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Environmentally Friendly Plasticizers for PVC: Improved Material Properties and Long-term Performance Through Plasticizer Design
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

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.

Place, publisher, year, edition, pages
Stockholm: KTH , 2007. , p. 66
Series
Trita-FPT-Report, ISSN 1652-2443 ; 2006:45
Keyword [en]
poly(butylene adipate), poly(vinyl chloride), plasticizers, miscibility, mechanical properties, surface segregation, migration, degradation products
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-4272ISBN: 978-91-7178-557-2 (print)OAI: oai:DiVA.org:kth-4272DiVA, id: diva2:11561
Public defence
2007-02-16, Sal F3, KTH, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100805Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2010-08-05Bibliographically approved
List of papers
1. 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
Open this publication in new window or tab >>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
2004 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1022, no 1-2, p. 171-177Article in journal (Refereed) Published
Abstract [en]

A solid-phase extraction (SPE) method was developed for the simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. Four commercial non-polar SPE columns, three silica based: C-8, C-18, C-18 (EC), and one resin based: ENV+, were tested for the extraction of succinic acid, adipic acid and 1,4-butanediol, the expected final hydrolysis products of PBS and PBA. ENV+ resin was chosen as a solid-phase, because it displayed the best extraction efficiency for 1,4-butanediol and succinic acid. Linear range for the extracted analytes was 1-500 ng/mul for adipic acid and 2-500 ng/mul for 1,4-butanediol and succinic acid. Detection and quantification limits for the analytes were between 1-2 and 2-7 ng/mul, respectively, and relative standard deviations were between 3 and 7%. Good repeatability and low detection limits made the developed SPE method and subsequent gas chromatography-mass spectrometry (GC-MS) analysis a sensitive tool for identification and quantification of hydrolysis products at early stages of degradation.

Keyword
Adipic acid; Butanediol; Organic acids; Poly(butylene adipate); Poly(butylene succinate); Succinic acid; Hydrolysis; Mass spectrometry; Organic acids; Polybutenes; Silica; Solid phase extraction (SPE); Gas chromatography; 1, 4 butanediol; adipic acid; adipic acid derivative; poly(butylene adipate); poly(butylene succinate); succinic acid; succinic acid derivative; unclassified drug; analytic method; article; gas chromatography; hydrolysis; mass spectrometry; priority journal; productivity; quantitative analysis; solid phase extraction; Adipic Acids; Butylene Glycols; Gas Chromatography-Mass Spectrometry; Hydrolysis; Molecular Weight; Polymers; Sensitivity and Specificity; Succinic Acid
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6754 (URN)10.1016/j.chroma.2003.09.036 (DOI)000187662700020 ()14753784 (PubMedID)2-s2.0-0242573152 (Scopus ID)
Note

QC 20100805

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2018-03-19Bibliographically approved
2. 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)
Open this publication in new window or tab >>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)
2004 (English)In: Polymer degradation and stability, ISSN 0141-3910, E-ISSN 1873-2321, Vol. 83, no 3, p. 487-493Article in journal (Refereed) Published
Abstract [en]

Low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (M) during hydrolysis were extracted, identified and quantified by solid phase extraction (SPE) and GC-MS. The combination of SPE and GC-MS proved to be a sensitive tool, able to detect small differences in the degradation rate during early stages of hydrolysis before any significant differences were observed by weight loss and molecular weight measurements. The detected low molecular weight products included monomers i.e. adipic acid and 1,4-butanediol for the PBA polymers and succinic acid and 1,4-butanediol for PBS. Several dimers and trimers i.e. hydroxybutyl adipate, hydroxybutyl succinate, di(hydroxybutyl) adipate, di(hydroxybutyl) succinate and hydroxybutyl disuccinate were also detected. Comparison of measured weight loss and the amount of monomeric products showed that weight loss during early stages of hydrolysis was mainly caused by the release of water-soluble oligomers. On prolonged ageing these oligomers continued to hydrolyse to monomeric species.

