All-Polylactones Nano-Objects Prepared by a One-Pot Ring-Opening Polymerization-Induced Self-Assembly Process

IF 5.1 1区化学 Q1 POLYMER SCIENCE

Macromolecules Pub Date : 2024-09-19 DOI:10.1021/acs.macromol.4c01334

Ding Shen, Boyang Shi, Peng Zhou, Di Li, Wenya Zhu, Guowei Wang

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Abstract

Ring-opening polymerization (ROP) has been acknowledged as an efficient approach to biodegradable polylactones. Herein, by a sequential ROP of d,l-lactic acid (D,L-LA) and l-lactic acid(L-LA) monomers in toluene, we reported a ROP-induced self-assembly (ROPISA) process. The poly(d, l-lactic acid)-b-poly(l-lactic acid) (PDLLA-b-PLLA)-based all-polylactones nano-objects were prepared in a one-pot manner. The crystalline PLLA served as a core-forming block, and amorphous PDLLA acted as a stabilizer block. The morphologies of the generated nano-objects included spheres and platelets by varying the polymerization parameters. Uniquely, the ROPISA was synergistically driven by crystallization and solubility of the PLLA core. The versatility of the ROPISA process was also demonstrated by the successful preparation of nano-objects with poly(ε-caprolactone) (PCL) or poly(δ-valerolactone) (PVL) as the stabilizer block, and PLLA as the core-forming block. Based on the living and controlled character of ROPISA, in the final polymerization, the living species in the PLLA core could be in situ cross-linked by 4,4′-bioxepanyl-7,7′-dione (BOD) and the nano-objects could be stabilized. The melting temperature (T_m) of the polylactone blocks in the core or shell region was independent and unaffected. Comparing with the unstabilized nano-objects, the thermal stability of stabilized nano-objects can be significantly enhanced.

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开环聚合（ROP）已被公认为是一种高效的生物降解聚内酯方法。在此，我们通过在甲苯中依次对 d,l-乳酸（D,L-LA）和 l-乳酸（L-LA）单体进行开环聚合，报道了一种开环聚合诱导的自组装（ROPISA）过程。我们以一锅法制备了基于聚（d，l-乳酸）-b-聚（l-乳酸）（PDLLA-b-PLLA）的全聚内酯纳米物体。结晶聚乳酸作为核心形成块，无定形 PDLLA 作为稳定块。通过改变聚合参数，生成的纳米物体的形态包括球状和板状。与众不同的是，ROPISA 是由聚乳酸核心的结晶性和可溶性协同驱动的。以聚(ε-己内酯)（PCL）或聚(δ-戊内酯)（PVL）为稳定剂嵌段，以聚乳酸（PLLA）为成芯嵌段，成功制备出纳米物体，也证明了 ROPISA 工艺的多功能性。基于 ROPISA 的活体和可控特性，在最终聚合过程中，PLLA 核心中的活体可通过 4,4′-二氧杂环庚烷-7,7′-二酮（BOD）原位交联并稳定纳米物体。核心或外壳区域的聚乳酸块的熔化温度（Tm）是独立的，不受影响。与未稳定的纳米物体相比，稳定纳米物体的热稳定性显著提高。

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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.

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