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Exploring bio-based monomers for UV-curable polymer networks
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology, Coating Technology.ORCID iD: 0000-0002-0813-0067
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Increased environmental awareness and concern has led to a high demand for sustainable, bio-based materials. Consequently, there is a need for research and development of new bio-based polymeric materials that can be synthesized via routes eliminating excessively toxic reactants and by-products. The work presented in this thesis has focused on the utilization of catalysis, mainly enzymatic, and photopolymerization in order to create efficient synthesis of polymeric networks from bio-based monomers.Polyesters from bio-based monomers have been polymerized in bulk and thereafter crosslinked by UV initiation to yield polymer networks with tunable properties. The synthesis was also studied more in detail by varying the different types of catalysts and comparing their effect on the polymer products. Polyesters are a promising class of polymers that can be made from bio-based resources due to the wide range of available bio-based carboxylic acids and alcohols that can be combined to yield many polymers with different properties. However, the synthesis of polyesters is rather time-consuming in order to reach high conversions.As a more efficient alternative, short chain esters monomers and oligomers that have vinyl ether (VE) functionalities were developed. These VE-esters can be synthesized partly from bio-based resources, such as acids, fatty acids and diols, and their synthesis is efficient with enzymatic catalysis. The VE functionality provides a reactive group which can be polymerized rapidly with cationic polymerization. In general, the vinyl ether-esters can be synthesized in less than one hour and crosslinked within a few minutes, which is significantly faster than traditional polyester-synthesis and crosslinking. The enzymatic synthesis of vinyl ether esters also provided a method for developing monomers with orthogonal functionality which was explored by developing functionalizable materials with a variety of macromolecular architectures.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. , p. 56
Series
TRITA-CBH-FOU ; 2019:30
Keywords [en]
Bio-based, polymers, vinyl ether, polyester, photopolymerization, lipase
National Category
Polymer Chemistry
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-249950ISBN: 978-91-7873-195-4 (print)OAI: oai:DiVA.org:kth-249950DiVA, id: diva2:1306861
Public defence
2019-05-24, Kollegiesalen, Brinellvägen 8, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2019-04-25 Created: 2019-04-25 Last updated: 2019-04-26Bibliographically approved
List of papers
1. Biobased UV-curable coatings based on itaconic acid
Open this publication in new window or tab >>Biobased UV-curable coatings based on itaconic acid
2017 (English)In: Journal of Coatings Technology Research, ISSN 1945-9645, Vol. 14, no 4, p. 851-861Article in journal (Refereed) Published
Abstract [en]

A series of renewable unsaturated polyesters were synthesized from itaconic acid (IA), succinic acid, and 1,4-butanediol by solvent-free polycondensation. Previous studies utilizing IA to make polyesters for coating applications have shown great potential; however, the curing and material properties have not been investigated in detail. The aim of this study was to investigate how the curing is affected by the amount of unsaturations and how well itaconate-based polyesters crosslink without the addition of any other unsaturated monomers or reactive diluents. The chemical structures of the polyesters were confirmed with FTIR, 1 HNMR, and THF-SEC. The degree of curing was studied with FTIR, and the mechanical properties of the crosslinked polyesters were evaluated with DMA, pendulum hardness, and microindentation. The degree of curing was found to be up to 75%, and furthermore, it was found that the final mechanical properties of the crosslinked coatings could be tuned by modifying the IA content in the monomer composition. The results from DMA showed that there is a clear trend between mechanical properties and crosslinking density.

