Relationship between structure and thermal stability of fluorosilicones at high temperatures

IF 7.4 2区化学 Q1 POLYMER SCIENCE Polymer Degradation and Stability Pub Date : 2025-04-13 DOI:10.1016/j.polymdegradstab.2025.111340

Leticia Pires , Alice Corfa , Vincent Ladmiral , Sylvain Caillol , Sébastien Roland , Emmanuel Richaud

{"title":"Relationship between structure and thermal stability of fluorosilicones at high temperatures","authors":"Leticia Pires , Alice Corfa , Vincent Ladmiral , Sylvain Caillol , Sébastien Roland , Emmanuel Richaud","doi":"10.1016/j.polymdegradstab.2025.111340","DOIUrl":null,"url":null,"abstract":"<div><div>The thermal stability of fluorosilicones at high temperatures has been investigated with thermogravimetric analysis (TGA) based on their chemical structure (copolymerization and crosslinking), and compounding (incorporation of silica and titanium dioxide particle fillers). This allowed the comparison of thermal degradation kinetics of model samples and commercial fluorosilicones rubbers. Increasing dimethylsiloxane content in copolymers enhances thermal stability, while the presence of vinyl groups accelerates degradation by promoting depolymerization and crosslinking reactions at an earlier stage. In model filled fluorosilicone rubbers (FSR), untreated silica particles were found to destabilize the polymer matrix in the short term, whereas commercial filled FSRs exhibited greater thermal stability due to treated silica surfaces. Additionally, commercial samples crosslinked with DCP mixed with CaCO<sub>3</sub> resulted in the highest thermal stability. FTIR transmission analysis of copolymer residues revealed that degradation does not favor the preferential release of any monomer (dimethylsiloxane or trifluoropropylmethylsiloxane). Elemental analysis of a model homopolymer suggested that depolymerization is the dominant degradation mechanism, but side group scissions also contribute to this process.</div></div>","PeriodicalId":406,"journal":{"name":"Polymer Degradation and Stability","volume":"238 ","pages":"Article 111340"},"PeriodicalIF":7.4000,"publicationDate":"2025-04-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Polymer Degradation and Stability","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0141391025001703","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"POLYMER SCIENCE","Score":null,"Total":0}

引用次数: 0

Abstract

The thermal stability of fluorosilicones at high temperatures has been investigated with thermogravimetric analysis (TGA) based on their chemical structure (copolymerization and crosslinking), and compounding (incorporation of silica and titanium dioxide particle fillers). This allowed the comparison of thermal degradation kinetics of model samples and commercial fluorosilicones rubbers. Increasing dimethylsiloxane content in copolymers enhances thermal stability, while the presence of vinyl groups accelerates degradation by promoting depolymerization and crosslinking reactions at an earlier stage. In model filled fluorosilicone rubbers (FSR), untreated silica particles were found to destabilize the polymer matrix in the short term, whereas commercial filled FSRs exhibited greater thermal stability due to treated silica surfaces. Additionally, commercial samples crosslinked with DCP mixed with CaCO₃ resulted in the highest thermal stability. FTIR transmission analysis of copolymer residues revealed that degradation does not favor the preferential release of any monomer (dimethylsiloxane or trifluoropropylmethylsiloxane). Elemental analysis of a model homopolymer suggested that depolymerization is the dominant degradation mechanism, but side group scissions also contribute to this process.

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

高温下氟硅酮的结构与热稳定性的关系

利用热重分析（TGA）研究了氟硅酮在高温下的热稳定性，研究了它们的化学结构（共聚和交联）和复合（掺入二氧化硅和二氧化钛颗粒填料）。这样就可以比较模型样品和商用氟硅橡胶的热降解动力学。共聚物中二甲基硅氧烷含量的增加提高了热稳定性，而乙烯基的存在通过促进早期解聚和交联反应加速了降解。在模型填充氟硅橡胶（FSR）中，未经处理的二氧化硅颗粒会在短期内破坏聚合物基体的稳定，而商业填充的氟硅橡胶由于处理过的二氧化硅表面而表现出更大的热稳定性。此外，与CaCO3混合的DCP交联的商业样品具有最高的热稳定性。对共聚物残基的FTIR透射分析表明，降解并不有利于任何单体（二甲基硅氧烷或三氟丙基甲基硅氧烷）的优先释放。模型均聚物的元素分析表明，解聚是主要的降解机制，但侧基断裂也有助于这一过程。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

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.