CHARACTERISTICS AND REACTIVITY PARAMETERS OF VEOVA MONOMERS

VV 0.1 Issued January 2001

Monomer characteristics
VeoVa 9, VeoVa 10 and VeoVa 11 represent a family of vinyl ester monomers with a unique highly branched carbon-rich structure (Figure 1). Their principal use is as modifying comonomers in vinyl and acrylic polymerisation. Typical properties and specifications are listed in their product data sheets. VeoVa 9, 10 and 11 are monomers with many similarities. Their main characteristics are as follows: A branched tertiary structure with bulky and hydrophobic hydrocarbon groups (Figure 1). 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 (Figure 2). 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.

O C H2C HC O

CH3 R1 R2
of VERSATIC 9, 10, 11

VINYL ESTER

Similar reactivity to vinyl acetate producing random copolymers Easily copolymerisable with ethylene, acrylates and methacrylates

Hydrophobic UV Resistant Hydrolytically stable Non-Hazardous

Figure 1: Structure of VeoVa monomers where R1 and R2 are (branched) alkyl groups containing together 6, 7 or 8 carbon atoms for VeoVa 9, 10 and 11 respectively.

H 2O

OH
H 2O

H2O

OH

H 2O H 2O

OH

OH

Polymer chain protected vinyl acetate VeoVa

Figure 2: Protection of vinyl acetate against hydrolysis by adjacent VeoVa groups 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 (Table 1), and consequently to a different behaviour as modifying comonomers. Whereas VeoVa 9 provides rigidity to the copolymer, VeoVa 10 is known as a flexibilising comonomer and VeoVa 11 is an even more efficient flexibiliser.

Table 1: Tg of homopolymers of VeoVa.

Monomer VeoVa 9 VeoVa 10 VeoVa 11 Tg (C) +70 -3 -40

(Glass transition temperature as described in VeoVa Technical Bulletin 6.1)

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 the monomers used (Table 2). VeoVa monomers copolymerise very easily with other vinyl esters, ethylene and most acrylic monomers.

VV 0.1

Page 2 of 4

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 (Table 2). During emulsion or solution polymerisation, VeoVa and vinyl acetate are converted at the same rate as illustrated in Figure 3. 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 to 80C, with potassium persulphate as initiator.

Table 2: Reactivity ratios of vinyl ester monomers with other monomer types
Monomer 1 styrene 2-ethylhexylmethacrylate methyl methacrylate ethyl acrylate butyl acrylate vinyl acetate Monomer 2 VeoVa 10 VeoVa 10 VeoVa 10 VeoVa 10 vinyl acetate VeoVa 9 ethylene VeoVa 10 VeoVa 9 ethylene Temp. (C) 140 170 140 170 60 60 60 60 130 r1 25 23 10.5 3.6 20 6 13.94 0.99 0.93 1.02 r2 0.04 0.06 0.08 0.06 0.015 0.10 0.01 0.92 0.90 0.97 Source 2 2 2 2 1 2 1 1 1 1

1.

2.

Young, Polymer handbook, Chapter II, J. Brandrub, E.H. Immergut and W. McDowell, Eds., Wiley-Interscience, NewYork, 1975. Laboratory measurements

Instantaneous conversion (%) 20 40 60 80 100

VeoVa 10 Vinyl acetate Start monomer addition

End monomer addition

0 0

50

100

150

200 250 Time (min)

300

350

400

Figure 3: Vinyl acetate and VeoVa 10 instantaneous monomer conversion determined by Gas Chromatography during a semi-continuous emulsion polymerisation process.
VV 0.1 Page 3 of 4

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 a 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. Methacrylate monomers can be polymerised with VeoVa monomers in any desired ratio. For acrylate monomers, there are some restrictions in emulsion polymerisation that are further explained in the VeoVa Technical Bulletin VV 2.4 series.

Reactivity of VeoVa monomers with styrene

VeoVa monomers do not polymerise with styrene in emulsion. 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 temperature around 160C are described in separate bulletins.

Handling precautions
For more detailed information on all aspects relating to Health, Safety and Handling, reference should be made to the Safety Data Sheets of VeoVa monomers, which are available from your local Resolution representative or distributor. The precautions advised therein should be strictly observed. For such details related to other products listed in this bulletin, please contact the suppliers of those products.

VeoVa and Versatic are trademarks of Resolution Performance Products. The information contained in this publication is to the best of our knowledge, true and accurate, but any recommendations or suggestions which may be made are without guarantee, since the conditions of use are beyond our control. Furthermore, nothing contained herein shall be construed as a recommendation to use any product in conflict with existing patents covering any material or its use.

VV 0.1

Page 4 of 4