Place, publisher, year, edition, pages
Springer-Verlag New York, 2017
Keywords
Biobased, Itaconic acid, UV, Polyester, Coatings
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-212950 (URN)10.1007/s11998-017-9949-y (DOI)000406744400011 ()2-s2.0-85020271318 (Scopus ID)
Conference
11th Coatings Science International Conference (COSI), June 22-26, 2015, Noordwijk, Netherlands
Note

QC 20170825

Available from: 2017-08-25 Created: 2017-08-25 Last updated: 2019-04-25Bibliographically approved
2. Itaconate based polyesters: Selectivity and performance of esterification catalysts
Open this publication in new window or tab >>Itaconate based polyesters: Selectivity and performance of esterification catalysts
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2018 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 103, p. 370-377Article in journal (Refereed) Published
Abstract [en]

The performance of different esterification catalysts was studied for the use in synthesis of renewable polyesters from dimethyl itaconate (DMI), dimethyl succinate (DMS) and 1,4-butanediol (BD). Itaconic acid and derivatives such as DMI are interesting monomers because of their multiple functionalities and previous work has shown great potential. However, the multiple functionalities also pose challenges to avoid side reactions such as thermally initiated, premature, radical crosslinking and/or isomerization of the 1,1-disubstituted unsaturation. Additionally, the two carboxylic acids have inherently different reactivity. One key factor to control reactions with IA is to understand the performance of different catalysts. In this study, six esterification catalysts were investigated; immobilized Candida antarctica lipase B (CalB), titanium(IV)butoxide (Ti(OBu)4), p-toluenesulfonic acid (pTSA), sulfuric acid (H2SO4), 1,8-diazabicycloundec-7-ene (DBU), and 1,5,7-triazabicyclodec-5-ene (TBD). CalB and Ti(OBu)4 were selected for further characterization with appreciable differences in catalytic activity and selectivity towards DMI. CalB was the most effective catalysts and was applied at 60 °C while Ti(OBu)4 required 160 °C for a reasonable reaction rate. CalB was selective towards DMS and the non-conjugated side of DMI, resulting in polyesters with itaconate-residues mainly located at the chain ends, while Ti(OBu)4 showed low selectivity, resulting in polyesters with more randomly incorporated itaconate units. Thermal analysis of the polyesters showed that the CalB-catalyzed polyesters were semi-crystalline, whereas the Ti(OBu)4-catalyzed polyesters were amorphous, affirming the difference in monomer sequence. The polyester resins were crosslinked by UV-initiated free radical polymerization and the material properties were evaluated and showed that the crosslinked materials had similar material properties. The films from the polyester resins catalyzed by CalB were furthermore completely free from discoloration whereas the film made from the polyester resins catalyzed with Ti(OBu)4 had a yellow color, caused by the catalyst. Thus, it has been shown that CalB can be used to attain sustainable unsaturated polyesters resins for coating applications, exhibiting equally good properties as resins obtained from traditional metal-catalysis.

Place, publisher, year, edition, pages
Elsevier, 2018
Keywords
Biobased, Coatings, Enzyme catalysis, Organometallic catalysis, UV-curing
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-229209 (URN)10.1016/j.eurpolymj.2018.04.017 (DOI)000434745200039 ()2-s2.0-85046353288 (Scopus ID)
Note

QC 20180601

Available from: 2018-06-01 Created: 2018-06-01 Last updated: 2019-09-04Bibliographically approved
3. Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization
Open this publication in new window or tab >>Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization
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2018 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 8, no 44, p. 24716-24723Article in journal (Refereed) Published
Abstract [en]

Increased environmental awareness has led to a demand for sustainable, bio-based materials. Consequently, the development of new benign synthesis pathways utilizing a minimum of reaction steps and available bio-based building blocks is needed. In the present study, vinyl ether alcohols and functional carboxylic acids were used to synthesize bifunctional vinyl ether esters using the immobilized enzyme Candida antarctica lipase B as a catalyst. Vinyl ethers are attractive alternatives to (meth)acrylates due to low allergenic hazards, low toxicity, and fast polymerization; however, difficult synthesis limits the monomer availability. The synthesis was performed in one-pot and the described method was successful within a broad temperature range (22-90 degrees C) and in various organic solvents as well as in the bulk. The synthesis of different vinyl ether esters reached high conversions (above 90%) after less than 1 h and products were purified by removing the enzyme by filtration using only small amounts of acetone. This approach is a straightforward route to reach monomers with multiple types of functionalities that can be used as different photo-curable thermoset resins. In this work, this was demonstrated by polymerizing the monomers with cationic and radical UV-polymerization. By changing the functional carboxylic acids, the architecture of the final polymer can be tailored, herein demonstrated by two examples. In the developed versatile method, carboxylic acids can be used directly as acyl donors, constituting a more sustainable alternative to the carboxylic acid derivatives used today.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2018
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-232801 (URN)10.1039/c8ra04636k (DOI)000438939300004 ()2-s2.0-85050160901 (Scopus ID)
Funder
Swedish Research Council Formas, 211-2013-70
Note

