Improved Epoxy Dispersions

Dr. Chip Palmer

Ethox Chemicals, LLC

CoatingsTech 2013
 Epoxy Chemistry
 Epoxy coatings are formed by the reaction of a
poly(epoxide)-based oligomer or resin with a
OH
O polyfunctional active hydrogen compound
O
O O O
(curing agent).
O
 The focus of this paper is 2K systems, with
separate epoxy and polyamine hardeners (a
polyamine pre-reacted with some epoxy or
dimer fatty acid curing agent). All epoxies are
x

based on bisphenol A (BPA).

Generic BPA epoxy oligomer structure  Organic solvents have been used to manage
viscosity and maintain compatibility between
components, but are VOCs. Water use is more
environmentally friendly, but requires
surfactants since epoxy resins are hydrophobic
and water reactive.
H2N NH2
 Waterborne epoxy dispersions are normally
created by shearing epoxy into water in the
presence of a surfactant. The surfactant
system must have good compatibility with the
Generic diamine epoxy and with the hardener.
 The use of water as the solvent has potential
drawbacks such as incompatibility with epoxy
or hardener, long term storage stability, and
freeze/thaw instability.

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 Epoxy Chemistry
OH
O
O O O
O
O

epoxy + OH
OH
O O O
O
or HO HN
NH2 NH2
NH
hardener
NH2
H2N hardener adduct

OH
OH
O O O
O
HO HN

NH

HO NH OH
N
H
O
O
cured epoxy resin

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Function of Surfactants
 Waterborne epoxy resin resides inside
micelles – stabilized by adsorbed
surfactant to prevent the reaction of water
with epoxy groups and to prevent
agglomeration of individual micelles into
larger particles
 Anionic surfactants provide charge
stabilization
 Nonionic surfactants provide steric
stabilization and chemical stability to the
waterborne epoxy particles
 Ideally surfactant molecules can provide
freeze/thaw stability
 Our thesis is that styrenated phenol-based
surfactants will give better properties to
BPA-based epoxy dispersions due to
strong interaction with the resin backbone.

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 Surfactant Structures
Subjects of Study O H

O O

O SO3-NH4+
19
O O

19

POE 20 DSP
POE 20 DSP sulfate
1-2

E-Sperse 703 nonionic

Controls
1-2

E-Sperse 704 anionic OSO3-Na+

Sodium lauryl sulfate O

O
C9H19 O SO3-NH4+ C
4 O
OSO3-Na+
O

NP 4 sulfate O

Sodium dioctyl sulfosuccinate (DOSS)

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 Topics

1. Epoxy Storage and Freeze/Thaw Stability in

Waterborne Micelles
2. Epoxy + Hardener Stability and Pot Life
3. Epoxy Dispersion Curing Time Study
4. Overall Conclusions

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 Study #1: Epoxy Stability
1 month at room 2 months at room 2 months at
Surfactant temperature (75% temperature (75% 50 C
solids) solids) (50% solids)
Sodium lauryl
sulfate one phase two phases two phases
Nonylphenol +
4 moles EO Sulfate
(NH4) two phases two phases two phases
Sodium dioctyl
sulfosuccinate (in
30% propylene
glycol solvent) one phase one phase one phase
Styrenated phenol
+ 20 moles EO
Sulfate (NH4) one phase one phase one phase

Used BPA-based epoxy resin EPON 828 – Hexion/Momentive

Surfactant loading is 0.5% on weight of epoxy

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 Epoxy Freeze/Thaw Stability
Freeze/thaw
Surfactant Flow
cycles passed 75% solids samples
were cooled at - 20 C
Sodium lauryl overnight, then allowed
none none
sulfate to warm to ambient.
Nonylphenol +
4 moles EO Sulfate none none
(NH4)
A 50/50 mixture of POE
Sodium dioctyl
20 DSP and POE 20
sulfosuccinate (in
30% propylene
none poor DSP sulfate at the same
glycol solvent) total surfactant level
gives 5 cycles of F/T
Styrenated phenol
stability.
+ 20 moles EO at least one normal
Sulfate (NH4)

CoatingsTech 2013 8
 Study #1: Epoxy Stability Conclusions

• Styrenated phenol-based and DOSS surfactants gave better

storage stability at both room and elevated temperatures to
epoxy resin dispersions than other anionic surfactants tested.
(DOSS had some solvent that could skew results).

• The styrenated phenol-based surfactant was the only anionic

surfactant of those tested that imparted any freeze/thaw
stability, even though DOSS had some antifreeze present.
This could be due to the longer ethoxylate chain or to stronger
interactions of the hydrophobe with the epoxy slowing
desorption off the micelle surface.

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 2. Dispersion Viscosity Stability and Pot Life
• 75% by weight in water epoxy dispersions were made using 2% and 5% by weight of solids of
various commercially available surfactants.

