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Exploring fatty acid derivatives from renewable resources as raw materials for coating applications
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Fibre- and Polymer Technology. Royal Institute of Technology.
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the work presented herein, epoxy fatty acid derivatives were explored in the formation of thermosets for coating applications. The epoxy fatty acid derivatives were obtained from renewable resources such as birch tree bark and epoxidized linseed oil. The birch bark was used to isolate 9,10-epoxy-18-hydroxyoctadecanoic acid (EFA) and the epoxidized linseed oil was used to retrieve methyl stearate and 3 different epoxy methyl esters: epoxy methyl oleate/linoleate/linolenate (EMO/EMLO/EMLEN). The obtained epoxy fatty acid derivatives were used in resin formulations together with other reactants or in the synthesis of multifunctional oligomer resins using enzyme catalysis. All resins were cured using different polymerization techniques to form thermosets with a wide variety of properties.Multifunctional oligomer resin were synthesized using Candida Antarctica lipase-B (CALB) as enzyme. It was demonstrated that the synthesis was efficient and the oligomers were obtained from “one-pot” route. In addition, the selectivity of CALB was useful in preserving a variety of functional groups (epoxides, alkenes and thiols) in the final oligomers. The oligomers were cross-linked by either thiol-ene chemistry or cationic polymerization resulting in functional thermosets. It was further shown that surface properties of the cured thermosets could be changed by using post-functionalization.Pure fatty acid methyl esters cure into soft materials. An approach in increasing the thermal and mechanical properties was investigated. The 3 different epoxy functional methyl esters together with a furan-2,5-dicarboxylic acid derivative were investigated in the formation of thermosets. Glass transition temperature (Tg) below 0 °C and above 100 °C were obtained by varying the stoichiometric feed of the reactants.The thermal curing of EFA as a one-component system was investigated by model studies showing that a self-catalyzed process occur. EFA thermally cures into a thermoset without the need of an added catalyst. Furthermore, the thermoset showed adhesive properties.Crude mixture containing methyl stearate, EMO, EMLO and EMLEN obtained from epoxidized linseed oil were investigated as reactive diluent in coil-coatings. The mixture was also compared with commercially available reactive diluents such as fatty acid methyl esters (FAME) obtained from rapeseed oil. The results obtained showed that more fatty methyl esters could be incorporated in the final thermoset when using the epoxidized linseed oil fatty acid derivatives.Real-time Fourier-transform infrared spectroscopy (RT-FTIR) was used during most of the work presented in the thesis and proved to be a powerful tool in monitoring the different reactions and comparing relative reaction rates.

Abstract [sv]

I arbetet som presenteras i denna avhandling undersöktes epoxifettsyraderivat vid bildandet av härdplaster för ytmodifieringsapplikationer. Förnybara råvarorna björkbark och epoxiderad linolja andändes för att erhålla epoxifettsyraderivaten. Björkbarken användes för att isolera 9,10-epoxi-18-hydroxidekansyra (EFA) och epoxoderad linolja användes för att extrahera metylstearat och 3 olika epoximetylestrar: epoximetyl oleat/linoleat/linolenat (EMO/EMLO/EMLEN). Epoxifettsyraderivaten användes i olika hartsformuleringar tillammans med andra reaktanter eller vid syntes av multifunktionella oligomerhartser med hjälp av enzymatisk katalys. Med hjälp av olika polymerisationstekniker så härdades alla hartser till härdplaster med en mängd olika egenskaper.Multifunktionella oligomerhartser syntetiserades med hjälp av enzymet Candida Antarctica lipas-b (CALB). Syntesen visade sig vara effektiv och oligomererna erhölls från en sats. Dessutom var selektiviteten hos CALB användbar för att bevara en mängd olika funktionella grupper (epoxider, alkener och tioler) i de slutliga oligomererna. Tiol-ene kemi eller katjonisk polymerisation användes sedan för att härda oligomererna, vilket resulterade i funktionella härdplaster. Vidare visades att ytegenskaperna kunde ändras genom möjlighet till funktionalisering av härdplasterna.Mjuka material återfås då man härdar rena fettsyrametylestrar. Ett sätt att öka de termiska och mekaniska egenskaperna undersöktes. De tre olika epoxifunktionella metylestrarna tillsammans med furan-2,5-dicarboxylsyraderivat blandades i hartser och härdades. Genom att variera de stökiometriska förhållanderna av reaktanterna så erhölls glastemperaturer (Tg) under 0°C och över 100 °C.Undersökningen av termisk härdning av EFA som ett komponentssystem studerades genom modelstudier. Studierna visade att en självkatalyserad process sker då EFA värms upp. Detta leder således till att EFA kan termiskt härda utan behov av en tillsatt katalysator. Dessutom uppvisade härdplasten limegenskaper.Rå blandning innehållande metylstearate, EMO, EMLO och EMLEN som erhölls från epoxiderad linolja undersöktes som en reaktiv utspädare i spolbeläggningar. Blandningen jämfördes även med kommersiellt tillgängliga utspädare så som fettsyrametylestrar (FAME) erhållna från rapsolja. De erhållna resultaten påvisade att fler feta metylestrar kunde integreras i slutliga beläggningen när fettsyraderivat från epoxideradlinolja användes.Realtids Fourier-transform infrarödspektroskopi (RT-FTIR) användes under det mesta av arbetet som presenteras i denna avhandling. RT-FTIR visade sig vara ett kraftfullt vektyg för att övervaka de olika reaktionerna samt jämföra relativa reaktionshastigheter.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. , p. 69
Series
TRITA-CBH-FOU ; 2019:28
Keywords [en]
epoxy, vegetable oils, birch bark, thermoset, bio-based, fatty acid, renewable resources
National Category
Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
URN: urn:nbn:se:kth:diva-250682ISBN: 978-91-7873-184-8 (print)OAI: oai:DiVA.org:kth-250682DiVA, id: diva2:1313255
Public defence
2019-05-29, Sal F3, Lindstedtsvägen 26, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20190506

