modification but is dependent
on acrylate ester type and molecular weight. In this
Property Enhancement
case, both the acrylate ester type and molecular weight
Table 3 shows the hardness, solvent resistance and
appear to affect abrasion resistance. The formulations
abrasion resistance, respectively, for all of the formu-
modified with the higher equivalent weight acrylate
lations tested. In all of the acrylate ester modified
esters M-CureĀ® 202 and M-CureĀ® 203 exhibit the best
formulations the hardness was the same or significantly
abrasion resistance in both systems. However, the low
improved versus the control formulations. In general,
equivalent weight acrylate esters M-CureĀ® 201 and
the pencil hardness of the modified formulations reached
M-CureĀ® 300 exhibit the best abrasion resistance in
their final hardness in 24 hours where the control
both systems. Formulations of system A based on the
formulations were slow to develop hardness. The
lower molecular weight epoxy resin exhibit better
pencil hardness values observed appeared to be depen-
abrasion results than the formulations of system B
dent on the equivalent weight of the acrylate ester. The
based on the higher molecular weight epoxy.
lower equivalent weight acrylate esters M-CureĀ®
201 and M-CureĀ® 300 exhibit the highest hardness.
37
Table 3. Property Enhancement Data for Acrylate Ester Modified Waterborne Epoxides
M-CureĀ® 100 M-CureĀ® 201 M-CureĀ® 202 M-CureĀ® 203 M-CureĀ® 300
None
Pencil Hardness
System A @ 24 hrs 2H 3H 3H 3H 3H 3H
@ 7 days 3H 3H 4H 3H 4H 5H
System B @ 24 hrs HB 4H 6H 4H 3H 6H
@ 7 days 3H 6H 6H 6H 5H 6H
System C @ 24 hrs 2H 2H 4H 3H 2H 6H
@ 7 days 4H 3H 5H 4H 3H 6H
System D @ 24 hrs 6B 6H 6H 4H 5H 5H
@ 7 days 2H 6H 6H 5H 6H 6H
MEK Double Rubs
System A @ 24 hrs 3 5 5 4 3 10
@ 7 days 30 20 15 51 8 70
System B @ 24 hrs 3 5 3 8 6 7
@ 7 days 28 120 30 70 20 >120
System C @ 24 hrs 5 10 8 6 8 8
@ 7 days 90 115 65 45 80 40
System D @ 24 hrs 3 3 6 3 3 3
@ 7 days 17 53 100 115 40 105
Abrasion Resistance
(mg wt. loss)
System A @ 7 days 69.3 70.6 55.5 56.5 58.9 53.8
System C @ 7 days 122.4 119.7 66.7 92.6 88.7 75.0
The effect of acrylate ester modification on humidity Surprisingly, the monofunctional acrylate ester mix-
ture M-CureĀ® 100 also exhibits slightly improved
resistance of waterborne epoxy dispersion systems
was also tested. The results of this study are summa- moisture resistance due in part to the lower amine
rized in Table 4. Overall, acrylate ester modification of curative loading. All of the unmodified formulations
waterborne epoxy sytems exhibited slight improve- exhibited a significant loss of clarity and gloss after
ment in the humidity resistance as tested. System C exposure to moisture. Formulations modified with the
formulations based on the lower molecular weight higher equivalent weight acrylate ester oligomer blends
M-CureĀ® 202 and M-CureĀ® 203 also exhibited poor
epoxy and cured with the polyamide/alkoxylated ali-
phatic amine blend were the only formulations that moisture resistance due to their lower crosslink density
exhibited blistering. All of the acrylate esters tested in the resulting cured film. This result was not as
improved the degree of blistering for this system. evident in the system A formulations with the solvent-
based polyamidoamine curing agent which helps to
Formulations modified with the lower equivalent weight maintain high gloss.
acrylate ester M-CureĀ® 201 and M-CureĀ® 300 appear
to improve moisture resistance the most due to their
higher crosslink density in the cured film.
38
Table 4. Humidity Resistance Data for Acrylate Ester Modified Waterborne Epoxies*
M-CureĀ® 100 M-CureĀ® 201 M-CureĀ® 202 M-CureĀ® 203 M-CureĀ® 300
None
Blisters
System A 0 0 0 0 0 0
System B 3 1 2 1 1 1
System C 0 0 0 0 0 0
System D 0 0 0 0 0 0
Clarity
System A sl. cloudy clear s.. cloudy clear sl. cloudy clear
System B cloudy clear clear cloudy clear clear
System c cloudy cloudy clear clear cloudy sl. cloudy
System D cloudy clear clear sl. cloudy cloudy clear
Gloss Retention (%)
System A 45 95 87 96 71 99
System B 40 80 87 35 33 82
System C 67 29 42 42 21 41
System D opaque 44 75 42 28 28
* Test results after 48 hours Q-U-V condensation exposure
ACKNOWLEDGEMENT
CONCLUSION
The authorās would like to thank Wayne McWhorter,
Waterborne epoxy dispersion technology is a good
Consultant, for his assistance in the design of this
alternative to solvent-based and 100% solids coating
study. We would also like to thank Tim Cauffman,
technology but it presents many challenges to the
Market Development Manager, and Frank Lordi,
formulator. In this paper it has been demonstrated that
Application Development Technician, of Sartomer
modification of the epoxy dispersion by an acrylate
Company for their market research and laboratory
ester monomer or oligomer provides another approach
assistance, respectively, on this paper.
