PMMA-PDMS-PMMA triblock copolymers as toughness modifiers for UV-curable methacrylate resins

IF 5.8 2区化学 Q1 POLYMER SCIENCE

European Polymer Journal Pub Date : 2025-06-02 DOI:10.1016/j.eurpolymj.2025.114049

Hien The Ho , Kai Rist , Iris Lamparth , Sadini Omeragic , Pascal Fässler , Fabrice Cousin , Loïc Vidal , Jacques Lalevée , Didier Gigmes , Yohann Catel , Trang N.T. Phan

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引用次数: 0

Abstract

Photocurable denture bases require both rigidity (high flexural strength and modulus) and high fracture toughness (to prevent cracking or breaking under mechanical stress). These antagonist properties can be provided by the incorporation of block copolymers (BCPs) due to their unique self-assembly properties conferring an overall improvement of fracture toughness and mechanical properties to denture base materials. In the present work, it was shown that poly(methyl methacrylate)-block-poly(dimethyl siloxane)-block-poly(methyl methacrylate) (PMMA-PDMS-PMMA) triblock copolymers are highly efficient toughening agents for (meth)acrylic resins, resulting in a significantly improved fracture toughness without compromising the mechanical strength or processing. The influence of the PMMA:PDMS block ratio and the weight fraction of triblock copolymer (3–10 wt%) in the resin was investigated and revealed that the most efficient toughening triblock copolymer is composed of PMMA and PDMS blocks having the similar molecular weight of 8000 g mol⁻¹.

The highest fracture toughness value (K_max = 2,25 MPa m^1/2) was obtained with this BCP at a concentration of 5 wt% in the resin, an improvement of 180 % compared to the BCP free resin. Small angle X-ray scattering measurements revealed that self-assembly of BCPs led to the formation of spherical micelles that transform to small clusters after curing if the compatible PMMA block is sufficiently long compared to the incompatible PDMS block. Otherwise, large aggregates were observed. Transmission electron microscopy confirmed the SAXS results, showing the clusters of spherical micelles. As toughening agents, PMMA-PDMS-PMMA BCPs showed better performance than the reference polycaprolactone-polysiloxane (PCL-PDMS-PCL) one. The influence of the nature of the compatible block (PMMA versus PCL) and of the PMMA:PDMS block ratio on the fracture toughness of radical-cured resin systems was clearly demonstrated in this study. The most promising formulation was shown to be suitable for digital light processing 3D printing.

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PMMA-PDMS-PMMA三嵌段共聚物在紫外光固化甲基丙烯酸酯树脂中的韧性改性作用

光固化义齿基托需要刚性（高弯曲强度和模量）和高断裂韧性（防止在机械应力下开裂或断裂）。嵌段共聚物（bcp）具有独特的自组装特性，可以全面提高义齿基托材料的断裂韧性和机械性能，因此可以通过嵌段共聚物（bcp）的掺入来提供这些拮抗剂性能。本研究表明，聚甲基丙烯酸甲酯-嵌段聚二甲基硅氧烷-嵌段聚甲基丙烯酸甲酯（PMMA-PDMS-PMMA）三嵌段共聚物是一种高效的（甲基）丙烯酸树脂增韧剂，在不影响机械强度或加工的情况下显著提高断裂韧性。研究了PMMA:PDMS嵌段比和三嵌段共聚物在树脂中的质量分数（3-10 wt%）对增韧性能的影响，发现由分子量相近的PMMA和PDMS嵌段组成的增韧效果最佳的三嵌段共聚物为8000 g mol−1。当BCP在树脂中的浓度为5 wt%时，获得了最高的断裂韧性值（Kmax = 2,25 MPa m1/2），与不含BCP的树脂相比，提高了180%。小角度x射线散射测量显示，与不相容的PDMS块体相比，如果相容的PMMA块体足够长，则bcp的自组装导致球形胶束的形成，并在固化后转变为小簇。否则，观察到大的聚集体。透射电子显微镜证实了SAXS的结果，显示球形胶束团簇。作为增韧剂，PMMA-PDMS-PMMA bcp的增韧性能优于聚己内酯-聚硅氧烷（PCL-PDMS-PCL）。相容性块的性质（PMMA与PCL）和PMMA:PDMS块比对自由基固化树脂体系断裂韧性的影响在本研究中得到了清楚的证明。最具前景的配方被证明适用于数字光处理3D打印。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

European Polymer Journal 化学-高分子科学

CiteScore

9.90

自引率

10.00%

发文量

691

审稿时长

23 days

期刊介绍： European Polymer Journal is dedicated to publishing work on fundamental and applied polymer chemistry and macromolecular materials. The journal covers all aspects of polymer synthesis, including polymerization mechanisms and chemical functional transformations, with a focus on novel polymers and the relationships between molecular structure and polymer properties. In addition, we welcome submissions on bio-based or renewable polymers, stimuli-responsive systems and polymer bio-hybrids. European Polymer Journal also publishes research on the biomedical application of polymers, including drug delivery and regenerative medicine. The main scope is covered but not limited to the following core research areas: Polymer synthesis and functionalization • Novel synthetic routes for polymerization, functional modification, controlled/living polymerization and precision polymers. Stimuli-responsive polymers • Including shape memory and self-healing polymers. Supramolecular polymers and self-assembly • Molecular recognition and higher order polymer structures. Renewable and sustainable polymers • Bio-based, biodegradable and anti-microbial polymers and polymeric bio-nanocomposites. Polymers at interfaces and surfaces • Chemistry and engineering of surfaces with biological relevance, including patterning, antifouling polymers and polymers for membrane applications. Biomedical applications and nanomedicine • Polymers for regenerative medicine, drug delivery molecular release and gene therapy The scope of European Polymer Journal no longer includes Polymer Physics.