降冰片烯制备工艺进展

doi:10.16085/j.issn.1000-6613.2023-1335

摘要/Abstract

摘要：

环烯烃聚合物是一类性能优良的热塑性工程塑料，其单体降冰片烯的制备工艺复杂且存在工程安全问题，长期被少数企业垄断，价格昂贵。关于降冰片烯合成的报道多为专利，年代跨度大且缺乏系统性综述。本文围绕降冰片烯的制备过程，首先对双环戊二烯裂解制备环戊二烯工艺进行了总结，按照液相法、气相法进行分类和比较，分析了两种方法在反应温度、停留时间、反应设备、稀释剂和阻聚剂等方面的区别，探讨了两种方法的优劣势。之后总结了液相法、气相法或超临界法下加成反应制备降冰片烯的工艺特点，分析了不同制备方法在温度、压力、反应器形式、稀释剂等方面的区别和优劣势，为降冰片烯制备工艺的设计与优化提供了参考借鉴。最后，对多环降冰片烯衍生物的制备工艺进行了介绍。

关键词: 降冰片烯, 环戊二烯, 乙烯, 反应工程, 工艺

Abstract:

Cyclic olefin copolymers are a class of high-performance thermoplastic engineering plastics. The preparation technology of monomer norbornene is complex and poses engineering safety challenges, leading to a long-term monopoly by a few enterprises and exorbitant prices. Reports on norbornene synthesis are mostly found in patents with spanning various periods and lacking systematic reviews. This review first summarized the cracking process of dicyclopentadiene for the preparation of cyclopentadiene and compared the liquid-phase with gas-phase methods. Their differences in temperature, residence time, equipment, diluents and inhibitors were analyzed, and the advantages and disadvantages of both methods were discussed. Subsequently, the characteristics of norbornene preparation through addition reactions using liquid-phase, gas-phase and supercritical methods were reviewed. The distinctions and pros and cons of different preparation methods in terms of temperature, pressure, equipment, diluents and other aspects were analyzed, providing valuable reference and guidance for the design and optimization of norbornene preparation processes. Finally, the preparation process of polycyclic norbornene derivatives was introduced.

Key words: norbornene, cyclopentadiene, ethylene, reaction engineering, process

中图分类号:

TQ231.2

李传玺, 鲁旭, 李阳, 李文冰, 魏晓慧, 李金, 刘时, 杨卫胜. 降冰片烯制备工艺进展[J]. 化工进展, 2024, 43(9): 4779-4792.

LI Chuanxi, LU Xu, LI Yang, LI Wenbing, WEI Xiaohui, LI Jin, LIU Shi, YANG Weisheng. Research progress on preparation technology of norbornene[J]. Chemical Industry and Engineering Progress, 2024, 43(9): 4779-4792.

