含苯并咪唑酮结构双酚A型聚芳醚酮共聚物的制备和表征

doi:10.11944/j.issn.1000-0518.2015.05.140330

摘要/Abstract

摘要：

通过双酚A-4, 4'-二氟二苯甲酮-苯并咪唑酮(BPA-DFK-HBI)无规共聚得到一系列聚芳醚酮共聚物。采用亲核缩聚和C—N偶联缩聚的方法, 获得了高相对分子质量聚合物。通过红外、核磁等技术手段表征了聚合物的结构, DSC、TGA分析了聚合物的热性能。结果表明, 随着苯并咪唑酮加入量的增大, 共聚物对DMF、NMP等极性溶剂的耐溶剂性能得到提升, 热稳定性增强, 玻璃化转变温度(T_g)也明显提高, T_g最高可达236 ℃。当苯并咪唑酮与双酚A的摩尔比大于7:3时, 溶解性降低, 反应出现前期沉淀, 难以得到高相对分子质量的聚合物。

关键词: 聚芳醚酮, 苯并咪唑酮, 双酚A, 共聚物, 特种工程塑料

Abstract:

A series of random copolymers of poly(aryl ether ketone) was prepared by copolymerization of bisphenol A, 4, 4'-difluorobenzophenone and benzimidazolone(BPA-DFK-HBI). High relative molecular mass copolymers were prepared via the nucleophilic polycondensation and C—N coupling polycondensation. The structure of the copolymers was characterized by FTIR and ¹H NMR. The heat resistant properties of the copolymers were studied by DSC and TGA. As the feed ratio of benzimidazolone and bisphenol A increases, the solvent resistance properties of copolymers are improved in polar solvents such as DMF and THF. The thermal stability is enhanced, and the T_g is significantly increased to as high as 236 ℃. It is difficult to obtain high relative molecular mass polymer when the molar ratio of benzimidazolone and bisphenol A is higher than 7:3 because precipitation occurs in the early stage of the reaction due to the poor solubility of copolymers.

Key words: poly(aryl ether ketone), benzimidazolone, bisphenol A, copolymer, special engineering plastics

中图分类号:

王志鹏, 王菲菲, 王红华, 周光远. 含苯并咪唑酮结构双酚A型聚芳醚酮共聚物的制备和表征[J]. 应用化学, 2015, 32(5): 504-509.

WANG Zhipeng, WANG Feifei, WANG Honghua, ZHOU Guangyuan. Preparation and Characterization of Poly(aryl ether ketone) Containing Bisphenol A and Benzimidazolone[J]. Chinese Journal of Applied Chemistry, 2015, 32(5): 504-509.

