异丁烯与对氯甲基苯乙烯正离子共聚合研究

杨科; 刘强; 文帅; 徐舒心; 施晨琦

doi:10.11777/j.issn1000-3304.2019.19179

您当前的位置：

首页 >

文章列表页 >

异丁烯与对氯甲基苯乙烯正离子共聚合研究

论文 | 更新时间：2021-01-26

- 异丁烯与对氯甲基苯乙烯正离子共聚合研究
- Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene
- 高分子学报 2020年51卷第4期页码：355-365
- 作者机构：
  
  橡塑材料与工程教育部重点实验室青岛科技大学　青岛 266042
- 作者简介：
  
  E-mail: liuqiang@qust.edu.cn
- 基金信息：
  
  青岛科技大学青年教师启动基金项目
- DOI：10.11777/j.issn1000-3304.2019.19179
  中图分类号：
- 纸质出版日期：2020-4，
  
  网络出版日期：2019-12-11，
  
  收稿日期：2019-9-30，
  
  修回日期：2019-10-30，
扫描看全文
杨科, 刘强, 文帅, 徐舒心, 施晨琦. 异丁烯与对氯甲基苯乙烯正离子共聚合研究[J]. 高分子学报, 2020,51(4):355-365.

Ke Yang, Qiang Liu, Shuai Wen, Shu-xin Xu, Chen-qi Shi. Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene[J]. Acta Polymerica Sinica, 2020,51(4):355-365.
杨科, 刘强, 文帅, 徐舒心, 施晨琦. 异丁烯与对氯甲基苯乙烯正离子共聚合研究[J]. 高分子学报, 2020,51(4):355-365. DOI： 10.11777/j.issn1000-3304.2019.19179.

Ke Yang, Qiang Liu, Shuai Wen, Shu-xin Xu, Chen-qi Shi. Study of Cationic Copolymerization of Isobutylene and p-(Chloromethyl)styrene[J]. Acta Polymerica Sinica, 2020,51(4):355-365. DOI： 10.11777/j.issn1000-3304.2019.19179.

摘要

以四氯化钛(TiCl

)、二氯乙基铝(AlEtCl

)、倍半铝(AlEt

1.5

)、三氯化铝(AlCl

)等路易斯酸为共引发剂，水或枯基醇(CumOH)为引发剂，在−80 °C下的正己烷/二氯甲烷(

= 6/4)的混合溶剂内，研究了异丁烯(IB)与对氯甲基苯乙烯(

-CMS)的正离子共聚合. 利用示差凝胶渗透色谱仪(GPC-RI)以及核磁氢谱(

H-NMR)对共聚物的表观分子量及分子量分布、共聚组成等进行分析，采用Kelen-Tüdős与Yezreielv-Brokhina-Roskin法计算了单体竞聚率，初步探讨了

-CMS与IB正离子共聚合的反应机理. 结果表明，AlEtCl

、AlEt

1.5

、AlCl

均可催化大分子间的烷基化反应，产生凝胶；TiCl

作为共引发剂，可以得到无凝胶单峰分布共聚物；邻位氯甲基苯乙烯(

-CMS)不能参与共聚，

-CMS的共聚活性较低，IB与

-CMS的单体竞聚率为

= 4.67，

CMS

= 0.70；随反应时间延长，共聚物中

-CMS的含量及共聚物分子量均逐渐增加；

-CMS单体自身几乎不参与引发，共聚到大分子链后，苄基氯缓慢参与引发，形成支化. 提高共聚合温度至− 60和− 40 °C，聚合速率降低，

-CMS的引发活性未发生明显变化.

