Reactive Compatibilization: Formation of Double-Grafted Copolymers by In Situ Binary Grafting and Their Compatibilization Effect

Reactive compatibilizers are usually used to enhance the compatibility of immiscible polymer blends. However, reactive linear compatibilizers containing reactive groups on the main chains form graft copolymers during reactive blending, and such graft copolymers with an asymmetric molecular structure are often "pulled in" or "pulled out" under mechanical shear. Double-grafted compatibilizers have a symmetric structure, and they usually exhibit higher compatibilizing efficiency. In this work, we propose a binary grafting strategy during melt blending to form compatibilizers located at the interface of an immiscible polymer blend. Specifically, poly(methyl methacrylate) (PMMA) oligomer with carboxylic end groups (PMMA-COOH) and poly(styrene-co-glycidyl methacrylate) (SG) copolymer were simultaneously incorporated into immiscible poly(vinylidene fluoride)/poly(l-lactic acid) (PVDF/PLLA) blends. The carboxylic acid groups of both the PMMA oligomer and PLLA can react with the epoxide groups on the SG main chains. Therefore, novel compatibilizing polymers with both PMMA and PLLA chains grafted onto the SG main chains form in situ. The grafted PMMA chains can entangle with PVDF, and the grafted PLLA chains are embedded in the PLLA phase, so the double-grafted copolymers act as effective compatibilizers for the PVDF/PLLA blends. Moreover, the effects of the PMMA molecular weight and PMMA loading (number of grafted PMMA side chains) on the compatibilization efficiency were investigated. The compatibilizing efficiency increases with increasing molecular weight and number of side chains in the ranges considered in this study. This one-pot synthesis of double-grafted compatibilizers by in situ grafting provides a new and simple method to prepare double-comb compatibilizers, and it offers the possibility of high-efficiency compatibilization.