Engineering tetraphenylethylene-based amphiphilic copolymers by dynamic covalent approach: Molecular origin from simple to complex aggregates

IF 2.3 4区化学 Q3 CHEMISTRY, PHYSICAL

Colloid and Polymer Science Pub Date : 2025-05-26 DOI:10.1007/s00396-025-05441-4

Chunhui Li, Han Bao, Xianhai Liu, Jinfeng Dong, Xuefeng Li

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引用次数: 0

Abstract

Herein, a series of block copolymers poly(N-(2-methacryloylxyethyl) ethyl pyrrolidone)-block-poly(4-(formaldehyde) phenyl methacrylate) (PNMP₁₃₆-b-PBFMA_m) were developed as the aldehyde precursors D_m. Three kinds of tetraphenylethylene-based dynamic covalent imine copolymers (D_m-A) were generated in situ from the aqueous mixtures of D_m and amino precursors A including 4-(1,2,2-triphenylvinyl) aniline (TPVA), N-(2-aminoethyl)-3-(4-(1,2,2-triphenylvinyl) phenoxy) propenamide (TPVC₂A) and N-(2-aminohexyl)-3-(4-(1,2,2-triphenylvinyl) phenoxy) propenamide (TPVC₆A) at the constant -NH₂/-CHO molar ratio of 1, resulting in D_m-TPVA, D_m-TPVC₂A, and D_m-TPVC₆A, respectively. D_m commonly formed spherical micelles in water, and spherical micelles were also formed by D_m-TPVA, D_m-TPVC₂A, and D_m-TPVC₆A with m below 135. However, D₁₉₄-TPVA, D₁₉₄-TPVC₂A, and D₁₉₄-TPVC₆A preferred to form long and entangled wormlike micelles. This indicates that the morphology of D_m-A aggregates is mainly determined by the degree m of polymerization of PBFMA segment in D_m. The emulsification of D_m, D_m-TPVA, D_m-TPVC₂A, and D_m-TPVC₆A micelles in the dodecane/water systems was depended on the compatibility between oil and copolymers. D_m and D_m-TPVC₆A micelles with m ranging from 44 to 135 were excellent Pickering emulsifiers, favoring the formation of O/W Pickering emulsions.

Graphical abstract

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工程四苯乙烯基两亲共聚物的动态共价方法：分子起源从简单到复杂的聚集体

本文制备了一系列嵌段共聚物聚（N-（2-甲基丙烯酰氧乙基）乙基吡啶酮）-嵌段聚（4-（甲醛）苯基甲基丙烯酸酯）（pnmp136 -b- pbmam）作为醛前体Dm。以Dm和氨基前体a为原料，原位合成了3种四苯基动态共价亚胺共聚物Dm- a，包括4-（1,2,2-三苯基乙烯基）苯胺（TPVA）、N-（2-氨基乙基）-3-（4-（1,2,2-三苯基乙烯基）苯氧基）丙烯酰胺（TPVC2A）和N-（2-氨基己基）-3-（4-（1,2,2-三苯基乙烯基）苯氧基）丙烯酰胺（TPVC6A）以恒定的- nh2 /- cho摩尔比为1，分别得到Dm-TPVA、Dm-TPVC2A和Dm-TPVC6A。Dm在水中通常形成球形胶束，Dm- tpva、Dm- tpvc2a和Dm- tpvc6a在m < 135时也形成球形胶束。而D194-TPVA、D194-TPVC2A和D194-TPVC6A则倾向于形成长而缠结的虫状胶束。这表明Dm- a聚集体的形态主要取决于Dm中pbma段的聚合度。Dm、Dm- tpva、Dm- tpvc2a和Dm- tpvc6a胶束在十二烷/水体系中的乳化作用取决于油与共聚物之间的相容性。Dm和Dm- tpvc6a胶束m在44 ~ 135之间，是优良的皮克林乳化剂，有利于形成O/W皮克林乳剂。图形抽象

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来源期刊

Colloid and Polymer Science 化学-高分子科学

CiteScore

4.60

自引率

4.20%

发文量

111

审稿时长

2.2 months

期刊介绍： Colloid and Polymer Science - a leading international journal of longstanding tradition - is devoted to colloid and polymer science and its interdisciplinary interactions. As such, it responds to a demand which has lost none of its actuality as revealed in the trends of contemporary materials science.