生物基乙酰丁香酮衍生聚芳醚酮的分子设计、合成与表征

Molecular Design, Synthesis and Characterization of Bio-based Acetosyringone-derived Poly(aryl ether ketone)s

摘要

合成了一种由生物基化合物乙酰丁香酮衍生的新型氧杂环哒嗪酮单体6-(4-羟基-3,5-二甲氧基苯基)-3(2H)-哒嗪酮(AGPZ). 利用Materials Studio软件对AGPZ的酚氧负离子与已报道的愈创木酚衍生物单体(GSPZ)的酚氧负离子进行了模拟计算, 通过对比发现GSPZ的酚氧负离子处的静电势极值更低, 表明AGPZ的亲核取代活性低于GSPZ. 同时, 通过AGPZ模型化合物的成功合成确定了AGPZ仍具备足够的亲核取代反应活性. 由AGPZ与2,5-呋喃二甲酸的衍生物2,5-双(4-氟苯甲酰基)呋喃(BFBF)和双酚芴(BHPF)进行三元共聚，得到一组新型生物基杂环聚芳醚酮AGPZ-BHPF-BFBF三元共聚物(PAFEKKs). 由PAFEKKs的结构与性能表征结果可知, 其玻璃化转变温度(T _g)介于217~226 ℃之间, 在N₂气氛围下5%热失重温度(T _d,5%)达到419~474 ℃, 表明PAFEKKs具有优异的耐热性能. 此外，PAFEKs在常温下还具有优良的溶解性. 该合成方法为生物基树脂的制备提供了新结构与新思路, 也为其它相关结构的单体与树脂的合成提供了可行路径.

Abstract

A novel oxygen heterocyclic pyridazinone monomer 6-(4-hydroxy-3,5-dimethoxyphenye)pyridazin-3(2H)-one(AGPZ) derived from the biobased compound acetosyringone was synthesized. Theoretical simulations of the phenoxide anions of AGPZ and the previously reported guaiacol-derived monomer 6-(4-hydroxy-3-methoxyphenyl)pyridazin-3(2H)-one(GSPZ) were conducted using Materials Studio. Comparative analysis reveals that the electrostatic potential extremum at the phenoxide anion of GSPZ is lower, indicating that the nucleophilic substitution activity of AGPZ is lower than that of GSPZ. Nevertheless, the successful synthesis of an AGPZ model compound confirmed that AGPZ still possesses sufficient nucleophilic substitution reactivity. A series of biobased poly(aryl ether ketone), named as PAFEKKs, was synthesized through ternary copolymerization of AGPZ with the 2,5-bis(4-fluorobenzoyl)furan(BFBF) and 9,9-bis(4-hydroxyphenyl)fluorene(BHPF). The synthesized PAFEKKs show a glass transition temperature(T _g, ℃) in the range of 217-226 °C and a 5% mass loss decomposition temperature(T _{d , 5%}, ℃) between 419 and 474 °C, demonstrating excellent thermal stability. Furthermore, PAFEKKs exhibit good solubility, readily dissolving in most common organic solvents at room temperature. This synthetic method strategy utilizing biomass-derived monomers offers a molecular design and synthetic route for biobased resins, presenting a promising avenue for the development of sustainable monomers and polymers with diverse structural architectures.

关键词

生物基高分子材料 / 聚芳醚酮 / 乙酰丁香酮 / 分子结构与性能

Key words

Biobased polymer material / Poly(aryl ether ketone)s / Acetosyringone / Molecular structure and performance

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基金资助

国家自然科学基金(52273005)