Synthesis of Brominated Polyolefin Rubbers

Yin-ran Wang; Ze-peng Zhao; Zhao-min Hou; Fang Guo

doi:10.11777/j.issn1000-3304.2023.23094

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Synthesis of Brominated Polyolefin Rubbers

Research Article | 更新时间：2023-11-03

- Synthesis of Brominated Polyolefin Rubbers
- Acta Polymerica Sinica Vol. 54, Issue 11, Pages: 1729-1739(2023)
- 作者机构：
  
  大连理工大学化工学院高分子材料系精细化工国家重点实验室大连 116024
- 作者简介：
  
  Fang Guo, E-mail: guofang@dlut.edu.cn
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2023.23094
  CLC：
- Published：20 November 2023，
  
  Published Online：15 June 2023，
  
  Received：07 April 2023，
  
  Accepted：28 April 2023
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王胤然,赵泽鹏,侯召民等.溴化聚烯烃橡胶的合成研究[J].高分子学报,2023,54(11):1729-1739.

Wang Yin-ran,Zhao Ze-peng,Hou Zhao-min,et al.Synthesis of Brominated Polyolefin Rubbers[J].Acta Polymerica Sinica,2023,54(11):1729-1739.
王胤然,赵泽鹏,侯召民等.溴化聚烯烃橡胶的合成研究[J].高分子学报,2023,54(11):1729-1739. DOI： 10.11777/j.issn1000-3304.2023.23094.

Wang Yin-ran,Zhao Ze-peng,Hou Zhao-min,et al.Synthesis of Brominated Polyolefin Rubbers[J].Acta Polymerica Sinica,2023,54(11):1729-1739. DOI： 10.11777/j.issn1000-3304.2023.23094.

摘要

考察了限定几何构型(CGC)钪配合物{Flu-(CH

)

-NHC}Sc(CH

SiMe

)

催化10-溴-1-癸烯(BrDC)与丙烯、乙烯两元及三元共聚合的性能，获得了一系列溴化聚烯烃橡胶，通过核磁共振波谱(NMR)、凝胶渗透色谱(GPC)和示差扫描量热(DSC)对所获溴化聚烯烃橡胶的结构和热性能进行了分析. 结果表明，室温下CGC钪催化BrDC均聚合60 min，即以91%的收率获得高分子量(

= 6.5×10

g·mol

-1

)的无规聚合物. 在0.2 MPa的丙烯压力下，CGC钪对BrDC和丙烯共聚合也表现出了极高的催化活性(10

g聚合物·mol

-1

·h

-1

)，通过改变BrDC用量，获得了BrDC含量在1.1 mol%~18.0 mol%间调控的高分子量(

= 1.35×10

~1.88×10

g·mol

-1

)丙烯-BrDC无规共聚物. 丙烯-BrDC无规共聚物中包含孤立分布的BrDC和无规聚丙烯嵌段. 不同组成的丙烯-BrDC共聚物在-7~-33 ℃范围内具有一个玻璃化转变温度(

). 该CGC钪对乙烯、丙烯和BrDC三元共聚合也表现出了极高的催化活性(10

g聚合物·mol

-1

·h

-1

)，获得了组成可控、高分子量(

= 2.31×10

~3.27×10

g·mol

-1

)的乙烯-丙烯-BrDC三元无规共聚物. 不同组成的三元共聚物在-43~-59 ℃范围内具有一个

，当三元共聚物中乙烯含量高于67.0 mol%时三元共聚物具有一个约100 ℃的熔点.

Abstract

The copolymerization of 10-bromo-1-decene (BrDC) with propylene and ethylene by the constrained geometry scandium complex {Flu-(CH

)

-NHC}Sc(CH

SiMe

)

was examined. The microstructures and thermal properties of the obtained polymers were characterized by NMR

GPC and DSC. The polymerization of BrDC within 60 min at room temperature afforded atactic homopolymer with high molecular weight (

= 6.50×10

g·mol

-1

) in 91% yield. The copolymerization of BrDC and propylene under 0.2 MPa of propylene was also successfully achieved at room temperature. The copolymerization activity reached up to 10

g of polymer·(mol of Sc)

-1

·h

-1

. The propylene-BrDC copolymers with controllable compositions (BrDC content = 1.1 mol%‒18.0 mol%)

high molecular weight (

= 1.35×10

‒1.88×10

) were conveniently obtained by changing the feed of BrDC. The random propylene-BrDC copolymers contained isolated BrDC and atactic polypropylene blocks. The propylene-BrDC copolymers with different compositions possessed glass transition temperatures (

) in the range from -7 ℃ to -33 ℃. The scandium complex also showed high activity (10

g of polymer·(mol of Sc)

-1

·h

-1

) for the terpolymerization of BrDC with propylene and ethylene. The random ethylene-propylene-BrDC copolymers with controllable compositions (ethylene content = 37.8 mol%‒75.2 mol%

BrDC content = 2.3 mol%‒12.2 mol%) and high molecular weight (

= 2.31×10

‒3.27×10

) were obtained at room temperature. The ethylene-propylene-BrDC terpolymers with different compositions possessed glass transition temperatures (

) in the range from -43 ℃ to -59 ℃. When the ethylene content was higher than 67.0 mol%

the ethylene-propylene-BrDC terpolymers showed a melting point of 100 ℃.

关键词

钪橡胶聚烯烃共聚合溴化

Keywords

ScandiumRubberPolyolefinCopolymerizationBrominated

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State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology

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Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology

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