酚酞聚芳醚酮酮环状齐聚物的合成及开环聚合

doi:10.3724/SP.J.1095.2014.40063

摘要/Abstract

摘要： 从4,4′-二氟三苯二酮（DFTBDK）和酚酞出发，利用“拟高稀(pseudo high dillution)”技术，一步法制备酚酞聚芳醚酮酮环状齐聚物（c-PEKK-C），成环率78%。基质辅助激光解吸电离飞行时间质谱MALDI-TOF MS数据表明，聚合产物系聚合度为n=2~8的环状低聚物，其中以二、三聚体为主要成分（占环化产物的85%）。运用J-S高分子环化理论证实4,4′-二氟三苯二酮的单体结构有利于形成环状化合物。以4,4′-联苯二酚钾盐为催化剂，在300～350 ℃范围内，N2气保护下，环状齐聚物进行熔融开环聚合反应得到相应的线性高相对分子质量酚酞聚芳醚酮酮（ROP-PEKK-C），GPC测得其Mw为12×105。

关键词: 芳香环状齐聚物, 酚酞聚芳醚酮酮, 拟高稀技术

Abstract: Under pseudo high dilution conditions, cyclic oligomers of phenolphthalein poly(ether ketone ketone)s(c-PEKK-C) were synthesized from phenolphthalein and 4,4′-difluorotribenzodiketone(DFTBDK) with a cyclization ratio of 78%. MALDI-TOF MS characterization indicates that c-PEKK-C has a broad size distribution(n=2~8) with cyclic dimers and trimers as main components(85%). The molecular structure of DFTBDK is prone to form cyclic structure that can be confirmed by Jacobson-Stockmayer theory. Melt ring-opening polymerization(ROP)(300~350 ℃) of cyclic oligomers catalyzed by potassium 4,4′-biohenol gives the corresponding linear products with high relative molecular mass(Mw 1.2×105).

Key words: aromatic cyclic oligomers, phenolphthalein poly(ether ketone ketone)s, pseudo high dillution technology

中图分类号:

O625.4

鲁丹丹, 王志鹏, 王红华, 周光远, 崔善子. 酚酞聚芳醚酮酮环状齐聚物的合成及开环聚合[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.40063.

LU Dandan1, WANG Zhipeng2, WANG Honghua2, ZHOU Guangyuan2,3, CUI Shanzi1*. Synthesis and Ring-Opening Polymerization of Cyclic Phenolphthalein Poly(ether ketone ketone) Oligomers[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.40063.

参考文献

[1] WANG Honghua,GUO Qingzhong,CHEN Tianlu. Progress in Synthesis of Aromatic Cyclic Oligomers[J]. Prog Chem,2005,17(4):716-721(in Chinese).

王红华,郭庆中,陈天禄. 芳香环状低聚体的制备方法[J]. 化学进展,2005,17(4):716-721.

[2] Li S H. Cyclic Aryl Ketone Oligomers Containing the ISO-Phthaloyl Moiety:Synthesis and Ring-Opening Polymerization[J]. Adv Mater Res,2013,781:411-414.

[3] Shukla D,Negi Y S,Uppadhyaya J S,et al. Synthesis and Modification of Poly(ether ether ketone) and Their Properties:A Review[J]. Polym Rev,2012,52(2):189-228.

[4] Brunelle D J. New Methods of Polymer Synthesis[M]. London:Blackie,1995.

[5] Chen K,Du X S,Meng Y Z,et al. The Preparation and Characterization of Novel Cocylic(arylene disulfide) oligomers[J]. Polym Adv Technol,2003,14(2):114-121.

[6] Bonauto D K,Brunelle D J. Hydroquinone-bisphenol Cyclic Copolycarbonate Oligomer:USPatent 4920200[P]. 1990-4-24.

[7] Hoskins J N,Grayson S M. Cyclic Polyesters: Synthetic Approaches and Potential Applications[J]. Polym Chem,2011,2(2):289-299.

[8] Xu D,Li X,Gao C,et al. Development of an Efficient Route to Hyperbranched Poly(aryl ether ketone)s[J]. High Perform Polym,2012,24(3):188-193.

[9] GUO Qingzhong,CHEN Tianlu. Study on the Relationship Between Aromatic Cyclic Oligomers Distribution and Monomer Structure[J]. Chem J Chinese Univ,2003,24(5):909-912(in Chinese).

郭庆中,陈天禄. 芳香环状低聚物组分分布与单体结构关系的研究[J]. 高等学校化学学报,2003,24(5):909-912.

[10] GUO Qingzhong,XIAO Ying. Characterization of Cyclic(arylene ketone) Oligomers by Matrix- assisted Laser Desorption Ionization Time-of-flight Mass Spectrometry[J]. J Wuhan Inst Technol,2011,33(5):5-7(in Chinese).

郭庆中,肖颖. MALDI-TOF质谱表征芳香环状聚酮低聚物及其组分分布[J]. 武汉工程大学学报,2011,33(5):5-7.