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Environmentally Friendly Plasticizers for PVC – Environmentally Friendly Plasticizers for PVC – Improved Material Properties and Long-Term Performance through Plasticizer Design Annika Lindström AKADEMISK AVHANDLING som med tillstånd av Kungliga Tekniska Högskolan framlägges till offentlig granskning för avläggande av teknisk doktorsexamen fredagen den 16 februari 2007, kl. 10.00 i sal F3, Lindstedtsvägen 26, Kungliga Tekniska Högskolan, Stockholm. Avhandlingen försvaras på svenska. Copyright © Annika Lindström All rights reserved Paper I © 2004 Elsevier Ltd. Paper II © 2004 Elsevier Ltd. Paper III © 2006 Wiley Periodicals, Inc. Paper IV © 2006 Wiley Periodicals, Inc. TRITA-FPT-Report 2006:45 ISSN 1652-2443 ISRN KTH/FPT/R-2006/45-SE ISBN 978-91-7178-557-2 Environmentally Friendly Plasticizers for PVC – Improved Material Properties and Long-Term Performance through Plasticizer Design Annika Lindström Fibre and Polymer Technology, School of Chemical Science and Engineering, Royal Institute of Technology, Stockholm, Sweden Abstract Linear and branched poly(butylene adipate) polyesters with number-average molecular weights ranging from 700 to 10 000 g/mol, and degrees of branching ranging from very low to hyperbranched were solution cast with PVC to study the effects of chemical structure, molecular weight, end-group functionality, and chain architecture on plasticizing efficiency and durability. Miscibility was evaluated by the existence of a single glass transition temperature and a shift of the carbonyl group absorption band. Desirable mechanical properties were achieved in flexible PVC films containing 40 weight-% of polyester plasticizer. Methyl-ester-terminated polyesters with a low degree of branching and an intermediate molecular weight enhanced the plasticizing efficiency, as shown by greater elongation, good miscibility, and reduced surface segregation. A solid-phase extraction method was developed to extract the low molecular weight products that migrated from pure poly(butylene adipate) and PVC/ poly(butylene adipate) films during aging in water. The effects of branching, molecular weight, end- group functionality, and polydispersity on plasticizer permanence were evaluated by quantification of low molecular weight hydrolysis products, weight loss, surface segregation, and the preservation of material properties during aging. A more migration- resistant polymeric plasticizer was obtained by combining a low degree of branching, hydrolysis-protecting end-groups, and higher molecular weight of the polyester. Films plasticized with a slightly branched polyester showed the best durability and preservation of material and mechanical properties during aging. A high degree of branching resulted in partial miscibility with PVC, poor mechanical properties, and low migration resistance. The thermal stability of polyester-plasticized films was higher than that of films containing a low molecular weight plasticizer, and the stabilizing effect increased with increasing plasticizer concentration. Keywords: poly(butylene adipate), poly(vinyl chloride), plasticizers, miscibility, mechanical properties, surface segregation, migration, degradation products Sammanfattning Lösningsmedelsgjutna filmer innehållande PVC och linjära eller förgrenade poly(butylen adipat)-polyestrar med molekylvikter på 700 till 10 000 g/mol (talmedelvärden) och förgreningsgrader som sträcker sig från mycket låga till hyperförgrenade, tillverkades för att studera effekten av kemisk struktur, molekylvikt, ändgruppsfunktionalitet och kedjearkitektur på mjukningskapacitet och hållbarhet. Blandbarheten utvärderades genom förekomsten av en gemensam glastransitions- temperatur och skiftning av karbonylgruppens absorptionsband. Önskvärda mekaniska egenskaper erhölls i mjukgjorda PVC filmer vid en polyester koncentration på 40 vikts- %. Metylesterterminerade polyestrar med låg förgreningsgrad och medelhög molekylvikt förbättrade mjukningskapaciteten genom ökad brottöjning, god blandbarhet och minskad ytvattring. En fastfasextraktionsmetod utvecklades för att extrahera de lågmolekylära produkter som migrerade från ren poly(butylen adipat) och PVC/poly(butylen adipat)-filmer under åldring i vatten. Effekten av förgreningsgrad, molekylvikt, ändgruppsfunktionalitet och polydispersitet på mjukningsmedels- beständighet utvärderades genom kvantifiering av lågmolekylära hydrolysprodukter, viktminskning, ytvattring och varaktighet av materialegenskaper under åldring. Ett mer migreringsresistent polymert mjukningsmedel erhölls genom att kombinera låg förgreningsgrad, hydrolysbeskyddande ändgrupper och en högre molekylvikt hos polyestern. Filmer mjukgjorda med en lätt förgrenad polyester visade bäst hållbarhet och bevarande av materialegenskaper och mekaniska egenskaper under åldring. Hög förgreningsgrad resulterade