图/表 8

参考文献 111

1	JOSHEL Lloyd M, BUTZ Lewis W. The synthesis of condensed ring compounds. Ⅷ. The successful use of ethylene in the Diels-Alder reaction[J]. Journal of the American Chemical Society, 1941, 63(12): 3350-3351.
2	WILSON Philip J, WELLS Joseph H. The chemistry and utilization of cyclopentadiene[J]. Chemical Reviews, 1944, 34(1): 1-50.
3	刘公召, 臧淑艳, 杨卫东. 从轻闪油中除去DCPD的研究[J]. 沈阳化工学院学报, 2000, 14(4): 266-268.
	LIU Gongzhao, ZANG Shuyan, YANG Weidong. Study on removing DCPD from low-flash oil[J]. Journal of Shenyang Institute of Chemical Technolgy, 2000, 14(4): 266-268.
4	宋美静. 双环戊二烯的解聚与加氢研究[D]. 上海: 华东理工大学, 2021.
	SONG Meijing. Study on depolymerization and hydrogenation of dicyclopentadiene[D]. Shanghai: East China University of Science and Technology, 2021.
5	STAUDINGER H, RHEINER A. Über die konstitution des dicyclopentadiens[J]. Helvetica Chimica Acta, 1924, 7(1): 23-31.
6	LENZ Terry G, VAUGHAN John D. Employing force-field calculations to predict equilibrium constants and other thermodynamic properties for the dimerization of 1,3-cyclopentadiene[J]. The Journal of Physical Chemistry, 1989, 93(4): 1592-1596.
7	陈均志, 马金才. 热二聚法萃取精馏分离C₅馏分[J]. 化工时刊, 2004, 18(8): 12-16.
	CHEN Junzhi, MA Jincai. A method to separate C₅ fraction[J]. Chemical Industry Times, 2004, 18(8): 12-16.
8	AHMED M, LAVIN M. Exothermic reactions of DCPD and protection against them[J]. Plant/Operations Progress, 1991, 10(3): 143-154.
9	白庚辛. 环戊二烯二聚过程动力学的研究[J]. 石油化工, 1981, 10(2): 84-94.
	BAI Gengxin. Study on kinetics of dimerization of cyclopentadiene[J]. Petrochemical Technology, 1981, 10(2): 84-94.
10	BIRMINGHAM John M. Dicyclopentadiene cracking process: US5877366[P]. 1999-03-02.
11	王宇飞, 李东风, 过良, 等. 一种反应精馏制备高纯度双环戊二烯的方法: CN105585415B[P]. 2017-11-07.
	WANG Yufei, LI Dongfeng, GUO Liang, et al. A method for preparing high-purity dicyclopentadiene by reactive distillation: CN105585415B[P]. 2017-11-07.
12	黄勇, 秦技强, 夏蓉晖, 等. 以粗双环戊二烯为原料制备高纯双环戊二烯的方法: CN112679307A[P]. 2021-04-20.
	HUANG Yong, QIN Jiqiang, XIA Ronghui, et al. A method for preparing high-purity dicyclopentadiene from crude dicyclopentadiene: CN112679307A [P]. 2021-04-20.
13	GRUDE Fritz, HALCOUR Kurt, SCHWERDTEL Wulf, et al. Process for the production of cyclopentadiene from dicyclopentadiene: US3719718[P]. 1973-03-06.
14	张敏. 裂解碳九综合利用[D]. 北京: 北京化工大学, 2013.
	ZHANG Min. Comprehensive utilization of cracked carbon nine[D]. Beijing: Beijing University of Chemical Technology, 2013.
15	冷志光, 郭世卓, 周飞, 等. 由碳九、碳十馏分精制环戊二烯的方法: CN1850746A [P]. 2006-10-25.
	LENG Zhiguang, GUO Shizhuo, ZHOU Fei, et al. A method for refining cyclopentadiene from Cand C fractions: CN1850746A [P]. 2006-10-25.
16	祝波, 娄大伟, 曲小姝, 等. 双环戊二烯液相解聚工艺的研究[J]. 化学工程师, 2004, 18(2): 59-60.
	ZHU Bo, LOU Dawei, QU Xiaoshu, et al. Study on liquid phase depolymeerization of dicyclopentadiene[J]. Chemical Engineer, 2004, 18(2): 59-60.
17	张鹏可, 王中锋, 崔富民, 等. 一种连续化裂解精馏装置: CN103977589B[P]. 2016-01-13.
	ZHANG Pengke, WANG Zhongfeng, CUI Fumin, et al. A continuous equipment for cracking and distillation: CN103977589B[P]. 2016-01-13.
18	袁贝. 微通道反应器中制备降冰片烯和乙烯基降冰片烯[D]. 杭州: 浙江大学, 2017.
	YUAN Bei. Preparation of norbornene and vinyl norbornene in microchannel reactor[D]. Hangzhou: Zhejiang University, 2017.
19	慎炼, 江华, 黄银华, 等. 一种高纯度双环戊二烯的生产工艺: CN1781887A[P]. 2006-06-07.
	SHEN Lian, JIANG Hua, HUANG Yinhua, et al. Production process of high-purity dicyclopentadiene: CN1781887A[P]. 2006-06-07.
20	HERNDON William C, GRAYSON C R, MANION Jerald M. Retro-Diels-Alder reactions. Ⅲ. Kinetics of the thermal decompositions of exo- and endo-dicyclopentadiene[J]. The Journal of Organic Chemistry, 1967, 32(3): 526-529.
21	刘锋, 李崇, 张曾, 等. 一种从乙烯副产C9中分离环戊二烯和甲基环戊二烯的方法: CN101066902B[P]. 2012-02-15.
	LIU Feng, LI Chong, ZHANG Zeng, et al. A method for separating cyclopentadiene and methylcyclopentadiene from C9 byproduct of ethylene: CN101066902B[P]. 2012-02-15.
22	BUSINGER Roger T, GERHART Howard L. High purity dicyclopentadiene: US2582920[P]. 1952-01-15.
