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通过创新的反应性增容提高聚乳酸/聚(己二酸丁二醇酯-对苯二甲酸丁二醇酯)共混物的界面相容性和性能

Enhancing interfacial compatibility and performance of polylactic Acid/ poly(butylene adipate-co-terephthalate) blends via innovative reactive compatibilization.

作者信息

Gao Guangxu, Zhang Yutong, Bai Xiaohan, Qiu Ying, Cong Fei, Wang Xiangyi, Wang Ning, Huang Jiangting, Leng Siyin, Gao Jialu, Li Yongchao, Hao Yongsheng, Wang Yuanxia, Song Lixin

机构信息

Liaoning Provincial Key Laboratory for Synthesis and Preparation of Special Functional Materials, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China.

Center of Implantology, School and Hospital of Stomatology, China Medical University, Shenyang 110122, Liaoning, China.

出版信息

Int J Biol Macromol. 2025 Aug;319(Pt 4):145603. doi: 10.1016/j.ijbiomac.2025.145603. Epub 2025 Jun 26.

DOI:10.1016/j.ijbiomac.2025.145603
PMID:40581003
Abstract

With the increasing global demand for sustainable materials, the development of high-performance bio-based polymer blends has become a critical direction in materials science research. To address environmental pollution and resource depletion, this study introduces poly(propylene glycol) diglycidyl ether (PPGDGE) as a reactive compatibilizer for the first time. Using melt blending technology, PPGDGE was blended with poly(lactic acid) (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) at a mass ratio of 70:30 to prepare a PLA/PBAT/PPGDGE (PBP) ternary blend system. The effects of PPGDGE on the multifaceted properties of the PLA/PBAT blend were systematically evaluated. The study found that the epoxy groups in PPGDGE can undergo ring-opening reactions with the nucleophilic end groups of PLA and PBAT, generating PLA-graft-PBAT copolymers in situ at the interface, thereby improving the compatibility of the blend to some extent. As the PPGDGE content in the system gradually increased, the processing, optical, and thermal properties of the blend improved progressively, while the notched impact strength and elongation at break first increased and then decreased. When the PPGDGE content reached 5 phr, the difference in glass transition temperatures (ΔT) of the blend reached its minimum. SEM images showed that the PBAT dispersed phase achieved the smallest size and most uniform distribution, while AFM revealed the smoothest surface and most continuous phase structure, indicating optimal compatibility between PLA and PBAT at this loading. At this point, the light transmittance and Vicat softening temperature of the blend increased from 76.8 % and 82.6 °C to 90 % and 88.8 °C, respectively, while the elongation at break and notched impact strength rose to 480.07 % and 14,370.34 J/m-4 times and 3.5 times higher than those of the blend without PPGDGE, respectively. The toughness of the blend was significantly enhanced, and the fracture surface exhibited the highest roughness, displaying clear ductile fracture characteristics. Meanwhile, in vitro cell experiments (L929 cells) confirmed that all PBP blends possessed excellent biocompatibility: live/dead staining showed high-density clusters of live cells and minimal dead cells on and around the material surface, while CCK-8 assays demonstrated stable and continuous cell proliferation on the blend surfaces (p < 0.05), with no negative impact on cell viability from PPGDGE addition. Regarding degradation performance, the polyether segments in PPGDGE imparted significant hydrophilicity, effectively promoting water molecule penetration and diffusion within the matrix and accelerating ester bond hydrolysis, thereby substantially increasing the blend's degradation rate (the absolute value of the mass loss rate constant k over time increased from 0.5711 to 0.8582). In summary, the introduction of PPGDGE not only effectively enhanced the mechanical, thermal, and optical properties of the PLA/PBAT blend but also ensured excellent cytocompatibility and tunable degradation rates, laying a theoretical foundation for its broad application in PLA-based biodegradable materials where predetermined service life and biosafety are equally critical.

摘要

随着全球对可持续材料的需求不断增加,高性能生物基聚合物共混物的开发已成为材料科学研究的一个关键方向。为了解决环境污染和资源枯竭问题,本研究首次引入聚丙二醇二缩水甘油醚(PPGDGE)作为反应性增容剂。采用熔融共混技术,将PPGDGE与聚乳酸(PLA)和聚己二酸丁二醇酯-对苯二甲酸丁二醇酯共聚物(PBAT)按质量比70:30进行共混,制备了PLA/PBAT/PPGDGE(PBP)三元共混体系。系统评估了PPGDGE对PLA/PBAT共混物多方面性能的影响。研究发现,PPGDGE中的环氧基团可与PLA和PBAT的亲核端基发生开环反应,在界面处原位生成PLA接枝PBAT共聚物,从而在一定程度上提高了共混物的相容性。随着体系中PPGDGE含量逐渐增加,共混物的加工性能、光学性能和热性能逐渐改善,而缺口冲击强度和断裂伸长率先升高后降低。当PPGDGE含量达到5 phr时,共混物的玻璃化转变温度差(ΔT)达到最小值。扫描电子显微镜(SEM)图像显示,PBAT分散相尺寸最小且分布最均匀,而原子力显微镜(AFM)显示表面最光滑且相结构最连续,表明此时PLA与PBAT之间具有最佳相容性。此时,共混物的透光率和维卡软化温度分别从76.8%和82.6℃提高到90%和88.8℃,而断裂伸长率和缺口冲击强度分别提高到480.07%和14370.34 J/m,分别是不含PPGDGE共混物的4倍和3.5倍。共混物的韧性显著增强,断裂表面粗糙度最高,呈现明显的韧性断裂特征。同时,体外细胞实验(L929细胞)证实,所有PBP共混物均具有优异的生物相容性:活/死染色显示材料表面及周围活细胞高密度聚集且死细胞极少,而CCK-8检测表明共混物表面细胞增殖稳定且持续(p < 0.05),添加PPGDGE对细胞活力无负面影响。关于降解性能,PPGDGE中的聚醚链段赋予显著亲水性,有效促进水分子在基体中的渗透和扩散,加速酯键水解,从而大幅提高共混物的降解速率(质量损失速率常数k随时间的绝对值从0.5711增加到0.8582)。综上所述,PPGDGE的引入不仅有效增强了PLA/PBAT共混物的力学、热学和光学性能,还确保了优异的细胞相容性和可调降解速率,为其在基于PLA的可生物降解材料中的广泛应用奠定了理论基础,在这些应用中,预定的使用寿命和生物安全性同样至关重要。

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