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二氧化碳共聚物的基本问题研究

批准号20634040 学科分类消化系统肿瘤 ( H1617 )
项目负责人郑华川 负责人职称 依托单位中国科学院长春应用化学研究所
资助金额0.00
万元
项目类别青年科学基金项目 研究期限2007 年 01 月 01 日 至
2010 年 12 月 31 日
中文主题词二氧化碳共聚物;催化剂;共聚反应;聚合物结构;非石油路线
英文主题词carbon dioxide copolymer; catalyst; copolymerization; intermolecular interaction; non-petroleum route

摘要

中文摘要 针对二氧化碳共聚物面临的催化剂活性较低、聚合物一次结构、聚集态结构难以控制等问题,主要开展以下研究:.1)合成了热稳定的SalenCo(III)和双功能催化剂;研制出高立体选择性的手性铬配合物催化剂;将衍生化的联-2-萘酚和有机碱TBD同时引入Salen配体,设计合成了新型的多手性位点的(S,S,S)-SalenCo(III)X 催化剂,具有近乎完美的区域选择性和良好的立体选择性。.2)提出了二氧化碳与环氧烷烃在三价钴离子中心上的高效配位聚合反应机理,证明锚定在配体上的位阻性有机碱所形成的碳酸酯单元中间体在聚合过程中的可逆配位与解离是稳定三价钴中心的主因。.3)通过制备交联型PPC,使其长期使用温度从250提高到650oC;采用富含羟基和氨基的酰化十二烷基壳聚糖、氨酯化合物等与PPC共混,引入分子间氢键增强分子间相互作用;引入可结晶的生物降解聚合物,同时实现了PPC的增韧和增强,为PPC薄膜专用料的研制提供了扎实的理论基础。.4)确立了从糠醛出发合成呋喃环氧单体的非石油路线,采用稀土三元催化剂合成了新型二氧化碳共聚物,并解决了聚合物中呋喃环的易氧化问题,获得了空气氛下稳定的聚合物。
英文摘要 Carbon dioxide copolymer is a biodegradable polymer from alternating copolymerization of CO2 and epoxide, it is an old polymer with new concept, but faces main challenges like low catalytic activity, difficulty for structure control. In this project, our research focused on high activity and high selectivity catalysts, definite structure copolymer and its copolymerization mechanism, intermolecular chain interaction, and non-petroleum route to new carbon dioxide based copolymer, the main results were summarized as follows:.1) Single site SalenCo(III) catalyst as well as bifunctional catalyst were prepared, which showed turnover frequency of 10000/h even at 1000C and extremely low catalyst concentration, while the obtained polymer showed carbonate content of over 99%, number average molecular weight of over 100 kg/mol; By means of weakening the acidity of central metal ion while raising the steric hindrance of the ligands, chiral Cr complex catalyst with high stereoselectivity was prepared, the obtained polymer showed carbonate content of over 99% and head-to-tail linkage of over 93%; Derivative of 2-binaphthol and steric-hindrance organic base TBD were introduced into Salen ligand to synthesize a multi-chral site catalyst (S,S,S)-SalenCo(III)X, which displayed excellent regioselectivity and stereoselectivity, giving polymer with head-to-tail linkages of over 99%, and its catalytic dynamic difference constant of (Krel) was as high as 24.4;.2) The importance of efficient coordination of CO2 and epoxide with Co(III) on copolymerization reaction was disclosed, the reversible complexation and dissociation of carbonate intermediate formed by the organic base anchored on the ligand in the complex was the main reason for stabilizing Co(III); As far as the electrophilc-nucleophilic bi-component SalenCo(III) catalyst or bi-functional single-component SalenCo(III) catalyst was concerned, the alternative growth and decomposition of polycarbonate chain upper and down in the Salen plane also stabilized the Co(III), which can catalyze the copolymerization at high temperature and low CO2 pressure..3) Crosslinkable poly(propylene carbonate)(PPC) was prepared, the long term use temperature of PPC was raised from 250C to 650C; Intermolecular chain interaction of PPC was enhanced by introducing hydroxyl group or amine group rich components like o-lauroyl chitosan, low molecular weight urethane, and hyperbranched polyesteramide, the mechanical and thermal performances of PPC were improved significantly, simultaneous toughening and plasticizing were realized, the elongation at break increased by 4-60 times while the tensile strength was maintained above 25MPa;Toughening and plasticizing of PPC were also realized by introducing crystallizable biodegradable plastics, the dart impact of the film was over 120g, and the film can resist -150C, well comparable with high density polyethylene(HDPE), opening a new era for film application of PPC.. 4) New epoxide monomer like furfural glycidyl ether was prepared from furfural, which can copolymerized with CO2 under rare earth ternary catalyst, and a new non-petroleum route to carbon dioxide copolymer was disclosed, the obtained copolymer showed number average molecular weight of 120 kg/mol, glass transition temperature of 4.9 0C, though it was unstable due to the oxidation reaction of furan ring, it can be stabilized by anti-oxidant, and air stable polymer can also be obtained by Diels-Alder reaction of furan ring.
结题摘要 针对二氧化碳共聚物面临的催化剂活性较低、聚合物一次结构、聚集态结构难以控制等问题,主要开展以下研究: 1)合成了热稳定的SalenCo(III)和双功能催化剂;研制出高立体选择性的手性铬配合物催化剂;将衍生化的联-2-萘酚和有机碱TBD同时引入Salen配体,设计合成了新型的多手性位点的(S,S,S)-SalenCo(III)X 催化剂,具有近乎完美的区域选择性和良好的立体选择性。 2)提出了二氧化碳与环氧烷烃在三价钴离子中心上的高效配位聚合反应机理,证明锚定在配体上的位阻性有机碱所形成的碳酸酯单元中间体在聚合过程中的可逆配位与解离是稳定三价钴中心的主因。 3)通过制备交联型PPC,使其长期使用温度从250提高到650oC;采用富含羟基和氨基的酰化十二烷基壳聚糖、氨酯化合物等与PPC共混,引入分子间氢键增强分子间相互作用;引入可结晶的生物降解聚合物,同时实现了PPC的增韧和增强,为PPC薄膜专用料的研制提供了扎实的理论基础。 4)确立了从糠醛出发合成呋喃环氧单体的非石油路线,采用稀土三元催化剂合成了新型二氧化碳共聚物,并解决了聚合物中呋喃环的易氧化问题,获得了空气氛下稳定的聚合物。

