Impact of Hydroxyl Functionalization and Unsaturation on Linear Poly(ethylene-co-vinyl alcohol)

IF 5.2 1区化学 Q1 POLYMER SCIENCE Macromolecules Pub Date : 2025-02-24 DOI:10.1021/acs.macromol.4c02575

Anne N. Radzanowski, Eli J. Fastow, Chien-Hua Tu, James Votruba-Drzal, Vivek Nair, Karen I. Winey, E. Bryan Coughlin

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Abstract

Functionalization of C═C in unsaturated polyolefins by hydroboration/oxidation successfully generates linear poly(ethylene-co-vinyl alcohol) (LEVOH) polymers. This postpolymerization modification expands upon previously reported chemistry to control the extent of functionalization through reagent stoichiometry. Partial functionalization (24–92% of C═C) of polycyclooctene produces materials with both C═C in the backbone and pendant OH and subsequent hydrogenation generate a LEVOH. We explore the thermal, structural, surface, and adhesive properties of these LEVOH and the partially unsaturated intermediate and find they are impacted by both the extent of OH incorporation and saturation. The presence of C═C significantly reduces the melting temperature and crystallinity while increasing surface polarity and adhesive strength compared with saturated polymers at equivalent functionalization. This investigation demonstrates linear analogs of EVOH with a wide range of properties tuned by extent of hydroxylation and presence of unsaturation.

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羟基功能化和不饱和对线性聚乙烯醇的影响

通过氢硼化/氧化作用对不饱和聚烯烃中的 C═C 进行官能化，成功生成了线性聚（乙烯-共-乙烯醇）（LEVOH）聚合物。这种后聚合改性技术在之前报道的化学方法的基础上进行了扩展，通过试剂的化学计量来控制官能化的程度。通过对聚环辛烯进行部分官能化（24-92% 的 C═C），可生产出骨架中含有 C═C 和悬垂羟基的材料，随后氢化生成 LEVOH。我们对这些 LEVOH 和部分不饱和中间体的热性能、结构性能、表面性能和粘合性能进行了研究，发现它们受到羟基掺入程度和饱和度的影响。与官能度相当的饱和聚合物相比，C═C 的存在大大降低了熔化温度和结晶度，同时增加了表面极性和粘合强度。这项研究证明，EVOH 的线性类似物可通过羟基化程度和不饱和度的存在来调整各种特性。

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来源期刊

Macromolecules 工程技术-高分子科学

CiteScore

9.30

自引率

16.40%

发文量

942

审稿时长

2 months

期刊介绍： Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.