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

刚性主链梳状聚合物及其结晶

• 批准号: 63470097
• 负责人: YOKOTA Kenji
• 金额: $ 3.9万
• 依托单位: Nagoya Institute of Technology, Dept. of Engineering
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1988
• 资助国家: 日本
• 起止时间: 1988 至 1989
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-63470097/
• 关键词: Comb-like polymer; Crystallization; Alternating styrene-acrylic ester copolymer; Polyester; Polyacetylene; Polyamide; Differential Scanning Calorimetry; 剛直高分子; 長鎖アルキル基

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.

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，并通过 DSC 方法测定了侧链结晶程度。1）交替苯乙烯-丙烯酸烷基酯共聚物，其中甲基累积两个单体单元的α位均被取代：苯乙烯单元中甲基和苯基的累积取代使共聚物主链变得越来越刚性，并抑制了侧链的结晶程度。2)由 2-烷基丙二醇和脂肪族二酸制成的聚酯：二酸直至二十二烷二酸，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。与聚合物一样，尽管它们的齿间隙很宽，但侧链结晶很容易发生。主链亚甲基也参与结晶。3）聚乙炔：采用W和Mo催化剂，由1-炔烃得到高分子量的聚乙炔。与相应的聚烯烃相比，聚乙炔的刚性主链由于其碳-碳双键而抑制了侧链结晶。4) 由 2-烷基三亚甲基二胺和脂肪族二酸制成的聚酰胺：酰胺键中 C-N 的双键特征使主链刚性化，侧链结晶程度比相应的聚酯梳状聚合物小。综上所述，各种材料的侧链结晶程度根据我们的结晶梳状聚合物的结构模型，梳状聚合物受到聚合物主链的刚性（或柔性）的影响。

项目成果

平林忠道,菊田友子,笠坊和生,横田健二: Polymer Journal. 20. 693-698 (1988)

Tadamichi Hirabayashi、Tomoko Kikuta、Kazuo Kasabo、Kenji Yokota：《聚合物杂志》20. 693-698 (1988)。

横田健二,大坪正男,平林忠道: "Synthesis of Polyacetylene-Type Comb-Like Polymers and Their Side-Chain Crystallization" Polymer Journal.

Kenji Yokota、Masao Otsubo、Tadamichi Hirabayashi：“聚乙炔型梳状聚合物的合成及其侧链结晶”聚合物杂志。

平林忠道,菊田友子,笠坊和生,横田健二: "Main-Chain Flexibility and Side-Chain Crystallization of Widely Spaced Comb-Like Polymers" Polymer Journal. 20. 693-698 (1988)

Tadamichi Hirabayashi、Tomoko Kikuta、Kazuo Kasabo、Kenji Yokota：“宽间隔梳状聚合物的主链灵活性和侧链结晶”聚合物杂志 20. 693-698 (1988)。

Kenji Yokota, Masao Ohtubo, and Tadamichi Hirabayashi: "Synthesis of Polyacetylene-Type Comb-Like Polymers and Their Side-Chain Crystallization" Polymer Journal.

Kenji Yokota、Masao Ohtubo 和 Tadamichi Hirabayashi：“聚乙炔型梳状聚合物的合成及其侧链结晶”聚合物杂志。

Tadamichi Hirabayashi, Tomoko Kikuta, Kazuo Kasabou, and Kenji Yokota: "Main-Chain Flexibility and Side-Chain Crystal-lization of Widely Spaced Comb-Like Polymers" Polymer Journal Vol. 20, No. 8, pp 693-698 1988.

Tadamichi Hirabayashi、Tomoko Kikuta、Kazuo Kasabou 和 Kenji Yokota：“宽间隔梳状聚合物的主链柔性和侧链结晶”聚合物杂志卷。