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Publications (10 of 46) Show all publications
Finnveden, M., Hendil-Forssell, P., Claudino, M., Johansson, M. & Martinelle, M. (2019). Lipase-Catalyzed Synthesis of Renewable Plant Oil-Based Polyamides.. Polymers, 11(11), Article ID 1730.
Open this publication in new window or tab >>Lipase-Catalyzed Synthesis of Renewable Plant Oil-Based Polyamides.
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2019 (English)In: Polymers, ISSN 2073-4360, E-ISSN 2073-4360, Vol. 11, no 11, article id 1730Article in journal (Refereed) Published
Abstract [en]

Enzyme catalyzed synthesis of renewable polyamides was investigated using Candida antarctica lipase B. A fatty acid-derived AB-type functional monomer, having one amine and one methyl ester functionality, was homopolymerized at 80 and 140 °C. Additionally, the organobase 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) was used as a catalyst. The results from the two catalysts were comparable. However, the amount of lipase added was 1.2 × 103 times lower, showing that the lipase was a more efficient catalyst for this system as compared to TBD. Moreover, the AB-type monomer was copolymerized with 1,12-diaminododecane to synthesize oligoamides of two different lengths.

Place, publisher, year, edition, pages
MDPI, 2019
Keywords
Candida antarctica lipase B, bio-based polyamides, enzymatic polymerization
National Category
Biocatalysis and Enzyme Technology
Research subject
Biotechnology
Identifiers
urn:nbn:se:kth:diva-264924 (URN)10.3390/polym11111730 (DOI)000503279200003 ()31652736 (PubMedID)2-s2.0-85075579461 (Scopus ID)
Funder
Swedish Research Council Formas, 211-2013-70EU, FP7, Seventh Framework Programme, 266025
Note

QC 20191205

Available from: 2019-12-05 Created: 2019-12-05 Last updated: 2020-01-10Bibliographically approved
Finnveden, M., Semlitsch, S., He, O. & Martinelle, M. (2019). Mono-substitution of symmetric diesters: selectivity of Mycobacterium smegmatis acyltransferase variants. Catalysis Science & Technology
Open this publication in new window or tab >>Mono-substitution of symmetric diesters: selectivity of Mycobacterium smegmatis acyltransferase variants
2019 (English)In: Catalysis Science & Technology, ISSN 2044-4753, E-ISSN 2044-4761Article in journal (Refereed) Published
Abstract [en]

A method for selectively reacting one, out of two identical carboxylic esters in a symmetric diester has been developed. An esterase from Mycobacterium smegmatis (MsAcT) has a restricted active site resulting in a narrow acyl donor specificity. This constraint was used to develop a selective synthesis route from divinyl adipate (a symmetric diester) towards mixed vinyl adipate esters. To find a suitable catalyst, the wild type (wt) MsAcT and two MsAcT variants: a single point mutant (L12A) and a double point mutant (T93A/F154A), were immobilized and studied under solvent-free conditions. Out of the tested catalysts, MsAcT L12A was the most selective for mono-transesterification of divinyl adipate. When divinyl adipate was reacted with 1.5 equivalents of a hydroxyl vinyl ether full conversion of DVA was observed yielding over 95% mixed diester. Furthermore, the limitations for longer dicarboxylic esters were studied, showing that MsAcT T93A/F154A tolerated up to at least dimethyl sebacate.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2019
National Category
Other Biological Topics
Identifiers
urn:nbn:se:kth:diva-256565 (URN)10.1039/C9CY01181A (DOI)000487788800006 ()2-s2.0-85072780268 (Scopus ID)
Funder
Swedish Research Council Formas, 211-2013-70
Note

