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Lipase-Catalyzed Syntheses of Telechelic Polyesters
KTH, School of Biotechnology (BIO), Biochemistry.
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Telechelic polyesters have successfully been synthesized with lipase-catalyzed polymerization. The produced telechelics had a high degree of di­functionalization, high purity (requiring little or no workup) and controlled degree of polymerization. The syntheses were performed in one-pot one-step reaction systems. The use of protection/deprotection chemistry was not necessary, since the lipase selectivity was utilized in the syntheses. Two different types of lipase-catalyzed polymerizations were applied – ring-opening polymerization and polycondensation. In ring-opening polymerization telechelics were produced by a combination of initiation, α-functionalization, and linking through termination, w-func­tionalization. In polycondensation different types of end-cappers were used to synthesize telechelics. Several exampels of functional groups were used for end-functionalization - epoxide, methacrylate and tetraallyls. Enzyme kinetic schemes describing the different functionalization met­hods of polyesters are presented and discussed. Stoichiometry and different reaction conditions have been studied to understand the effects these functions have on the final structure of the synthesized telechelics. Polyesters are classified as biodegradable, and can also be synthesized from materials that can be extracted or fermented from renewable sources like plants. Lipase-catalysts have several beneficial attributes, like high selectivity, they are renewable and biodegradable, are non-toxic and metal-free and can operate under mild reaction conditions.

The focus of this thesis has been on lipase-catalyzed syntheses and characterization of the produced telechelics, in addition some materials have been produced. Some uses of telechelics are surface modification, materials for block co-polymers, functional films and biomedical applications.

Place, publisher, year, edition, pages
Stockholm: KTH , 2010. , 57 p.
Series
Trita-BIO-Report, ISSN 1654-2312 ; 2010:3
Keyword [en]
Candida antarctica lipase B, lipase-catalysis, polymerization, telechelic, functional polyesters, ring-opening polymerization, polycondensation.
National Category
Medical Biotechnology (with a focus on Cell Biology (including Stem Cell Biology), Molecular Biology, Microbiology, Biochemistry or Biopharmacy)
Identifiers
URN: urn:nbn:se:kth:diva-12101ISBN: 978-91-7415-574-7 (print)OAI: oai:DiVA.org:kth-12101DiVA: diva2:301934
Public defence
2010-03-26, Svedbegssalen (FD5), Roslagstullsbacken 21, AlbaNova, KTH, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
QC20100726Available from: 2010-03-11 Created: 2010-03-03 Last updated: 2010-12-10Bibliographically approved
List of papers
1. Enzymatic One-Pot Route to Telechelic Polypentadecalactone Epoxide: Synthesis, UV Curing, and Characterization
Open this publication in new window or tab >>Enzymatic One-Pot Route to Telechelic Polypentadecalactone Epoxide: Synthesis, UV Curing, and Characterization
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2009 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 10, no 11, 3108-3113 p.Article in journal (Refereed) Published
Abstract [en]

In an enzymatic one-pot procedure immobilized lipase B from Candida antarctica was used to synthesize semicrystalline diepoxy functional macromonomers based on glycidol, pentadecalactone, and adipic acid. By changing the stoichiometry of the building blocks. macromonomers of controlled molecular weight front 1400 to 2700 g mol(-1) could be afforded. The enzyme-catalyzed reaction went to completion (conversion >= 95%) within 24 h at 60 degrees C. After removal of the enzyme, the produced macromonomers were used for photopolymerization without any purification. The macromonomers readily copolymerized cationically with a cycloaliphatic diepoxide (Cyracure UVR-6110; CA-dE) to high conversion. The cross-linked copolymers formed a durable film with a degree of crystallinity depending on the macromonomer size and amount of CA-dE used, without CA-dE the macromonomers homopolymerized only to a low degree. Combined with CA-dE conversions of 85-90% were determined by FT-Raman spectroscopy. The films became more durable once reinforced with CA-dE, increasing the cross-link density and reducing the crystallinity of the PDL segments in the films.