参考文献

[1]	RAO Xianhua, CAO Min, DAI Jingqi, et al.Production, Application and Development Prospects of Special Engineering Plastic Polyaryletherketone at Home and Abroad[J]. China Plast Ind, 2012, 40(9):18-22(in Chinese). 饶先花, 曹民, 代惊奇, 等. 国内外特种工程塑料聚芳醚酮的生产、应用及发展前景[J]. 塑料工业, 2012, 40(9):18-22.
[2]	XU Limin, ZHAO Jianfeng, LEI Yuping, et al.Application and Properties of Special Engineering Plastic PAEK[J]. Plast Sci Technol, 2006, 34(5), 66-68(in Chinese). 徐利敏, 赵剑锋, 雷玉平, 等. 特种工程塑料PAEK的性能及应用[J]. 塑料科技, 2006, 34(5):66-68.
[3]	McGrail P T. Polyaromatics[J]. Polym Int, 1996, 41(2):103-121.
[4]	LEI Yi. Selection Plastics Used in Aeroplane and Aerospace Industry[J]. Eng Plast Appl, 2000, 28(11): 34-36(in Chinese). 雷毅. 航天航空工业用塑料的选材[J]. 工程塑料应用, 2000, 28(11):34-36.
[5]	DAI Hua, GUAN Rong, WANG Lijuan. The Research Progress of Sulfonated Polysulfone Proton Exchange Membrane for Fuel Cells[J]. Prog Chem, 2006, 18(1):36-44(in Chinese). 代化, 管蓉, 汪丽娟. 燃料电池用磺化聚砜类质子交换膜研究[J]. 化学进展, 2006, 18(1):36-44.
[6]	Murari A, Barzon A. Comparison of New PEEK® Seals with Traditional Helicoflex for Ultra High Vacuum Applications[J]. Vacuum, 2003, 72(3):327-334.
[7]	LIU Jingang, FAN Lin, YANG Shiyong. Applications and Market of the Special Engineering Plastics[J]. China Synth Resin Plast, 2005, 22(6):67-70(in Chinese). 刘金刚, 范琳, 杨士勇. 特种工程塑料市场与应用[J]. 合成树脂及塑料, 2005, 22(6):67-70.
[8]	PANG Jinhui, ZHANG Haibo, JIANG Zhenhua. Synthesis, Molecular Design and Properties of Poly(arylene ether ketone) Resins[J]. Acta Polym Sin, 2013, 6:705-721(in Chinese). 庞金辉, 张海博, 姜振华. 聚芳醚酮树脂的分子设计与合成及性能[J]. 高分子化学, 2013, 6:705-721.
[9]	HE Wei, XING Tong, LIN Wei, et al.Progress in Research of Modification of High Performance Special Engineering Plastics[J]. China Plast Ind, 2008, 36(s):34-36(in Chinese). 何伟, 邢彤, 林伟, 等. 高性能特种工程塑料改性研究进展[J]. 塑料工业, 2008, 36(增刊):34-36.
[10]	JIA Baozhu, WANG Honghua, CUI Shanzi, et al.The Chloromethylation of a Phenolphthalein Polyetherketone Resin[J]. Chinese J Appl Chem, 2011, 28(9):1006-1011(in Chinese). 贾宝珠, 王红华, 崔善子, 等. 无定型酚酞聚芳醚酮的氯甲基化改性[J]. 应用化学, 2011, 28(9):1006-1011.
[11]	WANG Honghua, GUAN Xinghua, WANG Zhipeng, et al.Synthesis of Phenolphthalein Poly(ether ketone) with Epoxy Side Group and Its Self-Curing[J]. Chinese J Appl Chem, 2013, 30(8):974-976(in Chinese). 王红华, 关兴华, 王志鹏, 等. 含环氧侧基酚酞聚芳醚酮的合成及自固化[J]. 应用化学, 2013, 30(8):974-976.
[12]	ZHAO Xiaogang, JI Kejian, DENG Weihua, et al.Synthesis and Characterization of Poly(aryl ether ketone) Containing Bisphenol A[J]. Eng Plast Appl, 2009, 37(3):80-83(in Chinese). 赵晓刚, 冀克俭, 邓卫华, 等. 双酚A型聚芳醚酮的合成与表征[J]. 工程塑料应用, 2009, 37(3):80-83.
[13]	ZHANG Haichun, CHEN Tianlu, YUAN Yagui. Synthesis of a Novel Polyetheretherketone Containing Phthalein Cardo Side Group:CN, 85108751.A[P], 1985-11-25(in Chinese). 张海春, 陈天禄, 袁雅桂. 合成带有酞侧基的新型聚醚醚酮:中国, 85108751.A[P], 1985-11-25.
[14]	Chen L Z, Jian X G, Liu Y J, et al.Synthesis and Characterization of Poly(aryl ether ketone) Containing Biphenylphthalazinone Moiety[J]. Chinese J Polym Sci, 1999, 17(5):495-497.
[15]	Hergenrother P M, Jensen B J, Havens S J. Poly(arylene ethers)[J]. Polymer, 1988, 29(2):358-369.
[16]	ZHAO Xiaogang, CUI Botao, DENG Weihua, et al.Kinetic Studies on Thermal Degradation of Poly(aryl ether ketone) Containing BPA[J]. J Eng Plast Appl, 2009, 37(12):57-60(in Chinese). 赵晓刚, 崔伯涛, 邓卫华, 等. 双酚A型聚芳醚酮的热分解动力学研究[J]. 工程塑料应用, 2009, 37(12):57-60.
[17]	Aabid A. Mir, Sumiko Matsumura, Antisar R. Hlil, et al. Synthesis and Properties of Polymers Containing 2H-benzimidazol-2-one Moieties:Polymerization via N—C Coupling Reactions[J]. ACS Macro Lett, 2012, (1):194-197.