微反应器内丁基橡胶溶液法制备体系的反应特性研究

doi:10.11949/0438-1157.20200999

摘要/Abstract

摘要：

研究了微反应器内丁基橡胶溶液法制备体系的反应规律。结果表明以H₂O为质子源、EtAlCl₂为共引发剂时，控制反应温度为-60℃、水含量在0（control）到0.27 mmol/L之间，可在分钟级时间内高转化率地得到数均分子量高于300000的聚异丁烯产品，此时链转移得到有效抑制，强化反应物料的初始混合对提升产品质量有利；引入异戊二烯会显著降低产物分子量和转化速度，可以通过使用酸性更弱的Et₂AlCl代替EtAlCl₂来稳定碳阳离子，抑制链转移，在-60℃下得到数均分子量接近150000的共聚产物，但反应速度缓慢，需要进一步优化和控制反应体系中的水含量来强化该过程。

关键词: 丁基橡胶, 溶液聚合, 微反应器, 阳离子聚合, 制备, 聚合物

Abstract:

Reaction characteristics of solution polymerization system for butyl rubber preparation in microreactor has been studied. Results showed that polyisobutylene with M_n over 300000 can be quantitatively obtained in minutes when using H₂O as proton source, EtAlCl₂ as co-initiator, and keeping reaction temperature at -60℃, water concentration between 0 (control) and 0.27 mmol/L. Chain transfer was efficiently suppressed under this condition. Enhancing the initial mixing of reactants was good for improving product quality. Incorporating isoprene in the system will significantly decrease molecular weight of final products and reaction rate. Replacing EtAlCl₂ with less acidic Et₂AlCl can stabilize carbocation and inhibit chain transfer. Copolymer with M_n near 150000 can be obtained at -60℃, but the reaction rate was moderate and need further optimization of system water concentration to enhance this process.

Key words: butyl rubber, solution polymerization, microreactor, cationic polymerization, preparation, polymers

中图分类号:

TQ 333.6

何宇航, 刘晴捷, 吕阳成. 微反应器内丁基橡胶溶液法制备体系的反应特性研究[J]. 化工学报, 2021, 72(2): 1001-1008.

HE Yuhang, LIU Qingjie, LYU Yangcheng. Study on reaction characteristics of solution polymerization system for butyl rubber preparation in microreactor[J]. CIESC Journal, 2021, 72(2): 1001-1008.

