含“Si―H”基团聚乙烯的合成及功能化研究

林秀崇; 王胤然; 姜磊; 郭方

doi:10.11777/j.issn1000-3304.2020.20023

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含“Si―H”基团聚乙烯的合成及功能化研究

论文 | 更新时间：2021-01-26

- 含“Si―H”基团聚乙烯的合成及功能化研究
- Synthesis of “Si―H” Containing Polyethylene and Its Functionalization
- 高分子学报 2020年51卷第7期页码：771-776
- 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：
  
  E-mail: guofang@dlut.edu.cn Fang Guo, E-mail: guofang@dlut.edu.cn
- 基金信息：
  
  中央高校基本科研业务费专项资金(项目号 DUT19LK08)资助项目
- DOI：10.11777/j.issn1000-3304.2020.20023
  中图分类号：
- 纸质出版日期：2020-7，
  
  网络出版日期：2020-4-16，
  
  收稿日期：2020-2-7，
  
  修回日期：2020-3-10，
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林秀崇, 王胤然, 姜磊, 郭方. 含“Si―H”基团聚乙烯的合成及功能化研究[J]. 高分子学报, 2020,51(7):771-776.

Xiu-chong Lin, Yin-ran Wang, Lei Jiang, Fang Guo. Synthesis of “Si―H” Containing Polyethylene and Its Functionalization[J]. Acta Polymerica Sinica, 2020,51(7):771-776.
林秀崇, 王胤然, 姜磊, 郭方. 含“Si―H”基团聚乙烯的合成及功能化研究[J]. 高分子学报, 2020,51(7):771-776. DOI： 10.11777/j.issn1000-3304.2020.20023.

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