合成具有聚恶唑啉臂和大环钙[8]炔支链中心的米克托臂星形聚合物

IF 5.8 2区 化学 Q1 POLYMER SCIENCE European Polymer Journal Pub Date : 2024-11-01 DOI:10.1016/j.eurpolymj.2024.113547
N.D. Kozina, T.U. Kirila, A.N. Blokhin, A.P. Filippov, A.V. Tenkovtsev
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引用次数: 0

摘要

采用 "先接芯"(从芯接枝)和 "接枝到芯 "相结合的方法,开发了一种合成以钙钛矿[8]炔为芯的米克托臂星形聚(2-烷基-2-噁唑啉)的新方法。利用萼[8]炔基多功能支化中心、磺酰氯引发分子和酰肼终止分子,获得了具有接枝聚(2-乙基-2-噁唑啉)和聚(2-异丙基-2-噁唑啉)臂的 A8B8 型星形聚合物。1H NMR 光谱和紫外光谱证实了聚合物的结构。样品的摩尔质量特性是通过尺寸排阻色谱法和光散射法测定的。实验证实,所有合成聚合物都具有目标臂数,即 8 或 16。获得的米克托臂星形物具有摩尔质量分布窄的特点,臂的聚合度为 15。合成的星形物具有较高的分子内密度,并随着臂数的增加而增加。对于米克托臂星体,相分离温度并不取决于聚(2-乙基-2-噁唑啉)和聚(2-异丙基-2-噁唑啉)在卡利克[8]炔上缘或下缘的接枝构型。
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Synthesis of miktoarm star-shaped polymers with polyoxazoline arms and macrocyclic calix[8]arene branching center
A novel approach to the synthesis of miktoarm star-shaped poly(2-alkyl-2-oxazolines) with calix[8]arene core was developed using a combination of the “core first” (grafting from) and “grafting onto” methods. The star-shaped polymers of A8B8 type with grafted poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) arms were obtained using calix[8]arene based multifunctional branching center with sulfonyl chloride initiating moieties and as well as acyl hydrazide termination ones. The polymer structure has been confirmed by 1H NMR spectroscopy and UV spectroscopy. The molar mass characteristics of the samples were determined by size-exclusion chromatographic and light scattering. It was experimentally confirmed that all synthesized polymers had the target arm number, namely 8 or 16. The obtained miktoarm stars were characterized by narrow molar mass distributions, and the polymerization degree of the arms was 15. The synthesized stars had a high intramolecular density, which increased with the arm number. It is shown that the thermoresponsiveness of the studied stars depends on the number and structure of arms and on intramolecular density, while molecular mass is not a decisive factor determining their LCST behavior.
For miktoarm stars, phase separation temperatures do not depend on the grafting configuration of poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) on the upper or lower rim of calix[8]arene.
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来源期刊
European Polymer Journal
European Polymer Journal 化学-高分子科学
CiteScore
9.90
自引率
10.00%
发文量
691
审稿时长
23 days
期刊介绍: European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.
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