• Brookfield, KU, and ICI viscosities of these dispersions were measured.

• A hardener adduct was made by the reaction of a 4:1 weight ratio of 1,3 bis-(aminomethyl)
cyclohexane (BAC) to epoxy resin. This adduct was then combined with different commercially
available surfactants in order to evaluate the pot life of mixed 2K epoxy systems.

• These adduct and hardener compositions form water dispersible or waterborne hardeners that
are combined with the waterborne epoxy dispersions.

H2N NH2

BAC - 1,3-bis(aminomethyl) cyclohexane

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 Surfactants Used in Study
Moles
Surfactant Hydrophobe EO Charge Solids HLB
Tergitol NP15 NP 15 non-ionic 100 15

Tergitol NP30 NP 30 non-ionic 100 17

Tergitol S20 secondary alcohol 20 non-ionic 100 16

Esperse 703 DSP 20 non-ionic 100 14

ERS 1689 TSP 10 non-ionic 100 9.6

Tergitol S40 secondary alcohol 40 non-ionic 70 18

Aerosol OT-70 sodium dioctyl sulfosuccinate - sulfate (Na) 70 -

Esperse 704 DSP 20 sulfate (NH4) 50 -

Rhodapon UB STD sodium lauryl sulfate - sulfate (Na) 30 -

TSP is tristyrenated phenol, DSP is distyrenated phenol

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 Dispersion Viscosity Stability
Brookfield
Surf. Surfac- epoxy water Total RV#4,
Surfactant solids tant (g) (g) (g) (g) ICI KU 4 rpm
Esperse 704
POE 20 DSP sulfate 0.5 30 300 85 415 2.2 102.1 12,000

POE 10 TSP 1 15 300 100 415 0.5 69.7 1,000

Esperse 703
POE 20 DSP 0.5 30 300 85 415 2.5 91.6 8,000
POE 4 nonylphenol
sulfate 0.63 23.8 300 91.2 415 1.7 82.5 5,000
sodium dioctyl
sulfosuccinate 0.7 21.4 300 93.6 415 0.8 133 75,000

sodium lauryl sulfate 0.3 50.0 300 65.0 415 1.7 88.9 8,000

75% epoxy, 5% surfactant in water dispersions

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 Dispersion Viscosity Stability
Additional
amount epoxy Additional Brookfield RV
Surfactant 75/5 (g) (g) water (g) ICI KU #5, 4 rpm
Esperse 704
POE 20 DSP sulfate 166 180 60 1.4 98.5 14,700
POE 10 TSP 166 180 60 0.2 88.4 600
Esperse 703
POE 20 DSP 166 180 60 1.2 61.4 2,000
POE 4 Nonylphenol
sulfate 166 180 60 0.7 61.1 1,500
sodium dioctyl
sulfosuccinate 166 180 60 1 90.1 5,300

sodium lauryl sulfate 166 180 60 1 76.2 4,100

Dilute 75% epoxy, 5% surfactant to 2% surfactant in water and check viscosity

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 Dispersion Viscosity Stability Ratios
ICI Sum of
ratio KU Brookfield differences from
Surfactant % ratio % ratio % 100
Esperse 704
POE 20 DSP sulfate 64 96 123 62

POE 10 TSP 40 127 60 127

Esperse 703
POE 20 DSP 48 67 25 160
POE 4 nonylphenol
sulfate 41 74 30 155
sodium dioctyl
sulfosuccinate 125 68 7 150
sodium lauryl sulfate 59 86 51 104

POE 20 DSP sulfate holds its viscosity upon dilution best

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 2K Dispersion Pot Life
Adduct Preparation
A 4:1 1,3-bis(aminomethyl) cyclohexane (BAC) epoxy adduct was made by adding 400 grams of BAC
to a large glass jar. Next, 100 grams of EPON 828 epoxy was added to the jar. A stainless steel two-
blade stirrer was added to the jar and topped with a lid with a hole that allowed the stirrer shaft to
protrude through and rotate freely. The adduct was allowed to stir and react for 8 hours at room
temperature.

Epoxy Hardener Mixtures

Using the epoxy equivalent weight of the epoxy dispersion and the active hydrogen equivalent weight
of the hardener, the appropriate amounts of the epoxy dispersion and hardener were added at a 1:1
equivalence ratio to a small paint can and mixed with a stainless steel one-blade mixer for
approximately one minute and then immediately used to determine pot life.

Pot Life Determination

To determine pot life, the viscosity of a mixed 2K system was immediately measured with an RV
Brookfield Digital Viscometer. A number 6 spindle was used set at 4 RPM to minimize any shear
thinning effects. The initial viscosity was recorded and then subsequently every 5 minutes along with
the temperature of the mixture obtained by a thermocouple inserted into the mixed system. The pot
life was defined as the time required for the initial viscosity to double.

