立构规整性二氧化碳共聚物:从无定型到结晶型材料转变
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- 英文论文题名：Stereoregular CO_2 copolymers:from Amorphous to Crystalline Materials
- 论文作者：刘野 ; 任伟民 ; 吕小兵
- 英文论文作者：Ye Liu ; Wei-Min Ren ; Xiao-Bing Lu ; State Key Laboratory of Fine Chemicals ; Dalian University of University
- 年：2016
- 作者机构：大连理工大学精细化工国家重点实验室;
- 论文关键词：二氧化碳 ; 聚碳酸酯 ; 结晶 ; 立构规整性 ; 立体复合物
- 会议召开时间：2016-07-02
- 会议录名称：中国化学会第30届学术年会摘要集-论坛七：青年化学家论坛
- 语种：中文
- 分类号：O635
- 学会代码：ZGHY
- 会议名称：中国化学会第30届学术年会-论坛七 ; 青年化学家论坛
- 会议地点：中国辽宁大连
- 主办单位：中国化学会
- 学会名称：中国化学会
- 页数：1
- 文件大小：217k
- 原文格式：D
- 会议级别：全国
摘要
由二氧化碳与环氧烷烃交替共聚合成降解性聚碳酸酯是重要的绿色聚合反应之一[1,2]。然而,先前发展的二氧化碳基聚碳酸酯是非晶且玻璃化转变温度较低,存在高温强度迅速变差等问题。通过立构规整性聚合使碳酸酯单元在主链上有序排列是该类聚碳酸酯结晶的主要途径[3]。最近,作者利用所发展的手性优势双核钴催化剂[4,5],高效实现了二氧化碳与各种内消旋环氧烷烃的不对称交替共聚合反应,聚合产物的对映选择性高达99%,获得了系列结晶性的二氧化碳聚碳酸酯[6,7],但仍有许多手性聚碳酸酯是完全无定型的。进一步研究发现,不管是可结晶还是无定型的具有相同结构但不同构型的手性聚碳酸酯经简单的自组装,可以形成高结晶性的聚碳酸酯,耐热性能明显提高[8]。同时发现,具有不同结构和不同构型的无定型手性聚碳酸酯经简单的自组装也能形成结晶性材料[9]。采用外消旋催化剂,通过不同构型催化剂分子之间链穿梭,成功获得结晶性聚碳酸酯[10]。
Selective transformation of CO2 into degradable polycarbonates by the alternating copolymerization with epoxides represents an important green polymerization process.Although the commercialization of CO2 copolymers(CO2-based polycarbonates) has already obtained certain progress in recent years,the further development of this green technology is suffering from material performance as well as product type etc.The main problem is that all the previously reported CO2 copolymers are amorphous and have low glass transition temperatures,which make the strength sharply decrease at enhanced temperatures.Recently,we developed highly active dinuclear bimetallic complex catalysts for the enantioselective copolymerization of various meso-epoxides with CO2,affording the copolymers with >99% carbonate linkages and ≥99% enantioselectivity.A series of crystalline CO2 copolymers were found.Notably,it was found that the cocrystallization of crystalline or amorphous isotactic polycarbonates with identical or different chemical structures and opposite configurations provided novel crystalline stereocomplexes.
Selective transformation of CO2 into degradable polycarbonates by the alternating copolymerization with epoxides represents an important green polymerization process.Although the commercialization of CO2 copolymers(CO2-based polycarbonates) has already obtained certain progress in recent years,the further development of this green technology is suffering from material performance as well as product type etc.The main problem is that all the previously reported CO2 copolymers are amorphous and have low glass transition temperatures,which make the strength sharply decrease at enhanced temperatures.Recently,we developed highly active dinuclear bimetallic complex catalysts for the enantioselective copolymerization of various meso-epoxides with CO2,affording the copolymers with >99% carbonate linkages and ≥99% enantioselectivity.A series of crystalline CO2 copolymers were found.Notably,it was found that the cocrystallization of crystalline or amorphous isotactic polycarbonates with identical or different chemical structures and opposite configurations provided novel crystalline stereocomplexes.
引文
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[3]Lu,X.-B.;Ren,W.-M;Wu,G.-P.Acc.Chem.Res.2012,45:1721.
[4]Liu,Y.;Ren,W.-M;Liu,J.;Lu,X.-B.Angew.Chem.,Int.Ed.2013,52:11594.
[5]Liu,Y.;Ren,W.-M;Liu,C.;Fu,S.;Wang,M.;He,K.-K.;Li,R.-R.;Zhang,R.;Lu,X.-B.Macromolecules 2014,47:7775.
[6]Liu,Y.;Ren,W.-M;He,K.-K.;Lu,X.-B.Nature Communication 2014,5:5687.
[7]Liu,Y.;Wang,M.;Ren,W.-M;He,K.-K.;Xu,Y.-C;Liu,J.;Lu,X.-B.Macromolecules 2014,47,1269.
[8]Liu,Y.;Ren,W.-M;Wang,M.;Liu,C.;Lu,X.-B.Angew.Chem.Int.Ed.2015,54:2241.
[9]Liu,Y.;Wang,M.;Ren,W.-M;Xu,Y.-C;Lu,X.-B.Angew.Chem.Int.Ed.2015,54 7042.
[10]Liu,Y.;Ren,W.-M;Zhang,W.-P.;Zhang,R.-R.Nature Communication 2015,6:.8594
[2]Luinstra,G.A.Polym.Rev.2008,48:192.
[3]Lu,X.-B.;Ren,W.-M;Wu,G.-P.Acc.Chem.Res.2012,45:1721.
[4]Liu,Y.;Ren,W.-M;Liu,J.;Lu,X.-B.Angew.Chem.,Int.Ed.2013,52:11594.
[5]Liu,Y.;Ren,W.-M;Liu,C.;Fu,S.;Wang,M.;He,K.-K.;Li,R.-R.;Zhang,R.;Lu,X.-B.Macromolecules 2014,47:7775.
[6]Liu,Y.;Ren,W.-M;He,K.-K.;Lu,X.-B.Nature Communication 2014,5:5687.
[7]Liu,Y.;Wang,M.;Ren,W.-M;He,K.-K.;Xu,Y.-C;Liu,J.;Lu,X.-B.Macromolecules 2014,47,1269.
[8]Liu,Y.;Ren,W.-M;Wang,M.;Liu,C.;Lu,X.-B.Angew.Chem.Int.Ed.2015,54:2241.
[9]Liu,Y.;Wang,M.;Ren,W.-M;Xu,Y.-C;Lu,X.-B.Angew.Chem.Int.Ed.2015,54 7042.
[10]Liu,Y.;Ren,W.-M;Zhang,W.-P.;Zhang,R.-R.Nature Communication 2015,6:.8594