Keyword
RING-OPENING POLYMERIZATION, LIPASE-CATALYZED SYNTHESIS, POLY(OMEGA-PENTADECALACTONE), THIOL, POLY(EPSILON-CAPROLACTONE), POLYESTERS, ADHESIVES, NETWORKS, SOLVENT, ACID
National Category
Biochemistry and Molecular Biology
Identifiers
urn:nbn:se:kth:diva-12149 (URN)10.1021/bm9007925 (DOI)000271428800019 ()2-s2.0-70449500927 (Scopus ID)
Note
QC20100723Available from: 2010-03-11 Created: 2010-03-11 Last updated: 2017-12-12Bibliographically approved
2. One-step enzymatic polycondensation to telechelic methacrylate-functional polyesters used for film formation
Open this publication in new window or tab >>One-step enzymatic polycondensation to telechelic methacrylate-functional polyesters used for film formation
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(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-14192 (URN)
Note
QC20100723Available from: 2010-07-23 Created: 2010-07-23 Last updated: 2010-07-26Bibliographically approved
3. One-Pot Enzymatic Route to Tetraallyl Ether Functional Oligoesters: Synthesis, UV Curing, and Characterization
Open this publication in new window or tab >>One-Pot Enzymatic Route to Tetraallyl Ether Functional Oligoesters: Synthesis, UV Curing, and Characterization
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2010 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 48, no 23, 5289-5297 p.Article in journal (Refereed) Published
Abstract [en]

An enzymatic one-pot route in bulk was used to synthesize tetraallyl ether (tAE) functional oligomers based on divinyl adipate, 1,4-butanediol and trimethylolpropane diallyl ether. By using lipase B from Candida antarctica as catalyst and varying the stoichiometric ratio of monomers, it was possible to reach targeted molecular weights (from 1300 to 3300 g mol(-1)) of allyl-ether functional polyesters. The enzyme catalyzed reaction reached completion (>98% conversion based on all monomers) within 24 h at 60 degrees C, under reduced pressure (72 mbar) resulting in similar to 90% yield after filtration. The tAE-functional oligoesters were photopolymerized, without any purification other than removal of the enzyme by filtration, with thiol functional monomers (dithiol, tetrathiol) in a 1: 1 ratio thiol-ene reaction. The photo-initiator, 2,2-dimethoxy-2-phenylacetophenone, was used to improve the rate of reaction under UV light. High conversions (96-99% within detection limits) were found for all thiol-ene films as determined by FT-Raman spectroscopy. The tAE-functional oligoesters were characterized by NMR, MALDI, and SEC. The UV-cured homopolymerized films and the thiol-ene films properties were characterized utilizing DSC and DMTA.

Keyword
CaIB, enzymatic polycondensation, enzymes, films, networks, photopolymerization, polycondensation, polyesters, polyester films, thermoset, thiol-ene, UV curing
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-14199 (URN)10.1002/pola.24328 (DOI)000284225500003 ()2-s2.0-78349238609 (Scopus ID)
Note

QC 20100726. Uppdaterad från manuskript till artikel (20101210). Tidigare titel: One-pot enzymatic route to tetraallyl ether functional polyesters: Synthesis, UV curing, and characterization

Available from: 2010-07-26 Created: 2010-07-26 Last updated: 2017-12-12Bibliographically approved
4. Enzymatic one-pot polycondensation to telechelic epoxy oligomers
Open this publication in new window or tab >>Enzymatic one-pot polycondensation to telechelic epoxy oligomers
(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-14205 (URN)
Note
QC20100726Available from: 2010-07-26 Created: 2010-07-26 Last updated: 2010-07-26Bibliographically approved
5. One-pot synthesis to functional free-standing polymer film for sensor applications
Open this publication in new window or tab >>One-pot synthesis to functional free-standing polymer film for sensor applications
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(English)Manuscript (preprint) (Other academic)
Identifiers
urn:nbn:se:kth:diva-14206 (URN)
Note
QC20100726Available from: 2010-07-26 Created: 2010-07-26 Last updated: 2010-07-26Bibliographically approved

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