Volume contraction, vinyl monomer

It seems that increasing the surfactant concentration causes thinning of the films between adjacent droplets of dispersed phase. Above a certain level, the films become so thin that on polymerisation, holes appear in the material at the points of closest droplet contact. A satisfactory explanation for this phenomenon has not yet been postulated [132], It is evident, however, that the films must be intact until polymerisation has occurred to such an extent as to lend some structural stability to the monomer phase if not, large-scale coalescence of emulsion droplets would occur yielding a poor quality foam. In general, vinyl monomers undergo a volume contraction on polymerisation (i.e. the bulk density increases) and in the limits of a thin film, this effect may play a role in hole formation, especially at higher conversions in the polymerisation process. 

T he initiating effect of phenylacetaldehyde on the copolymerization of unsaturated polyesters with vinyl monomers has been described (9). The copolymerization proceeds at approximately the same rate as with the usual peroxide catalysts, but the reaction is much less exothermic hence, the effects of too rapid a polymerization such as fissures, bubble formation, and volume contraction do not occur. Investigation of a series of compounds of the benzene family showed that only enolizable phenyl-keto compounds were initiators (7). 

The chain reaction process can be used as a diagnostic aid to determine whether free radicals are generated from a drug when irradiated. Acrylamide is an acrylic monomer, which is widely used in gel electrophoresis, as a polymer formed in situ by peroxide or UV-initiated polymerization. This monomer is a water soluble solid, more easily handled than most other vinyl monomers, and the progress of its polymerization can be readily followed by measuring its contraction in volume utilizing dilatometry, or its increase in viscosity in a viscometer. Details of this experimental technique can be found in Moore and Burt (18). 

Continuous Dilatometric Measurement of y-Emulsion Polymerization. Polymerization of vinyl monomers causes a volume contraction up to 27% (vinyl acetate) of the volume of the monomer. This shrinkage is proportional to conversion and can be linearly interpolated, however consult Treloar (37). The dila-... 

The van der Waals bonds between monomer molecules are replaced by covalent bonds between the monomeric units in polymerization. Since van der Waals bond lengths are about 0.3-0.5 nm and covalent bond lengths are, in contrast, about 0.14-0.19 nm, a general contraction occurs. The contraction increases with decreasing monomer molecule size, since more van der Waals bonds per unit mass must be eliminated. Thus, ethylene contracts by about 66%, vinyl chloride by about 34%, styrene by about 14%, and W-vinyl carbazole by as little as about 7.5%. Polymerization of ethylene oxide leads to a volume contraction of 23%, of tetrahydrofuran to one of about 10%, but that of octamethyl cyclotetrasiloxane, however, to a contraction of only 2%. Some strained bicyclic ring systems even polymerize with an expansion. With polycondensation, the volume contraction is smaller with decreasing size of eliminated residue. Polycondensation of hexamethylene diamine with adipic acid leads to a contraction of 22% (water elimination), that of hexamethylene diamine and dioctyl phthalate, on the other hand, to one of 66% (elimination of octanol). 

---