Available from: 2019-05-06 Created: 2019-05-02 Last updated: 2019-05-06Bibliographically approved
List of papers
1. One-Component Thiol-Alkene Functional Oligoester Resins Utilizing Lipase Catalysis
Open this publication in new window or tab >>One-Component Thiol-Alkene Functional Oligoester Resins Utilizing Lipase Catalysis
2016 (English)In: Macromolecular Chemistry and Physics, ISSN 1022-1352, E-ISSN 1521-3935Article in journal (Refereed) Published
Abstract [en]

Chemo-enzymatic methods are powerful tools for the synthesis of novel materials. By combining the flexibility of chemical synthesis and the high selectivity of enzymes, a variety of functional materials can be achieved. In the present study, a series of α,ω-thiol telechelic oligoesters with varying amount of internal alkenes are prepared using selective lipase catalysis and are subsequently cross-linked by thiol-ene chemistry yielding alkene functional networks. Due to the reactivity of thiols and alkenes almost all present thiol-ene systems consist of two components. This work demonstrates that selective lipase catalysis in combination with renewable monomers with internal alkenes is a promising system for achieving one-component thiol-alkene functional resins with good storage stability and a high degree of thiol end-groups. The developed chemo-enzymatic route yields polymer networks with tailored amount of alkene functionalities in the final thermoset, which facilitate further postmodification.

Place, publisher, year, edition, pages
John Wiley & Sons, 2016
Keywords
Catalysis, Chemoselectivity, Functional network, Photochemistry, Telechelics, Crosslinking, Functional materials, Photochemical reactions, Resins, Synthesis (chemical), Chemo-selectivity, Enzymatic methods, Post-modification, Storage stability, Thiol-ene chemistries, Thiol-ene systems, Hydrocarbons
National Category
Chemical Sciences Physical Sciences
Identifiers
urn:nbn:se:kth:diva-186775 (URN)10.1002/macp.201500490 (DOI)000380018700002 ()2-s2.0-84959509216 (Scopus ID)
Note

QC 20160520

Available from: 2016-05-20 Created: 2016-05-13 Last updated: 2019-09-04Bibliographically approved
2. One-pot enzyme-catalyzed synthesis of dual-functional polyester macromers towards surface-active hydrophobic films
Open this publication in new window or tab >>One-pot enzyme-catalyzed synthesis of dual-functional polyester macromers towards surface-active hydrophobic films
2017 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 7, no 79, p. 50294-50299Article in journal (Refereed) Published
Abstract [en]

Selective enzyme catalysis is a valuable tool for the processing of monomers into value-added materials. In the present study natural resources were used to retrieve an omega-hydroxy fatty acid monomer containing an epoxide functionality. A procedure was developed for the synthesis of dual-functional oligomers by utilizing lipase catalysis in a one-pot synthesis route. The chemoselectivity of the enzyme allowed addition of thiol monomers to the retrieved epoxy monomers, without harming the epoxides, achieving a thiol-epoxy functional polyester resin. The synthesis reached full conversion (> 99%) after 8 h. It was possible to selectively crosslink the resin through UV-initiated cationic polymerization of the epoxides into thiol-functional thermosets. The curing performance was followed in situ by real-time FTIR. The thiol groups on the surface of the film were accessible for post-modification.

