采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯

doi:10.7503/cjcu20140776

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (12): 2698.doi: 10.7503/cjcu20140776

采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯

单东, 杨龙, 王继铭, 郑安呐()

华东理工大学材料科学与工程学院, 上海市先进聚合物材料重点实验室,超细材料制备与应用教育部重点实验室, 上海200237

收稿日期:2014-08-27 出版日期:2014-12-10 发布日期:2014-11-29
作者简介:联系人简介: 郑安呐, 男, 博士, 教授, 博士生导师, 主要从事阴离子聚合及反应挤出研究. E-mail:zan@ecust.edu.cn
基金资助:
国家自然科学基金(批准号: 50933002)和国家“八六三”计划项目(批准号: 2012AA040306)资助

Preparation of Styrene-isoprene-styrene Thermoplastic Elastomer by Three Times Feeding Method of Reactive Extrusion^†

SHAN Dong, YANG Long, WANG Jiming, ZHENG Anna^*()

School of Materials Science and Engineering, Shanghai Key Laboratory of Advanced Polymeric Materials,Key Laboratory for Ultrafine Materials of Ministry of Education,East China University of Science and Technology, Shanghai 200237, China

Received:2014-08-27 Online:2014-12-10 Published:2014-11-29
Contact: ZHENG Anna E-mail:zan@ecust.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(No.50933002) and the National High Techonology Research and Development Program of China(No.2012AA040306)

摘要/Abstract

摘要：

以同向啮合双螺杆挤出机为反应器, 采用苯乙烯和异戊二烯为聚合单体, 以正丁基锂为引发剂, 采用三次加料法合成苯乙烯/异戊二烯/苯乙烯(SIS)三嵌段热塑性弹性体. 氢核磁共振(¹H NMR)谱分析结果表明, 共聚物中聚异戊二烯嵌段以1,4-结构为主. 采用四氧化锇催化双氧水氧化降解聚合物分子链, 利用凝胶渗透色谱对氧化降解后的聚苯乙烯碎片进行分析, 证明共聚物分子为(聚苯乙烯-聚异戊二烯-聚苯乙烯)(PS-PI-PS)三嵌段结构. 动态力学分析(DMA)及透射电子显微镜(TEM)分析结果表明, SIS具有两相分离结构. 拉伸试验结果表明, 共聚物拉伸强度与苯乙烯含量有关.

关键词: 阴离子聚合, 反应挤出, 三次加料法, 热塑性弹性体, 苯乙烯/异戊二烯/苯乙烯三嵌段共聚物

Abstract:

Styrene/isoprene/styrene(SIS) triblock thermoplastic elastomer was polymerized by three times feeding method using a co-rotating intermeshing twin screw extruder as the reactor and n-butyllithium as the initiator. ¹H NMR spectra show that the polyisoprene block of the copolymer is mainly composed of 1,4-polyisoprene structure. The molecule chains of the copolymers were degraded using hydrogen peroxide catalyzed by osmium tetroxide, the segments of polystyrene after oxidization were characterized by gel permeation chromatography(GPC) cooperating with the multi-angle laser light scattering(MALLS) instrument. It was found that the copolymers consisted of polystyrene-polyisoprene-polystyrene(PS-PI-PS) three blocks. Cooperated with the survey of dynamic mechanical analysis(DMA) and transmission electron microscope(TEM) photographs, it was confirmed that styrene/isoprene/styrene(SIS) had two phase separation structure. Tensile testing showed the relationship between tensile strength of the copolymer with styrene content.

Key words: Anionic polymerization, Reactive extrusion, Three times charging method, Thermoplastic elastomer, Styrene/isoprene/styrene triblock copolymer

中图分类号:

O632.1

TrendMD:

单东, 杨龙, 王继铭, 郑安呐. 采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯. 高等学校化学学报, 2014, 35(12): 2698.

SHAN Dong, YANG Long, WANG Jiming, ZHENG Anna. Preparation of Styrene-isoprene-styrene Thermoplastic Elastomer by Three Times Feeding Method of Reactive Extrusion^†. Chem. J. Chinese Universities, 2014, 35(12): 2698.

