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Stereoselective Ring-Opening Deacetonation Polymerization of Racemic 2,2,5-Trimethyl-1,3-dioxolan-4-one by Using Homosalen–Aluminum Complexes: A Novel Approach to Isotactic ­Poly(rac-lactic acid)
Synlett ( IF 1.7 ) Pub Date : 2023-07-04 , DOI: 10.1055/s-0042-1751472
Kazuho Sakai , Yusuke Yagi , Nobuyoshi Nomura

A novel approach is reported for the synthesis of the highly isotactic poly(racemic lactic acid) [P(rac-LAA)] from racemic 2,2,5-trimethyl-1,3-dioxolan-4-one by using achiral homosalen–Al catalysts. The polymerization proceeded through two steps: stereoselective ring-opening and deacetonation. The effects of substituents on the homosalen–Al catalyst were clarified regarding the polymerization rates and polydispersity of the obtained P(rac-LAA), but were still unclear regarding the iso-stereoselectivity. The P(rac-LAA) obtained by using an isopropyl-substituted homosalen–Al catalyst showed the highest isotacticity (P m = 0.96), a moderate number-average molecular weight (M n = 6,200), and broad polydispersity (PDI = 2.20). Differential scanning calorimetric measurements indicated that the polymer was semicrystalline with a melting temperature of 156 °C.



中文翻译:

使用 Homosalen-铝配合物进行外消旋 2,2,5-三甲基-1,3-二氧戊环-4-酮的立体选择性开环脱丙酮聚合:全同立构聚(外消旋乳酸)的新方法

报道了一种利用非手性的homosalen从外消旋2,2,5-三甲基-1,3-二氧戊环-4-酮合成高度全同立构聚(外消旋乳酸)[P( rac -LAA)]的新方法。铝催化剂。聚合反应通过两个步骤进行:立体选择性开环和脱丙酮。取代基对Homosalen-Al催化剂的影响在所得P( rac -LAA)的聚合速率和多分散性方面得到阐明,但在异构立体选择性方面仍不清楚。使用异丙基取代的homosalen-Al催化剂得到的P( rac -LAA)表现出最高的全同立构规整度( P m = 0.96)、适中的数均分子量( M n = 6,200) 和广泛的多分散性 (PDI = 2.2 0 )。差示扫描量热测量表明该聚合物是半结晶的,熔化温度为156℃。

更新日期:2023-07-05
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