LIVING RING-OPENING METATHESIS POLYMERIZATIONS OF 3,4-DIFUNCTIONAL CYCLOBUTENES
LIVING RING-OPENING METATHESIS POLYMERIZATIONS OF 3,4-DIFUNCTIONAL CYCLOBUTENES
复制标题
DOI：
10.1021/ma00113a062
复制
发表时间：
1995-04-24
期刊：
影响因子：
5.5
通讯作者：
NOVAK, BM
中科院分区：
文献类型：
--
作者：
PERROTT, MG;NOVAK, BM
开环易位聚合（ROMP）由于能够产生不饱和聚合物而一直受到关注。定义明确的亚烷基化合物的发展，既容忍各种各样的官能团，并提供了一个活的引发剂的聚合应变烯烃已经催生了进一步的增长，在这一领域。1我们一直对3，4-二取代环丁烯的ROMP感兴趣，其产生具有非常高的侧基官能团密度的聚合物，但基于共同的1，4-聚丁二烯主链。诸如酯、羧酸酯、醚和酰亚胺的官能团都已成功地并入。以乙炔和马来酸酐的光化学环加成反应生成的酸酐1，2为原料，合成了一系列高官能度的环丁烯，并通过开环聚合反应合成了高分子。由1合成了二乙酯2，3二甲酯3，4二苄酯4，苄基酰亚胺5，二甲醚6，二苄醚7和双环四氢呋喃8（图1）.最初的研究表明，所有这些环丁烯在适当的条件下使用Schrock亚烷基络合物I-III 5 * 6作为引发剂聚合（图1）以形成高度官能化的聚合物，其具有类似的结构。
Ring-opening metathesis polymerization (ROMP) has always held interest due to the ability to generate unsaturated polymers. The development of well-defined alkylidene compounds that are both tolerant of a wide variety of functional groups and provide a living initia-tor for polymerization of strained olefins has spawned further growth in this field. 1 We have been interested in ROMP of 3, 4-disubstituted cyclobutenes that yield polymers with a very high density of pendant functionalities but are based on the common 1, 4-polybutadiene backbone. Functional groups such as esters, carboxylates, ethers and imides have all been successfully incorporated. The generation of very polar homopoly-mers, block copolymers, and mixtures is demonstrated in this work.A wide variety of highly functionalized cyclobutenes, attractive for the synthesis of polymers via ROMP, were synthesized from the anhydride l, 2 which was made from the photochemical cycloaddition of acetylene and maleic anhydride. From 1 we have synthesized the diethyl ester 2, 3 dimethyl ester 3, 4 dibenzyl ester 4, benzyl imide 5, dimethyl ether 6, dibenzyl ether 7, and the bicyclic tetrahydrofuran 8 (Figure 1). Initial studies showed that all of these cyclobutenes polymerized under the appropriate conditions using the Schrock alkylidene complexes I—III5* 6 as initiators (Figure 1) to form highly functionalized polymers, possessing structures analo-