AM2Net Advanced Macromolecular Materials By Transition Metal Catalysis; Group 2: "Post Metallocene Catalysis"; Functional and segmented copolymers via post-metallocene catalysis

通过烯烃、苯乙烯和极性烯烃与环己二烯的催化共聚，结合催化后聚合官能化，将制备新型聚烯烃和环烯烃共聚物。特别强调的是在主链或侧链中含有芳烃或低聚芳烃的“自增强”聚烯烃的开发。芳烃是通过氧化相应的环己烯单元的环己二烯共聚物得到的。将在高通量实验中检查各种茂金属和其他单点催化剂，包括从项目合作伙伴获得的新催化剂系统，以考察其环己二烯共聚能力。为了实现对烯烃/环己二烯共聚反应的控制，将通过反应红外光谱对配体和催化剂体系进行绘图，并对共聚反应进行在线监测。将进行波谱结构分析，以确定基本结构/性能相关性，并建立对所得共聚物的快速在线分析。主链上含有环己烯单元的烯烃/环己二烯共聚物将通过氢化、氧化、氢甲酰化等方法进行改性，得到各种新的功能聚烯烃。聚合物模拟氧化将被优化，以制备含有刚性芳烃和低聚芳烃单元的新型聚烯烃。将研究热、机械、形态和流变性，特别强调在熔融加工和分子增强过程中低聚芳烃链段自组装的作用。官能化刚性共聚物将用作工程热塑性塑料的共混组分。

Novel families of polyolefins and cycloolefin copolymers will be prepared by catalytic copolymerization of olefins, styrene and polar olefins with cyclohexadiene combined with catalytic postpolymerization functionalization. Special emphasis is being placed upon the development of "self-reinforced" polyolefins containing arylene or oligoarylene in the backbone or the side chain. Arylenes are obtained by oxidation of corresponding cyclohexene units of cyclohexadiene copolymers. Various metallocene and other single-site catalysts, including new catalyst systems obtained from the project partners, will be examined in high-throughput experiments with respect to their abilities of cyclohexadiene copolymerization. Mapping of ligand and catalyst systems and on-line monitoring of copolymerization reactions by means of ReactIR will be performed in order to achieve control of olefin/cyclohexadiene copolymerization. Spectroscopic structure analyses will be performed in order to identify basic structure/property correlations and to establisth rapid on-line analysis of the resulting copolymers. The olefin/cyclohexadiene copolymers containing cyclohexene units in the backbone will be modified by means of hydrogenation, oxidation, hydroformylation to produce a variety of new functional polyolefins. Polymer analoguous oxidation will be optimized to prepare novel polyolefins containing rigid arylene and oligoarylene units. Thermal, mechanical, morphological and rheological properties will be investigated with special emphasis being placed upon the role of at self-assembly of oligoarylene segments during melt processing and molecular reinforcement. Functionalized rigid copolymers will be used as blend components of engineering thermoplastics.