本体共聚合制备丙烯/1-丁烯合金及表征

doi:10.7503/cjcu20140399

高等学校化学学报 ›› 2014, Vol. 35 ›› Issue (9): 2014.doi: 10.7503/cjcu20140399

本体共聚合制备丙烯/1-丁烯合金及表征

张春雨^1,², 董博², 张贺新², 陈春海¹(), 张学全²()

1. 吉林大学化学学院, 麦克德尔米德实验室, 长春 130012
2.中国科学院合成橡胶重点实验室, 中国科学院长春应用化学研究所, 长春 130022

收稿日期:2014-04-25 出版日期:2014-09-10 发布日期:2019-08-01
作者简介:联系人简介: 陈春海, 男, 博士, 教授, 主要从事聚酰亚胺和聚芳醚酮研究. E-mail: cch@jlu.edu.cn。张学全, 男, 研究员. 主要从事高性能单烯、双烯烃催化剂及高性能聚烯烃、橡胶材料研究. E-mail: xqzhang@ciac.jl.cn。
基金资助:
国家自然科学基金创新研究群体科学基金(批准号: 50921062)资助

Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization^†

ZHANG Chunyu^1,², DONG Bo², ZHANG Hexin², CHEN Chunhai^1,^*(), ZHANG Xuequan^2,^*()

1. Alan G. MacDiarmid Laboratory, College of Chemistry, Jilin University, Changchun 130012, China
2. Key Laboratory of Synthetic Rubber Chinese Academy of Sciences, Changchun Institute of Applied Chemistry,Chinese Academy of Sciences, Changchun 130022, China

Received:2014-04-25 Online:2014-09-10 Published:2019-08-01
Contact: CHEN Chunhai,ZHANG Xuequan E-mail:cch@jlu.edu.cn;xqzhang@ciac.jl.cn
Supported by:
Supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.50921062)

摘要/Abstract

摘要：

以球形高效负载的TiCl₄/MgCl₂/邻苯二甲酸二异丁酯(DIBP)为催化剂, 采用本体聚合方法进行丙烯与1-丁烯共聚合研究. 考察了共单体效应对共聚活性及聚合物立构规整性的影响; 表征了共聚物的结构. 结果表明, 随着1-丁烯/丙烯投料比的增加, 聚合活性呈先升高后降低的趋势, 在1-丁烯/丙烯摩尔投料比为0.26条件下聚合活性达到最高, 并随着共聚物中1-丁烯含量的增加, 共聚物的熔点明显下降, 分子量降低, 分子量分布变窄, 同时共聚物力学性能有明显提高, 透明度逐渐增加.

关键词: 共单体效应, 丙烯/1-丁烯共聚合, 本体聚合

Abstract:

The spherical MgCl₂ supported TiCl₄ catalyst(TiCl₄/MgCl₂/DIBP) was applied to bulk copolymerization of propylene and 1-butene. The influence of comonomer feed ratio on catalyst activity and stereoregularity of the copolymers were studied. The composition and properties of copolymers were investigated by ¹³C nuclear magnetic resonance(¹³C NMR), differential scanning calorimetry(DSC), infrared(IR) and gel permeation chromatography(GPC). The results showed that the polymerization activity increased firstly and then decreased with the increasing 1-butene/propylene feed ratio(B/P). The highest polymerization activity was achieved at B/P=0.26. As the 1-butene content in the copolymers increased, the melting point of the copolymers decreased and the molecular weight distribution became narrow. Meanwhile, the mechanical properties of the copolymers were improved significantly, and the transparency was gradually increased.

Key words: Comonomer effect, Propylene/1-butene copolymerization, Bulk polymerization

中图分类号:

O631

TrendMD:

张春雨, 董博, 张贺新, 陈春海, 张学全. 本体共聚合制备丙烯/1-丁烯合金及表征. 高等学校化学学报, 2014, 35(9): 2014.

ZHANG Chunyu, DONG Bo, ZHANG Hexin, CHEN Chunhai, ZHANG Xuequan. Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization^†. Chem. J. Chinese Universities, 2014, 35(9): 2014.

图/表 8

Table 1 Copolymerization of 1-butene/propylene*

Run	Molar ratio of 1-butene/propylene	Content of 1-butene(¹³C NMR)^b(%)	10^-6 Activity/(g·g^-1Ti·h^-1)
1	0.054	0.42	1.70
2	0.12	2.04	3.97
3	0.26	4.95	4.36
4	0.30	5.61	2.71
5	0.39	6.33	2.11

Fig.1 FTIR spectra of poly(propylene-co-1-butene)s with different 1-butene feed ratios

Fig.2 13C NMR spectrum of poly(propylene-co-1-butene) with 4.95% 1-butene

Table 2 Sequence distribution of copolymers*

Run	Sequence composition											Average sequenc length
Run	P	B	PP	PB	BB	PPP	PPB	BPB	PBP	BBP	BBB	B	P
1	99.6	0.4	99.1	0.9	0	92.3	6.7	0.5	0.3	0	0	1	222
2	97.6	2.4	95.1	4.9	0	83.0	12.4	3.95	0.6	0	0	1	40.8
3	95.1	4.9	89.8	10.1	0.1	78.2	14.3	0.2	7.2	0.07	0	1	22.6
4	94.4	5.6	89.1	11.7	0.2	61.4	19.7	8.7	9.1	0.6	0.3	1	17.1
5	93.6	6.3	86.7	13.1	0.2	62.1	26.7	1.2	6.8	1.5	1.4	1	15.2

Fig.3 DSC curves of the resultant copolymers

Table 3 DSC and GPC data of copolymers with different 1-butene contents

Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n	Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n
1	0	165.9	112.3	4.32	3.44	4	4.95	145.1	91.0	3.11	2.30
2	0.42	163.3	107.5	3.11	2.82	5	5.61	145.8	95.0	3.41	2.25
3	2.04	156.0	99.7	3.25	2.61	6	6.33	142.6	92.5	3.13	2.86

Table 3 DSC and GPC data of copolymers with different 1-butene contents

Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n	Run	w(1-Butene) (%)	$T m *$ /℃	T_c/℃	10^-5 M_w	M_w/M_n
1	0	165.9	112.3	4.32	3.44	4	4.95	145.1	91.0	3.11	2.30
2	0.42	163.3	107.5	3.11	2.82	5	5.61	145.8	95.0	3.41	2.25
3	2.04	156.0	99.7	3.25	2.61	6	6.33	142.6	92.5	3.13	2.86

Fig.4 Polarized optical micrographs of the copolymers with different 1-butene contents w(1-Butene)(%): (A) 0; (B) 2.04; (C) 5.61; (D) 6.33.

Table 4 Mechanical properties of copolymers with different 1-butene contents

Run	w(1-Butene)(%)	Elongation at break(%)	Impact strength/(kJ·m^-2)	Yield strength/MPa
1	0	280	1.67	41.9
2	0.43	570	1.62	37.8
3	2.04	600	1.69	44.0
4	4.95	812	2.18	35.3
5	5.61	800	2.64	31.2
6	6.33	820	2.70	30.1

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本体共聚合制备丙烯/1-丁烯合金及表征

Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization^†

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本体共聚合制备丙烯/1-丁烯合金及表征

Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization†

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Preparation and Characterization of Propylene/1-Butene Alloy with Bulk Copolymerization^†