Ring-opening metathesis polymerization of cyclooctene derivatives with chain transfer agents derived from glycerol carbonate
Ring-opening metathesis polymerization of cyclooctene derivatives with chain transfer agents derived from glycerol carbonate
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DOI：
10.1039/c3py01639k
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发表时间：
2014-01-01
影响因子：
4.6
通讯作者：
Carpentier, Jean-Francois
中科院分区：
文献类型：
--
作者：
Diallo, Abdou K.;Annunziata, Liana;Carpentier, Jean-Francois
在作为链转移剂（CTA）的碳酸甘油酯（GC）的乙烯基或丙烯酰基衍生物的存在下，通过环辛烯（COE）衍生物的季铵盐催化的开环易位聚合（ROMP），已经实现了各种单-和二-（碳酸甘油酯）遥爪聚烯烃的合成。基于SEC和1H-1 NMR分析的反应监测表明，ROMP通过首先形成α-GC，ω-乙烯基-聚（环辛烯）（PCOE）中间体进行，其最终随时间演变成α，ω-二（GC）-PCOE。溶剂的性质被证明对单/双遥爪PCOE的反应速率和最终选择性都具有显著影响。3-烷基（甲基、乙基、正己基）-取代的COE（3-R-COE）的ROMP由于活性中间体周围的空间位阻而仅得到α-GC，ω-乙烯基-聚（3-R-COE），而5-乙基取代的COE（5-Et-COE）使得能够接近相应的α，ω-二（GC）-聚（5-Et-COE）。还实现了在丙烯酰基-GC作为CTA存在下5，6-环氧-、5-羟基-和5-氧代-官能化的COE的ROMP，由前两种单体提供在两端具有GC端基的聚合物，而在后一种情况下观察到单-和二-GC封端的P（5-O=COE）的60：40混合物。
The synthesis of a variety of mono-and di-(glycerol carbonate) telechelic polyolefins has been achieved upon ruthenium-catalyzed ring-opening metathesis polymerization (ROMP) of cyclooctene (COE) derivatives in the presence of a vinyl or acryloyl derivative of glycerol carbonate (GC) acting as a chain-transfer agent (CTA). Reaction monitoring based on SEC and H-1 NMR analyses suggested that the ROMP proceeds through the formation of first the alpha-GC,omega-vinyl-poly(cyclooctene) (PCOE) intermediate, which eventually evolves over time into the alpha,omega-di(GC)-PCOE. The nature of the solvent was shown to have a significant impact on both the reaction rates and the eventual selectivity for the mono-/di-telechelic PCOE. ROMP of 3-alkyl (methyl, ethyl, n-hexyl)-substituted COEs (3-R-COEs) afforded only the alpha-GC, omega-vinyl-poly(3-R-COE)s, as a result of the steric hindrance around the active intermediate, while a 5-ethyl substituted COE (5-Et-COE) enabled access to the corresponding alpha,omega-di(GC)-poly(5-Et-COE). The ROMP of 5,6-epoxy-, 5-hydroxy- and 5-oxo-functionalized COEs in the presence of acryloyl-GC as the CTA has also been achieved, affording from the first two monomers polymers with GC end-groups at both extremities, while a 60 : 40 mixture of mono-and di-GC terminated P(5-O=COE) was observed in the latter case.