THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl<sub>3</sub>

ZHANG Bei; WU Yixian; LI Yan; LIU Xun; XU Xu; WU Guanying

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THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl₃

Research Article | 更新时间：2021-08-24

- THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl₃
- Acta Polymerica Sinica Issue 11, Pages: 1040-1046(2007)
- 作者机构：
  
  1. 北京化工大学化工资源有效利用国家重点实验室
  2. 北京化工大学化工资源有效利用国家重点实验室,北京,100029
- 作者简介：
- 基金信息：
- DOI：
  CLC： O631
- Published：2007，
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[1]张蓓,吴一弦,李艳,刘迅,徐旭,武冠英.含氮试剂对p-DCC/AlCl_3引发异丁烯正离子聚合的影响[J].高分子学报,2007(11):1040-1046.

ZHANG Bei, WU Yixian, LI Yan, LIU Xun, XU Xu, WU Guanying. THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl₃. [J]. Acta Polymerica Sinica (11):1040-1046(2007)
[1]张蓓,吴一弦,李艳,刘迅,徐旭,武冠英.含氮试剂对p-DCC/AlCl_3引发异丁烯正离子聚合的影响[J].高分子学报,2007(11):1040-1046. DOI：

ZHANG Bei, WU Yixian, LI Yan, LIU Xun, XU Xu, WU Guanying. THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl₃. [J]. Acta Polymerica Sinica (11):1040-1046(2007) DOI：

摘要

以对-二枯基氯（DCC）/AlCl3体系引发异丁烯在二氯甲烷（CH2Cl2）正己烷（Hex）（40/60

V/V）混合溶剂中进行正离子聚合

探讨了DCC用量、含氮试剂2

6-二叔丁基吡啶（DtBP）和三苯胺（TPA）对异丁烯正离子聚合转化率、产物分子量及其分布的影响.结果表明

DCC和体系中微量水均可与AlCl3产生竞争络合

形成两种活性中心并引起相继的竞争引发

聚合产物的GPC谱图呈双峰分布

分子量分布宽;增加DCC用量有利于DCC与AlCl3的络合

致使链增长反应主要通过DCC与AlCl3络合形成的活性中心引发

但聚合产物分子量相对较低

分子量分布较宽;使用DtBP

可有效地抑制微量水引发及活性链向单体的转移反应

使分子量分布明显变窄

基本实现DCC的控制引发;采用DtBP与TPA共同调节聚合反应

可使聚合产物分子量分布变窄的同时

进一步提高分子量

从而得到相对较高分子量（Mw=103200）和单峰分子量分布（Mw/Mn=2.09）的聚异丁烯产物.

Abstract

The cationic polymerization of isobutylene（IB）by utilizing difunctional initiator p-dicumyl chloride（DCC）in conjunction with coinitiator AlCl

was carried out in CH

/Hex（40/60

V/V）solvent mixtures.The effects of concentrations of 2

6-di-tert-butylpyridine（DtBP）

triphenylamine（TPA）and AlCl

on monomer conversion

molecular weight and molecular weight distribution（MWD）of polyisobutylene（PIB）were investigated.The small amount of water in the polymerization system in conjunction with AlCl

could induce a conventional uncontrolled rapid polymerization of IB and lead to polyisobutylene with broad molecular weight distribution（M

=4.55）.It was found that the GPC trace of resultant polymers obtained by DCC/H

O/AlCl

systems exhibited a bimodal distribution

which was attributed to the competition of initiation from two different active centers

i.e.

H+AlCl

sub

3OH-（a）and AlCl-+

C（CH

）

（CH

）

C +-AlCl

（b）even at high DCC concentrations.The initiation by active center（b）was increased whereas the molecular weight of the polymer decreased with a decrease in AlCl

concentration.The addition of proton trap DtBP in the monomer solution could obviously decrease or even suppress the initiation from active center（a）and the chain transfer reaction to monomer

leading to the polymers with unimodal molecular weight distribution.The initiation from active center（a）could be suppressed by introduction of TPA and DtBP even at low DCC concentrations.A desirable cationic polymerization of IB would be achieved with the DCC/AlCl

initiation system in the presence of TPA and DtBP

and the telechelic tert-Cl-polyisobutylene with relatively high molecular weight（M

=103200）and unimodal molecular weight distribution（M

=2.09）could be obtained.

关键词

正离子聚合异丁烯聚异丁烯亲核试剂

Keywords

Cationic polymerizationIsobutylenePolyisobutyleneNucleophile

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State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology

Beijing University of Chemical Technology,Key state Laboratory of chemical resources Engineering,Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials

北京化工大学"化工资源有效利用"国家重点实验室北京市新型高分子材料制备与加工重点实验室

State Key Laboratory of Chemical Resource Engineering, Beijing Laboratory of Biomedical Materials, Beijing University of Chemical Technology

Key Laboratory of Rubber-Plastics of Ministry of Education, Qingdao University of Science & Technology

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THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl3

DOI：

摘要

Abstract

关键词

Keywords

references

THE EFFECTS OF NUCLEOPHILES CONTANING NITROGEN ON CATIONIC POLYMERIZATION OF ISOBUTYLENE INITITATED BY p-DCC/AlCl₃