Comb-Like Polymers with Rigid Main-Chain and Their Crystallization

为了研究该项目，合成了4种具有长烷基侧链的梳状聚合物，并用DSC法测定了侧链结晶的程度。1)交替苯乙烯-烷基丙烯酸酯共聚物，两个单体单元α -位置的甲基被累积取代：苯乙烯单元中甲基和苯基的累积取代使共聚物主链越来越刚性，抑制了侧链的结晶程度。2)由2-烷基三亚甲基二醇和脂肪二酸合成的聚酯：二酸到苯二酸，因此研究了每15、19、23、26个主链原子上出现烷基齿的梳状聚合物。在这种柔性聚酯型梳状聚合物中，尽管它们的齿隙很宽，但侧链结晶容易发生。主链亚甲基也参与了结晶。3)聚乙炔：用W和Mo催化剂从1-炔中得到高分子量的聚乙炔。与相应的聚烯烃相比，由于其碳碳双键，聚乙烯烃的刚性主链抑制了侧链结晶。4)由2-烷基三亚甲二胺和脂肪二酸制成的聚酰胺：酰胺链中C-N的双键特性使得主链刚性，侧链结晶程度小于相应的聚脂梳状聚合物。综上所述，根据我们的梳状聚合物结晶结构模型，各种梳状聚合物的侧链结晶受到聚合物主链的刚度（或柔韧性）的影响。

To investigate the titled project, 4 types of comb-like polymers with long alkyl side chains were synthesized and the extent of the side-chain crystallization was determined by DSC method.1) Alternating styrene-alkyl acrylate copolymers, in which methyl groups were cumulatively substituted at the alpha-positions of both monomer units: Cumulatively substituted methyl groups and the phenyl group in the styrene unit made the copolymer main-chain increasingly rigid and suppressed the extent of crystallization of the side-chain.2) Polyesters from 2-alkyltrimethylene glycols and aliphatic diacids: Diacids up to henicosanedioic acid, and therefore comb-like polymers with the alkyl teeth appearing on every 15, 19, 23, 26 main-chain atoms were studied.In such flexible polyester type comb-like polymers, side chain crystallization occurred easily in spite of their wide teeth spaces. The main-chain methylenes were also participated in the crystallization.3) Polyacetylenes: High molecular weight polyacetylenes were obtained from 1-alkynes by using W and Mo catalysts. The rigid main-chain of polyacetylenes due to their carbon-carbon double bonds suppressed the side-chain crystallization when compared to the corresponding polyolefins.4) Polyamides from 2-alkyltrimethylene diamines and aliphatic diacids: The double bond character of C-N in the amide linkage made the main-chain rigid and the extent of side-chain crystallization was smaller than the corresponding polyester comb-like polymers.In summary, it was shown that the side-chain crystallization of various comb-like polymers was influenced by the rigidness (or flexibility) of the polymer main-chain in accordance with our structural model of crystallized comb-like polymers.