环氧苯乙烷与二氧化碳共聚物微结构的研究
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摘要
二氧化碳(CO2)的利用和捕集已经成为世界范围内备受关注的战略性研究课题。在CO2参与的众多反应中,与环氧烷烃共聚反应是最有潜力的绿色聚合过程之一。该领域的研究重点是选择性催化制备高分子量和高碳酸酯结构单元含量的聚合物,而更具挑战性的研究内容则是如何有效地调控聚合产物的性能及其立体化学。本论文研究了环氧苯乙烷与CO2的不对称交替共聚,重点从聚合产物区域规整性和立构规整性的精确调控以及热力学性能的稳定提高方面开展以下工作：
针对环氧苯乙烷/CO2共聚物微结构(区域规整性和立构规整性)归属尚不清楚的问题,论文首先以外消旋2-甲氧基-1-苯基乙醇和2-甲氧基-2-苯基乙醇为反应底物,合成了三种不同连接方式的二元寡聚碳酸苯乙烯酯模型化合物,并通过碳核磁共振研究明确地表征了环氧苯乙烷/CO2交替共聚物的区域规整性；以外消旋环氧苯乙烷水解动力学拆分及羟基保护合成的手性2-甲氧基-2-苯基乙醇和2-甲氧基-1-苯基乙醇为反应原料,制备了十种具有不同手性中心排布方式的二元寡聚碳酸苯乙烯酯模型化合物,并通过其碳核磁共振研究,为评价环氧苯乙烷/CO2共聚物的立构规整性建立了数据平台。
将衍生化的联-2-萘酚和大位阻金刚烷基团同时引入Salen配体,合成出一种多手性位点的SalenCo(Ⅲ)X配合物作为主催化剂,以2,4-二硝基苯酚化双(三苯基正膦基)亚铵(PPN-DNP)为助催化剂,组成的具有双功能协同作用的催化体系,在温和条件下就能实现(R)-环氧苯乙烷与CO2的不对称、区域和立体选择性交替共聚反应。利用建立起的环氧苯乙烷/CO2共聚物微结构表征数据平台,评价制备出的聚碳酸苯乙烯酯产物,发现其具有良好的区域规整性和立构规整性。聚合物的头-尾连接单元含量为92.2%,立构规整度为96.0%。通过差示扫描量热法(DSC)对上述聚合物热力学性能研究发现,其抗热形变能力较无规聚碳酸苯乙烯酯有一定的提高,玻璃化转变温度(Tg)从80℃提高到90℃。
Utilization and capture of carbon dioxide (CO2) has become a strategic research topic which drew much worldwide attentions. The alternating copolymerization of epoxides and CO2produce biodegradable polycarbonates is one of the most attractive processes for the transformation of CO2due to its economic and environmental benefits. The catalytic synthesis of polycarbonates with high molecular weight and high carbonate linkages is one of the most important issues, while the accurate control of polymer properties and its stereochemistry remains challenge. This dissertation focuses on the asymmetric regio-and stereo-selective alternating copolymerization of styrene oxide and CO2with emphasis of regio-and stereochemistry, and thermodynamic properties.
Concerning on the issue that micro structures (regio-and stereo-chemistry) of copolymer from styrene oxide and CO2have not been identified clearly, three kinds of model compounds bearing different linkages were synthesized from racemic2-methoxy-2-phenylethanol and2-methoxy-1-phenylethanol. Therefore, the regional regularity of the copolymer from styrene oxide and CO2was characterized explicitly by the13C NMR studies of those model compounds. Ten kinds of model compounds with different stereochemistry were synthesized to simulate carbonate unit sequence using chiral2-methoxy-2-phenylethanol and2-methoxy-1-phenylethanol as substrates, which prepared by hydrolytic kinetic resolution of racemic styrene oxide and then protection of the hydroxyl groups. The13C NMR studies of those model compounds provided a data platform to test the microstructures of copolymer from styrene oxide and CO2.
A binary catalyst systems with a SalenCo(III)X complex in which bi(2-naphthol) and bulky sterically hindered adamantyl group were anchored on the ligand framework as catalyst and PPN-DNP as cocatalyst was developed. This catalyst system showed promising activity toward asymmetric regio-and stereo-selective alternating copolymerization of (R)-styrene oxide and CO2under mild conditions. According to the above-established data of microstructural characterization, the synthesized poly (styrene carbonate) has92.2%head-to-tail content and a highly regioregular ring-opening step was observed with a concomitant96.0%retention of configuration. The thermal deformation ability of the above poly (styrene carbonate)(Tg=90℃) has been improved compared with atactic poly (styrene carbonate)(Tg=80℃).
