使用钕基催化剂体系对可持续萜烯单体进行配位链转移聚合

Coordinative Chain Transfer Polymerization of Sustainable Terpene Monomers Using a Neodymium-Based Catalyst System.

作者信息

Córdova Teresa, Enríquez-Medrano Francisco Javier, Cartagena Eduardo Martínez, Villanueva Arnulfo Banda, Valencia Luis, Álvarez Edgar Nazareo Cabrera, González Ricardo López, Díaz-de-León Ramón

机构信息

Research Center for Applied Chemistry, Enrique Reyna Hermosillo, No.140, Col. San Joseé de los Cerritos, Saltillo 25294, Mexico.

Biofiber Tech Sweden AB, Norrsken Hourse, Birger Jarlsgatan 57 C, SE-11356 Stockholm, Sweden.

出版信息

Polymers (Basel). 2022 Jul 17;14(14):2907. doi: 10.3390/polym14142907.

DOI:10.3390/polym14142907

PMID:35890683

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9324384/

Abstract

The present investigation involves the coordinative chain transfer polymerization (CCTP) of biobased terpenes in order to obtain sustainable polymers from myrcene (My) and farnesene (Fa), using the ternary Ziegler-Natta catalyst system comprising [NdV]/[Al(-Bu)H]/[MeSiCl] and Al(-Bu)H, which acts as cocatalyst and chain transfer agent (CTA). The polymers were produced with a yield above 85% according to the monomeric consumption at the end of the reaction, and the kinetic examination revealed that the catalyst system proceeded with a reversible chain transfer mechanism in the presence of 15-30 of CTA. The resulting polyterpenes showed narrow molecular weight distributions (M/M = 1.4-2.5) and a high percent of 1,4- microstructure in the presence of 1 . of MeSiCl, having control of the molecular weight distribution in Ziegler-Natta catalytic systems that maintain a high generation of 1,4- microstructure.

摘要

本研究涉及生物基萜烯的配位链转移聚合（CCTP），以便使用由[NdV]/[Al(-Bu)H]/[MeSiCl]和作为助催化剂和链转移剂（CTA）的Al(-Bu)H组成的三元齐格勒-纳塔催化剂体系，从月桂烯（My）和法尼烯（Fa）获得可持续聚合物。根据反应结束时的单体消耗情况，聚合物的产率高于85%，动力学研究表明，在存在15-30%的CTA时，催化剂体系以可逆链转移机理进行。所得聚萜烯在存在1%的MeSiCl时显示出窄的分子量分布（M/M = 1.4-2.5）和高比例的1,4-微结构，在保持高生成1,4-微结构的齐格勒-纳塔催化体系中控制了分子量分布。