Cationic Alternating Copolymerization of Vinyl Esters and 3-Alkoxyphthalides: Side Chain-Crosslinkable Polymers for Acid-Degradable Single-Chain Nanoparticles

IF 5.2 Q1 POLYMER SCIENCE

ACS Macro Letters Pub Date : 2024-05-31 DOI:10.1021/acsmacrolett.4c00246

Kyonosuke Kamigaki, Sadahito Aoshima and Arihiro Kanazawa*,

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Abstract

Cationic copolymerization of vinyl acetate and 3-alkoxyphthalides (ROPTs) was demonstrated to proceed using GaCl₃ as a Lewis acid catalyst. Both monomers did not undergo homopolymerization, while copolymerization smoothly occurred via the crossover reactions, resulting in alternating copolymers with molecular weights of over 10⁴. The obtained copolymers could be degraded by acid due to the cleavage of the diacyloxymethine moieties, which were derived from the crossover reactions from vinyl acetate to ROPT, in the main chain. An advantage of not radical but cationic copolymerization of vinyl esters was exerted by copolymerizations of radically reactive group-containing vinyl esters with ROPTs. For example, vinyl cinnamate was successfully copolymerized with an ROPT by the cationic mechanism, while keeping the cinnamoyl groups intact. The obtained alternating copolymer was subjected to a photodimerization reaction of the cinnamoyl groups in the side chains, resulting in an acid-degradable single-chain nanoparticle via the intramolecular crosslinking reactions.

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乙烯基酯和 3-烷氧基邻苯二甲酸酯的阳离子交替共聚：用于酸性可降解单链纳米颗粒的侧链可交联聚合物。

使用 GaCl3 作为路易斯酸催化剂，证明了醋酸乙烯酯和 3-烷氧基邻苯二甲酸盐（ROPTs）的阳离子共聚。两种单体没有发生均聚，而通过交叉反应顺利发生了共聚，从而产生了分子量超过 104 的交替共聚物。所得到的共聚物可被酸降解，原因是主链中的二乙氧基甲烷分子被裂解，而这些分子是从醋酸乙烯酯与 ROPT 的交叉反应中产生的。乙烯基酯不是自由基共聚而是阳离子共聚的优点是含自由基反应基团的乙烯基酯与 ROPT 的共聚。例如，肉桂酸乙烯酯通过阳离子机理成功地与一种 ROPT 发生了共聚，同时保持了肉桂酰基的完整。得到的交替共聚物侧链中的肉桂酰基发生光二聚化反应，通过分子内交联反应生成可酸性降解的单链纳米粒子。

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来源期刊

ACS Macro Letters 化学-

CiteScore

10.40

自引率

3.40%

发文量

209

审稿时长

1 months

期刊介绍： ACS Macro Letters publishes research in all areas of contemporary soft matter science in which macromolecules play a key role, including nanotechnology, self-assembly, supramolecular chemistry, biomaterials, energy generation and storage, and renewable/sustainable materials. Submissions to ACS Macro Letters should justify clearly the rapid disclosure of the key elements of the study. The scope of the journal includes high-impact research of broad interest in all areas of polymer science and engineering, including cross-disciplinary research that interfaces with polymer science. With the launch of ACS Macro Letters, all Communications that were formerly published in Macromolecules and Biomacromolecules will be published as Letters in ACS Macro Letters.