Abstract

Cationic copolymerization of isobutylene (IB) and chloromethylstyrene was investigated with

-hexane (Hex)/dichloromethane (CH

) (

= 6/4) as solvent

TiCl

AlEt

1.5

AlEt

AlCl

as co-initiators and water or cumyl alcohol as initiators. The molecular weight

molecular weight distribution (MWD) and structure composition of the resulting copolymers were analyzed by gel permeation chromatography (GPC) and

H-NMR spectroscopy. The reactivity ratios were determined by Kelen-Tüdős and Yezreielv-Brokhina-Roskin formula

and the copolymerization mechanism was proposed. It was found that co-initiators with strong Lewis acidity

such as AlEtCl

AlEt

1.5

and AlCl

can catalyze intermolecular alkylations to form gels while no gel formed with the relatively weaker TiCl

. The chloromethylstyrene with para-substituent

-(chloromethyl)styrene (

-CMS) was found to have a low reactivity during the copolymerization with IB (

= 4.67

-CMS

= 0.70) while the ortho-isomer exhibited no activity. The chemical structure of resulting copolymers indicated that

-(chloromethyl)styrene cannot initiate the polymerization of IB which may be due to its low initiation rate compared to the highly active cumyl group at

-CMS/IB molar ratio of 4.11. However

the benzyl chloride group in the formed copolymer chain can slowly initiate polymerization of IB and

-(chloromethyl)styrene

forming branched structures. The content of

-(chloromethyl)styrene increased with increasing molecular weight and monomer conversion. Systematic research on the branched structure

rheological properties and other physical properties of the resulting copolymers is in progress.

关键词

异丁烯对氯甲基苯乙烯竞聚率正离子共聚合支化

Keywords

Isobutylenep-(Chloromethyl)styreneReactivity ratioCationic copolymerizationBranching

references

Malmberg S E, Parent J S, Pratt D A. Macromolecules , 2010 . 20 8456 - 8461.

Xie Zhonglin(谢忠麟). Journal of Rubber Technology Market(橡胶科技市场) , 2008 . ( 11 ): 7 - 8.

Jones G D. US patent, 3067182. 1962-11-04

Jones G D, Runyon J R, Ong J. J Appl Polym Sci , 1961 . 16 452 - 459.

Jones G D, Runyon J R, Ong J. Ind Eng Chem , 1961 . 53 291 - 298.

Powers K W. US patent, 4074035. 1978-03-14

Powers K W. US patent, 3948868. 1976-04-06

Wang H C. CN patent, CN1468282A. 2004-01-14

Wang H C. CN patent, CN1636036A. 2005-07-06

Nuyken O, Gruber F, Pask S D. Makromol Chem , 1993 . 194 3415 - 3432 . DOI:10.1002/macp.1993.021941220http://doi.org/10.1002/macp.1993.021941220 .

Nuyken O, Sanchez J R, Voit B. Macromol Rapid Commun , 1997 . 18 125 - 131 . DOI:10.1002/marc.1997.030180209http://doi.org/10.1002/marc.1997.030180209 .

Grasmuller M, Rueda-sanchez J C, Nuyken O. Macromol Symp , 1998 . 127 109 - 114 . DOI:10.1002/masy.19981270115http://doi.org/10.1002/masy.19981270115 .

Nuyken O, Vierle M. Des Monomer Polym , 2005 . 8 91 - 105 . DOI:10.1163/1568555053603233http://doi.org/10.1163/1568555053603233 .

Osman A. US patent, 5629386. 1997-05-13

Schafer M, Wieland, P C, Nuyken O. J Polym Sci, Part A: Polym Chem , 2002 . 40 3725 - 3733 . DOI:10.1002/pola.10472http://doi.org/10.1002/pola.10472 .

Kennedy J P. US patent, 4327201. 1982-04-27

Yan P F, Guo A R, Liu Q, Wu Y X. J Polym Sci, Part A: Polym Chem , 2012 . 50 3383 - 3392 . DOI:10.1002/pola.26126http://doi.org/10.1002/pola.26126 .

Liu Q, Wu Y X, Yan P F, Zhang Y, Xu R W. Macromolecules , 2011 . 44 1866 - 1875 . DOI:10.1021/ma1027017http://doi.org/10.1021/ma1027017 .

Kanaoka S, Sawamoto M, Higashimura T. Macromolecules , 1996 . 29 1778 - 1783 . DOI:10.1021/ma951320jhttp://doi.org/10.1021/ma951320j .

Kamigaito M, Nakashima J, Satoh K, Sawamoto M. Macromolecules , 2003 . 36 3540 - 3544 . DOI:10.1021/ma0216876http://doi.org/10.1021/ma0216876 .