to further the technology and achieve even lower VOC
or zero VOC systems with improved coating perfor-
REFERENCES
mance. This approach would allow the formulator to
1
McWhorter, W., U.S Patent 4,051,195
meet both the demands of regulatory compliance and
āPolyepoxide-Polyacrylate Ester Compositionsā?,
better products.
Issued to Celanese Polymer Specialties
September 27, 1977
Initial studies indicate that acrylate esters can act as
reactive diluents and coalescing aids for waterborne
2
Costin, C.R., Bailey, M., Cauffman, T.,
epoxy dispersions. This technology allows the use of
āAcrylate-Modified 2-Part Epoxies for Coatings
higher molecular weight epoxy resins and less water
and Adhesives ā?, Technical Paper presented to the
soluble amine curatives that provide better durability.
SPI Epoxy Resin Formulators Conference in
Waterborne epoxy systems that are modified with an
May 1996 in Aspen, CO.
acrylate ester monomer or oligomer and cured with a
polyamine curative are very complex. However, by
3
Oldring, Dr. P., Hayward, G.,
proper selection and incorporation of the acrylate ester
āResins for Surface Coatingsā?, Vol. II,
into the system, coatings with improved VOC, cure
SITA Technology Ltd., Copyright 1987
performance, hardness, abrasion, solvent and humidity
resistance can be achieved.
39
SAFETY, HANDLING & STORAGE INFORMATION
OLIGOMERS:
TOXICOLOGY AND SAFE USE
Most epoxy, urethane, and aromatic acid methacrylate
INFORMATION
oligomers tend to have low skin and eye irritation. Skin
absorption, ingestion and inhalation hazards are mini-
As with any chemical, the potential health and safety
mized because of their higher molecular weight com-
hazards associated with these products should be
pared to most monomers. However, oligomers may be
understood to ensure that they are used safely. Review
supplied as blends with monomers. See previous sec-
each productās Material Safety Data Sheet (MSDS),
tion on monomers.
which includes specific hazard and precautionary in-
formation, prior to working with these materials.
METALLIC MONOMERS:
These products may cause skin irritation, particularly
Should you require assistance in an emergency situa-
if skin contact is prolonged. Skin sensitization may also
tion involving a Sartomer Company product, call us at
occur. Metallic monomers are supplied as solids--dust
610-692-8401, twenty-four hours a day.
from these products, or vapors created by thermal
processing, may cause irritation of the respiratory tract
TOXICOLOGY
and other mucous membranes. Metallic monomers may
also cause severe eye irritation, or may be corrosive to
MONOMERS:
the eyes as demonstrated in animals tests. These
ā? Skin & Eye Irritation: These products range
materials are typically low ingestion hazards.
from minimally irritating to corrosive in acute
animal skin and eye irritation tests. Monomers may
cause redness, dryness, swelling and in severe
HANDLING PROCEDURES & PRECAUTIONS
cases, blistering (burns) if skin contact occurs -- the
As with all industrial chemicals, it is important to
skin irritation response will depend on the condi-
prevent exposure through the use of protective equip-
tions of exposure and the irritation potential of the
ment, proper work practices and engineering controls.
product. Symptoms of skin irritation may be
delayed.
The following precautions should be observed for
general handling practices:
ā? Oral Toxicity: These products are typically
minimal ingestion hazards, as demonstrated in
ā? ensure a clean, well ventilated working area;
animal tests.
ā? avoid skin contact by wearing impervious gloves;
ā? wear eye protection such as goggles;
ā? Inhalation Toxicity: Liquid monomers are typi-
ā? review the MSDS prior to working with a material.
cally non-volatile and have high boiling points (>
1500C); consequently, they do not pose an inhala-
ā? If skin contact does occur, wash affected areas
tion hazard at room temperature. However, aero-
immediately with soap and water. Rinse thoroughly.
sols or vapors (which can be generated from
spraying or heating these materials, respectively)
ā? Transfer liquid materials in stainless steel lined
of liquid monomers may cause upper respiratory
hoses. Tygon and other similar plastics can also be
tract irritation if inhaled.
utilized in transferring these materials.