图/表 13

Scheme 1 Syntheses routes of the polymerization

Table 1 Protons distribution of SIS

Chemical shift, δ	Relative proton	Chemical shift, δ	Relative proton
7.05	Phenylic meta and para	4.68, 4.76	3,4-Ip
6.55	Phenylic ortho	1.68	cis-1,4 methyl
5.13	1,4-Ip	1.60	trans-1,4 and 3,4 methyl

Fig.1 1H NMR spectra of SIS-0328(a) and SIS-1209(b)

Table 2 Chemical shift(δ) of H and the computing method of the mass fraction

δ	Peak area	Double bond structure	Mass fraction of monomer
6.25—7.15	A₁	Isoprene	$68 × [A 3 + (1 / 2) A 4] 68 × [A 3 + (1 / 2) A 4] + 104 × (1 / 5) A 1$
1.64—1.72	A₂	3,4-Ip	A₄/(2A₃+A₄)
4.97—5.22	A₃
4.63—4.78	A₄	cis-1,4-Ip	A₂/(A₂+A₅)
1.56—1.64	A₅	trans-1,4-Ip	[A₅/(A₂+A₅)]-[A₄/(2A₃+A₄)]
6.25—6.75	A₆	Random-St	(A₁-A₆)/A₁

Table 2 Chemical shift(δ) of H and the computing method of the mass fraction

δ	Peak area	Double bond structure	Mass fraction of monomer
6.25—7.15	A₁	Isoprene	$68 × [A 3 + (1 / 2) A 4] 68 × [A 3 + (1 / 2) A 4] + 104 × (1 / 5) A 1$
1.64—1.72	A₂	3,4-Ip	A₄/(2A₃+A₄)
4.97—5.22	A₃
4.63—4.78	A₄	cis-1,4-Ip	A₂/(A₂+A₅)
1.56—1.64	A₅	trans-1,4-Ip	[A₅/(A₂+A₅)]-[A₄/(2A₃+A₄)]
6.25—6.75	A₆	Random-St	(A₁-A₆)/A₁

Table 3 Microstructure and its content of SIS-0328 and SIS-1209

Compd.	Mass fraction(%)
Compd.	Ip	cis-1,4-Ip	trans-1,4-Ip	3,4-Ip
SIS-0328	60.9	64.6	27.9	7.5
SIS-1209	70.8	65.2	26.0	8.8

Scheme 2 Mechanism of the oxidative reaction

Fig.2 GPC curves of SIS-0328(a) and SIS-1209(b) before(A) and after degradation(B)

Table 4 GPC data for SIS-0328 and SIS-1209 before and after degradation

Sample	Before degradation		After degradation
			First peak		Second peak
	10^-4M_n	M_w/M_n	10^-4M_n	M_w/M_n	10^-3M_n	M_w/M_n
SIS-1209	9.3	1.0	1.4	1.4	4.7	2.2
SIS-0328	11.0	1.8	3.1	2.0	14.6	1.6

Fig.3 TEM images of SIS-0328(A) and SIS-1209(B)

Fig.4 Effect of loss factor of SIS-0328(a) and SIS-1209(b) on temperature

Fig.5 Loss modulus(A) and storage modulus(B) of SIS-0328(a) and SIS-1209(b) on temperature

Fig.6 Tensile strength tests for SIS-0328(a) and SIS-1209(b)

Table 5 Physicomechanical properties of SIS-1209 and SIS-0328

Sample	Maximum tensile strength/MPa	Maximum ultimate elongation(%)	300% Stretching strength/MPa
SIS-1209	13.0	1860	2.2
SIS-0328	12.2	1197	5.8

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采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯

Preparation of Styrene-isoprene-styrene Thermoplastic Elastomer by Three Times Feeding Method of Reactive Extrusion^†

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采用反应挤出三次加料法合成苯乙烯/异戊二烯/苯乙烯

Preparation of Styrene-isoprene-styrene Thermoplastic Elastomer by Three Times Feeding Method of Reactive Extrusion†

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Preparation of Styrene-isoprene-styrene Thermoplastic Elastomer by Three Times Feeding Method of Reactive Extrusion^†