23	吴重言, 孙琴, 曾从余, 等. 双环戊二烯连续裂解新型工艺: CN101070262A[P]. 2007-11-14.
	WU Zhongyan, SUN Qin, ZENG Congyu, et al. A new process for continuous cracking of dicyclopentadiene: CN101070262A[P]. 2007-11-14.
24	朱岳中, 周飞, 黄勇, 等. 气相解聚法制取高纯度双环戊二烯的研究[J]. 石油化工技术与经济, 2008, 24(1): 43-46.
	ZHU Yuezhong, ZHOU Fei, HUANG Yong, et al. Study on preparation of high-purity dicyclopentadiene with vapor-phase depolymerization process[J]. Technology-Economics in Petrochemicals, 2008, 24(1): 43-46.
25	朱效中, 郑辛生, 郭宇, 等. 高纯度环戊二烯的制备方法: CN1093527C[P]. 2002-10-30.
	ZHU Xiaozhong, ZHENG Xinsheng, GUO Yu, et al. Method for prepare high-purity cylopentadiene: CN1093527C[P]. 2002-10-30.
26	马黎明, 杨正银, 张立, 等. 双环戊二烯的新型分解法[J]. 化学世界, 1992, 33(10): 471-474.
	MA Liming, YANG Zhengyin, ZHANG Li, et al. A new decomposition method of dicyclopentadiene[J]. Chemical World, 1992, 33(10): 471-474.
27	BOESENBERG H, FRENSCH H, LORENZ H. Process for depolymerizing dicylopentadiene: US3772396[P]. 1973-11-13.
28	胡竞民, 徐宏芬, 田保亮, 等. 一种制备高纯度环戊二烯的方法及其专用设备: CN1163459C[P]. 2004-08-25.
	HU Jingmin, XU HongFen, TIAN Baoliang, et al. A method for preparing high-purity cyclopentadiene and its dedicated equipment: CN1163459C[P]. 2004-08-25.
29	范伟云, 吕艳, 陈新华, 等. 一种制备高纯度环戊二烯的方法: CN1150942A [P]. 1997-06-04.
	FAN Weiyun, Yan LYU, CHEN Xinhua, et al. A method for preparing high-purity cyclopentadiene: CN1150942A[P]. 1997-06-04.
30	史晋宜, 王亚红, 钟方丽. 环戊二烯的制备研究[J]. 吉林化工学院学报, 2004, 21(2): 41-42.
	SHI Jinyi, WANG Yahong, ZHONG Fangli. Preparation of cyclopentadiene[J]. Journal of Jilin Institute of Chemical Technology, 2004, 21(2): 41-42.
31	刘菁, 李德才, 王禹, 等. 一种制备高纯度环戊二烯和双环戊二烯的方法: CN1389444A[P]. 2003-01-08.
	LIU Jing, LI Decai, WANG Yu, et al. A method for preparing high-purity cyclopentadiene and dicyclopentadiene: CN1389444A[P]. 2003-01-08.
32	侯琳. 双环戊二烯气-液相解聚工艺的研究[J]. 科协论坛(下半月), 2010(12): 82-83.
	HOU Lin. Study on gas-liquid depolymerization process of dicyclopentadiene[J]. Science & Technology Association Forum, 2010(12): 82-83.
33	XIONG Zhongqiang, MI Zhentao, ZHANG Xiangwen. Study on the oligomerization of cyclopentadiene and dicyclopentadiene to tricyclopentadiene through Diels-Alder reaction[J]. Reaction Kinetics and Catalysis Letters, 2005, 85(1): 89-97.
34	ZHANG Xiangwen, JIANG Qiang, XIONG Zhongqiang, et al. Diels-Alder addition of dicyclopentadiene with cyclopentadiene in polar solvents[J]. Chemical Research in Chinese Universities, 2008, 24(2): 175-179.
35	PALMOVÁ I, KOSEK J, SCHÖNGUT J, et al. Experimental and modeling studies of oligomerization and copolymerization of dicyclopentadiene[J]. Chemical Engineering Science, 2001, 56(3): 927-935.
36	LANE JR Parley C. Vapor phase cracking of dicyclopentadiene and synthesis of 2,3-dihydroxycyclopentadiene and cyclopentene: US4139569[P]. 1979-02-13.
37	LATTNER James R, MCMULLEN Harry C, SANCHEZ Leonel E, et al. Process for forming cyclopentane from dicyclopentadiene: EP0922019A1[P]. 1999-06-16.
38	刘威廉, 郭世卓, 周飞, 等. 一种制备高纯度双环戊二烯的方法: CN103664472A[P]. 2014-03-26.
	LIU Weilian, GUO Shizhuo, ZHOU Fei, et al. A method for preparing high-purity dicyclopentadiene: CN103664472A[P]. 2014-03-26.
39	刘威廉, 周飞, 黄勇. 裂解碳十作稀释剂的双环戊二烯解聚过程[J]. 石化技术与应用, 2013, 31(2): 119-122.
	LIU Weilian, ZHOU Fei, HUANG Yong. Depolymerization process of dicyclopentadiene using pyrolysis C₁₀ as diluent[J]. Petrochemical Technology & Application, 2013, 31(2): 119-122.
40	HUELS Chemische Werke A G. Improvements in the production of cyclopentadiene by deploymerisation of dicyclopentadiene: GB769813A[P]. 1957-03-13.
41	ROGERSON Walter Alan. Improvements in the production of cyclopentadiene: GB612893A[P]. 1948-11-18.
42	KREPS Robert W F. Depolymerization of dicyclopentadiene: US2831904A[P]. 1958-04-22.
43	宋吉亮, 孟凡强, 张新. 实验室制备环戊二烯装置的研制与应用[J]. 实验室科学, 2020, 23(6): 10-12.
	SONG Jiliang, MENG Fanqiang, ZHANG Xin. Development and application of a device for preparing cyclopentadiene in laboratory[J]. Laboratory Science, 2020, 23(6): 10-12.