ā? Skin Sensitization: Some of these products have
ā? Avoid localized high temperatures in mixing and
been shown to be skin sensitizers (substances which
transferral procedures to avoid premature polymer-
cause an allergic skin reaction in susceptible indi-
ization of monomers and oligomers.
viduals after repeated exposure) in animal tests.
Cases of sensitization in workers have been re-
ā? Minimize the potential for dust explosion, which
ported in the published literature for a limited
can be associated with handling organic powders,
number of products. It is important that skin
such as the metallic monomers and solid
contact with these products be prevented to ensure
photoinitiators. Eliminate and control ignition
that skin sensitization does not occur.
sources and use good housekeeping practices dur-
ing storage, transfer and handling of these prod-
ucts.
40
FIRE HAZARDS & PRECAUTIONS STORAGE INFORMATION
In the event of a fire, these materials can become As with any chemical, the potential health and safety
inhalation hazards -- they can be carried by smoke; hazards associated with these products should be un-
vapors and combustion products from burning materi- derstood to ensure that they are used safely. Review
als may be extremely irritating. Heat from a fire may each productās Material Safety Data Sheet (MSDS),
also initiate an uncontrolled polymerization of prod- which includes specific hazard and precautionary infor-
ucts containing monomer or oligomer, which can mation, prior to working with these materials.
cause closed containers of these products to rupture,
possibly spreading the fire. Should you require assistance in an emergency situa-
tion involving a Sartomer Company product, call us at
Fire fighters should wear self-contained breathing ap- 610-692-8401, twenty-four hours a day.
paratus, in addition to eye, face and body protection.
Extinguish fires with dry chemical, foam, carbon SHELFLIFE STABILITY
dioxide, or water fog and spray from a safe distance or Sartomer products (Monomers, Oligomers, Metallic
protected location. Extinguishing media should be Monomers, and other Specialty Products) should be
applied gently to metallic monomers and solid photo- used within six months of receipt for optimum product
initiators to avoid raising dust clouds, which can create performance. Monomers and oligomers contain inhibi-
an explosion risk. Cool fire or heat exposed containers tors such as HQ and MEHQ that have been added to
with water fog or spray from a safe distance. enhance shelf life stability in the presence of air.
DISPOSAL PROCEDURE STORAGE CONDITIONS, HAZARDS &
Persons handling empty product containers should SAFETY PRECAUTIONS
wear protective equipment and handle containers in an Store all Sartomer products away from direct sun-
area away from ignition sources because they may light, oxidizing agents and materials which may gener-
contain residual product. Recommended cleaning ate free radicals. Storage temperatures should not
procedures for empty steel drums include washing the exceed 90Ā°F.
containers with a strong soap and water solution,
followed by a thorough water rinse. If necessary, a MONOMERS AND OLIGOMERS:
15% caustic solution followed by a water rinse can be Store in epoxy-phenolic lined carbon steel, stainless
used to further clean containers. All wash and rinse steel or polyethylene lined drums, or glass containers.
solutions must be disposed of in accordance with
federal, state and local regulations. These materials can polymerize prematurely under
improper storage conditions. The following steps are
Properly inhibited monomers, oligomers and metallic recommended to prevent premature polymerization:
coagents are generally not RCRA hazardous wastes.
However, it is the responsibility of the waste generator ā? maintain a head space in storage containers to
to determine if the product meets the criteria of a support the oxygen requirements of the inhibitor(s);
hazardous waste at the time of disposal (see 40 CFR
ā? avoid contact with contaminants such as iron and
261). Disposal options for these products include
copper (which can initiate polymerization);
landfilling solids at permitted sites, fuel blending or
incinerating liquids. Disposal must comply with fed- ā? check inhibitor levels periodically.
eral, state and local regulations. Metal recovery should
be considered for metallic monomers. STORAGE TEMPERATURE
Store containers at temperatures above 50Ā°F and below
90Ā°F. Recommended bulk storage temperatures should
remain within 60Ā°-80Ā°F range. If freezing should occur
with monomers or oligomers, heat material to 90Ā°F
(104Ā°F for most urethane acrylate products) and mix
thoroughly with low shear to disperse inhibitor evenly
throughout the solution. These precautions are neces-
sary to standardize the properties of the product and to
avoid premature polymerizations.
41
Notes
Notes
Corporate Headquarters
Sartomer Company, Inc.
Oaklands Corporate Center
502 Thomas Jones Way
Exton, PA 19341
Tel: 610-363-4100
Fax: 610-363-4140
Cust. Serv.: 800-SARTOMER
E-mail: contact@sartomer.com
Web: www.sartomer.com
For updated contact information worldwide, please refer to Sartomer's web site at:
http://www.sartomer.com/sales.asp
The information in this bulletin is believed to be accurate, but all recommendations are made without warranty since the conditions of use are beyond SARTOMER Company's
control. The listed properties are illustrative only, and not product specifications. SARTOMER 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.
3951 06/06
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