QC 20190903

Available from: 2019-08-28 Created: 2019-08-28 Last updated: 2019-10-28Bibliographically approved
Brännström, S., Finnveden, M., Johansson, M., Martinelle, M. & Malmström, E. (2018). Itaconate based polyesters: Selectivity and performance of esterification catalysts. European Polymer Journal, 103, 370-377
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
Finnveden, M., Brännström, S., Johansson, M., Malmström, E. & Martinelle, M. (2018). Novel sustainable synthesis of vinyl ether ester building blocks, directly from carboxylic acids and the corresponding hydroxyl vinyl ether, and their photopolymerization. RSC Advances, 8(44), 24716-24723
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
Brännström, S., Finnveden, M., Razza, N., Martinelle, M., Malmström, E., Sangermano, M. & Johansson, M. (2018). Tailoring Thermo-Mechanical Properties of Cationically UV-Cured Systems by a Rational Design of Vinyl Ether Ester Oligomers using Enzyme Catalysis. Macromolecular Chemistry and Physics, 219(21), Article ID 1800335.
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
Nameer, S., Semlitsch, S., Martinelle, M. & Johansson, M. (2017). One-pot enzyme-catalyzed synthesis of dual-functional polyester macromers towards surface-active hydrophobic films. RSC Advances, 7(79), 50294-50299
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
Torron, S., Johansson, M., Malmström, E., Fogelström, L., Hult, K. & Martinelle, M. (2017). Telechelic polyesters and polycarbonates prepared by enzymatic catalysis. In: Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers: (pp. 29-64). Pan Stanford Publishing Pte. Ltd.
Open this publication in new window or tab >>Telechelic polyesters and polycarbonates prepared by enzymatic catalysis
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2017 (English)In: Handbook of Telechelic Polyesters, Polycarbonates, and Polyethers, Pan Stanford Publishing Pte. Ltd. , 2017, p. 29-64Chapter in book (Other academic)
Abstract [en]

The majority of polyesters and polycarbonates are traditionally synthesized through conventional metal-based catalysis. Although effective, due to environmental concerns, their substitution for other more environmentally friendly alternatives has received increasing interest during the last decades. The search for catalytic systems that also allow milder reaction conditions has been intensified, owing to 30the unwanted side reactions, for example, backbone scissoring, that the metal-based catalysts may cause [1]. In this context, enzymes are anticipated as suitable alternatives [2,3,4,5,6,7,-8]. 

Place, publisher, year, edition, pages
Pan Stanford Publishing Pte. Ltd., 2017
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-236854 (URN)10.1201/9781315364469 (DOI)2-s2.0-85053748623 (Scopus ID)9789814745635 (ISBN)9789814745628 (ISBN)
Note

QC 20181219

Available from: 2018-12-19 Created: 2018-12-19 Last updated: 2018-12-19Bibliographically approved
Torron, S., Semlitsch, S., Martinell, M. & Johansson, M. (2016). Biocatalytic Synthesis of Epoxy Resins from Fatty Acids as a Versatile Route for the Formation of Polymer Thermosets with Tunable Properties. Biomacromolecules, 17(12), 4003-4010
Open this publication in new window or tab >>Biocatalytic Synthesis of Epoxy Resins from Fatty Acids as a Versatile Route for the Formation of Polymer Thermosets with Tunable Properties
2016 (English)In: Biomacromolecules, ISSN 1525-7797, E-ISSN 1526-4602, Vol. 17, no 12, p. 4003-4010Article in journal (Refereed) Published
Abstract [en]

The work herein presented describes the synthesis and polymerization of series of bio-based epoxy resins prepared through lipase catalyzed transesterification. The epoxy-functional polyester resins with various architectures (linear, hi branched, and tetra-branched) were synthesized through condensation of fatty acids derived from epoxidized soybean oil and linseed oil with three different hydroxyl cores under bulk conditions. The selectivity of the lipases toward esterification/transesterification reactions allowed the formation of macromers with up to 12 epoxides in the backbone. The high degree of functionality of the resins resulted in polymer thermosets with T-g values ranging from 25 to over 100 degrees C prepared through cationic polymerization. The determining parameters of the synthesis and the mechanism for the formation of the species were determined through kinetic studies by H-1 NMR, SEC, and molecular modeling studies. The correlation between macromer structure and thermoset properties was studied through real-time FTIR measurements, DSC, and DMA.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016
National Category
Biochemistry and Molecular Biology Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-199493 (URN)10.1021/acs.biomac.6b01383 (DOI)000389787200017 ()27809488 (PubMedID)2-s2.0-85006106040 (Scopus ID)
Note

