Synthesis of Fluorine-containing Functionalized Polyolefin Block Copolymers by A Tandem Strategy Combining Polyhomologation of Ylides with Thermally/Light Induced Degenerative Iodine Transfer Polymerization

Fang XU; He-ying WANG; Kun CUI; Jin HUANG; Qiao-ling ZHAO; Tao JIANG; Zhi MA

doi:10.14028/j.cnki.1003-3726.2021.06.010

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Synthesis of Fluorine-containing Functionalized Polyolefin Block Copolymers by A Tandem Strategy Combining Polyhomologation of Ylides with Thermally/Light Induced Degenerative Iodine Transfer Polymerization

Special Issue: In Celebration of the 80th Birthday of Professor HU You-liang | 更新时间：2022-08-30

- Synthesis of Fluorine-containing Functionalized Polyolefin Block Copolymers by A Tandem Strategy Combining Polyhomologation of Ylides with Thermally/Light Induced Degenerative Iodine Transfer Polymerization
- Polymer Bulletin Vol. 34, Issue 6, Pages: 104-113(2021)
- 作者机构：
  
  1.中国科学院上海有机化学研究所,中国科学院有机功能分子合成与自组装化学重点实验室,上海 200032
  2.天津科技大学化工与材料学院,天津 300457
- 作者简介：
- 基金信息：
- DOI：10.14028/j.cnki.1003-3726.2021.06.010
  CLC：
- Published：20 June 2021，
  
  Received：20 October 2020，
  
  Revised：18 February 2021，
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Fang XU, He-ying WANG, Kun CUI, Jin HUANG, Qiao-ling ZHAO, Tao JIANG, Zhi MA. Synthesis of Fluorine-containing Functionalized Polyolefin Block Copolymers by A Tandem Strategy Combining Polyhomologation of Ylides with Thermally/Light Induced Degenerative Iodine Transfer Polymerization. [J]. Polymer Bulletin 34(6):104-113(2021)
DOI：

Fang XU, He-ying WANG, Kun CUI, Jin HUANG, Qiao-ling ZHAO, Tao JIANG, Zhi MA. Synthesis of Fluorine-containing Functionalized Polyolefin Block Copolymers by A Tandem Strategy Combining Polyhomologation of Ylides with Thermally/Light Induced Degenerative Iodine Transfer Polymerization. [J]. Polymer Bulletin 34(6):104-113(2021) DOI： 10.14028/j.cnki.1003-3726.2021.06.010.

摘要

首先利用叶立德同源聚合及后功能化反应合成得到新型

-碘

-双烯丙基遥爪型聚烯烃大分子引发剂(BA-PM-I)

然后在十羰基二锰[Mn

(CO)

]存在下

通过热/光诱导退化碘转移聚合制备得到结构可控的含氟功能化聚烯烃嵌段共聚物—聚亚甲基-

-聚五氟苯乙烯(BA-PM

-P(PFSt)) (

NMR

=10500和14600g/ mol

氟含量为13.5%和20.8%

wt) 和聚亚甲基-

-聚(苯乙烯-

-五氟苯乙烯) [BA-PM

-P(St-

-PFSt)](

GPC

=5200~7130g/mol

氟含量为1.8%~5.4%

wt)

利用核磁共振氢谱和氟谱、凝胶渗透色谱和元素分析等表征并确证了聚合物的分子结构。另外

对静态呼吸图法制备聚亚甲基-

-聚(苯乙烯-

-五氟苯乙烯)多孔薄膜进行了初步研究。结果表明:在25℃

95%相对湿度以及不同聚合物浓度(1、5和10mg/mL)条件下

获得平均孔径在5.0~1.5mm 的多孔薄膜。

Abstract

New iodo-terminated polyolefin based macroinitiators were synthesized for the first time by one-pot method combining polyhomologation of ylides and post functionalization. Then

well-defined polymethylene-b-poly(2

6- pentafluoro styrene) with terminal bi-allyl groups (BA-PM

-P(PFSt) (

NMR

=10500 and 14600g/mol

Fluorine content=13.5wt% and 20.8wt%))

polymethylene-

-poly(styrene-

-2

6-pentafluoro styrene) with terminal biallyl groups (BA-PM

-P(St-

-PFSt)) (

GPC

=5200~7130kg/mol

Fluorine content=1.8wt% ~5.4wt%) were achieved efficiently via thermally/light induced degenerative iodine transfer polymerization in the presence of Mn

(CO)

. The chain structures of the obtained copolymers were characterized by

H-NMR

F-NMR

GPC and elemental analysis. In addition

the BA-PM2-

-P(St-

-PFSt)

porous films with average pore sizes of 5.0~1.5m m were fabricated via a static breath-figure process at 25℃ under 95% relative humidity with different copolymer concentration of 1

5 and 10mg/ mL

respectively.

关键词

叶立德同源聚合碘端基聚烯烃大分子引发剂热/光诱导退化碘转移聚合含氟嵌段聚合物多孔薄膜

Keywords

Polyhomologation of ylidesIodo-terminated polyolefin macroinitiatorThermally/light induced degenerative iodine transfer polymerizationFluorine-containing block copolymerPorous films

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