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 Effect of Surfactant Addition to Hardener on Pot Life
POE 20
POE 40 secondary
secondary sodium dioctyl POE 20 DSP POE 20 DSP NP15 alcohol
4:1 BAC adduct + alcohol sulfosuccinate sulfate (50%) (50%) (50%) (50%)
AHEW 89.6 89.6 108.1 108.1 108.1 108.1
phr 5% 704 75% epoxy 35.7 35.7 43.1 43.1 43.1 43.1
initial viscosity cps 1,100 1,200 1,200 1,100 1,100 600

HLB 18 14.3 15 16.3

time for viscosity
doubling 15 17 28 28 17 16
time to reach 70 C 16 21 35 35 19 19
viscosity t=5 900 1,200 1,700 800 900 500
viscosity t=10 900 1,300 1,300 600 800 500
viscosity t=15 2,200 1,800 1,100 700 600 700
viscosity t=20 - - 700 700 - -
viscosity t=25 - - 1,300 900 - -
viscosity t=30 - - - - - -

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 Effect of POE 20 DSP Addition to Hardener on Pot Life
POE 20
Testing as on previous Anquamine 401 + DSP Anquamine only
chart, but with AHEW 350 200
Anquamine 401, a
commercial phr 5% 704 75% epoxy 139.6 79.8
waterborne hardener. initial viscosity cps 2,700 18,500
HLB 14.3
time for viscosity doubling 31 23
time to reach 70 C 35+ 35+

Addition of POE 20 viscosity t=5 2,700 20,400

DSP nonionic viscosity t=10 2,600 24,000
surfactant to the viscosity t=15 2,800 26,700
hardener extended the
viscosity t=20 3,300 32,400
pot life and kept the
viscosity more viscosity t=25 3,700 40,300
manageable. viscosity t=30 5,300 -

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 Effect of POE 20 DSP Addition to Hardener on Pot Life

BAC 4:1 BAC adduct 2:1 BAC adduct

0.8 equivalent of POE 20 POE 20 POE 20

hardener + DSP (50%) none DSP (50%) none DSP (50%) none

initial viscosity 2,100 300 900 700 5,400 1,900

time for viscosity

doubling (min) 30 7 24 11 30 14

time to reach 70°C 34 55 MAX 37 MAX 48 MAX 37 60 MAX

time to max
temperature n/a 15 35 25 n/a 30
No Immediate Separation Separation No Immediate
Stability separation Separation after 15 within 5 separation Separation
minutes minutes

Addition of POE 20 DSP to hardener or hardener adduct extends pot life and improves the
stability of the epoxy/hardener dispersion.

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 Effect of POE 20 DSP Addition to Hardener on Pot Life

The solid red line indicates no surfactant. The dotted blue line represents inclusion of POE 20 DSP.

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 Effect of POE 20 DSP Addition to Hardener on Pot Life

The solid red line indicates no surfactant. The dotted blue line represents inclusion of POE 20 DSP.

The extension of pot life with the addition of POE 20 DSP is independent of whether
hardener or hardener adduct is used for curing. Presumably in both cases the surfactant
is slowing the rate that hardener reactive groups are finding epoxy groups.

CoatingsTech 2013 20
 Study #2: Conclusions
• POE 20 DSP sulfate shows very good ICI and KU viscosity with a
reasonable Brookfield viscosity, better than POE 10 TSP and POE 20
DSP nonionics, and much better than the aromatic group-containing NP
or other surfactants.
• When the POE 20 DSP sulfate dispersion is diluted from 5% to 2%
surfactant, very little drop in ICI, KU, and Brookfield viscosities occurs.
This suggests that lot-to-lot variability in production would be reduced.
• The stability of waterborne epoxy and hardener mixes is greatly improved
by the addition of POE 20 DSP.
• Both POE 20 DSP and POE 20 DSP sulfate show the best performance
in terms of longest pot life as measured by the time for viscosity doubling
and time to reach 70 C after mixing.
• Given that DSP surfactants produce similar pot lives for different adducts,
it may be possible to produce hardeners without adduct formation for use
in waterborne epoxies with longer pot lives.

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 Study #3: Epoxy Dispersion
Curing Time Study
Surfactants Used In Waterborne Epoxy Curing Study

Hydrophobe EO Charge Solids HLB

NP 15 non-ionic 100 15
NP 30 non-ionic 100 17
secondary alcohol 20 non-ionic 100 16
DSP 20 non-ionic 100 14
TSP 10 non-ionic 100 9.6
secondary alcohol 40 non-ionic 70 18
dioctyl sulfosuccinate - Sulfate (Na) 70 -
DSP 20 Sulfate (NH4) 50 -

A master batch of epoxy dispersion was created at 75% solids using 5% by weight
DSP POE 20 sulfate. A 4:1 BAC:epoxy adduct was made with 400 grams of BAC and
100 grams of epoxy.

