Vinyl acetate chain-transferring impurities

Table 10.1 presents typical specifications for a polymerization-grade product, as well as some physical properties. Prohibited impurities refer to inhibitors (croton-aldehyde, vinyl acetylene), chain-transfer agents (acetic acid, acetaldehyde, acetone) and polymerizable species (vinyl crotonate), while methyl and ethyl acetate impurities are tolerated. [Pg.288]

Chain transfer also occurs to the emulsifying agents, leading to their permanent iacorporation iato the product. Chain transfer to aldehydes, which may be formed as a result of the hydrolysis of the vinyl acetate monomer, tends to lower the molecular weight and slow the polymerisation rate because of the lower activity of the radical that is formed. Thus, the presence of acetaldehyde condensates as a poly(vinyl alcohol) impurity strongly retards polymerisation (91). Some of the initiators such as lauryl peroxide are also chain-transfer agents and lower the molecular weight of the product. [Pg.466]

In cationic polymerizations, electron-deficient initiators (mostly Bronsted or Lewis acids) react with electron-rich monomers. The active chain end (ACE) bears a positive charge with the active sites being either carbenium or 0x0-nium ions. Molecular weights are often limited by the inherent sensitivity to impurities, chain transfer, and rearrangement reactions. Suitable monomers for cationic polymerizations are vinyl monomers with electron-donating moieties or cyclic structures containing heteroatoms, while the latter case is termed cationic ROP. Eligible monomers include cyclic ethers, acetals, and amines as well as lactones and lactams (Scheme 3). [Pg.573]