QC 20170118

Available from: 2017-01-18 Created: 2017-01-09 Last updated: 2020-03-09Bibliographically approved
Semlitsch, S., Torron, S., Johansson, M. & Martinelle, M. (2016). Enzymatic catalysis as a versatile tool for the synthesis of multifunctional, bio-based oligoester resins. Green Chemistry, 18(7), 1923-1929
Open this publication in new window or tab >>Enzymatic catalysis as a versatile tool for the synthesis of multifunctional, bio-based oligoester resins
2016 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 18, no 7, p. 1923-1929Article in journal (Refereed) Published
Abstract [en]

The use of enzymes as selective catalysts for processing renewable monomers into added value polymers and materials has received increased attention during the last decade. In the present work Candida antarctica lipase B (CalB) was used as catalyst in one-pot routes to synthesise multifunctional oligoester resins based on an epoxy-functional omega-hydroxy-fatty acid (EFA) extracted from birch bark. The chemoselective enzymatic process resulted in three different EFA-based telechelic oligomers with targeted molecular weights; containing maleimide, methacrylate or oxetane as end-groups, respectively. The enzyme catalysed synthesis of the maleimide and the oxetane telechelic oligomers reached full conversion of monomers (>95%) after 2 h. In the case of methacrylate functional oligomer the EFA monomer reached full conversion (>98%) after 2 h but the integration of the methacrylate moiety took more than 10 h. This was due to a rate limiting reaction path using ethylene glycol dimethacrylate as substrate. The oligomer products were characterised by NMR, MALDI-TOF-MS and SEC.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016
Keywords
Ring-Opening Polymerization, Suberin Monomer, Lipase, Polyesters, Route, Chemistry, Polymers, Acids, Bark
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-185665 (URN)10.1039/c5gc02597d (DOI)000372981400012 ()2-s2.0-84962377189 (Scopus ID)
Funder
EU, FP7, Seventh Framework Programme, 289253
Note

QC 20160426

Available from: 2016-04-26 Created: 2016-04-25 Last updated: 2018-04-11Bibliographically approved
Çakir, S., Eriksson, M., Martinelle, M. & Koning, C. E. (2016). Multiblock copolymers of polyamide 6 and diepoxy propylene adipate obtained by solid state polymerization. European Polymer Journal, 79, 13-22
Open this publication in new window or tab >>Multiblock copolymers of polyamide 6 and diepoxy propylene adipate obtained by solid state polymerization
2016 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 79, p. 13-22Article in journal (Refereed) Published
Abstract [en]

Polyesteramide multiblock copolymers based on polyamide 6 and diepoxy propylene adipate blocks were synthesized. For this purpose a carboxyl-terminated polyamide 6 (Mn = 2400 g/mol, Tm = 205.5 °C) and diepoxy propylene adipate (Mn = 450 g/mol) were separately synthesized and characterized. The incorporation of the oligoester into the polyamide 6 backbone was performed by solid state polymerization (SSP) well below the melting temperature of the polyamide (80-140 °C) so that the physical and thermal properties of the original polyamide 6 block were retained. Formation of the multiblock structure was confirmed by following the increase in molecular weight by SEC, reaction of the end groups by 1H NMR and by following the maintained melting temperature after the copolymerization. These segmented copolymers have molecular weights up to 10 kg/mol, thermal stability of 325 °C at 5% weight loss and a melting temperature of 205 °C.

Place, publisher, year, edition, pages
Elsevier, 2016
Keywords
Biodegradable polyamides, Multiblock copolymers, Polyamide 6, Polyesteramide, Melting, Melting point, Molecular weight, Polymerization, Thermodynamic stability, Multi-block structures, Multiblock co-polymers, Polyesteramides, Propylene adipate, Segmented copolymer, Solid state polymerization, Propylene
National Category
Polymer Technologies
Identifiers
urn:nbn:se:kth:diva-186949 (URN)10.1016/j.eurpolymj.2016.04.009 (DOI)000377322100002 ()2-s2.0-84962860357 (Scopus ID)
Note

QC 20160527

Available from: 2016-05-27 Created: 2016-05-16 Last updated: 2017-05-17Bibliographically approved
Organisations
Identifiers
ORCID iD: ORCID iD iconorcid.org/0000-0002-2993-9375

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