i partiell blandbarhet med PVC, svaga mekaniska egenskaper och låg migreringsresistens. Den termiska stabiliteten hos filmer mjukgjorda med polyester var bättre än den termiska stabiliteten hos filmer innehållande ett lågmolekylärt mjukningsmedel. Den stabiliserande effekten ökade med ökande koncentration mjukningsmedel. Nyckelord: poly(butylen adipat), poly(vinyl klorid), mjukningsmedel, blandbarhet, mekaniska egenskaper, ytvattring, migrering, nedbrytningsprodukter List of Papers This thesis is a summary of the following papers: I “Development of a solid-phase extraction method for simultaneous extraction of adipic acid, succinic acid and 1,4-butanediol formed during hydrolysis of poly(butylene adipate) and poly(butylene succinate)” Annika Lindström, Ann-Christine Albertsson, Minna Hakkarainen Journal of Chromatography A, Vol. 1022, 171-177, 2004 II “Quantitative determination of degradation products an effective means to study early stages of degradation in linear and branched poly(butylene adipate) and poly(butylene succinate)” Annika Lindström, Ann-Christine Albertsson, Minna Hakkarainen Polymer Degradation and Stability, Vol. 83, 487-493, 2004 III “Environmentally friendly plasticizers for poly(vinyl chloride)- Improved mechanical properties and compatibility by using branched poly(butylene adipate) as a polymeric plasticizer” Annika Lindström, Minna Hakkarainen Journal of Applied Polymer Science, Vol. 100, 2180-2188, 2006 IV “Migration-resistant polymeric plasticizer for poly(vinyl chloride)” Annika Lindström, Minna Hakkarainen Journal of Applied Polymer Science, Accepted, 2006 V “Miscibility and surface segregation in PVC/polyester blends – the influence of chain architecture and composition” Annika Lindström, Minna Hakkarainen Manuscript VI “Designed chain architectures for enhanced migration-resistance and property preservation in PVC/polyester blends” Annika Lindström, Minna Hakkarainen Manuscript The contribution of the author of this thesis to these papers is: I-IV All the experiments except the polyester synthesis and most of the writing. V-VI All the experiments and most of the writing. Table of Contents 1 Purpose of the Study .........................................................................................................1 2 Introduction .......................................................................................................................1 2.1 Poly(vinyl chloride), PVC.............................................................................................1 2.1.1 Additives................................................................................................................2 2.2 Plasticizers....................................................................................................................2 2.2.1 Health Issues Related to the Use of Phthalate Ester Plasticizer in Medical Plastics............................................................................................................................2 2.2.2 Polymeric Plasticizers in Flexible PVC Films ......................................................4 2.2.3 Phase Behavior in Polymer Blends .......................................................................7 2.3 Aliphatic Polyesters......................................................................................................7 2.3.1 Polyester Degradation ...........................................................................................8 2.3.2 Degradation Product Analysis...............................................................................9 3 Experimental....................................................................................................................11 3.1 Chemicals ...................................................................................................................11 3.2 Synthesis of Polyesters................................................................................................12 3.3 Aging of Polyesters and Films in an Aqueous Environment ......................................13 3.4 Development of a Solid Phase Extraction Method.....................................................14 3.5 Extraction of Degradation Products Formed during Aging ......................................14 3.6 Gas Chromatography - Mass Spectrometry, GC-MS.................................................15 3.7 Weight Loss and Water Absorption Measurements....................................................16 3.8 Size Exclusion Chromatography, SEC .......................................................................16 3.9 Nuclear Magnetic Resonance, NMR ..........................................................................17 3.10 Differential Scanning Calorimetry, DSC..................................................................18
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