Keyword
GC-MS, Hydrolysis, Poly(butylene adipate), Poly(butylene succinate), Degradation, Dimers, Hydrochloric acid, Hydrolysis, Molecular weight, Monomers, Oligomers, pH effects, Polyesters, Degradation products, GC-MS, Poly(butylene adipate), Poly(butylene succinate), Butenes
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6755 (URN)10.1016/j.polymdegradstab.2003.07.001 (DOI)000189214900017 ()2-s2.0-1142291788 (Scopus ID)
Note

QC 20150727

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2017-12-14Bibliographically approved
3. Environmentally friendly plasticizers for poly(vinyl chloride)- Improved mechanical properties and compatibility by using branched poly(butylene adipate) as a polymeric plasticizer
Open this publication in new window or tab >>Environmentally friendly plasticizers for poly(vinyl chloride)- Improved mechanical properties and compatibility by using branched poly(butylene adipate) as a polymeric plasticizer
2006 (English)In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 100, no 3, p. 2180-2188Article in journal (Refereed) Published
Abstract [en]

Linear and branched poly(butylene adipate)s (PBA) with molecular weights ranging from 2000 to 10,000 g/mol, and a branching agent content between 0 and 1.8%, were solution cast with poly(vinyl chloride) (PVC) to form 50- to 60-mu m thick flexible films. Dry films were analyzed by tensile testing, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and optical microscopy (OM) to study the effects of molecular weight and branching on the plasticizing efficiency of the polyester. PBA formed a semimiscible two-phase system with PVC, where the amorphous part exhibited a single glass transition temperature. The degree of crystallinity for the polyester, Surface composition, and mechanical properties of the films depended on the blend composition, molecular weight, and degree of branching of the polyester. Plasticizing efficiency was improved by higher degree of branching.

Keyword
Blends; Mechanical properties; Plasticizer; Poly(butylene adipate); Poly(vinyl chloride); Differential scanning calorimetry; Fourier transform infrared spectroscopy; Glass transition; Mechanical properties; Molecular weight; Optical microscopy; Polyesters; Polyvinyl chlorides; Tensile testing; Thick films; calorimetry; crystallinity; molecular weight; plasticizing agent; polyester; polymer blend; polyvinyl chloride; spectroscopy; tensile property
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6756 (URN)10.1002/app.23633 (DOI)000236150300061 ()2-s2.0-33646015702 (Scopus ID)
Note

QC 20100805

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2017-12-14Bibliographically approved
4. Migration-resistant polymeric plasticizer for poly(vinyl chloride)
Open this publication in new window or tab >>Migration-resistant polymeric plasticizer for poly(vinyl chloride)
2007 (English)In: Journal of Applied Polymer Science, ISSN 0021-8995, E-ISSN 1097-4628, Vol. 104, no 4, p. 2458-2467Article in journal (Refereed) Published
Abstract [en]

Flexible films of poly(vinyl chloride) (PVC) and linear or branched poly(butylene adipate) (PBA), synthesized from 1,4-butanediol and adipic acid or dimethyl ester of adipic acid, were aged in an aqueous environment for 10 weeks to study how branching, molar mass, and end-group functionality affect the leaching of polyester plasticizer from thin films. Principal component analysis was applied to reveal patterns and correlations between mechanical properties, material characteristics, and aging behavior. Introduction of branches in the polyester structure increased the miscibility between PVC and the polyester, resulting in improved mechanical properties and lower water absorption. Methyl ester end-group in PBA polyester stabilized the polymeric plasticizer toward hydrolysis, and reduced the formation and migration of monomeric degradation products from the blends during aging in water. The combination of branched structure with methyl ester end-groups resulted in a migration resistant polymeric plasticizer.

Keyword
Blends; Chromatography; Degradation; Poly(vinyl chloride); Polyester; Carboxylic acids; Mechanical properties; Polymers; Polyvinyl chlorides; Principal component analysis; Synthesis (chemical); Thin films; Aging behavior; End-group functionality; Polymeric plasticizer; aging; degradation; film; plasticizing agent; polybutylene; polyvinyl chloride; synthesis
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6757 (URN)10.1002/app.24777 (DOI)000245141400051 ()2-s2.0-34147211164 (Scopus ID)
Note

QC 20100805

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2017-12-14Bibliographically approved
5. Miscibility and surface segregation in PVC/polyester blends: the influence of chain architecture and composition
Open this publication in new window or tab >>Miscibility and surface segregation in PVC/polyester blends: the influence of chain architecture and composition
2007 (English)In: Journal of Polymer Science Part B: Polymer Physics, ISSN 0887-6266, E-ISSN 1099-0488, Vol. 45, no 13, p. 1552-1563Article in journal (Refereed) Published
Abstract [en]