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 Curing Time Determination

BYK dry time

recorder

1:1 epoxy:hardener mixtures were drawn down on acrylic plastic slides. A needle slides across
the slide left to right over a 24 hour period.

Description of end Points 1 to 5 (Numbers at bottom of figure above)

• End of 2 - Set to touch (also described as tack free or thin film set)
• End of 4 – Surface dry (also called dust free or cotton free)
• End of 5 – Through dry

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 Hardener Compositions
Surfactant 4:1 BAC Solids Surf. AHEW viscosity phr % surf. on % surf. in
(g) (g) epoxy hardener
Tergitol NP15 25 100 18.8 75.7 500 30.2 12.9 42.9

Tergitol S20 25 100 18.8 75.7 750 30.2 12.9 42.9

Esperse 703 25 100 18.8 75.7 wax 30.2 12.9 42.9

Tergitol NP30 25 100 18.8 75.7 wax 30.2 12.9 42.9

Esperse 1689 25 100 18.8 75.7 500 30.2 12.9 42.9

Tergitol NP15 25 50 37.5 108.1 250 43.1 12.9 30.0

Tergitol S20 25 50 37.5 108.1 250 43.1 12.9 30.0

Esperse 703 25 50 37.5 108.1 250 43.1 12.9 30.0

Tergitol S40 25 70 26.8 89.6 500 35.7 12.9 36.2

Aerosol OT 25 70 26.8 89.6 3750 35.7 12.9 36.2

Esperse 704 25 50 37.5 108.1 250 43.1 12.9 30.0

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 Cure Time Data
End Pt 1.5 End Pt 2 End Pt 4 End Pt 5
Surfactant solids (hrs) (hrs) (hrs) (hrs)
Tergitol NP15 100 1.3 3.8 6.0
Tergitol S20 100 4.8 4.6 8.5
Esperse 703 100 1.4 7.8 24
Tergitol NP30 100 1.4 4.4 7.1

POE 10 TSP 100 1.4 2.1 3.8 5.9

Tergitol NP15 50 1.4 9.5 10.8
Tergitol S20 50 1.5 20.1 >24
Esperse 703 50 1.1 not cured not cured >24
Tergitol S40 70 1.5 10.3 not cured >24
Aerosol OT-70 70 0.5 1.0 3.3 4.5
Esperse 704 50 1.3 2.4 4.0 5.8

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 Cure Time Data

Sodium dioctyl sulfosuccinate and POE 20 DSP sulfate have the shortest ‘through-
dry” cure times, much less than the nonionic POE 20 DSP or NP surfactants. It
appears that anionics cure much faster than nonionics.

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 Study #3: Conclusions

• POE 20 DSP sulfate (E-Sperse 704) shows the best performance in terms of longest pot life and fastest cure time
when compared to other surfactants in a waterborne epoxy dispersion.
• POE 20 DSP sulfate (E-Sperse 704) cures at nearly an identical rate as dioctyl sulfosuccinate (OT-70, a VOC-
containing surfactant) coupled with an extended pot life.
• POE 20 DSP, the nonionic analog of POE 20 DSP sulfate, does not show through-dry curing in 24 hours (with and
without water added to the hardener) suggesting the sulfate group may play a significant part in imparting faster cure
times. Perhaps the cation associated with the sulfate is being coordinated by the amine group of the hardener,
accelerating its approach to the epoxy ring, or perhaps the cation catalyzes the opening of the epoxy ring through
coordination to the oxygen atom.

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 Surfactant - Epoxy Interaction
OH
O
O O O
O

x epoxy resin

O
distyrenated phenol ethoxylate

O
Strong overlap of π–system in surfactant
hydrophobe with epoxy resin aromatic moieties
promotes adhesion of surfactant to epoxy resin
O
particle leading to more stable dispersions.
+
H4N-O3S

CoatingsTech 2013 28
 Overall Conclusions
• Freeze/thaw stability can be imparted to low or no-VOC
waterborne epoxy dispersions by the inclusion of certain
distyrenated phenol-based surfactants.
• The pot life of waterborne 2K epoxy dispersions can be extended
with no extension of curing time by the use of styrenated phenol-
based nonionic or sulfated surfactants in the epoxy or hardener.
• Styrenated phenol surfactants appear to have much better affinity
for BPA-based epoxies than other aromatic hydrophobe
surfactants such as nonylphenols or tristyrenated phenols. The
TSP surfactant used had only 10 EO units compared to 20 in the
DSPs, however. Further work would have to be done to elaborate
on the contribution to the EO chain length to these surfactants.

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Thanks for your attention!

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