含引发单体交联聚合物的光调控可逆生长

熊新红; 王宏; 杨莉; 崔家喜

doi:10.11777/j.issn1000-3304.2023.23081

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含引发单体交联聚合物的光调控可逆生长

快报 | 更新时间：2023-09-25

- 含引发单体交联聚合物的光调控可逆生长
- Photo-regulated Reversible Growth of Inimer-containing Crosslinked Polymers
- 高分子学报 2023年54卷第10期页码：1386-1394
- 作者机构：
  
  1.电子科技大学基础与前沿研究院成都 610054
  2.电子科技大学长三角研究院(湖州) 湖州 313001
  3.成都大学高等研究院成都 610106
- 作者简介：
  
  E-mail: jiaxi.cui@uestc.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 ┣52202135;52003035);51973023┫
- DOI：10.11777/j.issn1000-3304.2023.23081
  中图分类号：
- 纸质出版日期：2023-10-20，
  
  网络出版日期：2023-06-28，
  
  收稿日期：2023-03-29，
  
  录用日期：2023-05-17
扫描看全文
熊新红,王宏,杨莉等.含引发单体交联聚合物的光调控可逆生长[J].高分子学报,2023,54(10):1386-1394.

Xiong Xin-hong,Wang Hong,Yang Li,et al.Photo-regulated Reversible Growth of Inimer-containing Crosslinked Polymers[J].ACTA POLYMERICA SINICA,2023,54(10):1386-1394.
熊新红,王宏,杨莉等.含引发单体交联聚合物的光调控可逆生长[J].高分子学报,2023,54(10):1386-1394. DOI： 10.11777/j.issn1000-3304.2023.23081.

Xiong Xin-hong,Wang Hong,Yang Li,et al.Photo-regulated Reversible Growth of Inimer-containing Crosslinked Polymers[J].ACTA POLYMERICA SINICA,2023,54(10):1386-1394. DOI： 10.11777/j.issn1000-3304.2023.23081.

摘要

受真涡虫可逆生长现象的启发，设计了一种光控可逆生长材料. 该设计基于一种可光解的引发单体(vinyl-

NB-Br)，当把其共聚到交联聚合物内部后，可通过可见光引发在交联聚合物中溶胀的单体(

-异丙基丙烯酰胺，NIPAAm)接枝聚合，实现材料增大生长，而通过紫外光切断所接枝的聚合物(PNIPAAm)，并通过洗涤移除游离的聚合物来使得材料收缩，达到逆生长的目的. 材料的生长和逆生长均可通过交联材料中引发单体的含量和营养液中接枝单体的浓度来调控；在可逆生长过程中，材料的本体疏水性和力学性质均可明显改变：材料韧性在生长了PNIPAAm后明显增加(从0.15 MJ/m

到1.18 MJ/m

)，而在逆生长后降低(0.25 MJ/m

). 可见，光控可逆生长是一种原位后调节交联聚合物材料性能的简单、高效方法.

Abstract

Inspired by the reversible growth of planaria

we develop a class of photo-regulated reversible growing materials. The materials are made from a photolabile inimer (vinyl-

NB-Br) consisting of three functional moieties

i.e.

acrylate-based double bond for incorporation within a network

Br group for further visible light-induced grafting polymerization

and

-nitro benzyl (

NB) moiety for UV light-triggered cleavage. This inimer is copolymerized with di(ethylene glycol)ethyl ether acrylate to prepare "seed" elastomers (I-PDEEA). For growth

these seed elastomers are soaked in "nutrient" solutions containing monomer (NIPAAm) and photoinitiator (Mn

(CO)

). The swollen samples are then irradiated by visible light (460 nm)

which induces successful polymerization of NIPAAm from the polymer networks to get the grown material (I-PDEEA-PNIPAAm). For degrowth

the grown samples are exposed to UV light (360 nm)

under which the

NB undergoes photocleavage reaction to free the grafted PNIPAAm chains. The samples shrink when these free chains are extracted from the polymer network

showing a degrowing effect. The degrowth can be directly conducted in a DMF solution

leading to direct contraction. Our study indicates that the network topologies and the neat mass change in growth and degrowth can be regulated by the inimer fractions in the seed polymer networks and the concentrations of NIPAAm in nutrient solutions. This reversible growth method allows post-modifying crosslinked polymers in mass

size

bulk

and mechanical properties. For example

the growth of PNIPAAm can lead to a neat increase of up to 0.55 mg/cm

and tune the hydrophobic matrices to be hydrophilic. Moreover

the materials are stiffened and toughened (toughness: from 0.15 MJ/m

to 1.18 MJ/m

). After degrowth

the samples return to hydrophobic

soft

and brittle states (toughness: 0.25 MJ/m

). These results indicate that photo-regulated reversible growth is a facile

efficient method for post-regulating the properties of crosslinked polymer materials

in situ

关键词

可逆生长光调控交联聚合物力学性能

Keywords

Reversible growthPhoto-regulatedCrosslinked polymersMechanical property

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