Biodegradable thermoplastic elastomers synthesized from C7–C10 aliphatic dicarboxylic acids, 2-methyl-1,3-propanediol, and L-lactide

IF 6.3 2区化学 Q1 POLYMER SCIENCE

Polymer Degradation and Stability Pub Date : 2024-08-23 DOI:10.1016/j.polymdegradstab.2024.110978

Yuushou Nakayama , Takayoshi Matsu-ura , Ryo Tanaka , Takeshi Shiono , Shodai Hino , Norioki Kawasaki , Naoko Yamano , Atsuyoshi Nakayama , Rie Tezuka , Kazuya Tanaka

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引用次数: 0

Abstract

Elastic materials with high biodegradability should replace those with low biodegradability in some applications. We previously reported biodegradable thermoplastic elastomers (TPEs) composed of poly(l-lactide) (PLLA) as a hard segment and aliphatic polyesters from 2-methyl-1,3-propanediol (MP) and short aliphatic dicarboxylic acids as soft segments. In this study, we synthesized the biodegradable thermoplastic elastomers using longer aliphatic dicarboxylic acids to develop the TPEs with lower glass-transition temperature (T_g) and high biodegradability. A series of aliphatic polyesters were prepared by polycondensation of MP and aliphatic dicarboxylic acids bearing 7–10 carbons. Among them, poly(2-methyl-1,3-propylene azelate) (PMP9) was found to have lower T_g, amorphous nature, and high biodegradability in seawater. The ring-opening polymerization of l-lactide (LLA) using PMP9 as a macroinitiator afforded triblock copolymers, PLLA-b-PMP9-b-PLLA (TPE9). The successive addition of LLA to in-situ generated PMP9 resulted in the successful one-pot synthesis of high molecular weight TPE9. The TPE9s showed both low T_g of the PMP9 segment and high melting temperature of the PLLA segment. The TPE9s exhibited elastic behavior showing elongation at break of up to 2500 % in tensile tests and also high biodegradability in seawater. Thus, we developed potentially practical TPE with tunable physical properties and high biodegradability obtainable from easily available and renewable starting materials.

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由 C7-C10 脂肪族二羧酸、2-甲基-1,3-丙二醇和 L-内酯合成的可生物降解的热塑性弹性体

在某些应用中，生物降解性高的弹性材料应取代生物降解性低的材料。我们曾报道过可生物降解的热塑性弹性体（TPE），其组成包括作为硬段的聚（l-内酰胺）（PLLA）和作为软段的由 2-甲基-1,3-丙二醇（MP）和短脂肪族二羧酸组成的脂肪族聚酯。在这项研究中，我们使用较长的脂肪族二羧酸合成了可生物降解的热塑性弹性体，以开发具有较低玻璃化转变温度（Tg）和较高生物降解性的热塑性弹性体。通过 MP 与含 7-10 个碳原子的脂肪族二羧酸缩聚，制备了一系列脂肪族聚酯。其中，聚（2-甲基-1,3-丙烯壬二酸酯）（PMP9）具有较低的 Tg 值、无定形性质以及在海水中的高生物降解性。使用 PMP9 作为大引发剂对 l-内酰胺（LLA）进行开环聚合，可得到三嵌段共聚物 PLLA-b-PMP9-b-PLLA（TPE9）。在原位生成的 PMP9 中连续添加 LLA 后，成功地实现了高分子量 TPE9 的一锅合成。TPE9 的 PMP9 部分具有较低的 Tg 值，而 PLLA 部分则具有较高的熔融温度。TPE9s 具有弹性行为，在拉伸试验中的断裂伸长率高达 2500%，在海水中的生物降解性也很高。因此，我们开发出了具有可调物理性质和高生物降解性的实用 TPE，这些 TPE 可从易于获得的可再生原材料中获得。

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来源期刊

Polymer Degradation and Stability 化学-高分子科学

CiteScore

10.10

自引率

10.20%

发文量

325

审稿时长

23 days

期刊介绍： Polymer Degradation and Stability deals with the degradation reactions and their control which are a major preoccupation of practitioners of the many and diverse aspects of modern polymer technology. Deteriorative reactions occur during processing, when polymers are subjected to heat, oxygen and mechanical stress, and during the useful life of the materials when oxygen and sunlight are the most important degradative agencies. In more specialised applications, degradation may be induced by high energy radiation, ozone, atmospheric pollutants, mechanical stress, biological action, hydrolysis and many other influences. The mechanisms of these reactions and stabilisation processes must be understood if the technology and application of polymers are to continue to advance. The reporting of investigations of this kind is therefore a major function of this journal. However there are also new developments in polymer technology in which degradation processes find positive applications. For example, photodegradable plastics are now available, the recycling of polymeric products will become increasingly important, degradation and combustion studies are involved in the definition of the fire hazards which are associated with polymeric materials and the microelectronics industry is vitally dependent upon polymer degradation in the manufacture of its circuitry. Polymer properties may also be improved by processes like curing and grafting, the chemistry of which can be closely related to that which causes physical deterioration in other circumstances.