H2O-Initiated Polymerization of L-Lactide

IF 4.7 3区工程技术 Q2 ENGINEERING, ENVIRONMENTAL

Journal of Polymers and the Environment Pub Date : 2025-04-05 DOI:10.1007/s10924-025-03565-w

Hans R. Kricheldorf, Steffen M. Weidner

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引用次数: 0

Abstract

Water-initiated ring-opening polymerizations (ROPs) of L-lactide (LA) were performed in bulk at 140 °C, whereupon 11 different salts or complexes of low-toxic metal ions such as tin (II), Zn(II), Zr(IV), and Bi(III) were used as catalysts. Only four catalysts gave satisfactory results despite a long reaction time (24 h). The influence of the temperature was studied with tin (II) 2-ethylhexanoate (SnOct₂), dibutyltin oxide (Bu₂SnO), and zinc bis-acetylacetonate (Zn(acac)₂) and zirconium acetylacetonate (Zr(acac)₄). With SnOct_2, Bu₂SnO and Zr(acac)₄ the time was varied at 140 °C to compare their reactivity. Furthermore, two series of ROPs were carried out with variation of the LA/H₂O ratio to verify the control of the molecular weight by the monomer-initiator ratio. Bi- or tri-modal molecular weight distributions (MWD) were found for most of the ROPs and bimodal melting endotherms in the differential scanning calorimetry (DSC) heating traces. The thickness and dependence of the 3D packing of the crystallites were monitored by small-angle X-ray scattering (SAXS) measurements.

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l -丙交酯的水引发聚合

采用11种不同的盐或低毒金属离子络合物，如锡（II）、锌（II）、锆（IV）和铋（III）作为催化剂，在140°C下进行了l -丙交酯（LA）的水引发开环聚合（ROPs）。尽管反应时间较长（24 h），但只有4种催化剂的反应结果令人满意。用锡（II） 2-乙基己酸盐（SnOct2）、二丁基氧化锡（Bu2SnO）、双乙酰丙酮锌（Zn(acac)2）和乙酰丙酮锆（Zr(acac)4）研究了温度的影响。用SnOct2、Bu2SnO和Zr(acac)4在140℃下改变反应时间，比较它们的反应性。此外，通过改变LA/H2O比进行了两个系列的rop实验，验证了单体引发剂比对分子量的控制作用。在差示扫描量热法（DSC）的热迹中，大多数rop和双峰熔融吸热物均存在双峰或三峰分子量分布。用小角x射线散射（SAXS）测量了晶体的厚度和三维堆积的依赖性。

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来源期刊

Journal of Polymers and the Environment 工程技术-高分子科学

CiteScore

9.50

自引率

7.50%

发文量

297

审稿时长

9 months

期刊介绍： The Journal of Polymers and the Environment fills the need for an international forum in this diverse and rapidly expanding field. The journal serves a crucial role for the publication of information from a wide range of disciplines and is a central outlet for the publication of high-quality peer-reviewed original papers, review articles and short communications. The journal is intentionally interdisciplinary in regard to contributions and covers the following subjects - polymers, environmentally degradable polymers, and degradation pathways: biological, photochemical, oxidative and hydrolytic; new environmental materials: derived by chemical and biosynthetic routes; environmental blends and composites; developments in processing and reactive processing of environmental polymers; characterization of environmental materials: mechanical, physical, thermal, rheological, morphological, and others; recyclable polymers and plastics recycling environmental testing: in-laboratory simulations, outdoor exposures, and standardization of methodologies; environmental fate: end products and intermediates of biodegradation; microbiology and enzymology of polymer biodegradation; solid-waste management and public legislation specific to environmental polymers; and other related topics.