Progress on ionic liquid catalyst for α-olefin polymerization

doi:10.16085/j.issn.1000-6613.2019-0823

Abstract

Abstract:

Compared with traditional catalysts, ionic liquid (IL) catalysts have the advantages of easy separation and recycling，which renders them great potential in the polymerization of α-olefins. This article introduces the basic properties of ILs and describes the reaction mechanism of α-olefin polymerization with ILs as catalyst. Then, the applications of Lewis acid ILs in the α-olefin polymerization are reviewed. The catalytic activity and product properties are analyzed. In addition, the researches of novel liquid coordination complexes (LCCs) also have been summarized. From the reported results, high conversions have been realized with ILs and LCCs as catalysts. However, the selectivity needs to be further improved with lots of experimental investigations. Although ILs and LCCs catalysts cannot replace the traditional catalysts at present, they have shown great application prospect，and will be one hotspot of future researches.

Key words: ionic liquid, catalysts, polymerization, polymers, α-olefin

摘要：

离子液体催化剂具有易分离、可回收、能循环使用等优点，在α-烯烃聚合领域表现出巨大的潜力。本文首先介绍了离子液体的基本物化性质，简述了离子液体催化α-烯烃聚合的反应机理。之后以阳离子结构为基础，详细回顾了路易斯酸型离子液体在α-烯烃聚合反应中的应用，并对其催化活性和产物性质进行了分析。最后，对新型类离子液体催化剂的研究也进行了总结。从报道的结果来看，离子液体催化剂和类离子液体催化剂都已经能够实现较高的产物转化率，但是产物的选择性有待提高，仍然需要更多的实验探索。尽管短时间内还无法取代传统催化剂，但它们已经表现出巨大的应用前景，是未来的研究热点之一。

关键词: 离子液体, 催化剂, 聚合, 聚合物, α-烯烃

CLC Number:

O643.3

Huan LI,Yinong LIU. Progress on ionic liquid catalyst for α-olefin polymerization[J]. Chemical Industry and Engineering Progress, 2020, 39(2): 513-520.

李欢,刘依农. 离子液体催化α-烯烃聚合的研究进展[J]. 化工进展, 2020, 39(2): 513-520.