44	NAKAMURA Takao, KAWAKITA Masaru, MINOMIYA Katsumi. Process for the vapor-phase thermal cracking of dicyclopentadiene and a process for the manufacture of high-purity dicyclopentadiene: US5321177[P]. 1994-06-14.
45	邱慎海. 高纯度双环戊二烯的制备研究[D]. 南京: 南京工业大学, 2006.
	QIU Shenhai. Study on preparation of high-purity dicyclopentadiene[D]. Nanjing: Nanjing University of Technology, 2006.
46	邱慎海, 包宗宏. 共沸物进料裂解双环戊二烯实验研究[J]. 石油学报(石油加工), 2006, 22(4): 25-29.
	QIU Shenhai, BAO Zonghong. Experimental study on the vapor-phase thermal cracking of dicyclopentadiene by using azeotrope feed[J]. Acta Petrolei Sinica (Petroleum Processing Section), 2006, 22(4): 25-29.
47	吴卓, 周飞, 华建英, 等. 共沸气相解聚法制备环戊二烯的工艺研究[J]. 上海化工, 2010, 35(4): 4-7.
	WU Zhuo, ZHOU Fei, HUA Jianying, et al. Study on vapor-phase depolymerization of dicyclopentadiene by azeotrope[J]. Shanghai Chemical Industry, 2010, 35(4): 4-7.
48	窦晓冬, 袁向前, 张濂. 双环戊二烯解聚制环戊二烯的工程开发研究[J]. 化学工业与工程技术, 2000, 21(6): 7-9.
	DOU Xiaodong, YUAN Xiangqian, ZHANG Lian. Engineering research on preparation of cyclopentadiene by decomposition of dicyclopentadiene[J]. Journal of Chemical Industry & Engineering, 2000, 21(6): 7-9.
49	李兴存, 陈兴权, 单敏, 等. 双环戊二烯气相解聚工艺的研究[J]. 石油化工, 2001, 30(11): 841-843.
	LI Xingcun, CHEN Xingquan, SHAN Min, et al. Study on vapor-phase depolymerization of dicyclopentadiene[J]. Petrochemical Technology, 2001, 30(11): 841-843.
50	王建华, 丁文光. 双环戊二烯的气相高温解聚中试[J]. 石化技术与应用, 2000, 18(6): 341-343.
	WANG Jianhua, DING Wenguang. Pilot-plant test of gas-phase depolymerization of dicyclopentadiene at high temperature[J]. Science and Technology of Lcic, 2000, 18(6): 341-343.
51	丁文光, 王建华. 双环戊二烯解聚制环戊二烯的方法和设备: CN1129686A[P]. 1999-10-27.
	DING Wenguang, WANG Jianhua. A method and apparatus for the depolymerization of dicyclopentadiene to produce cyclopentadiene: CN1129686A[P]. 1999-10-27.
52	李兴存, 单敏. 双环戊二烯气相解聚工艺的改进[J]. 石油化工, 2008, 37(11): 1152-1154.
	LI Xingcun, SHAN Min. Improvement of vapor-phase depolymerization of dicyclopentadiene[J]. Petrochemical Technology, 2008, 37(11): 1152-1154.
53	TAWARA Shinichiro, KIKUCHI Takayuki. Method and apparatus for thermally decomposing dicyclopentadiene in vapor phase: JP2001302559A[P]. 2010-06-02.
54	KIKUCHI Takayuki, TAWARA Shinichiro. Evaporation method for dicyclopentadiene, evaporating apparatus and thermal cracking method: JP2002226407A[P]. 2010-03-24.
55	KIKUCHI Takayuki, TAWARA Shinichiro. Dicyclopentadiene vaporization method, vaporizer and thermal decomposition method: JP4438921B2[P]. 2010-03-24.
56	吴启龙, 吴浩, 邓后碌, 等. 脱丙烷塔再沸器结垢分析[J]. 乙烯工业, 1998, 10(2): 11-14.
	WU Qilong, WU Hao, DENG Houlu, et al. Scaling analysis of reboiler in depropanizer[J]. Ethylene Industry, 1998, 10(2): 11-14.
57	蒋明敬. 阻聚措施在丁二烯抽提装置和乙烯装置的应用[J]. 石油化工, 2021, 50(3): 258-263.
	JIANG Mingjing. Application of polymerization inhibition measures in butadiene extraction unit and ethylene unit[J]. Petrochemical Technology, 2021, 50(3): 258-263.
58	NURULLINA Elena-Valentinovna, SOLOVIEVA Natalia-Borisovna, SAMUILOV Yakov-Dmitrievich, et al. Production method of dicyclopentadiene from C5-fraction of hydrocarbon pyrolysis: WO2002036529A1[P]. 2002-05-10.
59	刘保霞, 谢冰, 马啸华, 等. 降冰片烯类化合物的合成及其表征研究[J]. 邢台职业技术学院学报, 2007, 24(1): 46-47.
	LIU Baoxia, XIE Bing, MA Xiaohua, et al. Synthesis and characterization of norbornene derivatives[J]. Journal of Xingtai Polytechnic College, 2007, 24(1): 46-47.
60	蔡智. 高效分离裂解碳五环戊二烯制取聚丙烯成核剂技术研究[D]. 上海: 华东理工大学, 2011.
	CAI Zhi. Study on preparation of polypropylene nucleating agent by efficient separation and cracking of C₅-cyclopentadiene[D]. Shanghai: East China University of Science and Technology, 2011.
61	陈万友, 李正, 石大川, 等. 一种制备高纯度环戊二烯的方法: CN102060649B[P]. 2013-02-13.
	CHEN Wanyou, LI Zheng, SHI Dachuan, et al. A method for preparing high-purity cyclopentadiene: CN102060649B[P]. 2013-02-13.
62	谢美妮. 从裂解C₉馏分中分离提纯双环戊二烯的技术研究[D]. 青岛: 中国石油大学(华东), 2018.
	XIE Meini. The study of separation and purification from cracked C₉ fractions to produce high-purity dicyclopentadiene[D]. Qingdao: China University of Petroleum (EastChina), 2018.