图/表 6

参考文献 30

1	武冠英, 吴一弦. 控制阳离子聚合及其应用[M]. 北京: 化学工业出版社, 2005: 384.
	Wu G Y, Wu Y X. Controlled Cationic Polymerization and Its Application[M]. Beijing: Chemical Industry Press, 2005: 384.
2	McDonald M F, Shaffer T D, Tsou A H. Commercial Isobutylene Polymers[M]. John Wiley & Sons, Inc., 2016.
3	Takahashi S, Goldberg H A, Feeney C A, et al. Gas barrier properties of butyl rubber/vermiculite nanocomposite coatings [J]. Polymer, 2006, 47(9): 3083-3093.
4	Giller C B, Roland C M. Strength enhancement in miscible blends of butyl rubber and polyisobutylene [J]. Macromolecules, 2013, 46(7): 2818-2822.
5	崔小明. 国内外丁基橡胶供需现状及发展前景分析[J]. 中国橡胶, 2018, 34(1): 34-39.
	Cui X M. Analysis of current situation and development prospects of butyl rubber supply and demand at home and abroad[J]. Chinese Rubber, 2018, 34(1): 34-39.
6	Chen J F, Gao H, Zou H K, et al. Cationic polymerization in rotating packed bed reactor: Experimental and modeling [J]. AIChE Journal, 2009, 56(4): 1053-1062.
7	Sofronova O V, Markina E A, Chelnokova S M, et al. Synthesis of butyl rubber by cationic polymerization in methyl chloride in the presence of alkyl chlorides[J]. Russian Journal of Applied Chemistry, 2011, 84(8): 1430-1433.
8	Gronowski A A. Synthesis of butyl rubber in hexane using a mixture of Et₂AlCl and EtAlCl₂ in the initiating system[J]. Journal of Applied Polymer Science, 2003, 87(14): 2360-2364.
9	Garratt S, Carr A G, Langstein G, et al. Isobutene polymerization and isobutene-isoprene copolymerization catalyzed by cationic zirconocene hydride complexes[J]. Macromolecules, 2003, 36(12): 4276-4287.
10	Pi Z, Jacob S, Kennedy J P. Cationic polymerizations at elevated temperatures by novel initiating systems having weakly coordinating counteranions 1. high molecular weight polyisobutylenes[J]. Ionic Polymerizations and Related Processes, 1999, (359): 1-12.
11	Jacob S, Pi Z, Kennedy J P. Cationic polymerizations at elevated temperatures by novel initiating systems having weakly coordinating counteranions 2. Isobutylene/isoprene copolymerizations[J]. Polymer Bulletin, 1998, 41(5): 503-510.
12	Li Y, Wu Y X, Xu X, et al. Electron-pair-donor reaction order in the cationic polymerization of isobutylene coinitiated by AlCl₃[J]. Journal of Polymer Science Part A: Polymer Chemistry, 2007, 45(14): 3053-3061.
13	Huang Q, He P, Wang J, et al. Synthesis of high molecular weight polyisobutylene via cationic polymerization at elevated temperatures[J]. Chinese Journal of Polymer Science, 2013,31(8): 1139-1147.
14	Li Y, Wu Y X, Liang L H, et al. Cationic polymerization of isobutylene coinitiated by AlCl₃ in the presence of ethyl benzoate[J]. Chinese Journal of Polymer Science, 2010, 28(1): 55-62.
15	Kaszas G, Puskas J E, Chen C C, et al. Electron pair donors in carbocationic polymerization. I. Introduction into the synthesis of narrow molecular weight distribution polyisobutylenes [J]. Polymer Bulletin, 1988, 20(5): 413-419.
16	Kaszas G, Puskas J E, Chen C C, et al. Electron pair donors in carbocationic polymerization. 2. Mechanism of living carbocationic polymerizations and the role of in situ and external electron pair donors[J]. Macromolecules, 1990, 23(17): 3909-3915.
17	Gyor M, Wang H C, Faust R. Living carbocationic polymerization of isobutylene with blocked bifunctional initiators in the presence of di-tert-butylpyridine as a proton trap[J]. Journal of Macromolecular Science Part A, 1992, 29(8): 639-653.
18	Fodor Z, Gyor M, Wang H C, et al. Living carbocationic polymerization of styrene in the presence of proton trap[J]. Journal of Macromolecular Science Part A: Pure and Applied Chemistry, 1993, 30(5): 349-363.
19	Yoshida J I, Suga S. Basic concepts of “cation pool” and “cation flow” methods and their applications in conventional and combinatorial organic synthesis[J]. Chemistry—A European Journal, 2002, 8(12): 2650-2658.
20	Tonhauser C, Wilms D, Wurm F, et al. Multihydroxyl-functional polystyrenes in continuous flow[J]. Macromolecules, 2010, 43(13): 5582-5588.
21	Iwasaki T, Yoshida J I. Free radical polymerization in microreactors. Significant improvement in molecular weight distribution control[J]. Macromolecules, 2005, 38(4): 1159-1163.
22	Iwasaki T, Kawano N, Yoshida J I. Radical polymerization using microflow system: numbering-up of microreactors and continuous operation[J]. Organic Process Research & Development, 2006, 10(6): 1126-1131.
23	Nagaki A, Kawamura K, Suga S, et al. Cation pool-initiated controlled/living polymerization using microsystems[J]. Journal of the American Chemical Society, 2004, 126(45): 14702-14703.
24	骆广生, 王凯, 王佩坚, 等. 微反应器内聚合物合成研究进展[J]. 化工学报, 2014, 65(7): 2563-2573.
	Luo G S, Wang K, Wang P J, et al. Advances in polymer synthesis in microreactors[J]. CIESC Journal, 2014, 65(7): 2563-2573.
25	Lu Y C, Zhu S, Wang K, et al. Generation of poly(isobutene-co-isoprene) in a microflow device[J]. Industrial & Engineering Chemistry Research, 2016, 55(5): 1215-1220.
26	Yang R. Analytical Methods for Polymer Characterization[M]. Boca Raton: CRC Press, 2018: 172.
27	Yan P F, Guo A R, Liu Q, et al. Living cationic polymerization of isobutylene coinitiated by FeCl₃ in the presence of isopropanol[J]. Journal of Polymer science Part A: Polymer Chemistry, 2012, 50(16): 3383-3392.
28	Bartelson K J, De P, Kumar R, et al. Cationic polymerization of isobutylene by FeCl₃/ether complexes in hexanes: an investigation of the steric and electronic effects of ethers [J]. Polymer, 2013, 54(18): 4858-4863.
29	Shiman D I, Vasilenko I V, Kostjuk S V. Cationic polymerization of isobutylene by complexes of alkylaluminum dichlorides with diisopropyl ether: an activating effect of water [J]. Journal of Polymer Science Part A: Polymer Chemistry, 2014, 52(16): 2386-2393.
30	Kennedy J P, Squires R G. Fundamental studies on cationic polymerization Ⅳ. Homo- and co-polymerizations with various catalysts[J]. Polymer, 1965, 6(11): 579-587.

