Abstract
To induce degradabilities in polymers in response to environmental conditions, endm odification reactions of poly(α‐methylstyrene) (PMS) derivatives were carried out. 2‐Phenylallyl halide derivatives such as 2‐phenylallyl bromide, 2‐(p‐tolyl)allyl bromide, and α‐trifluoromethylstyrene were found to be suitable end‐modification agents. For example, the ω‐2‐phenylallyl‐PMS derivative was prepared with almost quantitative functionality by the reaction of the living PMS derivative with 2‐phenylallyl bromide. In a similar way, ω‐3,3‐difluoro‐2‐phenylallyl‐ and ω‐2‐(4‐toly)allyl‐PMS derivatives were synthesized. Based on thermogravimetric analysis, the onset of the degradation temperature of the endmodified PMS derivatives decreased in the following order: ω‐hydrogen‐ > ω‐3,3‐difluoro‐2‐phenylallyl‐ > ω‐2‐phenylallyl‐ > ω‐2‐(p‐tolyl)allyl‐PMS. Actually, the onset temperature of ω‐2‐(p‐tolyl)allyl‐PMS derivatives was 50°C lower than that of ω‐H‐PMS derivatives. These results indicate that the active species is produced effectively at the endunsaturated bond, which initiates depolymerization of the polymer at rather low temperatures. Therefore, it is concluded that a 2‐phenylallyl substituent at the end of the PMS chain induces effective degradation through a radical mechanism.