63	WALSH Robin, WELLS Jean M. The enthalpy of formation and thermodynamic functions of bicyclo[2,2,1]hept-2-ene[J]. The Journal of Chemical Thermodynamics, 1976, 8(1): 55-60.
64	COHEN N. Revised group additivity values for enthalpies of formation (at 298K) of carbon-hydrogen and carbon-hydrogen-oxygen compounds[J]. Journal of Physical and Chemical Reference Data, 1996, 25(6): 1411-1481.
65	周菊英, 马永祥. 环戊二烯综合利用——降冰片烯类化合物的合成和应用[J]. 金山油化纤, 1989(4): 39-44.
	ZHOU Juying, MA Yongxiang. Comprehensive utilization of cyclopentadiene—Synthesis and application of norbornene compounds[J]. Petrochemical Technology in Jinshan, 1989(4): 39-44.
66	郭利兵, 李江涛, 张海洋, 等. 5-降冰片烯-2,3 -二甲酸酐生产方法: CN101481368B[P]. 2011-04-13.
	GUO Libing, LI Jiangtao, ZHANG Haiyang, et al. Production method for 5-norbornene-2,3-dicarboxylic anhydride: CN101481368B [P]. 2011-04-13.
67	孙敏青, 马欣, 屈凤波, 等. 降冰片烯类化合物的合成与表征[J]. 合成材料老化与应用, 2018, 47(1): 48-50.
	SUN Minqing, MA Xin, QU Fengbo, et al. The synthesis and characterization of the norbornene and its derivates[J]. Synthetic Materials Aging and Application, 2018, 47(1): 48-50.
68	张松林, 董佳佳, 张文泉, 等. 含有醚类长链的降冰片烯类化合物的制备方法: CN111072460A[P]. 2020-04-28.
	ZHANG Songlin, DONG Jiajia, ZHANG Wenquan, et al. Preparation method for norbornene compounds containing ether-type long chains: CN111072460A[P]. 2020-04-28.
69	张松林, 张浩然, 黄佳斯, 等. 一种制备含三氟甲基的降冰片烯类化合物: CN111039747A[P]. 2020-04-21.
	ZHANG Songlin, ZHANG Haoran, HUANG Jiasi, et al. A method for preparing norbornene compounds containing trifluoromethyl groups: CN111039747A[P]. 2020-04-21.
70	FUKADA Isao, MIZUTANI Sukeyoshi, NUMA Akio, et al. Manufacture of cyano norbornene involves recovering unreacted acrylonitrile, cyclopentadiene or dicyclopentadiene from upper portion of refining tower and recycling recovered unreacted compound as raw material: JP2002348271A[P]. 2002-12-04.
71	FUKADA Isao, MATSUURA Akira, MIZUTANI Sukeyoshi. New silyl norbornene compound and silyl tetracyclo dodecene compound, used as raw material in various organic chemical industries such as pharmaceutical and agrochemical intermediates: JP2003252881A[P]. 2003-09-10.
72	MIZUTANI S, KARASAWA M, MEJIKA I, et al. Prepn. of cyano-norbornene: JP3402499B2[P]. 2003-05-06.
73	INOMATA Masasane, TAKENO Masahiro, NUMA Akio, et al. Prepn. of cyano: Norbornene, useful as raw material for polymer: JPH09227489A[P]. 1997-09-02.
74	KAIZU Mitsutaka, MASUTANI Masataka, NISHIMURA Toshiro. Manufacture of norbornene diol derivative: JP2008044918A[P]. 2008-02-28.
75	TAGUCHI Kenji, IKEDA Yoshihiro, ISHINO Yoshiki. Method of producing norbornene derivative: JP2009227614A[P].
76	SONE Takaaki. Method of producing exo-type norbornene compound: JP2014185124A[P]. 2014-10-02.
77	SONE Takaaki. Production method of exo-type norbornene compound: JP2015003879A[P]. 2015-01-08.
78	JOSHEL Lloyd M. Manufacture of alicyclic compounds: US2349232[P]. 1944-05-16.
79	THOMAS Charles L. Hydrocarbon synthesis: US2340908[P]. 1944-02-08.
80	HILL Arthur B, MAISEL Daniel S, WOOD Donald W. Manufacture of norbornylene: US3007977[P]. 1961-11-07.
81	R·科特维卡, A·马尔巴赫. 降冰片烯的生产方法及反应器: CN1284052A[P]. 2001-02-14.
	KOTWICA R， MARBACH A. Fabrication and reactor of norbornene: CN1284052A[P]. 2001-02-14.
82	晁建平, 焦玉海. 降冰片烯的合成[J]. 石油化工高等学校学报(自然科学版), 1995, 8(3): 9-10.
	CHAO Jianping, JIAO Yuhai. Synthesis of norbornene[J]. Journal of Petrochemical Universities of Sinopec, 1995, 8(3): 9-10.
83	周崎. 降冰片烯合成工艺的研究[J]. 石油化工技术与经济, 2011, 27(3): 40-44.
	ZHOU Qi. Study on synthesizing process of norbornene[J]. Technology & Economics in Petrochemicals, 2011, 27(3): 40-44.
84	姚臻, 傅建松, 曹堃, 等. 一种制备降冰片烯的方法: CN103664470A[P]. 2014-03-26.
	YAO Zhen, FU Jiansong, CAO Kun, et al. A method for preparing norbornene: CN103664470A[P]. 2014-03-26.
85	LEE Sang-Beom, CHO Sung-Hwan, PARK Young-Whan, et al. Kinetics of norbornene synthesis and continuous reactor modeling study[M]//New Developments and Application in Chemical Reaction Engineering. Amsterdam: Elsevier, 2006: 709-712.
