Research progress in synthetic technology of bisphenol⁃A epoxy resin

doi:10.19491/j.issn.1001-9278.2023.02.015

Abstract

Abstract:

This paper introduced the synthetic mechanism and industrial production methods of bisphenol⁃A epoxy resin. The research progress in the synthesis technology of bisphenol⁃A epoxy resin by using one⁃ and two⁃step methods was reviewed. The one⁃step technology includes the addition of catalysts， alkali⁃fixing method， solvent method， sodium salt method， and atmospheric and vacuum azeotrope method. The two⁃step technology includes the two⁃step kinetics， usage of catalysts， and decrease of hydrolyzed chlorine. The problems existing in the synthetic technologies were analyzed， and the future development direction of the synthetic technology for bisphenol⁃A epoxy resin was prospected.

Key words: bisphenol?A epoxy resin, synthetic mechanism, production method

CLC Number:

TQ322.4

YANG Chen, TANG Xiaodong, LI Jingjing, FENG Xuefeng, CAO Yefei, GAO Zhiqiang. Research progress in synthetic technology of bisphenol⁃A epoxy resin[J]. China Plastics, 2023, 37(2): 106-112.

Figures/Tables 4

References 30

1	李清. 全球胶粘剂行业发展现状及研究进展［J］. 中国胶粘剂， 2017，26（6）： 46⁃50.
	LI Q. Development status and research progress of global adhesive industry［J］. China Adhesives， 2017，26（6）： 46⁃50.
2	肖艳. 环氧树脂分类、应用领域及市场前景［J］. 化学工业， 2014，32（9）： 19⁃24.
	XIAO Y. Classification， application fields and market prospect of epoxy resin［J］. Chemical Industry， 2014，32（9）： 19⁃24.
3	齐姝婧，殷丽文，宋丕双，等. 国内外环氧树脂生产现状及市场分析［J］. 弹性体， 2012，22（5）： 84⁃89.
	QI S J， YIN L W， SONG P S，et al. Production status & market analysis of epoxy resin at home and abroad［J］. China Elastomerics， 2012，22（5）： 84⁃89.
4	周菊兴. 合成树脂与塑料工艺［M］. 北京：化学工业出版社， 2000： 469.
5	Jakob F H. Production of solid glycidyl ethers of polyhydric phenols： Germany，DE1282653 B［P］. 1968⁃11⁃14.
6	陆华，赵春霞. 双酚A型环氧树脂的合成［J］. 精细化工中间体， 2016，46（5）： 45⁃47.
	LU H. Synthesis of bisphenol A type epoxy resin［J］. Fine Chemical Intermediates， 2016，46（5）： 45⁃47.
7	Becker W. Process for preparing glyceidyl ethers： Germany，DE2108207 A1［P］. 1971⁃10⁃07.
8	Frank G， Wegler R， Schmitz⁃Josten R， et al. Process for preparing glycidyl ethers of polyhydric phenols： United States，US3336342 A［P］. 1967⁃08⁃15.
9	John L A， George S J. Process for the continuous production of glycidyl polyethers： Germany，DE1131413 B［P］. 1962⁃06⁃14.
10	Klaus P. Polyglycidyl ethers of polyhydric phenols⁃esp of bisphenol A and epichloro⁃hydrin prepd in presence of ethanol or methanol： Germany，DE2241393 A1［P］. 1974⁃02⁃28.
11	Clair W E S. Process for the production of monomeric and polymeric glycidyl ethers： Germany， DE1128667 B［P］. 1962⁃04⁃26.
12	Wang C S， Bowden R L. Method for preparing advanced epoxy or phenoxy resins with low aliphatic halide content： United States，US4684701 A［P］. 1987⁃08⁃04.
