Hypermer RangeTM

For water soluble polymers

At the core of your innovation

www.croda.com/watertreatment
Expertise in emulsification
Croda is recognised worldwide as a leading supplier of
primary emulsifiers for the inverse emulsion
polymerisation process in water soluble polymer
manufacture. The Hypermer™ trade name provides a
unique range of proprietary polymeric surfactants which
have proven high performance in demanding commercial
applications.
Features of the Hypermer™ range
Croda’s Hypermer™ polymeric surfactants can offer
several performance advantages in inverse emulsion
polymerisation:
I Hypermers enable the manufacture of inverse polymer
emulsions with excellent mechanical stability.
This allows high temperature/vacuum processing of
emulsions to increase the polymer/actives content.
I Use of Hypermers results in inverse emulsions having
a very fine particle size and narrow particle size
distribution. This leads to very low coagulum formation.
I Hypermers allow the production of inverse polymer
emulsions with reduced viscosity, even at higher
polymer loading
I Hypermers exhibit excellent performance at a lower
usage level (up to 30% lower loading than conventional
Sorbitan ester stabiliser packages)
Hypermer™ range
Processes and formulations for inverse emulsion
polymerisation vary considerably within the speciality
chemicals industry. The polymerisation process involves
the dissolution of the monomers and the appropriate
additives in water before the resulting solution (aqueous
phase) is emulsified in a continuous oil phase.
Polymerisation takes place in the water droplets.
Blends of non-ionic surfactants, such as sorbitan esters and
polyoxyethylene derivatives are often used as primary
emulsifiers. Owing to the low polarity of the continuous
phase, the electrostatic stabilisation mechanism is very
ineffective and surfactants with low HLB values - typically
between 4 and 6 are the most commonly used. Numerous
parameters such as temperature, nature and number of
components and the type of surfactants used influence the
stability of the emulsion.
A major issue encountered in water in oil (W/O) emulsions
is their instability. This is particularly true in inverse
emulsion polymerisation, where the presence of monomer
in large concentrations (up to 50%) affects the interfacial
properties of the system.
The advantage brought about by polymeric surfactants
over conventional species is a consequence of the multiple
and extensive interactions with both the continuous and
dispersed phases. In the classical chemistry of surface-
active agents, ionic or non-ionic polar groups and
hydrophobes of C12 - C18 chain length are combined to
produce molecules that have one single weak point of
interaction with each of the immiscible phases. Hypermers
however are adsorbed onto the particle surface, their
polymeric chains penetrate into the medium and provide a
barrier which prevents strong interactions between
particles.
Use of Hypermer™ polymeric surfactants results in much
better steric stabilisation because the entropic contribution
is significantly larger. For efficient steric stabilisation the
polymeric chain should be compatible with the medium
and have a molecular weight designed to give the optimal
steric stabilisation barrier. The production of a very fine
polymer emulsion with a narrow particle size distribution
and a reduced amount of insoluble and coagulated
material are the direct consequences of this enhanced
stabilisation effect.
Furthermore in some cases, a vacuum distillation may be
employed after the polymerisation in order to concentrate
the polymer emulsion. Because of the extra stress involved
in this process, a conventional low molecular weight
emulsifier is no longer able to effectively stabilise the W/O
polymer emulsion. Hypermer™ polymeric surfactants,
however, can stabilise the emulsion.
Croda offers a wide range of proprietary polymeric
surfactants which are effective as emulsifiers for inverse
emulsion polymerisation. These products, available under
the Hypermer™ trade name, have demonstrated
outstanding performance in demanding commercial
applications. The table below lists the physical
characteristics of these products together with relative
performance information.
Hypermer™ Polymeric Surfactants
Product Physical Form @ 25°C Typical Viscosity (cp1) Density (g/cm3) HLB2 FDA Clearance3
Class: ABA (Hydrophobe-hydrophile-hydrophobe) copolymers
HYPERMER 1599 Brown liquid 2000-4000 0.97 5.0 Yes
HYPERMER 1083 Amber to brown liquid 1000-3000 0.98 4.6 Yes
HYPERMER 1031 Brown liquid 1000-3000 0.97 4.4 Yes
HYPERMER 1631 Brown liquid 1000-3000 0.97 3.8 Yes
Class: Oligomeric Ester
HYPERMER 2524 Brown liquid 1300-3500 0.96 4.9 Yes
HYPERMER 2800 Brown liquid 2000-8000 0.97 6.0 Yes

