Polymerization of allyl esters of unsaturated acids. IV. Cyclopolymerization of diallyl maleate

Abstract

SynopsisRadical polymerization of diallyl maleate is kinetically discussed in terms of cyclopolymerization using 2,2'-azobisisobutyronitrile as an initiator and benzene as a solvent a t 60°C. Thus, the kinetic equations involving bicyclo-intramolecular cyclization are derived by assuming steady-state conditions for the different types of radicals, and various parameters involved in the equations are then estimated approximately from an extension of the corresponding model experimental results. The validity of these treatments is confirmed from the comparison with the experimental data including the relationships between the contents of the unreacted allylic and maleic double bonds and the monomer concentrations. In addition, the sequence distribution of the structural units of the polymer produced is discussed; for example, the content of the bicyclic structural units is estimated to be 47.2% a t a 10% dilution of the pure monomer. EXPERIMENTALDAM, a commercially available reagent, was distilled in vacuo under nitrogen. 2,2'-Azobisisobutyronitrile (AIBN) as an initiator and benzene as a solvent were purified by conventional methods. Polymerization procedure and analyses of polymers obtained were similar to the methods described in a previous article.'

Synthesis and polymerization of multiallyl monomer in matrix of poly(methacryloyl chloride)

“…The polymerization of allyl monomers results usually in polymers of low molecular weights due to the degradative chain transfer.'1. '6i22* 23, 25 Th e results of the MW measurements of the obtained polymers, shown in Table I, should be considered as approximate and semi-quantitative since the values of molecular weights vary with the time of centrifuging the sample solution. This would suggest the presence of branched structures (microgels) which on centrifuging migrate to the bottom of the measuring cell and bring about decrease in the Mw value.…”

Polymerization of allyl esters of unsaturated acids. VIII. Highly enhanced polymerizability of allyl maleates by the use of morpholine

“…Analyses of residual double bonds of the polymers were carried out in a similar manner as described previously (1,8,9). The composition of the copolymer was calculated from the carbon content.…”

Polymerization of allyl esters of unsaturated acids. VII. Copolymerization of methyl allyl maleate and fumarate with styrene

“…We have studied kinetically in detail the polymerization mechanism of allyl esters of unsaturated acids bearing two different types of carbon-carbon double bonds in terms of cyclopolymerization. [1][2][3][4][5][6] In particular, the difference in polymerization behaviors between two isomeric monomers, i.e., maleates and fumarates, was remarkable, as reflected in the rate and degree of polymerization, gelation, and cyclopolymerization results, including the contents of the unreacted allylic and vinylic double bonds, the cyclic structural units, and the five-membered ring of the resulting polymer.…”