13	孙万平. 溶剂法生产粉末涂料树脂：E⁃12环氧树脂［J］. 粉末涂料与涂装， 2001，10（3）： 11⁃14.
	SUN W P. 溶剂法生产粉末涂料树脂：E⁃12环氧树脂［J］. 粉末涂料与涂装， 2001，10（3）： 11⁃14.
14	Joachim B， Otto G， Walter T. Process for the production of epoxy resins： Germany， DE1081666 B ［P］. 1960⁃05⁃12.
15	邢殿香，谭学杰，张长花. 液态双酚⁃A型环氧树脂的合成工艺改进研究［J］. 山东轻工业学院学报（自然科学版）， 2003，17（ 2）： 6⁃8.
	XING D X， TAN X J， ZHANG C H. Improvement on the synthesis process of liquid bisphenol⁃a diglycidyl ether［J］. Journal of Shandong Polytechnic University， 2003，17（2）： 6⁃8.
16	汪国庆. 低黏度环氧树脂体系的合成及性能研究［D］. 武汉：武汉理工大学， 2010.
17	Goppel J M. Process for manufacture of glycidyl ethers of polyhydric phenols： United States，US2801227［P］. 1953⁃10⁃19.
18	Gino V S P M. Process for manufacturing liquid epoxy resins： Germany， DE2656865 A1［P］. 1977⁃06⁃30.
19	Larkin B T， Slickville， William E. Method for preparation of glycidyl ether of polyhydric phenols： United States， US2995583 A［P］. 1961⁃08⁃08.
20	钱祖荣. 降低双酚A型环氧树脂可水解氯含量方法的研究［J］. 上海化工， 1996，21（2）： 12⁃15.
	QIAN Z R. Studies on ways of reducing hydrolyzable chlorine content for bisphenol A epoxy resin［J］. Shanghai Chemcal Industry， 1996，21（2）： 12⁃15.
21	Wang C S， Pham H Q. Preparation of epoxy resins： United States，US4499255 A［P］. 1985⁃02⁃12.
22	高俊刚，史林启，王逢利，等. 两步法合成环氧树脂的反应动力学［J］. 涂料工业， 1989，19（5）： 1⁃5.
	GAO J G， SHI L Q， WANG F L，et al. Kinetics of two⁃step epoxy resin synthesis［J］. Paint & Coatings Industry， 1989，19（5）： 1⁃5.
23	于浩，路太平. 液态双酚A型环氧树脂醚化反应初探［J］. 热固性树脂， 1992，7（3）： 18⁃22.
	YU H， LU T P. Studies on etherifying reaction of liquid bisphenol A epoxy resin［J］. Thermosetting Resin， 1992，7（3）： 18⁃22.
24	于浩，路太平. 液态双酚A环氧树脂合成反应动力学［J］. 热固性树脂， 1995，10（1）： 10⁃15.
	YU H， LU T P. Reaction kinetics of synthesis of liquid bisphenol A epoxy resin［J］. Thermosetting Resin， 1995，10（1）： 10⁃15.
25	Sinnema F， Vegter G. Polyglycidyl ether with a low molecular weight： Canada，CA939372 A［P］. 1974⁃01⁃01.
26	喻林，程珏. 新工艺合成低黏度双酚A型液态环氧树脂［J］. 热固性树脂， 2010，25（3）： 31⁃34.
	YU L， HENG Y. Synthesis of low viscosity bisphenol A type liquid epoxy resin by a new process ［J］. Thermosetting Resin， 2010，25（3）： 31⁃34.
27	Wilhelm B. Process for the manufacture of glycidyl ethers of monohydric or polyhydric phenols， having improved properties： United States，US3980679 A［P］. 1976⁃09⁃14.
28	张军营，李建华，李婧婧，等. 高纯和低可水解氯含量环氧树脂的制备［J］. 石油化工， 2005，34（11）： 1 091⁃1 094.
	ZHANG J Y， LI JIAN H， LI J J. Preparation of high pure epoxy resin with low hydrolyzable chlorinity content［J］. Petrochemical Technology， 2005，34（11）： 1 091⁃1 094.
29	夏宇，陶纯初，汝国兴，等.分子蒸馏双酚A环氧树脂的性能研究［J］.热固性树脂， 2012，27（5）：48⁃51.
	XIA Y， TAO C C， RU G X，et al. Research on the performance of molecular distillation bisphenol⁃A epoxy resin［J］. Thermosetting Resin， 2012，27（5）：48⁃51.
30	邢军. 两步法生产电子级环氧树脂的方法：中国， CN105153402A［P］. 2015⁃12⁃16.