1. Measured at 25°C, unless otherwise noted, 2.Hydrophile-Lipophile balance, 3. Clearance under 21 CFR 176.170

Protocol for the evaluation of hypermers Evaluation of Hypermer™ performance

in inverse emulsion polymerisation
A. Monomer Pre-emulsion
Dissolve acrylamide and/or other monomer and
additives into the aqueous phase under an inert
atmosphere and adjust the pH to the required level.
B. Oil Phase
Mix the solvent and surfactants into the reaction
vessel and maintain the oxygen-free atmosphere.
The aqueous phase should be slowly emulsified
into the oil phase using a high shear device.
in typical emulsion formulations
Croda has evaluated the performance of the Hypermer™
range of polymeric surfactants in four typical emulsion
formulation types. Each of these formulations was made up
to both 35% and 45% solids in order to test the performance
against a control sorbitan ester emulsifier package.
The results clearly illustrate the benefits of Hypermer™
polymeric surfactants:
I The solid loading possible in a stable polymer emulsion
made with Hypermer™ is 22% higher than with the control
I The median particle size is finer for polymer emulsions
made with Hypermer™ polymeric surfactants
I Polymer emulsion viscosity is significantly lower with
Hypermer™ polymeric surfactants relative to the control
I Coagulum formation is significantly reduced with
Hypermer™ polymeric surfactants

C. Emulsion polymerisation
Polymerisation should be initiated by the addition
of a free-radical source such as a redox initiator
solution or azobisisobutyronitrile.

D. Activation
An appropriate inverting agent or breaker surfactant
should then be added to the polymer emulsion.
Typical formulation containing 30% cationic polymer
Parts by Weight (g)
Component 45wt% Solids 35wt% Solids
Aqueous Phase:
Acrylamide 294 246
DMA EMA-MeCl (80 wt% aq.) 158 105
EDTA (5 wt% aq.) 4 4
Distilled Water 208 259
Potassium Bromate (1.5 wt% aq.) 8 8
CuSO4(5H20) (1wt% aq.) 4 4
Oil Phase:
Isoparaffinic Solvent 286 336
Surfactant 22 22
Initiatior:
Na-metabisulfite (0.15 wt% aq.) 16 16
Total: 1000 g 1000 g
The table below shows the results of a typical cationic inverse emulsion polymerisation, using 70% acrylamide and 30%
dimethylaminoethyl methacrylate-methyl chloride

Results
Surfactant Total solids Emulsifier Loading Median Particle Emulsion Coagulum Selection
(wt%) (wt%) Size (microns) viscosity (cps) (wt%) Guide
Sorbitan Ester Control 35 2.2 0.449 225 0.20 Suitable for
low solids
Sorbitan Ester Control 45 Failed Failed Failed Failed Not suitable
for high solids
HYPERMER 1599 45 2.2 0.653 203 0.40 Recommended
HYPERMER 1083 45 2.2 0.515 679 0.60 Recommended
HYPERMER 1031 45 2.2 0.552 392 0.02 Highly recommended
HYPERMER 1631 45 2.2 0.514 532 0.39 Recommended
HYPERMER 2524 45 2.2 0.523 413 0.02 Highly recommended
HYPERMER 2800 45 2.2 0.604 162 0.02 Highly recommended

Guide for Hypermer™ selection

Median Particle Size in 30% Cationic Polymer Emulsions Coagulum in 30% Cationic Polymer Emulsions Emulsion viscosity in 30% Cationic Polymer Formulations
0.7 0.7 800

0.6
Median Particle Size (microns)

600
Emulsion viscosity (cps)

0.5
0.6
Coagulum (wt%)

0.4
400
0.3
0.5
0.2
200
0.1

0.4 0 0
31

83

24

31

00

99

00

31

24

31

99

83

00

99

31

24

31

83
16

10

25

10

28

15

28

10

25

16

15

10

28

15

10

25

16

10
er

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rm

rm

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rm

rm

rm

rm

rm

rm
pe

pe

pe

pe

pe

pe

pe

pe

pe

pe

pe

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pe
Hy

Hy

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Typical formulation containing 10% cationic polymer
Parts by Weight (g)
Component 45wt% Solids 35wt% Solids
Aqueous Phase:
Acrylamide 377 297
DMA EMA-MeCl (80 wt% aq.) 54 33
EDTA (5 wt% aq.) 4 4
Distilled Water 229 280
Potassium Bromate (1.5 wt% aq.) 8 8
CuSO4(5H20) (1wt% aq.) 4 4
Oil Phase:
Isoparaffinic Solvent 286 336
Surfactant 22 22
Initiatior:
Na-metabisulfite (0.15 wt% aq.) 16 16
Total: 1000 g 1000 g

The table below shows the results of a low cationic inverse emulsion polymerisation using 90% acrylamide and 10%
dimethylaminoethyl methacrylate-methyl chloride.

Results
Surfactant Total solids Emulsifier Loading Median Particle Emulsion Coagulum Selection
(wt%) (wt%) Size (microns) viscosity (cps) (wt%) Guide
Sorbitan Ester Control 35 Failed Failed Failed Failed Not suitable
Sorbitan Ester Control 45 Failed Failed Failed Failed Not suitable
HYPERMER 1599 45 2.2 0.401 203 0.19 Highly recommended
HYPERMER 1631 45 2.2 0.465 476 0.39 Recommended
HYPERMER 2524 45 2.2 0.503 378 0.38 Recommended
HYPERMER 2800 45 2.2 0.544 196 0.02 Highly recommended

Guide for Hypermer™ selection

Median Particle Size in 10% Cationic Polymer Emulsions Coagulum in 10% Cationic Polymer Emulsions Emulsion viscosity in 10% Cationic Polymer Formulations
0.7 0.7 800

