氢键接枝法抑制聚合物单链交联过程中的链间交联

晋慧芸; 窦金康; 徐佳印; 黄霞芸; 陈道勇

doi:10.11777/j.issn1000-3304.2020.20061

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氢键接枝法抑制聚合物单链交联过程中的链间交联

论文 | 更新时间：2021-01-26

- 氢键接枝法抑制聚合物单链交联过程中的链间交联
- Prohibition of Interchain Cross-linking by H-bonding Grafting of the Polymer Chain
- 高分子学报 2020年51卷第9期页码：1021-1028
- 作者机构：
  
  聚合物分子工程国家重点实验室复旦大学高分子科学系　上海 200438
- 作者简介：
  
  E-mail: huangxiayun@fudan.edu.cn
  E-mail: chendy@fudan.edu.cn
- 基金信息：
  
  国家自然科学基金(基金号 51721002，21871057，21574025)和国家重点基础研究发展计划(973计划，项目号 2016YFA0203302)资助
- DOI：10.11777/j.issn1000-3304.2020.20061
  中图分类号：
- 纸质出版日期：2020-8-15，
  
  网络出版日期：2020-5-27，
  
  收稿日期：2020-3-9，
  
  修回日期：2020-4-3，
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晋慧芸, 窦金康, 徐佳印, 黄霞芸, 陈道勇. 氢键接枝法抑制聚合物单链交联过程中的链间交联[J]. 高分子学报, 2020,51(9):1021-1028.

Hui-yun Jin, Jin-kang Dou, Jia-yin Xu, Xia-yun Huang, Dao-yong Chen. Prohibition of Interchain Cross-linking by H-bonding Grafting of the Polymer Chain[J]. Acta Polymerica Sinica, 2020,51(9):1021-1028.
晋慧芸, 窦金康, 徐佳印, 黄霞芸, 陈道勇. 氢键接枝法抑制聚合物单链交联过程中的链间交联[J]. 高分子学报, 2020,51(9):1021-1028. DOI： 10.11777/j.issn1000-3304.2020.20061.

Hui-yun Jin, Jin-kang Dou, Jia-yin Xu, Xia-yun Huang, Dao-yong Chen. Prohibition of Interchain Cross-linking by H-bonding Grafting of the Polymer Chain[J]. Acta Polymerica Sinica, 2020,51(9):1021-1028. DOI： 10.11777/j.issn1000-3304.2020.20061.

摘要

当三嵌段聚合物的中间嵌段较长时，要在较高的聚合物浓度(例如：2.0 mg/mL)下交联该中间嵌段，得到纯的中间嵌段链内塌缩的聚合物单链粒子是相对困难的. 其在交联过程中容易发生链间交联. 因此，开发可有效抑制链间交联的方法是实现在较高聚合物浓度下制备较高纯度单链粒子的关键. 选用中间嵌段较长的聚苯乙烯-

-聚(2-乙烯基吡啶)-

-聚环氧乙烷(PS

1596

-P2VP

2895

-PEO

726

；下标是对应嵌段的聚合度)，通过在其共同溶剂

-二甲基甲酰胺中利用1

4-二溴丁烷交联其中间P2VP嵌段，制备出该中间嵌段链内塌缩的单链聚合物粒子. 为了抑制链间交联，首先对交联反应的条件(如前驱体浓度、交联剂用量等)进行了优化，可使得高纯度单链粒子的制备浓度达到0.5 mg/mL. 在此基础上，利用硬脂酸(SA)在P2VP嵌段氢键接枝的方法可进一步抑制链间交联，使得较高纯度单链粒子的制备浓度提高至2.0 mg/mL. SA的氢键接枝显著降低了交联过程中P2VP链间碰触概率，从而抑制链间交联反应的发生. 同时，由于其可逆特性，SA对P2VP的氢键接枝不会对单链粒子的结构与组成产生显著影响.

Abstract

It is difficult to intramolcularly cross-link the relatively long middle block of the triblock copolymer to obtain pure polymeric single-chain particles at a relatively high concentration (

i.e

. 2.0 mg/mL). The polymer is prone to intermolecular cross-linking during the cross-linking process. Hence

developing an effective approach to suppress the intermolecular cross-linking of the polymer helps to obtain the high purity polymeric single-chain particles at a relatively high concentration. The triblock copolymer

polystyrene-

-poly(2-vinylpyridine)-

-polyethylene oxide (PS

1596

-P2VP

2895

-PEO

726

the subscript is the corresponding degree of polymerization)

was chosen

in which the polymer has a relatively long P2VP block. The single-chain particles were prepared by intramolecularly crosslinking the middle block using 1

4-dibromobutane in the common solvent

-dimethylforamide. In order to efficiently suppress the interchain cross-linking

the cross-linking reaction conditions were firstly optimized

such as precursor concentration

amount of cross-linking agent

etc

to increase the preparation concentration of high purity single-chain particles to 0.5 mg/mL. Moreover

stearic acids (SA) were added to graft on the P2VP block

via

hydrogen bonding interaction before crosslinking. During the single-chain cross-linking procedure

the interchain cross-linking can be further suppressed and the preparation concentration of high purity single-chain particles can increase to 2.0 mg/mL. It is because the SA grafting on the P2VP blocks significantly reduced the contact probability between P2VP chains and thereby the occurrence of interchain cross-linking was inhibited. In addition

since the hydrogen bonding interaction is a noncovalent and reversible interaction

the existence of SA grafts will not have a significant influence on the structure and composition of the single-chain particles.

关键词

聚合物单链粒子链内交联氢键接枝三嵌段聚合物

Keywords

Polymeric single-chain particleIntrachain cross-linkingH-bonding graftingTriblock copolymers

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