牌号	ECH/BPA摩尔比	NaOH/BPA摩尔比	NaOH质量分数/%	NaOH滴加总时长/h	环氧值/eq·（100 g）^-1
E⁃44	2.80	2.20	30、15	4（30 %）、0.5（15 %）	0.41~0.47
E⁃42	2.40	1.90	30、15	4（30 %）、0.5（15 %）	0.38~0.45
E⁃35	2.04	2.04	15	6	0.26~0.40
E⁃31	1.73	1.73	15	6	0.29~0.32

牌号	ECH/BPA摩尔比	NaOH/BPA摩尔比	NaOH质量分数/%	NaOH滴加总时长/h	环氧值/eq·（100 g）^-1
E⁃44	2.80	2.20	30、15	4（30 %）、0.5（15 %）	0.41~0.47
E⁃42	2.40	1.90	30、15	4（30 %）、0.5（15 %）	0.38~0.45
E⁃35	2.04	2.04	15	6	0.26~0.40
E⁃31	1.73	1.73	15	6	0.29~0.32

[1]	DONG Youbang, ZHANG Zeqi, YANG Rongjie. Synthesis and characterization of aminopropyl oligomeric silsesquioxane and its amidation products [J]. China Plastics, 2022, 36(8): 1-9.
[2]	OUYANG Yufei, WANG Huashan. Pre⁃plating properties of ABS treated with non⁃thermal plasma [J]. China Plastics, 2022, 36(8): 80-86.
[3]	HUANG Suyuan, CAO Lin, LI Wei, LIN Zhidan, ZHANG Peng. Preparation and performance evaluation of tantalum boride⁃reinforced polyether ether ketone composite coatings [J]. China Plastics, 2022, 36(6): 60-68.
[4]	WANG Yang, CHENG Lisheng, TAN Jing, YANG Weimin, WANG Ruixue, ZHANG Zhenghe. Moldflow analysis of influence of filler on polyether ether ketone injection molding [J]. China Plastics, 2022, 36(5): 68-74.
[5]	SONG Kunpeng, WANG Yinjie, LIU Jiping, FANG Zhuqing, YANG Weiwei, ZHENG Dongsen. Research Progress in Applications of Phosphazene Compounds in Flame⁃retardant Polymers Field [J]. China Plastics, 2021, 35(2): 107-118.
[6]	Sha LI, Jiayu ZHAN, Yanjun LI, Zhenxin LIU, Feihua YANG. Study on Leaching of Heavy Metal Lead from Unplasticized Poly(vinyl chloride) Drainpipes [J]. China Plastics, 2020, 34(7): 69-73.
[7]	Zhu LIU, Ziqian LIN, Hongping XIANG, Minzhi RONG, Mingqiu ZHANG. Preparation and Properties of UV⁃curable Silicone Resin for LED Package [J]. China Plastics, 2020, 34(5): 68-76.
[8]	Xiaolong LU, Xuanyu LIU, Enpu DING, Beibei ZHANG, Xiang YU, Gang QIN. Preparation and Performance Investigation of PAN/TiO₂ Nanofiber Membranes [J]. China Plastics, 2020, 34(4): 30-34.
[9]	. Preparation and Characterization of Soluble Polyimide Based on a Novel Pyridine-containing Aromatic Diamine [J]. China Plastics, 2013, 27(09): 57-62 .
[10]	LI Side LUO Jianxun GAO Li MAO Lixin. Study on Processing and Property of Three-layer Co-extrusion Barrier Films [J]. China Plastics, 2011, 25(10): 19-23 .
[11]	ZHANG Yi YAN Hong-xia LI Peng-bo SONG Chang-wen. Research Progress of Thermosetting Resins/Carbon Nanotubes Composites [J]. China Plastics, 2009, 23(10): 10-14 .
[12]	KONG Zhen-Xing. Research on diallyl phthalate resin toughened by vinyl ester oligomers [J]. China Plastics, 2009, 23(04): 36-40 .