AbstractThis article focuses on the synthesis and thermal properties of poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s with regulated regio- and stereochemistry. Pd complexes with diimine ligands promote controlled isomerization polymerization of 4-alkylcyclopentenes to afford polymers with 1,3-trans-cyclopentylene groups and oligomethylene spacers alternating along the polymer chain. Pd complexes with a C2 symmetric structure enable isospecific polymerization of 4-alkylcyclopentenes, and the resultant isotactic polymers show liquid-crystalline properties. Cyclopolymerization of 1,6-heptadiene by bis(imino)pyridine Fe and Co catalysts produces poly(ethylene-1,2-cyclopentylene) with cis and trans-stereochemistry, respectively. Synthesis of poly(oligomethylene-1,4-cyclohexylene)s with trans or cis structure can be achieved by Pd-catalyzed isomerization polymerization of alkenylcyclohexanes or methylenecyclohexanes. The polymers with 1,4-trans-cyclohexylene show a high melting point that depends on the length of the oligomethylene spacer in the polymer. The thermal properties of the poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s are compared to those of previously reported polymers with different regio- or stereochemistry.Synthesis and thermal properties of poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s with regulated regio- and stereochemistry are described. Pd complexes with diimine ligands promote controlled isomerization polymerization of 4-alkylcyclopentenes and alkenylcyclohexanes to afford poly(oligomethylene-1,3-cyclopentylene)s with trans structure and poly(oligomethylene-1,4-cyclohexylene)s with trans or cis structure, respectively. Poly(ethylene-1,2-cyclopentylene) with cis and trans-stereochemistry can be obtained by Fe- and Co-catalyzed cyclopolymerization of 1,6-heptadiene, respectively. The thermal properties of the poly(oligomethylene-cyclopentylene)s and poly(oligomethylene-cyclohexylene)s are compared to those of previously reported polymers with different regio- or stereochemistry.

中文翻译：

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具有调节区域和立体化学的聚（低聚亚甲基-亚环烷基）的合成和热性能

摘要本文重点研究具有调节区域和立体化学的聚（低聚亚甲基-亚环戊基）和聚（低聚亚甲基-亚环己基）的合成和热性能。与二亚胺配体的 Pd 配合物促进 4-烷基环戊烯的受控异构化聚合，以提供具有 1,3-反式环戊烯基团和沿聚合物链交替的低聚亚甲基间隔基的聚合物。具有 C2 对称结构的 Pd 配合物可实现 4-烷基环戊烯的等规聚合，所得等规聚合物显示出液晶特性。双（亚氨基）吡啶 Fe 和 Co 催化剂对 1,6-庚二烯的环聚合分别产生具有顺式和反式立体化学的聚（乙烯-1,2-环戊烯）。聚（低聚亚甲基-1，具有反式或顺式结构的4-亚环己基可以通过Pd催化的烯基环己烷或亚甲基环己烷的异构化聚合来实现。具有 1,4-反式-亚环己基的聚合物显示出高熔点，这取决于聚合物中低聚亚甲基间隔基的长度。将聚（低聚亚甲基-亚环戊基）和聚（低聚亚甲基-亚环己基）的热性能与先前报道的具有不同区域或立体化学的聚合物的热性能进行比较。聚（低聚亚甲基-环戊基）和聚（低聚亚甲基-环戊基）的合成和热性能描述了具有调节的区域和立体化学的低聚亚甲基-亚环己基。与二亚胺配体的 Pd 配合物促进 4-烷基环戊烯和烯基环己烷的受控异构化聚合，得到聚（低聚亚甲基-1，分别具有反式结构的 3-亚环戊基和具有反式或顺式结构的聚（低聚亚甲基-1,4-亚环己基）。具有顺式和反式立体化学的聚（乙烯-1,2-环戊烯）可以分别通过 Fe 和 Co 催化的 1,6-庚二烯环聚合反应获得。将聚（低聚亚甲基-亚环戊基）和聚（低聚亚甲基-亚环己基）的热性能与先前报道的具有不同区域或立体化学的聚合物的热性能进行比较。