Synthesis of “Si―H” Containing Polyethylene and Its Functionalization

Xiu-chong Lin; Yin-ran Wang; Lei Jiang; Fang Guo

doi:10.11777/j.issn1000-3304.2020.20023

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Synthesis of “Si―H” Containing Polyethylene and Its Functionalization

更新时间：2021-01-26

- Synthesis of “Si―H” Containing Polyethylene and Its Functionalization
- Acta Polymerica Sinica Vol. 51, Issue 7, Pages: 771-776(2020)
- 作者机构：
  
  大连理工大学化工学院精细化工国家重点实验室　大连 116024
- 作者简介：
- 基金信息：
- DOI：10.11777/j.issn1000-3304.2020.20023
  CLC：
- Published：2020-7，
  
  Published Online：16 April 2020，
  
  Received：7 February 2020，
  
  Revised：10 March 2020，
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Xiu-chong Lin, Yin-ran Wang, Lei Jiang, Fang Guo. Synthesis of “Si―H” Containing Polyethylene and Its Functionalization. [J]. Acta Polymerica Sinica 51(7):771-776(2020)
DOI：

Xiu-chong Lin, Yin-ran Wang, Lei Jiang, Fang Guo. Synthesis of “Si―H” Containing Polyethylene and Its Functionalization. [J]. Acta Polymerica Sinica 51(7):771-776(2020) DOI： 10.11777/j.issn1000-3304.2020.20023.

摘要

采用(C

SiMe

)Sc(CH

NMe

)

(

)、(C

SiMe

)Sc(CH

SiMe

)

(THF) (

)两种单茂钪催化剂，考察了其催化10-二甲基硅基-1-癸烯(Decene-SiH)均聚合以及与乙烯共聚合的性能，并通过NMR、GPC和DSC对所获共聚物的微观结构和热性能进行了分析. 结果表明，在室温1.01 × 10

Pa 乙烯压力下，单茂钪

对乙烯与Decene-SiH共聚合表现了极高的催化活性(10

g聚合物mol

−1

)，Decene-SiH转化率达99%. 改变Decene-SiH用量，获得了组成可控(Decene-SiH含量8 mol% ~ 50 mol%)、高分子量(7.2 × 10

~ 10.0 × 10

)、窄分布(

= 1.35 ~ 1.63)的乙烯/Decene-SiH共聚物. 当共聚物中Decene-SiH含量小于12 mol%时，Decene-SiH孤立插入聚乙烯链中；当共聚物中Decene-SiH含量大于26 mol%时，Decene-SiH可孤立和连续插入聚乙烯链中. 不同组成的乙烯/Decene-SiH共聚物具有一个118 ~ 130 °C的熔点，共聚物中Decene-SiH含量为50 mol%时具有一个−71 °C的玻璃化转变温度. 共聚物中Decene-SiH含量增加，聚乙烯结晶度明显降低. 乙烯/Decene-SiH共聚物中“Si―H”基团与烯丙基缩水甘油醚、

-二甲基丙烯酰胺、

-二甲基氨基苯乙烯和甲基丙烯酸甲酯4种物质在Karstedt's催化剂作用下发生硅氢加成反应，实现了“Si―H”基团100%转化，有效地将乙烯/Decene-SiH共聚物中“Si―H”基团转变为其他的极性基团，获得了4种具有亲水性质的功能化聚乙烯.

Abstract

The polymerization of 10-dimethylsilyl-1-decene (Decene-SiH) and its copolymerization with ethylene by the half-sandwich scandium complexes (C

SiMe

)Sc(CH

NMe

)

(

) and (C

SiMe

)Sc(CH

SiMe

)

(THF) (

) have been examined. The microstructures and thermal properties of the obtained polymers were characterized by NMR

GPC and DSC. The copolymerization of ethylene with Decene-SiH under 1.01 × 10

Pa of ethylene has also been successfully achieved at room temperature. The copolymerization activity reached up to 10

g of polymer (mol of Sc)

−1

and the conversion of Decene-SiH reached up to 99%. The ethylene/Decene-SiH copolymers with controllable compositions (Decene-SiH content = 8 mol% ~ 50 mol%)

high molecular weight (

= 7.2 × 10

~ 10.0 × 10

) and narrow molecular weight distribution (

= 1.35 ~ 1.63) were conveniently obtained by changing the feed of Decene-SiH. When the content was less than 12 mol%

the isolated insertion of Decene-SiH into polyethylene chain was achieved. When the content was more than 26 mol%

the isolated and continuous insertion of Decene-SiH into polyethylene chain was also achieved. The ethylene/Decene-SiH copolymers with different compositions possessed a melting point (118 − 130 °C) and the copolymers possessed a glass transition temperature at −71°C when the Decene-SiH content of the copolymer was 50 mol%. The crystallinity of polyethylene decreased significantly with the Decene-SiH content of the copolymers. The “Si―H” group in the ethylene/Decene-SiH copolymers reacted with allyl glycidyl ether

-dimethylacrylamide

-dimethylaminostyrene and methyl methacrylate under the Karstedt’s catalyst. The conversion of “Si―H” groups reached 100%. Versatile functionalized polyethylene with hydrophilic properties were obtained by efficiently transforming the “Si―H” groups of the resulting copolymers into other polar groups.

关键词

钪聚乙烯功能化共聚合硅氢加成

Keywords

ScandiumPolyethyleneFunctionalizedCopolymerizationHydrosilylation

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Related Author

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Related Institution

Department of Polymer Science and Engineering, University of Science and Technology of China

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

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

Key Laboratory of Engineering Plastics, Institute of Chemistry, Chinese Academy of Sciences

Beijing Key Laboratory of Clothing Materials R&D and Assessment, Beijing Engineering Research Center of Textile Nanofiber, School of Materials Design & Engineering, Beijing Institute of Fashion Technology

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