Place, publisher, year, edition, pages
ROYAL SOC CHEMISTRY, 2017
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-217462 (URN)10.1039/c7ra09828f (DOI)000413944200060 ()2-s2.0-85032902830 (Scopus ID)
Note

QC 20171117

Available from: 2017-11-17 Created: 2017-11-17 Last updated: 2019-05-02Bibliographically approved
3. Biobased Cationically Polymerizable Epoxy Thermosets from Furan and Fatty Acid Derivatives
Open this publication in new window or tab >>Biobased Cationically Polymerizable Epoxy Thermosets from Furan and Fatty Acid Derivatives
Show others...
2018 (English)In: ACS Sustainable Chemistry and Engineering, ISSN 2168-0485, Vol. 6, no 7, p. 9442-9450Article in journal (Refereed) Published
Abstract [en]

In the pursuit of environmentally friendly building blocks in polymer chemistry the utilization of biobased monomers is highly desired. In the present study, the biobased monomer 2,5-furandicarboxylic acid (FDCA) has been extended into epoxy thermosets. The study presents the synthesis of diallyl furan-2,5-dicarboxylate (DAFDC) followed by an epoxidation of the allyls to form diglycidyl furan-2,5-dicarboxylate (DGFDC). DGFDC was then copolymerized in both stoichiometric and off-stoichiometric ratios with epoxidized fatty methyl esters to form a range of thermosets. The cross-linking reaction was either thermally or UV-induced cationic polymerization utilizing onium salt initiators where the reactivity was studied by DSC and real-time fourier transform infrared analysis. Furthermore, the structure-property relationships of the final thermosets were determined by dynamic mechanical thermal analysis revealing a possibility to tune the properties over a wide range. In addition thermosets were made from diglycidyl Bisphenol-A (DGEBA) with epoxidized fatty methyl esters made for comparative purposes.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2018
Keywords
Renewable, Epoxy, FDCA, UV, Thermoset
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-235900 (URN)10.1021/acssuschemeng.8b01817 (DOI)000444924500149 ()2-s2.0-85048372457 (Scopus ID)
Note

QC 20181009

Available from: 2018-10-09 Created: 2018-10-09 Last updated: 2019-05-02Bibliographically approved
4. Fully bio-based aliphatic thermoset polyesters via self-catalyzed self-condensation of multifunctional epoxy monomers directly extracted from natural sources
Open this publication in new window or tab >>Fully bio-based aliphatic thermoset polyesters via self-catalyzed self-condensation of multifunctional epoxy monomers directly extracted from natural sources
2017 (English)In: Journal of Coatings Technology Research, ISSN 1945-9645, Vol. 14, no 4, p. 757-765Article in journal (Refereed) Published
Abstract [en]

The use of bio-based raw material is regarded as a sustainable way to address environmental concerns. A naturally occurring monomer, 9,10-epoxy-18-hydroxyoctadecanoic acid (EFA), was retrieved from outer birch bark. A series of model experiments revealing relative reaction rates for epoxide, carboxylic acid, and alcohol functional groups was investigated. Real-time Fourier transform infrared spectroscopy and nuclear magnetic resonance were used to follow the different model experiments. The results on the model systems were then compared to the thermoset formation of thermally cured EFA. Finally, the adhesive properties of crosslinked EFA on different substrates were evaluated.

Place, publisher, year, edition, pages
Springer, 2017
Keywords
Bio-based monomer, Epoxide, Self-catalysis, Thermoset
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-212949 (URN)10.1007/s11998-017-9920-y (DOI)000406744400002 ()2-s2.0-85016397686 (Scopus ID)
Conference
12th Coatings Science International Conference (COSI), JUN 27-JUL 01, 2016, Noordwijk, Netherlands
Funder
Swedish Research Council Formas, 211-2013-70
Note

QC 20170825

Available from: 2017-08-25 Created: 2017-08-25 Last updated: 2019-05-02Bibliographically approved
5. Bio-based multifunctional fatty acid methyl esters as reactive diluents in coil coatings
Open this publication in new window or tab >>Bio-based multifunctional fatty acid methyl esters as reactive diluents in coil coatings
(English)Manuscript (preprint) (Other academic)
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-250659 (URN)
Note

QC 20190503

Available from: 2019-05-02 Created: 2019-05-02 Last updated: 2019-05-03Bibliographically approved

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The full text will be freely available from 2020-05-01 10:00
Available from 2020-05-01 10:00

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