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

Abstract

Controlling the copolymer composition distribution (CCD) and achieving quantitative functionalization of polyolefins are essential for tailoring material properties. In this paper, three tertiary-amine functional monomers, vinylbenzyl-N,N-dimethylamine (VBDMA), (vinylbenzyl)pyrrolidine (VBTHP) and vinylbenzyl-piperidine (VBMP), were designed and synthesized. Living ternary anionic copolymerizations of styrene (ST), 1,3-pentadiene (PD) and these functional monomers were conducted in cyclohexane using ⁿBuLi as an initiator at temperatures above room temperature. By exploiting the in situ copolymerization strategy and the intrinsic weak regulatory effect of the tertiary amine polar monomers, copolymers with a constant CCD and quantitative functionalization were successfully obtained. The copolymerization kinetics were systematically investigated, and the microstructures of the functionalized products were characterized by ¹H NMR, FTIR and DSC analysis. This work establishes a facile and efficient method for the quantitative incorporation of tertiary amine functional groups into polymer chains with narrow CCD under mild polymerization conditions, offering a promising platform for elucidating the relationship between sequence distribution and the properties of functional polyolefin materials.