Electrostatic-Mediated Intramolecular Cross-Linking Polymers in Concentrated Solutions,CCS Chemistry

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Electrostatic-Mediated Intramolecular Cross-Linking Polymers in Concentrated Solutions
CCS Chemistry ( IF 9.4 ) Pub Date : 2019-09-24 , DOI: 10.31635/ccschem.019.20190035
Dao Xiang _{1,

2} , Xi Chen _{1,

2} , Lin Tang _{1,

2} , Bingyin Jiang ₁ , Zhenzhong Yang _{1,

2,

3}

Affiliation

cross-linking of isolated single-polymer chains in dilute solutions, the method has been extensively employed to achieve single-chain colloids and tadpole colloids (Janus ones) from homopolymers and copolymers, respectively. After understanding that the conventional fabrication methods were based only on short-ranged protections, it has become an urgent requirement to develop new conceptual general methods toward the intramolecular cross-linking in concentrated solutions to determine the improvement of stability. Thus we immediately proposed that if long-ranged, electrostatic-mediated intramolecular cross-linking of polymers could be achieved in concentrated solutions, it would benefit the establishment of more stable supermicelle aggregates. We thought it wise to employ previously developed electrostatic repulsion technique via modification with monovalence agents and performed sequential cross-linking with multiple-valence agents. For the fabrication of polyvinylpyridine-contained polymers, iodoethane and 1,5-diiodopentane were used as a modification agent and a cross-linker. For the polyacrylic-acid-contained polymers, 1-methylimidazole and 1,6-hexanediisothiocyanate were used for the intramolecular cross-linking. Polyisoprenecontained polymers were chosen because they were cheap. After click reaction with mercaptoacetic acid, the fabricated polymers resembled polyacrylic-acidcontained polymers. Intramolecular cross-linking of polystyrene-block-poly(4-vinylpyridine)-block-poly (ethylene oxide) (PS-b-P4VP-b-PEO) was achieved at 300 mg/mL. We found that the composition and performance of the colloidal domains were broadly tunable by favorable growth of functional materials, unveiling new perspectives for deriving a huge family of functional composite Janus colloidal single chains.

中文翻译：

浓溶液中静电介导的分子内交联聚合物

分离的单聚合物链在稀溶液中发生交联，该方法已被广泛采用，分别从均聚物和共聚物中获得单链胶体和t胶体（Janus胶体）。在了解到传统的制造方法仅基于短距离保护后，迫切需要开发一种新的概念性通用方法，以解决浓缩溶液中分子内交联的问题。因此，我们立即提出，如果可以在浓缩溶液中实现聚合物的长程静电介导的分子内交联，则将有利于建立更稳定的超胶束聚集体。我们认为明智的做法是使用以前开发的静电排斥技术，通过单价试剂进行改性，并与多价试剂进行顺序交联。为了制造含聚乙烯基吡啶的聚合物，使用碘乙烷和1,5-二碘戊烷作为改性剂和交联剂。对于含聚丙烯酸的聚合物，将1-甲基咪唑和1，6-己二异硫氰酸酯用于分子内交联。选择含聚异戊二烯的聚合物是因为它们很便宜。与巯基乙酸发生点击反应后，制成的聚合物类似于含聚丙烯酸的聚合物。聚苯乙烯-嵌段-聚（4-乙烯基吡啶）-嵌段-聚（环氧乙烷）（PS-b-P4VP-b-PEO）的分子内交联达到300 mg / mL。

更新日期：2020-06-24

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