Cationic polymerization of α,β‐disubstituted olefins. VI. Steric structure of poly(methyl propenyl ether) obtained by cationic catalysts

The steric structure of poly(methyl propenyl ether) obtained by cationic polymerization was studied by NMR spectra. From the analysis of β‐methyl and α‐methoxyal spectra, it was found that the tacticities of the α‐carbon were different from those of the β‐carbon in all polymers obtained. In the crystalline polymers obtained from the trans isomer by homogeneous catalysts, BF 3 ·O(C 2 H 5 ) 2 or Al(C 2 H 5 )Cl 2 , and from the cis isomer by a heterogeneous catalyst, Al 2 (SO 4 ) 3 –H 2 SO 4 complex, the structure of polymers was threo‐di‐isotactic. Though the configurations of all α‐carbons were isotactic, a small amount of syndiotactic structure was observed in the β‐carbon. On the other hand, in the amorphous polymer obtained from cis isomer by the homogeneous catalyst, the configuration of the α‐carbon was isotactic, but that of the β‐carbon was atactic. These facts suggest that the type of opening of a monomeric double bond is complicated, or that carbon–carbon double bond in an incoming monomer rotates in the transition state. From these experimental results, a probability treatment was proposed from the diad tacticity of α,β‐disubstituted polymers. It shows that the tacticity is decided by a polymerization mechanism different from that proposed by Bovey.