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Product Bulletin

Coatings / Paints / Additives / Adhesives


VeoVa Monomers
Characteristics and Reactivity Parameters

VeoVa 9 monomer and VeoVa 10


monomer represent a family of vinyl
ester monomers with a unique, high-

VeoVa 9 and 10 are monomers with


many similarities. Their main
characteristics are as follows:

ly branched, carbon-rich structure.


Their principal use is as modifying
comonomers in vinyl and acrylic
polymerisation. Typical properties
and specifications are listed in their
respective product data sheets.

A branched tertiary structure with


bulky and hydrophobic hydrocarbon
groups. This provides the monomers
with a very low surface tension and
a hydrophobic nature. As a consequence, the monomers possess a
strong resistance to saponification.
Furthermore, VeoVa monomers do
not degrade under the influence of UV
light.
Reactivity: VeoVa monomers polymerise with various other comonomers through reaction of their vinyl
ester functional group. In this way,
the specific properties of the VeoVa
monomers can be imparted to their
copolymers.

CH 3

O
C
CH 2

CH

R1

R2

Structure of VeoVa monomers where R1 and R2 are


(branched) alkyl groups containing 6 or 7 carbon
atoms for VeoVa 9 and 10 monomers respectively.

Vinyl Ester
Structure and Properties:
Similar reactivity to vinyl acetate producing random copolymers

Easily copolymerisable with ethylene,


acrylates and methacrylates
Versatic Acid 9 and 10

Structure and Properties:


Hydrophobic

UV resistant

Hydrolytically stable

Non-hazardous

Protection of vinyl acetate


against hydrolysis by adjacent
VeoVa monomer groups

H2O

OH

H2O

OH

H2O

H2O

H2O

OH

OH

Polymer chain
Protected
vinyl acetate

The various VeoVa monomers mainly


differ in the degree of branching and the
length of the hydrocarbon groups. This
leads to differences in the glass transition temperature of their homopolymers,
and consequently to a different behaviour as modifying comonomers. Whereas VeoVa 9 monomer provides rigidity
to the copolymer, VeoVa 10 monomer is
known as a flexibilising comonomer.

Reactivity of VeoVa monomers

VeoVa monomers can be used with a


variety of other monomer types to produce copolymers. The ease of polymerisation depends on the reactivity ratios of

VeoVa monomer

Tg of homopolymers
Monomer

Tg [ C ]

VeoVa 9

+ 70

VeoVa 10

-3

the monomers used. VeoVa monomers


copolymerise very easily with other
vinyl esters, ethylene and most acrylic
monomers.

Reactivity ratios of vinyl ester monomers with other monomer types


Monomer 2

Temp. [ C ]

r1

r2

Source

Styrene

VeoVa 10
VeoVa 10

140
170

25
23

0.04
0.06

2
2

2-Ethylhexylmethacrylate

VeoVa 10
VeoVa 10

140
170

10.5
3.6

0.08
0.06

2
2

Monomer 1

Methyl Methacrylate

Vinyl Acetate

60

20

0.015

Ethyl Acrylate

VeoVa 9

60

0.10

Butyl Acrylate

Vinyl Acetate

5.89

0.05

Vinyl Acetate

VeoVa 10
VeoVa 9
Ethylene

60
60
130

0.99
0.93
1.02

0.92
0.90
0.97

1
1
1

Young, Polymer handbook, Chapter II, J. Brandrub, E.H. Immergut


and W. McDowell, Eds., Wiley-Interscience, New York, 1975
2 Laboratory measurements

Reactivity of VeoVa monomers


with vinyl acetate

VeoVa monomers are commonly used


as comonomers for vinyl acetate in
emulsion polymerisation because they
exhibit a similar reactivity. During emulsion or solution polymerisation, VeoVa
monomer and vinyl acetate are converted at the same rate. They can be copolymerised in any desired ratio, producing

polymers with a random microstructure.


This allows the key performance characteristics of VeoVa monomers to be
fully exploited. Commonly used emulsion polymerisation temperatures are in
the range of 76 80 C, with potassium
persulphate as initiator.

Vinyl acetate and VeoVa 10 instantaneous monomer conversion determined by


Gas Chromatography during a semi-continuous emulsion polymerisation process

Instantaneous conversion [ % ]

100

80

60
Start
monomer addition

End
monomer addition

Post cooling allows reducing


the residual monomer content
down to < 100 ppm levels

40

20

50

100

150

200

250

300

350

400

Time [ min ]
VeoVa 10

Vinyl acetate

Reactivity of VeoVa monomers


with (meth)acrylates

VeoVa monomers can be polymerised


with acrylate and methacrylate monomers in emulsion, in solution or in bulk.
Optimum results are generally obtained
by using a semi-continuous process.
This results in better control of the reactor temperature and in polymers with a
more random microstructure.

For emulsion polymerisation, a slightly


higher reaction temperature of 85C is
recommended to achieve a more random polymer structure. For solution or
bulk polymerisation, the best results are
obtained at 140C and above.

Reactivity of VeoVa monomers


with styrene

VeoVa monomers do not polymerise


with styrene in emulsions. Higher
temperatures are required to achieve
good control over the reaction, and
acrylate monomers should be present

to bridge the reactivity differences.


Suitable recipes for solution and mass
polymerisation at temperatures around
160C are described in separate bulletins.

Handling precautions

For more detailed information on all


aspects of Health, Safety and Handling,
please reference the Safety Data Sheets
of VeoVa monomers, which are available
from your local Momentive representative or distributor. The precautions

advised therein should be strictly observed. For details related to other products listed in this bulletin, please contact
the suppliers of those products.

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