成果

序号 标题 类型 作者
1 CATALYTIC MECHANISM OF TERNARY RARE-EARTH-MATAL COORDINATION CATALYSTS IN THE COPOLYMERIZATION OF CARBON DIOXIDE AND EPOXIDE 期刊 Wang Fosong|Zhao Xiaojiang|Zhang Yaming|Chen Yuyan|Min Jiadong|Wang Xianhong|
2 Synthesis and Stabilization of Novel Aliphatic Polycarbonate from Renewable Resource 期刊 Wang, Fosong|Qiao, Lijun|Chen, Xuesi|Zhao, Xiaojiang|Hu, Yuxi|Qin, Yusheng|Wang, Xianhong|
3 COPOLYMERIZATION OF FURFURYL GLYCIDYL ETHER AND CARBON DIOXIDE 期刊 Wei Jun|Hu Yuxi|Qiao Lijun|Wang Fosong|Hou Jiqiang|Zhao Xiaojiang|Wang Xianhong|
4 Alternating copolymerization of carbon dioxide and propylene oxide by single-component cobalt salen complexes with various axial group 期刊 Zhao, Xin|Liu, Binyuan|Yang, Min|Wang, Xianhong|Gao, Yanhao|Guo, Hongfei|
5 Binding of 4-(N,N-dimethylamino)pyridine to Salen- and Salan-Cr(III) Cations: A Mechanistic Understanding on the Difference in Their Catalytic Activity for CO2/Epoxide Copolymerization 期刊 Zhang, Rong|Li, Bo|Wang, Hui|Rao, Dun-Yan|Lu, Xiao-Bing|

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