Photodegradation behavior of nanosilica-filled PMMA composite: synergistic effect of mixed solvents and interfacial functional groups

Photodegradation behavior of nanosilica-filled PMMA composite: synergistic effect of mixed solvents and interfacial functional groups | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Photodegradation behavior of nanosilica-filled PMMA composite: synergistic effect of mixed solvents and interfacial functional groups Zhiping Xu, Liangchen Li, Ying Liu, Rui Yang This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6475289/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Poly(methyl methacrylate) (PMMA) and its composites are widely used in industrial applications, therefore their durability is of great concern. In this work, we systematically investigate the photooxidative degradation behavior of nanosilica-filled PMMA composite films and the synergistic effect of mixed solvents of tetrahydrofuran (THF) and chloroform (TCM) and interfacial functional groups. The results indicated that the surface functional groups of nanosilica fillers—such as polar, aryl, and alkyl moieties—significantly affect the photodegradation kinetics and pathways of PMMA. The key mechanism lies in the modulation of solvent–solvent reaction selectivity at the polymer–filler interface. Functional groups that selectively promote the chlorination reaction between THF and TCM accelerate PMMA photodepolymerization, while those that suppress this reaction hinder degradation. This interfacial effect is validated by trends in molecular weight loss, volatile product profiles, and MMA yields during aging. Our findings reveal that the photodegradation behavior of PMMA composites is not only governed by environmental conditions but also critically influenced by interfacial chemistry. This study provides new insight into the interfacial aging mechanism of polymer nanocomposites and offers guidance for the rational design of PMMA-based materials with improved durability. Interfacial interaction Photodegradation of PMMA Solvent reactions Py-GC-MS Aging mechanism Full Text Additional Declarations No competing interests reported. Supplementary Files SupplementaryMaterial.docx Cite Share Download PDF Status: Posted Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6475289","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":475673985,"identity":"0787dae2-4095-4404-99c0-e76af47a89da","order_by":0,"name":"Zhiping Xu","email":"","orcid":"","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Zhiping","middleName":"","lastName":"Xu","suffix":""},{"id":475673986,"identity":"89f36e85-ec98-4c50-8fb7-7f42c0de9a94","order_by":1,"name":"Liangchen Li","email":"","orcid":"","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Liangchen","middleName":"","lastName":"Li","suffix":""},{"id":475673987,"identity":"384b2ffb-b8c4-4313-94d4-81867648f27f","order_by":2,"name":"Ying Liu","email":"","orcid":"","institution":"Tsinghua University","correspondingAuthor":false,"prefix":"","firstName":"Ying","middleName":"","lastName":"Liu","suffix":""},{"id":475673992,"identity":"479451a8-6e17-4d0b-a29b-d6d6f68c38bf","order_by":3,"name":"Rui Yang","email":"data:image/png;base64,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","orcid":"","institution":"Tsinghua University","correspondingAuthor":true,"prefix":"","firstName":"Rui","middleName":"","lastName":"Yang","suffix":""}],"badges":[],"createdAt":"2025-04-18 02:23:10","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-6475289/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-6475289/v1","draftVersion":[],"editorialEvents":[],"editorialNote":"","failedWorkflow":false,"files":[{"id":85659589,"identity":"16c7f0f1-5ca5-48d0-b4af-f7b3fada8f02","added_by":"auto","created_at":"2025-06-30 11:24:01","extension":"pdf","order_by":1,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":1494349,"visible":true,"origin":"","legend":"","description":"","filename":"Manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-6475289/v1_covered_8eb67d63-ae83-425b-bf75-49a3ba58027e.pdf"},{"id":85458428,"identity":"9d528743-2cf6-477a-af0b-cfff8c04fdeb","added_by":"auto","created_at":"2025-06-26 06:59:13","extension":"docx","order_by":0,"title":"","display":"","copyAsset":false,"role":"supplement","size":1860061,"visible":true,"origin":"","legend":"","description":"","filename":"SupplementaryMaterial.docx","url":"https://assets-eu.researchsquare.com/files/rs-6475289/v1/bc20055435ac9ff90999cf74.docx"}],"financialInterests":"No competing interests reported.","formattedTitle":"Photodegradation behavior of nanosilica-filled PMMA composite: synergistic effect of mixed solvents and interfacial functional groups","fulltext":[],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":false,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":true,"highlight":"","institution":"","isAcceptedByJournal":false,"isAuthorSuppliedPdf":true,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":true,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Interfacial interaction, Photodegradation of PMMA, Solvent reactions, Py-GC-MS, Aging mechanism","lastPublishedDoi":"10.21203/rs.3.rs-6475289/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-6475289/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003ePoly(methyl methacrylate) (PMMA) and its composites are widely used in industrial applications, therefore their durability is of great concern. In this work, we systematically investigate the photooxidative degradation behavior of nanosilica-filled PMMA composite films and the synergistic effect of mixed solvents of tetrahydrofuran (THF) and chloroform (TCM) and interfacial functional groups. The results indicated that the surface functional groups of nanosilica fillers\u0026mdash;such as polar, aryl, and alkyl moieties\u0026mdash;significantly affect the photodegradation kinetics and pathways of PMMA. The key mechanism lies in the modulation of solvent\u0026ndash;solvent reaction selectivity at the polymer\u0026ndash;filler interface. Functional groups that selectively promote the chlorination reaction between THF and TCM accelerate PMMA photodepolymerization, while those that suppress this reaction hinder degradation. This interfacial effect is validated by trends in molecular weight loss, volatile product profiles, and MMA yields during aging. Our findings reveal that the photodegradation behavior of PMMA composites is not only governed by environmental conditions but also critically influenced by interfacial chemistry. This study provides new insight into the interfacial aging mechanism of polymer nanocomposites and offers guidance for the rational design of PMMA-based materials with improved durability.\u003c/p\u003e","manuscriptTitle":"Photodegradation behavior of nanosilica-filled PMMA composite: synergistic effect of mixed solvents and interfacial functional groups","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2025-06-26 06:59:08","doi":"10.21203/rs.3.rs-6475289/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"221db5b3-9c21-4a3b-8928-360d8c498160","owner":[],"postedDate":"June 26th, 2025","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"posted","subjectAreas":[],"tags":[],"updatedAt":"2025-06-30T11:23:13+00:00","versionOfRecord":[],"versionCreatedAt":"2025-06-26 06:59:08","video":"","vorDoi":"","vorDoiUrl":"","workflowStages":[]},"version":"v1","identity":"rs-6475289","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-6475289","identity":"rs-6475289","version":["v1"]},"buildId":"8U1c8b4HqxoKbykW_rLl7","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}