Syndiotactic Homo- and Co-polymerization of <italic style="font-style: italic">p</italic>-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes

Na Jiao; Fang Guo; Yang Li

doi:10.11777/j.issn1000-3304.2017.17051

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Syndiotactic Homo- and Co-polymerization of p-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes

Research Article | 更新时间：2021-01-26

- Syndiotactic Homo- and Co-polymerization of p-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes
- Acta Polymerica Sinica Issue 12, Pages: 1922-1929(2017)
- 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.issn1000-3304.2017.17051
  CLC：
- Published：20 December 2017，
  
  Received：20 March 2017，
  
  Revised：3 April 2017，
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Na Jiao, Fang Guo, Yang Li. Syndiotactic Homo- and Co-polymerization of p-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes. [J]. Acta Polymerica Sinica (12):1922-1929(2017)
DOI：

Na Jiao, Fang Guo, Yang Li. Syndiotactic Homo- and Co-polymerization of p-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes. [J]. Acta Polymerica Sinica (12):1922-1929(2017) DOI： 10.11777/j.issn1000-3304.2017.17051.

摘要

采用（C

SiMe

）Sc（CH

NMe

）

（

）和（C

SiMe

）Sc（CH

SiMe

）

（THF）（

）2种单茂钪催化剂，考察了其催化对氟苯乙烯均聚合以及与乙烯共聚合的性能，并通过

H-NMR、

C-NMR、GPC和DSC对所获聚合物的微观结构和热性能进行了分析.结果表明，单茂钪

可以催化对氟苯乙烯均聚合，获得间规聚合物，但聚合活性较低.采用单茂钪

，控制溶剂种类和用量可以获得间规和无规2类聚合物：控制对氟苯乙烯单体在氯苯溶剂中浓度低于2.4 mol/L，可获得间规聚对氟苯乙烯（

rrrr

≥ 99%，

≥ 319℃），且聚合活性高达10

g polymer mol

-1

；控制对氟苯乙烯单体在氯苯溶剂中浓度高于4.8 mol/L或者选用氟苯做溶剂，可获得无规聚对氟苯乙烯；固定单体浓度调控对氟苯乙烯和催化剂的比例，可获得分子量（

）在3.10×10

~2.08×10

间调控的间规和无规聚对氟苯乙烯.在常压乙烯下，单茂钪

和

还可以催化对氟苯乙烯与乙烯共聚合，获得了组成（对氟苯乙烯含量41 mol%~88 mol%）和分子量（3.10 x 10

~1.84 x 10

）可控的两元共聚物，共聚合活性高达10

g polymer mol

-1

.当共聚物中乙烯含量高于对氟苯乙烯含量时，共聚物仅有源自聚乙烯嵌段的熔点（119~126℃）.当共聚物中对氟苯乙烯含量高于乙烯含量时，共聚物出现聚对氟苯乙烯嵌段；由单茂钪

获得聚对氟苯乙烯嵌段为间规结构，共聚物具有熔点（269~282℃）和玻璃化转变温度（

，79~82℃）；单茂钪

获得聚氟苯乙烯嵌段为无规结构，共聚物仅有1个

（94~96℃）.

Abstract

Syndiotactic polymerization of

-fluorostyrene and its copolymerization with ethylene catalyzed by half-sandwich scandium complex (C

SiMe

)Sc(CH

NMe

-o)

(

) and (C

SiMe

)Sc(CH

Si-Me

)

(THF) (

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

H-NMR

C-NMR

GPC and DSC. Scandium complex

showed syndiotactic selectivity for the polymerization of

-fluorostyrene with low activity (10

g polymer mol

-1

). Scandium complex

proved to be a high activity catalyst for the polymerization of

-fluorostyrene to afford syndiotactic or atactic poly(

-fluorostyrene) by controlling the type and the volume of the solvent. When the concentration of

-fluorostyrene in chlorobenzene was below 2.4 mol/L

the syndiotactic poly(

-fluorostyrene) (

rrrr

99%) was obtained with scandium complex

possessing high activity (10

g polymer mol

-1

). The melting point (

) of syndiotactic poly(

-fluorostyrene) reached up to 324℃

suggesting the semicrystalline morphology of this polymer. The molecular weight of the syndiotactic poly(

-fluorostyrene) (

=3.10×10

-2.08×10

) was easily controlled by changing the feed ratio of

-fluorostyrene to catalyst. When the concentration of

-fluorostyrene in chlorobenzene was above 4.8 mol/L or fluorobenzene used as solvent

atactic poly(

-fluorostyrene) with controllable molecular weight (3.80×10

-1.88×10

) was obtained. Moreover

the copolymerizations of

-fluorostyrene with ethylene catalyzed by complexes

have also been prepared

leading to novel copolymers with controlled composition (

-fluorostyrene content:41 mol% -88 mol%) and molecular weight (3.10×10

-1.84×10

)

and with high activity (up to 10

g polymer mol

-1

). When ethylene content in the copolymer is higher than that of

-fluorostyrene

the copolymers showed a

around 119 -126℃ owing to polyethylene blocks. When

-fluorostyrene content in the copolymer is higher than that of ethylene

the obtained copolymers with syndiotactic poly(

-fluorostyrene) blocks

prepared by scandium complex

showed a

around 269 -282℃ and a

around 79 -82℃; In contrast

the copolymers with atactic poly(

-fluorostyrene) blocks prepared by scandium complex

showed their

around 94 -96℃.

关键词

钪对氟苯乙烯间规聚合乙烯共聚

Keywords

Scandiump-FluorostyreneSyndiotactic polymerizationEthyleneCopolymerization

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MOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University

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

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⁰

Syndiotactic Homo- and Co-polymerization of p-Fluorostyrene and Ethylene Catalyzed by Half-sandwich Scandium Complexes

DOI：10.11777/j.issn1000-3304.2017.17051

摘要

Abstract

关键词

Keywords

references