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Synthesis of Sequential Wholly Aromatic Polyketones Having Terphenyl Moiety in the Main Chain

主链含三联苯的序列全芳香聚酮的合成

基本信息

批准号：
09650971
负责人：
YONEZAWA Noriyuki
金额：
$ 2.05万
依托单位：
Tokyo University of Agriculture and Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
1997
资助国家：
日本
起止时间：
1997 至 1998
项目状态：
已结题

项目摘要

The preparation of wholly aromatic polyketones having terphenyl skeleton in the main chain by aromatic coupling reaction of o-terphenyl derivative bearing two chlorobenzoyl moieties (a) and the synthesis and polymerization of novel monomers containing trifluoromethyl side group for sequential polymers having ring-assembly structures (b) were investigated. (a) Two synthetic routes for bis(p-chlorobenzoyl)-o-terphenyl monomer were studied. Cross-coupling synthesis of the monomer was unsuccessful because of the failure of double cross-aromatic coupling of adjacent carbons on the aromatic ring. Synthesis of the o-terphenyl monomer was achieved by chemo- and regioselective direct acylation of o-terphenyl by p-chlorobenzoic acid. Aromatic coupling reaction of the o-terphenyl monomer was carried by use of transition metal (nickel) complex catalyst having triphenylphosphine and bipyridyl ligands in the presence of zinc powder as reducing reagent in an aprotic polar solvent such as dimethylacet … More amide, N-methyl-2-pyrolidone, or dimethylformamide. Because of the precipitation of the product in the early stage of polymerization, high-molecular-weight was not achieved. The highest inherent viscosity of the polyketones obtained was 0.17 dL/g (0.3 g/dL in conc. H_2SO_4, 30ﾟC). The resulting polyketone has glass transition temperature (Tg) at 184ﾟC.The weight loss was not observed till 450ﾟC, and the 10%-weight loss temperature was found to be 570ﾟC.(b) The synthesis of sequential polyketones having ring-assembly skeleton and fluorine-containing side group was undertaken. Three types of monomers were synthesized : 1) self-polymerization type monomer for head-to-tail polymer skeleton having both an acyl cation accepting moiety and an electrophile part with high regioselectivity, 2) a symmetric macro-monomer having three biphenylene units with two carboxyl groups giving head-to-head type polyketone structure by the reaction with 2,2'-dimethoxybiphenyl, and 3) biphenylenedicarboxylic acid monomer bearing one trifluoromethyl group giving random sequenced polyketone molecule. The polymerization was undertaken through direct polycondensation in P_2O_5-MsOH.The resulting three types polyketones have molecular-weights of 2800(head-to-head polyketone), 3300(head-to-tail), and 5800(random) based on the terminating group analysis using ^1H-NMR spectra. Less

本文研究了含两个氯苯甲酰基团的邻苯甲酰衍生物(a)的芳香偶联反应制备主链上有三苯基骨架的全芳香聚酮，以及含三氟甲基侧基的环组装序贯聚合物(b)的新型单体的合成和聚合。(a)研究了双（对氯苯甲酰）-邻苯基单体的两条合成路线。由于芳香环上相邻碳的双交叉芳香偶联失败，导致单体的交叉偶联合成失败。对氯苯甲酸通过化学选择性和区域选择性的直接酰化反应合成了邻terphenyl单体。采用以三苯基膦和联吡啶为配体的过渡金属（镍）络合催化剂，以锌粉为还原剂，在非质子极性溶剂如二甲基乙酸、n -甲基-2-吡啶酮或二甲基甲酰胺中进行邻三苯基单体的芳族偶联反应。由于产物在聚合初期析出，没有得到高分子量的产物。所得聚酮的最高固有粘度为0.17 dL/g （conc为0.3 g/dL）。H_2so_4, 30 / h / c)。所得聚酮的玻璃化转变温度（Tg）为184℃。直到450ºC才出现失重现象，10%失重温度为570ºC。(b)进行了具有环组装骨架和含氟侧基的序贯聚酮的合成。合成了三种单体：1)自聚合型单体，具有首尾相连的聚合物骨架，具有酰基阳离子接受部分和高区域选择性的亲电部分；2)对称大单体，具有三个联苯单元和两个羧基，通过与2,2'-二甲氧基联苯反应形成首尾相连的聚酮结构；3)带有一个三氟甲基的联苯二羧酸单体，产生随机序列的聚酮分子。聚合是通过在P_2O_5-MsOH中直接缩聚进行的。所得的三种聚酮的分子量分别为2800（头对头聚酮），3300（头对尾）和5800（随机），基于终止基分析使用^1H-NMR光谱。少