86	张冬梅. 降冰片烯精馏分离过程的模拟及实验[J]. 石油化工技术与经济, 2012, 28(3): 14-16.
	ZHANG Dongmei. Simulation and experiment on the rectifying separation process of norbornene[J]. Technology & Economics in Petrochemicals, 2012, 28(3): 14-16.
87	WING M, MATHEWS G. Vapor phase preparation of norbornenes: US3763253[P]. 1973-10-02.
88	DECKERT Hans-Christoph, EHRIG Rainer, JAUCH Ruth, et al. Continuous method for the production of norbornes: DD140874A1[P]. 1980-04-02.
89	MOLL Karl-Klaus, STEINBRECHER Martin, RAMHOLD Klaus. Method for the continuous production of pure norbornes: DD215078A1[P]. 1984-10-31.
90	杨春育, 丁明, 晁建平, 等. 由环戊二烯合成降冰片烯的动力学[J]. 石油化工高等学校学报, 1999, 12(3): 35-38.
	YANG Chunyu, DING Ming, CHAO Jianping, et al. Kinetics of norbornene synthesis from cyclopentadiene[J]. Journal of Petrochemical Universities, 1999, 12(3): 35-38.
91	徐鑫. 微通道反应器中超临界态制备降冰片烯和乙烯基降冰片烯[D]. 杭州: 浙江大学, 2020.
	XU Xin. Preparation of norbornene and vinyl norbornene in supercritical state in microchannel reactor[D]. Hangzhou: Zhejiang University, 2020.
92	姚臻, 曹堃, 戴斌斌, 等. 在环管反应器中制备降冰片烯的方法: CN102249839A[P]. 2011-11-23.
	YAO Zhen, CAO Kun, DAI Binbin, et al. A method for preparing norbornene in a tubular reactor: CN102249839A[P]. 2011-11-23.
93	NIST Chemistry WebBook, 2023. .
94	Chemical Properties of 1,3-Cyclopentadiene (CAS 542-92-7), 2023. .
95	Chemical Properties of Dicyclopentadiene (CAS 77-73-6), 2023. .
96	LORETTE N. Preparation of norbornenes: US3766283[P]. 1973-10-16.
97	DOKURNO Mark G. Manufacture of norbornene: CA1215399A[P]. 1986-12-16.
98	SCHNEIDER Wolfgang. Process for the preparation of substituted norbornene derivatives: US4168282[P]. 1979-09-18.
99	范慧军, 张文泉, 朱萌, 等. 降冰片烯的生产工艺: CN104262074A[P]. 2015-01-07.
	FAN Huijun, ZHANG Wenquan, ZHU Meng, et al. Production process for norbornene: CN104262074A[P]. 2015-01-07.
100	NISHI Giichi, OSHIMA Masayoshi. Poly-cyclic norbornene monomers for polymeric protective film: JP1149738A[P]. 1989-06-12.
101	YAMATO Mototoshi, OKUMURA Kinichi, NAKANO Munetoshi. Monomers for thermosetting resins: JP63234017A[P]. 1988-09-29.
102	AIDA Fuyuki, SUZUKI Takashi, MATSUMURA Yasuo. Method for continuous production of tetracyclododecene: JP2001139502A[P]. 2001-05-22.
103	AIDA Fuyuki, SUZUKI Takashi, MATSUMURA Yasuo. Simultaneous production of both norbornene and high-purity tetracyclododecene: JP2001139500A[P]. 2001-05-22.
104	KANAMORI Daisuke, HORIE Michitaka. Method for simultaneously producing norbornene and tetracyclododecene: JP2003137820A[P]. JP 2003137820A.
105	HORIE Michitaka, TAKEMATSU Minoru, KIKUCHI Takayuki, et al. Method for producing norbornene-based monomer: JP2002173452A[P]. 2002-06-21.
106	SHIMIZU Yasuhiro. Norbornene monomer and use of the same: JP2014218569A[P]. 2014-11-20.
107	TAGATA Sumimasa, OZEKI Natsuki. Spiro ring-containing norbornene derivative, norbornene-based ring-opened polymer, norbornene-based ring-opened polymer hydrogenated product, optical resin material and optical form: JP2008007733A[P]. 2008-01-17.
108	TAGATA Sumimasa, IKEDA Shintaro, OBUCHI Kazuyuki. Spiro ring-containing norbornene derivative, norbornene-based polymer, norbornene-based ring-opening polymer hydride, optical resin material and optical molded product: JP2008222663A[P]. 2008-09-25.
109	OBATA Atsuo, UEDA Naohiro, SUZUKI Tomohiro, et al. Method for producing cyclic olefin: JP2009120569A[P]. 2009-06-04.
110	宫本佳和, 宫木伸行, 后藤幸平, 等. 降冰片烯衍生物、降冰片烯开环(共)聚合物以及制备该开环(共)聚合物的方法: CN1787983A[P]. 2006-06-14.
	MIYAMOTO Yoshikazu, MIYAKI Nobuyuki, GOTO Kohei, et al. Norbornene derivative, norbornene polymer produced by ring-opening ()polymerization, and process for producing the polymer by ring-opening (co)polymerization: CN1787983A[P]. 2006-06-14.
111	KAWASHIMA Naoyuki, MIYAKI Nobuyuki, MIYAMOTO Yoshikazu, et al. Manufacture of norbornene derivative used as raw material monomer of cyclic olefin containing (co)polymer, involves performing Diels-Alder reaction of cycloolefin and cyclopentadiene: JP2006225316A[P]. 2006-08-31.