0.6
Median Particle Size (microns)

600
Emulsion viscosity (cps)

0.5
0.6
Coagulum (wt%)

0.4
400
0.3
0.5
0.2
200
0.1

0.4 0 0
99

31

24

00

00

99

24

31

00

99

24

31
15

16

25

28

28

15

25

16

28

15

25

16
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rm

rm

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pe

pe

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pe

pe

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pe

pe

pe

pe

pe

pe
Hy

Hy

Hy

Hy

Hy

Hy

Hy

Hy

Hy

Hy

Hy

Hy
Typical formulation containing 30% anionic polymer
Component Parts by Weight (g)
45wt% Solids 35wt% Solids
Aqueous Phase:
Acrylamide 282 212
Acrylic Acid 121 91
NaOH 50% aquous solution to adjust pH to 6-7 N/A N/A
EDTA (5 wt% aq.) 4 4
Distilled Water 231 281
Potassium Bromate (1.5 wt% aq.) 8 8
CuSO4(5H20) (1wt% aq.) 4 4
Oil Phase:
Isoparaffinic Solvent 272 322
Surfactant 22 22
Initiatior:
Na-metabisulfite (0.15 wt% aq.) 16 16
Total: 1000 g 1000 g

The table below shows the results of a typical anionic inverse emulsion polymerisation using acrylic acid as the co-monomer.

Results
Surfactant Total solids Emulsifier Loading Median Particle Emulsion Coagulum Selection
(wt%) (wt%) Size (microns) viscosity (cps) (wt%) Guide
SMO/POESMO 35 2.2 0.38 221 0.40 Recommended
SMO/POESMO 45 Failed Failed Failed Failed NA
HYPERMER 1599 45 2.2 0.345 280 0.19 Recommended
HYPERMER 1083 45 2.2 0.427 154 0.79 Recommended
HYPERMER 1031 45 2.2 0.369 140 0.02 High Rec
HYPERMER 1631 45 2.2 0.295 112 0.59 Recommended
HYPERMER 2524 45 2.2 0.543 196 0.02 High Rec
HYPERMER 2800 45 2.2 0.818 182 0.02 High Rec

Guide for Hypermer™ selection

Median Particle Size in 30% Anionic Polymer Formulations Coagulum in 30% Anionic Polymer Formulations Emulsion viscosity in 30% Anionic Polymer Formulations
0.9 0.9 300

0.8
0.8
Median Particle Size (microns)

0.7
Emulsion viscosity (cps)

0.7
0.6 200
Coagulum (wt%)

0.6 0.5

0.5 0.4
0.3 100
0.4
0.2
0.3 0.1
0.2 0 0
31

99

31

83

24

00

31

24

00

99

31

83

31

31

83

00

24

99
16

15

10

10

25

28

10

25

28

15

16

10

16

10

10

28

25

15
er

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pe

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Hy

Hy

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Hy

Hy

Hy

Hy

Hy

Hy

Hy

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Hy

Hy
Typical formulation containing 70% anionic polymer
Component Parts by Weight (g)
45wt% Solids 35wt% Solids
Aqueous Phase:
Acrylamide 121 91
Acrylic Acid 282 212
NaOH 50% solution to adjust pH to 5-6 N/A N/A
EDTA (5 wt% aq.) 4 4
Distilled Water 233 283
Potassium Bromate (1.5 wt% aq.) 8 8
CuSO4(5H20) (1wt% aq.) 4 4
Oil Phase:
Isoparaffinic Solvent 274 324
Surfactant 22 22
Initiatior:
Na-metabisulfite (0.15 wt% aq.) 16 16
Total: 1000 g 1000 g

The table below shows the results of a high acid inverse emulsion polymerisation, using 30% acrylamide and 70% acrylic acid.

Results
Surfactant Total solids Emulsifier Loading Median Particle Emulsion Coagulum Selection
(wt%) (wt%) Size (microns) viscosity (cps) (wt%) Guide
Sorbitan Ester Control 35 Failed Failed Failed Failed Not suitable
Sorbitan Ester Control 45 Failed Failed Failed Failed Not suitable
HYPERMER 2800 45 2.2 1.044 32 0.02 Highly recommended

Conclusion
The Hypermer™ range are a unique set of polymeric surfactants that offer excellent emulsion stability while allowing high
temperature and vacuum processing to increase polymer/actives content. The use of Hypermers prevents coagulum
formation and gives very fine particle size and narrow particle size distribution. The ability to produce inverse polymer
emulsions at higher polymer loading while preserving a reduced viscosity further differentiates the Hypermer™ products
from other conventional stabiliser products.
Further information
Croda sales and distribution are coordinated through an extensive worldwide network of
associates and agents. If you would like product samples, formulation advice, or technical
assistance, please contact your nearest Croda regional office.

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email: marketing-usa@croda.com email: watertreatment@croda.com email: marketingla@croda.com email: is-asia@croda.com

www.croda.com/watertreatment
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