By Frank A. Bovey (Eds.)
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Example text
The following initiation scheme may be written for the M n ( C O ) - C C l system (Bamford and Denyer, 1966). The trichloromethyl radical is the initiating species. 2. /CH 3 x CH X 3 CH 3 Propagation Propagation involves the successive addition of m o n o m e r units to the active radicals generated in the initiation step. 4, addition occurs in the head-to-tail con figuration. In dienes with isolated double bonds, both bonds can react independently of each other and cross-linking can result. In certain cases, cooperative addition reactions of one double b o n d to the other on the same molecule lead to polymers with cyclic repeating units in a process known as cyclopolymerization (McCormick and Butler, 1972; Solomon, 1975).
Effect of Temperature. The effect of temperature on the rate of polymerization and molecular weight is of prime importance in polymer production. Quantitatively, temperature effects are complex since R depends on a combination of three rate constants, fc , / c , and k . 19) E/RT where A is the collision frequency factor and Ε the activation energy, then the temperature dependence of the ratio k (kjk ) in Eq. 20) 2. , initiation by thermal decomposition of a chemical initiator, E is of the order of 3 0 - 4 0 kcal/mole for the chemical initiators commonly used.
The active species then reacts with the m o n o m e r Μ to produce an activated molecule by opening the double bond. R* + Μ RM' Polymerization then proceeds by successive addition of further m o n o m e r molecules t o the activated end of the growing chain. Thus the mechanism is termed addition or chain polymerization and polymers from this type of reaction are called addition polymers. The addition of m o n o m e r molecules to the activated chain end is known as propagation and this reaction will proceed until the reactive center is de stroyed by one of a number of termination reactions or until the supply of monomer is exhausted.