QC 20180802

Available from: 2018-08-02 Created: 2018-08-02 Last updated: 2019-09-04Bibliographically approved
4. Tailoring Thermo-Mechanical Properties of Cationically UV-Cured Systems by a Rational Design of Vinyl Ether Ester Oligomers using Enzyme Catalysis
Open this publication in new window or tab >>Tailoring Thermo-Mechanical Properties of Cationically UV-Cured Systems by a Rational Design of Vinyl Ether Ester Oligomers using Enzyme Catalysis
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2018 (English)In: Macromolecular Chemistry and Physics, ISSN 1022-1352, E-ISSN 1521-3935, Vol. 219, no 21, article id 1800335Article in journal (Refereed) Published
Abstract [en]

There is a demand for new sustainable polymeric materials. Vinyl ethers are, in this context, attractive oligomers since they polymerize fast, are non-toxic, and can be polymerized under ambient conditions. The availability of vinyl ether oligomers is, however, currently limited due to difficulties in synthesizing them without using tedious synthesis routes. This work presents the synthesis of a series of vinyl ether ester oligomers using enzyme catalysis under solvent-free conditions and the subsequent photoinduced cationic polymerization to form polymer thermosets with T(g)s ranging from -10 to 100 degrees C. The whole process is very efficient as the synthesis takes less than 1 h with no need for purification and the crosslinking is complete within 2 min.

Place, publisher, year, edition, pages
WILEY-V C H VERLAG GMBH, 2018
Keywords
biocatalysis, cationic polymerization, photopolymerization, solvent free, vinyl ethers
National Category
Chemical Engineering
Identifiers
urn:nbn:se:kth:diva-239808 (URN)10.1002/macp.201800335 (DOI)000449760300003 ()2-s2.0-85054513248 (Scopus ID)
Note

QC 20190107

Available from: 2019-01-07 Created: 2019-01-07 Last updated: 2019-09-04Bibliographically approved
5. Enzymatically Synthesized Vinyl Ether-Disulfide Monomer Enablingan Orthogonal Combination of Free Radical and Cationic Chemistrytoward Sustainable Functional Networks
Open this publication in new window or tab >>Enzymatically Synthesized Vinyl Ether-Disulfide Monomer Enablingan Orthogonal Combination of Free Radical and Cationic Chemistrytoward Sustainable Functional Networks
2019 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 20, no 3, p. 1308-1316, article id 10.1021/acs.biomac.8b01710Article in journal (Refereed) Published
Abstract [en]

This work demonstrates a versatile and environmentally friendly route for the development of new orthogonal monomers that can be used for postfunctionalizable polymer networks. A monomer containing both vinyl ether (VE) and cyclic disulfide moieties was synthesized via enzyme catalysis under benign reaction conditions. The bifunctional monomer could be polymerized to form macromolecues with differing architectures by the use of either cationic or radical photo polymerization. When cationic polymerization was performed, a linear polymer was obtained with pendant disulfide units in the side chain, whereas in the presence of radical initiator, the VE reacted with the disulfide to yield a branched structure. The monomer was thereafter used to design networks that could be postfunctionalized; the monomer was cross-linked with cationic initiation together with a difunctional VE oligomer and after cross-linking the unreacted disulfides were coupled to RhodamineVE by radical UV-initiation.

National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-249949 (URN)10.1021/acs.biomac.8b01710 (DOI)000461270500018 ()
Note

QC 20190425

Available from: 2019-04-23 Created: 2019-04-23 Last updated: 2019-10-24Bibliographically approved

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