Ren Ping(任苹), Wu yibo(伍一波), Guo wenLi(郭文莉), Li ShuXin(李树新), Wang HongLiang(王洪亮), Xiao Fei(肖菲), Liu KeLong(刘克龙). China Elastomerics(弹性体) , 2012 . 22 ( 1 ): 25 - 28 . DOI:10.3969/j.issn.1005-3174.2012.01.006http://doi.org/10.3969/j.issn.1005-3174.2012.01.006 .

Kelen T, Tüdős F. J Macromol Sci Part A , 1975 . A9 ( 1 ): 1 - 27.

Cao Lina(曹丽娜), Luo Qingzhi(罗青枝), Xiao Libin(肖丽彬), Wang Desong(王德松), Dou Haiyang(窦海洋). Journal of Hebei University of Science and Technology(河北科技大学学报) , 2010 . 31 ( 3 ): 195 - 200 . DOI:10.7535/hbkd.2010yx03003http://doi.org/10.7535/hbkd.2010yx03003 .

Held D, Ivan B, Muller A H E. Macromolecules , 2001 . 34 2418 - 2426 . DOI:10.1021/ma000641ehttp://doi.org/10.1021/ma000641e .

Ashbaugh J R, Ruff C R, Shaffer T D. J Polym Sci, Part A: Polym Chem , 2000 . 38 1680 - 1686 . DOI:10.1002/(SICI)1099-0518(20000501)38:9<1680::AID-POLA34>3.0.CO;2-Yhttp://doi.org/10.1002/(SICI)1099-0518(20000501)38:9<1680::AID-POLA34>3.0.CO;2-Y .

Fodor Z, Bae Y C, Faust R. Macromolecules , 1998 . 31 4439 - 4446 . DOI:10.1021/ma980193zhttp://doi.org/10.1021/ma980193z .

Fréchet J M J, Henmi M, Gitsov I, Ashima S, Leduc M R, Grubbs R B. Science , 1995 . 269 1080 - 1083 . DOI:10.1126/science.269.5227.1080http://doi.org/10.1126/science.269.5227.1080 .

Simon P F W, Muller A H E. Macromolecules , 2001 . 34 6206 - 6213 . DOI:10.1021/ma002156phttp://doi.org/10.1021/ma002156p .

Zhang C B, Zhou Y, Liu Q, Li S X, Perrier S, Zhao Y L. Macromolecules , 2011 . 44 2034 - 2049 . DOI:10.1021/ma1024736http://doi.org/10.1021/ma1024736 .

Wang Z M, He J P, Tao J F, Yang L, Jiang H J, Yang Y L. Macromolecules , 2003 . 36 7446 - 7452 . DOI:10.1021/ma025673bhttp://doi.org/10.1021/ma025673b .

Hull D L, Kennedy J P. J Polym Sci, Part A: Polym Chem , 2001 . 39 1515 - 1524 . DOI:10.1002/pola.1128http://doi.org/10.1002/pola.1128 .

Safa K D, Babazadeh M. Eur Polym J , 2004 . 40 1659 - 1669 . DOI:10.1016/j.eurpolymj.2004.04.005http://doi.org/10.1016/j.eurpolymj.2004.04.005 .

Voit B I, Lederer A. Chem Rev , 2009 . 109 5924 - 5973 . DOI:10.1021/cr900068qhttp://doi.org/10.1021/cr900068q .

Gao C, Yan D. Prog Polym Sci , 2004 . 29 183 - 275 . DOI:10.1016/j.progpolymsci.2003.12.002http://doi.org/10.1016/j.progpolymsci.2003.12.002 .

更多指标>

浏览量

下载量

CSCD

文章被引用时，请邮件提醒。

提交

工具集

关联资源

二氧化碳与环氧化物的三元共聚反应动力学过程控制

α-二亚胺镍钯配合物合成及催化混合癸烯低聚研究

乙丙共聚物的微结构测定及调控

L-丙烯酸薄荷酯与2,5-二(4'-己氧基苯基)苯乙烯无规共聚物的合成和旋光性质