Figures/Tables 12

References 37

1	吴艳. 浅谈合成润滑油的特点与前景. 合成润滑材料[J]. 2012, 39(3): 19-21.
	WU Y. Discussion on characteristics and prospects of synthetic lubricants in brief[J]. Synthetic Lubricants, 2012, 39(3): 19-21.
2	叶思景, 韩生. 聚α烯烃合成润滑油发展及其应用研究[J]. 上海化工, 2014, 39(4): 24-28.
	YE S J, HAN S. Development and application research of poly alphaolefin in synthetic lubricant[J]. Shanghai Chemical Industry, 2014, 39(4): 24-28.
3	黄丽敏. 全球合成基础油市场现状与发展趋势[J]. 石油炼制与化工, 2019, 50(2): 44.
	HUANG L M. Current situation and development trend of global synthetic base oil market[J]. Petroleum Processing and Petrochemicals, 2019, 50(2): 44.
4	RAY S, RAO P V, CHOUDARY N V. Poly‐α‐olefin‐based synthetic lubricants: a short review on various synthetic routes[J]. Lubrication Science, 2012, 24(1): 23-44.
5	张耀, 段庆华, 刘依农, 等. α-烯烃齐聚制备聚α-烯烃合成油催化剂的研究进展[J]. 精细石油化工, 2011, 28(1): 82-86.
	ZHANG Y, DUANG Q H, LIU Y N, et al. Progress on research of catalysts for 1-olefins oligomerization to poly(alpha) olefin[J]. Speciality Petrochemicals, 2011, 28(1): 82-86.
6	孙维, 徐婷婷, 霍宏亮, 等. α-烯烃聚合制低黏度聚α-烯烃催化剂的研究进展[J]. 精细石油化工进展, 2017, 18(6): 22-25.
	SUN W, XU T T, HUO H L, et al. Progress of research on catalysts for preparation of low viscosity PAO by α-olefin polymerization[J]. Advances in Fine Petrochemicals, 2017, 18(6): 22-25.
7	孙恩浩, 王海英, 蒋岩, 等. 高黏度聚α-烯烃基础油催化剂研究进展[J]. 精细石油化工进展, 2018, 19(6): 35-37.
	SUN E H, WANG H Y, JIANG Y, et al. Advances in catalyst for high viscosity poly-α-olefin preparation[J]. Advances in Fine Petrochemicals, 2018, 19(6): 35-37.
8	赵东滨, 寇元. 室温离子液体: 合成、性质及应用[J]. 大学化学, 2002(1): 42-46.
	ZHAO D B, KOU Y. Room temperature ionic liquids: synthesis, properties and applications[J]. University Chemistry, 2002(1): 42-46.
9	王婧菲, 李凌飞. 离子液体的发展历程及其应用研究[J]. 山东工业技术, 2015(8): 161-171.
	WANG J F, LI L F. Development and application of ionic liquids[J]. Shandong Industrial Technology, 2015(8): 161-171.
10	赵智, 殷彤蛟, 田鹏. 离子液体在有机合成中的应用研究[J]. 山东化工, 2017, 46(4): 65-66.
	ZHAO Z, YIN T J, TIAN P. Study on the application of ionic liquids in organic synthesis[J]. Shandong Chemical Industry, 2017, 46(4): 65-66.
11	BROWN L C, HOGG J M, SWADZBA-KWASNY M. Lewis acidic ionic liquids[J]. Topics in Current Chemistry, 2017, 375(5): 78.
12	AMARASEKARA A S. Acidic ionic liquids[J]. Chemical Reviews, 2016, 116(10): 6133-6183.
13	SHUBKIN R L, BAYLERIAN M S, MALER A R. Olefin oligomer synthetic lubricants: structure and mechanism of formation[J]. Industrial & Engineering Chemistry Product Research and Development, 1980, 19(1): 15-19.
14	ESTAGER J, HOLBREY J, SWADŹBA-KWAŚNY M. Halometallate ionic liquids–revisited[J]. Chemical Society Reviews, 2014, 43(3): 847-886.
15	WILKES J S, LEVISKY J A, WILSON R A, et al. Dialkylimidazolium chloroaluminate melts: a new class of room-temperature ionic liquids for electrochemistry, spectroscopy and synthesis[J]. Inorganic Chemistry, 1982, 21(3): 1263-1264.
16	WILKES J S, ZAWOROTKO M J. Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J]. Journal of the Chemical Society, Chemical Communications, 1992(13): 965-967.
17	DING H S, ZHANG B Y, LIU J. Study on preparation process of lubrication from 1-decene with acidic ionic liquid catalyst[J]. Petroleum Science and Technology, 2009, 27(17): 1919-1925.
18	张大伟. 离子液体催化1-癸烯齐聚物的合成及其应用研究[D]. 济南: 山东大学, 2013.
	ZHANG D W. Study on ionic liquid catalyst for oligomerization of 1-decene and application of synthetic base oil[D]. Jinan: Shandong University, 2013.
19	田凡. 合成聚α-烯烃离子液体催化剂的研究[J]. 应用化工, 2012, 41(3): 483-485.
	TIAN F. Study on catalytic system of ionic liquid for polymerization of α-olefin[J]. Applied Chemical Industry, 2012, 41(3): 483-485.
20	贺丽丽, 丁洪生, 刘进, 等. 新型离子液体催化1-癸烯齐聚反应研究[J]. 化工科技, 2010, 18(3): 7-10.
	HE L L, DING H S, LIU J, et al. Study on 1-decene oligomerication catalyzed by novel ionic liquid system[J]. Science & Technology in Chemical Industry, 2010, 18(3): 7-10.
21	王维伟, 蒋山, 王永彬, 等. 离子液体催化合成高黏度指数基础油工艺研究[J]. 润滑与密封, 2015, 40(11): 19-22.
	WANG W W, JIANG S, WANG Y B, et al. Study of synthetic process of high viscosity index base oil with ionic liquid as catalyst[J]. Lubrication Engineering, 2015, 40(11): 19-22.
22	杨宁. 离子液体催化PAO的合成[D]. 大连: 大连海事大学, 2010.
	YANG N. Synthesis of PAO using ionic liquid as catalysts[D]. Dalian: Dalian Maritime University, 2010.
23	HOPE K D, DRIVER M S, HARRIS T V. High viscosity polyalphaolefins prepared with ionic liquid catalyst: US6395948[P]. 2000-5-31.
24	HOPE K D, TWOMEY D W, DRIVER M S, et al. Method for manufacturing high viscosity polyalphaolefins using ionic liquid catalysts: US2008161623[P]. 2008-07-03.
25	王成欢, 毕玉琦, 杨明, 等. 润滑材料1-癸烯齐聚物的合成与性能研究[J]. 航空材料学报, 2015, 35(1): 45-50.
	WANG C H, BI Y Q, YANG M, et al. Synthesis and properties of 1-decene oligomer lubricant[J]. Journal of Aeronautical Materials, 2015, 35(1): 45-50.
26	吕春胜, 李东凯, 许云飞, 等. 离子液体催化1-癸烯齐聚制备润滑油基础油[J]. 现代化工, 2013, 5: 79-81.
	LÜ C S, LI D K, XU Y F, et al. Preparation of lubricant base oil from 1-decene oligomerization catalyzed by ionic liquid[J]. Modern Chemical Industry, 2013, 5: 79-81.
27	吕春胜, 许云飞, 颜子龙, 等. 1-C₁₂烯烃齐聚制备高性能润滑油基础油[J]. 石油学报(石油加工), 2014, 30(3): 446-452.
	LÜ C S, XU Y F, YAN Z L, et al. The oligomerization of 1-dodecene to synthesize high performance lubricating base oil[J]. Acta Petrolei Sinica(Petroleum Processing Section), 2014, 30(3): 446-452.
28	吕春胜, 李艺超, 杨阳, 等. 1-C₁₄烯烃齐聚制备高性能润滑油基础油[J]. 应用化工, 2015, 44(1): 76-80.
	LÜ C S, LI Y C, YANG Y, et al. Oligomerization of 1-tetradecene to synthesize high performance lubricating base oil[J]. Applied Chemical Industry, 2015, 44(1): 76-80.
29	ELOMARI S, KRUG R. Process for making and composition of superior lubricant or lubricant blendstock: US7572944[P]. 2009-08-11.
30	BISCHOF S M, COFFIN R C, HOPE K D, et al. Method for making polyalphaolefins using ionic liquid catalyzed oligomerization of olefins: WO2017030753A1[P]. 2017-02-23.
31	COFFIE S, HOGG J M, CAILLER L, et al. Lewis superacidic ionic liquids with tricoordinate borenium cations[J]. Angewandte Chemie International Edition, 2015, 54(49): 14970-14973.
32	COLEMAN F, COFFIE S, ATKINS M P, et al. Oligomerisation process: WO2016005769A1[P]. 2016-01-14.
33	KORE R, BERTON P, KELLEY S P, et al. Group IIIA halometallate ionic liquids: speciation and applications in catalysis[J]. ACS Catalysis, 2017, 7(10): 7014-7028.
34	孙进贺, 贾永忠. 类离子液体及其应用[J]. 中国科学:化学, 2016, 46(12): 1317-1329.
	SUN J H, JIA Y Z. Pseudo ionic liquids and their applications[J]. Scientia Sinica(Chimica), 2016, 46(12): 1317-1329.
35	HOGG J M, COLEMAN F, FERRER-UGALDE A, et al. Liquid coordination complexes: a new class of Lewis acids as safer alternatives to BF₃ in synthesis of polyalphaolefins[J]. Green Chemistry, 2015, 17(3): 1831-1841.
36	DERBALA H A. Chemoselectivity of 2‐arylmethyleneaminoisoindolin‐1, 3‐diones toward arenes under friedel-crafts conditions: an efficient synthesis of benzophenones integrated with 2‐substituted hydrazone moieties[J]. Journal of Heterocyclic Chemistry, 2012, 49(3): 700-704.
37	FRINGUELLI F, GIROTTI R, PIZZO F, et al. [AlCl₃+2THF]: a new and efficient catalytic system for diels-alder cycloaddition of α,β-unsaturated carbonyl compounds under solvent-free conditions[J]. Organic Letters, 2006, 8(12): 2487-2489.

