Study on reaction characteristics of solution polymerization system for butyl rubber preparation in microreactor

doi:10.11949/0438-1157.20200999

Abstract

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

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

CLC Number:

TQ 333.6

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.

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.

Figures/Tables 6

References 30

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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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