No.	Flow rate/(ml/min)			T^①/℃	t/s	[EtAlCl₂]/(mmol/L)	[H₂O]/(mmol/L)	M_n	PDI	Conv./%
No.	IB	Initiator	Diluent	T^①/℃	t/s	[EtAlCl₂]/(mmol/L)	[H₂O]/(mmol/L)	M_n	PDI	Conv./%
1	2	6	8	-60	0.32	1.5	0.27	136190	2.58	1.6
2	2	6	8	-60	1.06	1.5	0.27	198770	3.01	2.8
3	2	6	8	-60	2	1.5	0.27	147130	3.19	3.0
4	2	6	8	-60	2.65	1.5	0.27	110440	3.50	2.5
5	2	6	8	-60	4	1.5	0.27	108030	3.92	0.80
6	2	6	8	-60	60	1.5	0.27	377060	2.67	70.4
7	2	6	8	-60	60	1.5	0.33	394630	3.08	16.5
8	2	6	8	-60	60	1.5	0.46	ND	ND	trace
9	2	6	8	-60	60	1.5	0	328360	2.33	100
10	1	3	4	-60	120	1.5	0	254510	2.64	60.8
11	0.5	1.5	2	-60	240	1.5	0	244190	2.86	100
12	2	6	8	-45	60	1.5	0	113530	2.90	100
13	2	6	8	-30	60	1.5	0	73960	2.07	79.4
14	2	6	8	-15	60	1.5	0	19850	2.77	62.5
15	2	6	8	0	60	1.5	0	3710	3.86	95.8
16	2	6	8	-30	60	1.5	0.04	112950	2.08	37.09
17	2	6	8	-30	60	1.5	0.18	84910	2.21	40.86
18	2	6	8	-30	60	1.5	0.27	34550	2.79	93.73

No.	Flow rate/(ml/min)			T^①/℃	t/s	[EtAlCl₂]/(mmol/L)	[H₂O]/(mmol/L)	M_n	PDI	Conv./%
No.	IB	Initiator	Diluent	T^①/℃	t/s	[EtAlCl₂]/(mmol/L)	[H₂O]/(mmol/L)	M_n	PDI	Conv./%
1	2	6	8	-60	0.32	1.5	0.27	136190	2.58	1.6
2	2	6	8	-60	1.06	1.5	0.27	198770	3.01	2.8
3	2	6	8	-60	2	1.5	0.27	147130	3.19	3.0
4	2	6	8	-60	2.65	1.5	0.27	110440	3.50	2.5
5	2	6	8	-60	4	1.5	0.27	108030	3.92	0.80
6	2	6	8	-60	60	1.5	0.27	377060	2.67	70.4
7	2	6	8	-60	60	1.5	0.33	394630	3.08	16.5
8	2	6	8	-60	60	1.5	0.46	ND	ND	trace
9	2	6	8	-60	60	1.5	0	328360	2.33	100
10	1	3	4	-60	120	1.5	0	254510	2.64	60.8
11	0.5	1.5	2	-60	240	1.5	0	244190	2.86	100
12	2	6	8	-45	60	1.5	0	113530	2.90	100
13	2	6	8	-30	60	1.5	0	73960	2.07	79.4
14	2	6	8	-15	60	1.5	0	19850	2.77	62.5
15	2	6	8	0	60	1.5	0	3710	3.86	95.8
16	2	6	8	-30	60	1.5	0.04	112950	2.08	37.09
17	2	6	8	-30	60	1.5	0.18	84910	2.21	40.86
18	2	6	8	-30	60	1.5	0.27	34550	2.79	93.73

No.	Flow rate/(ml/min)			（IP/IB）/%(mol)	t/s	[EtAlCl₂]/(mmol/L)	[Et₂AlCl]/(mmol/L)	M_n	PDI	Conv./%
No.	IB	Initiator	Diluent+IP	（IP/IB）/%(mol)	t/s	[EtAlCl₂]/(mmol/L)	[Et₂AlCl]/(mmol/L)	M_n	PDI	Conv./%
19	2	6	8	1.91	60	1.5	0	77040	1.66	26.38
20	2	6	8	1.91	300	1.5	0	64030	1.87	69.83
21	2	6	8	2.39	60	1.5	0	34250	1.77	24.74
22	2	6	8	2.86	60	1.5	0	12760	1.87	24.49
23	2	6	8	3.82	60	1.5	0	ND	ND	trace
24	2	6	8	1.91	60	15	0	75190	2.11	23.67
25	2	6	8	1.91	300	15	0	87210	1.88	49.03
26	2	6	8	1.91	60	0	1.5	129430	2.97	1.04
27	2	6	8	1.91	300	0	1.5	147750	2.73	2.08

No.	Flow rate/(ml/min)			（IP/IB）/%(mol)	t/s	[EtAlCl₂]/(mmol/L)	[Et₂AlCl]/(mmol/L)	M_n	PDI	Conv./%
No.	IB	Initiator	Diluent+IP	（IP/IB）/%(mol)	t/s	[EtAlCl₂]/(mmol/L)	[Et₂AlCl]/(mmol/L)	M_n	PDI	Conv./%
19	2	6	8	1.91	60	1.5	0	77040	1.66	26.38
20	2	6	8	1.91	300	1.5	0	64030	1.87	69.83
21	2	6	8	2.39	60	1.5	0	34250	1.77	24.74
22	2	6	8	2.86	60	1.5	0	12760	1.87	24.49
23	2	6	8	3.82	60	1.5	0	ND	ND	trace
24	2	6	8	1.91	60	15	0	75190	2.11	23.67
25	2	6	8	1.91	300	15	0	87210	1.88	49.03
26	2	6	8	1.91	60	0	1.5	129430	2.97	1.04
27	2	6	8	1.91	300	0	1.5	147750	2.73	2.08

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