Facile synthesis of quantitatively tertiary-amine functionalized poly(styrene-co-1,3pentadiene) copolymers with controlled narrow composition distributions by LAP

Abstract

Designing and controlling of the copolymer composition distribution (CCD) and quantitative functionalization degree (QFD) of polyolefin is the key to obtain the tailor-made properties. In this paper, three kinds of tertiary-amine functional monomers, including vinylbenzyl-N,N-dimethylamine (VBDMA), (vinylbenzyl)pyrrolidine (VBTHP) and vinylbenzyl-piperidine (VBMP), were designed and synthesized, and the living ternary anionic polymerization of styrene (ST), 1,3-pentadiene (PD) and N-functional monomers was conducted in cyclohexane with n BuLi as initiator above room temperature. The constant CCD control and quantitative functionalization of poly(ST-co-PD) copolymers were realized by utilizing the in situ copolymerization strategy and the own weak regulation effect of tertiary amine polar monomers.The copolymerization kinetics was investigated in detail, and the microstructure characteristics of the functionalized products were characterized by 1 H NMR, FTIR and DSC analysis. In conclusion, we found a suitable method for quantitative introduction of tertiary amine functional groups into the narrow CCD polymer chain under mild polymerization conditions, which provides a feasible way for further study of the relationship between sequence distribution and properties of functional polyolefin materials.