离子液体	转化率/%	产物分布/%					参考文献
离子液体	转化率/%	C20	C30	C40	C50	C60	参考文献
1-丁基-3-甲基咪唑盐	74	21.07	52.28	20.96	5.39	—	[17]
1-乙基-3-甲基咪唑溴盐	83	8.13	46.18	26.19	14.78	4.72	[20]

离子液体	转化率/%	产物分布/%					参考文献
离子液体	转化率/%	C20	C30	C40	C50	C60	参考文献
1-丁基-3-甲基咪唑盐	74	21.07	52.28	20.96	5.39	—	[17]
1-乙基-3-甲基咪唑溴盐	83	8.13	46.18	26.19	14.78	4.72	[20]

循环次数	转化率/%	100℃运动黏度/mm²·s^-1	黏度指数
1	91.3	11.68	141
2	89.9	10.97	138
3	92.1	12.35	149
4	88.9	11.67	145
5	90.5	11.22	139
6	90.3	11.01	143

循环次数	转化率/%	100℃运动黏度/mm²·s^-1	黏度指数
1	91.3	11.68	141
2	89.9	10.97	138
3	92.1	12.35	149
4	88.9	11.67	145
5	90.5	11.22	139
6	90.3	11.01	143

离子液体	转化率/%	100℃运动黏度/mm²·s^-1	黏度指数	参考文献
1-丁基-3-甲基咪唑盐	—	5.30	148	[18]
1-乙基-3-甲基咪唑盐	86.9	≥10.34	143	[21]
N,N-二甲基咪唑盐	91.3	11.68	141	[22]