New Chemistries and Technologies Derived from a Common Reaction of α‐Methylstyrene at 61 °C

Abstract

In textbooks, there is a dynamic equilibrium between the monomer α‐methylstyrene (AMS) and its polymer (PAMS) when the temperature is greater than 61 °C. When giving these phenomena deliberate thought we come to the basic conclusion that there probably exists a dynamic equilibrium between fragmentation and coupling of polymeric chains by a radical mechanism when heated. Thus, a systematic exploration of the synthesis of AMS copolymers as potential sources of chain radicals has been carried out in our laboratory. This paper reviews the results we have achieved in the past decade: (1) The preparation of various AMS copolymers including (meth) acrylate, acrylic acid, styrene, and maleic anhydride. (2) The application of copolymers containing AMS structural units as very efficient free radical initiators. (3) The preparation of various functional copolymers including block copolymers and core‐shell polymer particles with AMS copolymers as macroinitiators. (4) The steady increase of the molecular weight of the copolymer with the monomer conversion for some systems, which is characteristic of living polymerization. (5) The finding that AMS copolymers with functional groups can act as in situ compatibilizers through the formation of graft polymers, and that AMS copolymers can be used to modify MWCNTs by a free radical grafting‐onto mechanism.