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Poly (butylene succinate) and poly (butylene adipate): quantitative determination of degradation products and application as PVC plasticizers
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology.
2005 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

A solid phase extraction (SPE) method was developed for simultaneous extraction of dicarboxylic acids and diols formed during hydrolysis of poly(butylene succinate), PBS, and poly(butylene adipate), PBA. The developed SPE method and subsequent GC-MS analysis were used to extract, identify and quantify low molecular weight products migrating from linear and branched poly(butylene adipate) (PBA) and poly(butylene succinate) (PBS) during aging in aqueous media. 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. Best extraction efficiency for 1,4-butanediol and succinic acid was achieved with a hydroxylated polystyrene-divinylbenzene resin as solid phase. Linear range for the extracted analytes was 1-500 ng/ml for adipic acid and 2-500 ng/ml for 1,4-butanediol and succinic acid. Detection and quantification limits for all analytes were between 1-2 ng/ml (S/N=3) and 2-7 ng/ml (S/N=10) respectively. Relative standard deviations were between 3 % and 7 %. 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 that on prolonged ageing were further hydrolyzed to monomeric species. Significant differences in degradation rate could be assigned to degree of branching, molecular weight, aging temperature and degradation medium.

Linear and branched PBA was mixed with PVC in solution cast films to study the effects of molecular weight and branching on plasticizer efficiency. Used as polymeric plasticizer, PBA formed a semi-miscible two-phase system with PVC where the amorphous part exhibited one single glass transition temperature and the degree of polyester crystallinity was dependent on molecular weight, degree of branching and blend composition. Plasticizing efficiency was favored by higher degree of branching and a 40 weight-percent polyester composition.

Place, publisher, year, edition, pages
Stockholm: KTH , 2005. , 60 p.
Series
Trita-FPT-Report, ISSN 1652-2443 ; 2004:43
Keyword [en]
Biochemistry, solid phase extraction, degradation products, poly(butylene succinate), poly(butylene adipate), GC-MS, PVC, plasticizer
Keyword [sv]
Biokemi
National Category
Biochemistry and Molecular Biology
Identifiers
URN: urn:nbn:se:kth:diva-325ISBN: 91-7283-942-2 (print)OAI: oai:DiVA.org:kth-325DiVA: diva2:9031
Presentation
2005-02-11, Salongen, KTHB, Osquars backe 31, Stockholm, 10:15
Supervisors
Note
QC 20101209Available from: 2005-07-25 Created: 2005-07-25 Last updated: 2010-12-09Bibliographically 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, 171-177 p.Article 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: 2016-05-30Bibliographically 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, 487-493 p.Article 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: 2015-07-27Bibliographically approved

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