针对环氧苯乙烷/CO2共聚物微结构(区域规整性和立构规整性)归属尚不清楚的问题,论文首先以外消旋2-甲氧基-1-苯基乙醇和2-甲氧基-2-苯基乙醇为反应底物,合成了三种不同连接方式的二元寡聚碳酸苯乙烯酯模型化合物,并通过碳核磁共振研究明确地表征了环氧苯乙烷/CO2交替共聚物的区域规整性；以外消旋环氧苯乙烷水解动力学拆分及羟基保护合成的手性2-甲氧基-2-苯基乙醇和2-甲氧基-1-苯基乙醇为反应原料,制备了十种具有不同手性中心排布方式的二元寡聚碳酸苯乙烯酯模型化合物,并通过其碳核磁共振研究,为评价环氧苯乙烷/CO2共聚物的立构规整性建立了数据平台。
将衍生化的联-2-萘酚和大位阻金刚烷基团同时引入Salen配体,合成出一种多手性位点的SalenCo(Ⅲ)X配合物作为主催化剂,以2,4-二硝基苯酚化双(三苯基正膦基)亚铵(PPN-DNP)为助催化剂,组成的具有双功能协同作用的催化体系,在温和条件下就能实现(R)-环氧苯乙烷与CO2的不对称、区域和立体选择性交替共聚反应。利用建立起的环氧苯乙烷/CO2共聚物微结构表征数据平台,评价制备出的聚碳酸苯乙烯酯产物,发现其具有良好的区域规整性和立构规整性。聚合物的头-尾连接单元含量为92.2%,立构规整度为96.0%。通过差示扫描量热法(DSC)对上述聚合物热力学性能研究发现,其抗热形变能力较无规聚碳酸苯乙烯酯有一定的提高,玻璃化转变温度(Tg)从80℃提高到90℃。
Utilization and capture of carbon dioxide (CO2) has become a strategic research topic which drew much worldwide attentions. The alternating copolymerization of epoxides and CO2produce biodegradable polycarbonates is one of the most attractive processes for the transformation of CO2due to its economic and environmental benefits. The catalytic synthesis of polycarbonates with high molecular weight and high carbonate linkages is one of the most important issues, while the accurate control of polymer properties and its stereochemistry remains challenge. This dissertation focuses on the asymmetric regio-and stereo-selective alternating copolymerization of styrene oxide and CO2with emphasis of regio-and stereochemistry, and thermodynamic properties.
Concerning on the issue that micro structures (regio-and stereo-chemistry) of copolymer from styrene oxide and CO2have not been identified clearly, three kinds of model compounds bearing different linkages were synthesized from racemic2-methoxy-2-phenylethanol and2-methoxy-1-phenylethanol. Therefore, the regional regularity of the copolymer from styrene oxide and CO2was characterized explicitly by the13C NMR studies of those model compounds. Ten kinds of model compounds with different stereochemistry were synthesized to simulate carbonate unit sequence using chiral2-methoxy-2-phenylethanol and2-methoxy-1-phenylethanol as substrates, which prepared by hydrolytic kinetic resolution of racemic styrene oxide and then protection of the hydroxyl groups. The13C NMR studies of those model compounds provided a data platform to test the microstructures of copolymer from styrene oxide and CO2.
A binary catalyst systems with a SalenCo(III)X complex in which bi(2-naphthol) and bulky sterically hindered adamantyl group were anchored on the ligand framework as catalyst and PPN-DNP as cocatalyst was developed. This catalyst system showed promising activity toward asymmetric regio-and stereo-selective alternating copolymerization of (R)-styrene oxide and CO2under mild conditions. According to the above-established data of microstructural characterization, the synthesized poly (styrene carbonate) has92.2%head-to-tail content and a highly regioregular ring-opening step was observed with a concomitant96.0%retention of configuration. The thermal deformation ability of the above poly (styrene carbonate)(Tg=90℃) has been improved compared with atactic poly (styrene carbonate)(Tg=80℃).
引文
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