项目	气相工艺	液相工艺	气液相结合
反应温度	≥300℃	170~260℃	170~350℃
停留时间	0.3s~1.5min	2~5h	—
优点	转化率高	操作温度低，相对安全	兼顾气相、液相解聚的优点
缺点	温度高，反应剧烈，壁面易形成高聚物	反应时间长，釜底容易生成多聚物结焦	—
稀释剂	CO₂、N₂、水蒸气、脂肪烃、芳烃等	高沸点脂肪烃、芳香烃	—
阻聚剂	丁炔二酸、对苯二酚、苯醌、四甲基哌啶醇、四甲基儿茶酚、复配阻聚剂

项目	气相工艺	液相工艺	气液相结合
反应温度	≥300℃	170~260℃	170~350℃
停留时间	0.3s~1.5min	2~5h	—
优点	转化率高	操作温度低，相对安全	兼顾气相、液相解聚的优点
缺点	温度高，反应剧烈，壁面易形成高聚物	反应时间长，釜底容易生成多聚物结焦	—
稀释剂	CO₂、N₂、水蒸气、脂肪烃、芳烃等	高沸点脂肪烃、芳香烃	—
阻聚剂	丁炔二酸、对苯二酚、苯醌、四甲基哌啶醇、四甲基儿茶酚、复配阻聚剂

