中华医学超声杂志

应用化学 ›› 2011, Vol. 28 ›› Issue (09): 1006-1011.DOI: 10.3724/SP.J.1095.2011.00708

• 研究论文 • 上一篇    下一篇

无定型聚芳醚酮的氯甲基化改性

贾宝珠1,2,王红华2,崔善子1*,周光远2*   

  1. (1.长春工业大学化学工程学院 长春 130012；2.中国科学院长春应用化学研究所 长春 130022)
  • 收稿日期:2010-11-26 修回日期:2011-01-06 出版日期:2011-09-10 发布日期:2011-09-10
  • 通讯作者: 崔善子，教授; Tel:0431-87015543; Fax:0431-85716462; E-mail:cui-shan-zi@163.com; 研究方向：高分子材料的老化
  • 基金资助:
    吉林省科技发展重大项目(20106017)

The Chloromethylation of a Phenolphthalein Polyetherketone Resin

JIA Baozhu1,2, WANG Honghua2, CUI Shanzi1*, ZHOU Guangyuan2*   

  1. (1.School of Chemical Engineering,Changchun University of Technology,Changchun 130012;
    2.Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022)
  • Received:2010-11-26 Revised:2011-01-06 Published:2011-09-10 Online:2011-09-10

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摘要：

采用硫酸作溶剂及催化剂，1,4-二氯甲氧基丁烷（BCMB）为氯甲基化试剂，在均相反应体系中对酚酞聚芳醚酮（PEK-C）进行氯甲基化改性。 采用无致癌性的BCMB作为氯甲基化试剂实现了环境友好，并且成本低，效率高。 试验结果表明，反应机理由苯环亲电取代与亲核取代2种反应构成。 为避免交联反应的发生，反应要在较低温度下进行（10~30 ℃）。 在此温度范围内可制得氯甲基化程度达3.4且完全线型的氯甲基化酚酞聚芳醚酮。 通过反应温度及时间可对树脂氯甲基化程度（χCH2Cl-）实施有效的调控。 CMPEK-C的结构由IR和1H NMR进行了表征，测定了CMPEK-C的Tg与χCH2Cl-之间的依赖关系及CMPEK-C的耐热及溶解性能。

关键词: 酚酞聚芳醚酮（PEK-C）, 氯甲基化反应, 高分子改性

Abstract:

A detailed research on the chloromethylation process was carried out. The chloromethylation of a phenolphthalein polyetherketone resin(PEK-C) was performed in a homogeneous reaction system using 1,4-bis(chloromethoxyl)butane as the chloromethylation reagent and concentrated sulforic acid as the solvent and catalyst. This method is environmentally friendly because of the absence of cancerogenic toxicity of BCMB. Furthermore, this method is more economical because of the low cost of BCMB. The effects of various factors on the chloromethylations were examined. The chemical structure and composition of the chloromethyled phenolphthalein polyetherketone resin(CMPEK-C) were characterized by Fourier transform infrared spectroscopy(FT-IR) and nuclear magnetic resonance(1H NMR). The experimental results show that the reaction mechanism consists of two kinds of reactions including electrophilic substitution on benzene ring and nucleophilic substitution accompanying by ether linkage fissiond. During the process in preparing CMPEK-C, along with the increase of chlorine content, Friedel-Crafts crosslinking reaction will occur. To prepare the chloromethylated PEK-C with high chlorine content and without obvious cross-linking, the suitable reaction conditions, such as reaction time, temperature influence and the used amount of 1,4-bis(chloromethoxy)butane(BCMB), need to be controlled. The reaction should be carried out at lower temperatures(about 10~30 ℃) because of the sensitivity of Friedel-Crafts reaction to temperature. Namely, there are two types of effects of reaction conditions on the chloromethylation of PEK-C, one is the influence on PEK-C chloromethylation degree, and the other is the influence on the remaining linearity for PEK-C. The CMPEK-C with 3.4 of chloromethylation degree and complete linearity was obtained under the optimized reaction conditions. The properties of CMPEK-C such as solubility in common organic solvents and thermal stability compared with PEK-C were also studied.

Key words: phenolphthalein polyetherketone resin(PEK-C), chloromethylation reaction, polymer modification

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