Four poly(butylene adipate) (PBA) polyesters, the structure ranging from linear to highly branched, were synthesized and solution casted with poly(vinyl chloride) (PVC) in 20 or 40 wt % concentrations to evaluate the influence of polyester chain architecture on miscibility, surface segregation, and mechanical properties. The miscibility of PVC and polyesters is based on specific interactions between the carbonyl group in the polyester and PVC. These interactions cause a shift in the carbonyl absorption band in the FTIR spectra. The shifting of the carbonyl absorption band was more significant for all the 40 wt % blends compared with the blends containing 20 wt % of the same polyester. In the 20 wt % blends surface segregation and enrichment of polyester at the blend surface increased as a function of branching. However, all the films containing 40 wt % of polyester had similar surface composition. This is explained by better miscibility and stronger intermolecular interactions in the 40 wt % blends, which counteract the effect of branching on the surface segregation. High degree of branching resulted in poor miscibility with PVC and poor mechanical properties. A linear or slightly branched polyester structure, however, resulted in good miscibility and desirable blend properties.

Keyword
Blends; Branched; Miscibility; Poly(vinyl chloride); Polyesters; Fourier transform infrared spectroscopy; Molecular interactions; Polyesters; Polyvinyl chlorides; Solubility; Surface segregation; Branched polyester structure; Polybutylene adipate (PBA) polyesters; Polyester chains; Polyester enrichment
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6758 (URN)10.1002/polb.21149 (DOI)000247282100006 ()2-s2.0-34547281828 (Scopus ID)
Note

QC 20100805

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2017-12-14Bibliographically approved
6. Designed chain architecture for enhanced migration resistance and property preservation in poly(vinyl chloride)/polyester blends
Open this publication in new window or tab >>Designed chain architecture for enhanced migration resistance and property preservation in poly(vinyl chloride)/polyester blends
2007 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 8, no 4, p. 1187-1194Article in journal (Refereed) Published
Abstract [en]

Blends of poly(vinyl chloride) (PVC) and poly(butylene adipate) (PBA) with varying degrees of branching were analyzed with respect to migration resistance during aging in water, preservation of material properties, and thermal stability. Gas chromatography-mass spectrometry, water absorption, weight loss, thermogravimetric analysis, Fourier transform infrared spectroscopy, contact angle, tensile testing, and differential scanning calorimetry were used to analyze the blends before and after aging in water for 6 weeks. Films plasticized with slightly branched polyester maintained their material and mechanical properties best during aging. High degree of branching was accompanied by poor miscibility, increased hydrophilicity, and polydispersity, and highly branched PBA was not favorable as a plasticizer. Strong intermolecular interactions reduced the water absorption and increased the migration resistance of the blends. Polymeric plasticizers with no, low, or moderate degree of branching improved the thermal stability of films compared to films plasticized with a traditional phthalate plasticizer. Proper design of plasticizer architecture led, thus, to improved migration resistance, long-term properties, and thermal stability in PVC/polyester blends.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2007
Keyword
Absorption; Contact angle; Differential scanning calorimetry; Fourier transform infrared spectroscopy; Gas chromatography; Mass spectrometry; Polybutenes; Polyesters; Polymer blends; Tensile testing; Thermodynamic stability; Enhanced migration resistance; Intermolecular interactions; Polybutylene adipate; Polyvinyl chlorides; phthalic acid; plasticizer; polyester; polyvinylchloride; water; article; differential scanning calorimetry; film; gas chromatography; hydrophilicity; infrared spectroscopy; mass spectrometry; preservation; priority journal; tensile strength; thermogravimetry; thermostability; water absorption; Butylene Glycols; Membranes, Artificial; Plasticizers; Polymers; Polyvinyl Chloride; Surface Properties; Temperature; Water
National Category
Polymer Chemistry Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-6759 (URN)10.1021/bm070001k (DOI)000245510100019 ()17343406 (PubMedID)2-s2.0-34247617673 (Scopus ID)
Note

QC 20100805. Uppdaterad från Manuskript till Artikel i tidskrift 20100805. QC 20160212

Available from: 2007-02-14 Created: 2007-02-14 Last updated: 2017-12-14Bibliographically approved

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