参数	乙烯	CPD	NB	DCPD	甲苯
熔点^①/℃	-169.4	-90	44.5	33.6	-95
沸点^①/℃	-104.1	41	96	170	110.6
临界温度/℃	9.3^①	233.9^②/259.5^③	316.8^①	386.9^②/391.3^③	319.8^①
临界压力/MPa	5.06^①	5.15^②/5.01^③	4.86^①	3.06^②/3.36^③	4.1^①

参数	乙烯	CPD	NB	DCPD	甲苯
熔点^①/℃	-169.4	-90	44.5	33.6	-95
沸点^①/℃	-104.1	41	96	170	110.6
临界温度/℃	9.3^①	233.9^②/259.5^③	316.8^①	386.9^②/391.3^③	319.8^①
临界压力/MPa	5.06^①	5.15^②/5.01^③	4.86^①	3.06^②/3.36^③	4.1^①

项目	气相工艺	液相工艺	超临界工艺
特点	使DCPD/CPD汽化，与乙烯混合进行反应	DCPD/CPD在反应过程中呈液态，乙烯气体溶于液相后进行加成反应	反应物处于超临界状态
温度	220~340℃	150~320℃	180~300℃
压力	1.22~6.9MPa	1.2~68.9MPa	5~30MPa
停留时间	4s~30min	6min~10h	—
优点	物料混合充分，选择性高	相对安全，易于实现规模化生产	强化传质、传热效率，减少副反应发生
缺点	物料摩尔体积大，高温带来更多安全隐患	副反应多，容易产生多聚物堵塞设备，加入惰性溶剂可以有效抑制副反应	—
稀释剂	H₂等	高沸点惰性烷烃溶剂、卤代烃溶剂	—