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Macromolecular design: UV-curable thiol-ene networks based on renewable resources
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology, Coating Technology.
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Plant oils and terpenes are ubiquitous natural renewable compounds. The double bonds contained in most of these monomers can be utilized via the photo-induced free-radical thiol–ene reaction to create novel bio-derived polymer thermosets representing a valuable ‘green’ alternative to petrochemical olefins and resulting synthetic plastic materials. Nevertheless, there are several factors limiting their applicability, the first one being the relatively slow reaction rates towards thiol–ene coupling and many times the need to modify these natural olefins to make them more reactive. The latter process necessarily introduces additional pre-synthesis steps which has implications related both to cost and synthetic routes employed thereafter, those of which may or may not follow the principles of Green Chemistry. Therefore, this thesis intends to gain primary insight about the thiol–ene mechanism, kinetics and reactivity involving these multi-substituted olefins and then use the resulting knowledge to design semi-synthetic thermosets by incorporating these natural monomers into thiol–ene networks in the most environmentally friendly way possible. Mechanistic kinetic results show that internal 1,2-disubstituted enes found in mono-unsaturated vegetable oils and some macrolactones undergo a fast reversible cis/trans-isomerization process in favour of trans-isomer formation coupled with the thiol–ene mechanism. The slow reactivity of these enes has been accredited not just to the isomerization itself, but predominantly to the chain-transfer hydrogen-abstraction step. This rate-limiting step, however, does not seem to compromise their use in the creation of thiol–ene networks as demonstrated by photopolymerization in the melt of a series of linear globalide/ε-caprolactone-based copolyesters differing in amount of unsaturations along the backbone crosslinked with a tri-functional thiol propionate ester monomer. The resulting thermoset films were amorphous elastomers exhibiting different thermal and mechanical properties depending on the comonomer feed ratio. D-limonene, a renewable diolefinic substrate, proved to be an important terpene in free-radical thiol–ene additions. Empirical results show that the 1,1-disubstituted exo-vinylidene bond is about 6.5 times more reactive than the endocyclic 1,1,2-trisubstituted 1-methyl-cyclohexene moiety when reacting with mercapto propionate esters in organic solution conditions. Kinetic modeling results suggest that the differences in double bond reactivity are partially ascribed to steric impediments coupled with differences in electron-density controlling thiyl-radical insertion onto the two unsaturations but predominantly to differences in relative energy between the two tertiary insertion carbon-centered radical intermediates. Off-stoichiometric manipulations in the thiol–limonene mole ratio, assisted by numerical model simulations, offer a convenient method to visualize and assess the overall reaction system kinetics irrespective of time, thus being regarded as an important guiding tool for organic and polymer chemists aiming at designing thiol–ene reaction systems based on limonene. Multifunctional limonene-terminated thiol–ene macromonomer resins were synthesized in ethyl acetate solution and then reacted in different combinations with polyfunctional mercapto propionate esters to afford semi-synthetic thiol–ene networks with different thermo-viscoelastic properties depending on functionality, crosslink density, homogeneity and excess ofthiol occluded into the networks. The bulky cycloaliphatic ring structure of limonene locked between thioether linkages introduce a certain degree of rigidity to the final networks and increase the glass-transition temperature when compared tomore standard thiol–allyl systems. In all cases evaluated, high thiol–ene conversions were achieved with minimum or no side-reactions such as chain-growth homopolymerization and at reasonable reaction rates.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. , 79, v p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:36
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-129549ISBN: 978-91-7501-845-4 (print)OAI: oai:DiVA.org:kth-129549DiVA: diva2:652895
Public defence
2013-10-03, F3, Lindstedtsvägen 26, KTH, Stockholm, 14:30 (English)
Opponent
Supervisors
Note

QC 20131002

Available from: 2013-10-02 Created: 2013-10-02 Last updated: 2013-10-07Bibliographically approved
List of papers
1. Thiol-ene coupling of 1,2-disubstituted alkene monomers: The kinetic effect of cis/trans-isomer structures
Open this publication in new window or tab >>Thiol-ene coupling of 1,2-disubstituted alkene monomers: The kinetic effect of cis/trans-isomer structures
2010 (English)In: European Polymer Journal, ISSN 0014-3057, E-ISSN 1873-1945, Vol. 46, no 12, 2321-2332 p.Article in journal (Refereed) Published
Abstract [en]

The free-radical induced reaction between a tri-functional thiol (2-ethyl-(hydroxymethyl)-1,3-propanediol trimercapto propionate) and two 1,2-disubstituted alkenes (methyl oleate and methyl elaidate) has been investigated under photochemical conditions. The photoreaction was monitored via time-resolved FUR, Raman and NMR spectroscopy to provide insights about the kinetics and efficiency in end-product formation. The information collected was subjected to numerical modelling using the GEPASI software using pre-established literature values for the rate coefficients in order to verify the proposed reaction scheme. The results confirm the thiol-ene reaction mechanism showing a very fast cis/trans-isomerization (<1.0 min) when compared with the total disappearance of unsaturations, indicating that the rate-limiting step controlling the reaction is the hydrogen transfer from the thiol involved in the formation of product. High thiol-ene conversions can be obtained at reasonable rates without major influence of side-reactions when performed in bulk indicating that this reaction is suitable for network forming purposes with mono-unsaturated fatty acid methyl esters derivatives. The kinetic and mechanistic information collected provides a basis for the design of new thiol-ene systems aiming at material and coating applications.

Keyword
Thiol-ene chemistry, Real-time FTIR, Photopolymerization, Fatty acids, Isomer/isomerization, Coatings
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-28194 (URN)10.1016/j.eurpolymj.2010.10.001 (DOI)000285128700013 ()2-s2.0-79954618129 (Scopus ID)
Funder
Swedish Research Council, 621-2007-5723
Note
QC 20110110Available from: 2011-01-10 Created: 2011-01-10 Last updated: 2017-12-11Bibliographically approved
2. Photoinduced thiol-ene cross-linking of globalide/ε-caprolactone copolymers: curing performance and resulting thermoset properties
Open this publication in new window or tab >>Photoinduced thiol-ene cross-linking of globalide/ε-caprolactone copolymers: curing performance and resulting thermoset properties
Show others...
2012 (English)In: Journal of Polymer Science Part A: Polymer Chemistry, ISSN 0887-624X, E-ISSN 1099-0518, Vol. 50, no 1, 16-24 p.Article in journal (Refereed) Published
Abstract [en]

The increasing demand for bioderived polymers led us to investigate the potential use of the macrolactone globalide in thermoset synthesis via the photoinduced thiolene reaction. A series of six lipase-catalyzed poly(globalide-caprolactone) copolyesters bearing internal main-chain unsaturations ranging from 10 to 50 and 100 mol % were successfully crosslinked in the melt with equal amounts of thiol groups from trimethylolpropane-trimercapto propionate affording fully transparent amorphous elastomeric materials with different thermal and viscoelastic properties. Three major conclusions can be drawn from this study: (i) high thiol-ene conversions (> 80%) were easily attained for all cases, while maintaining the cure behavior, and irrespective of functionality at reasonable reaction rates; (ii) parallel chain-growth homopropagation of the ene monomer is insignificant when compared with the main thiolene coupling route; and (iii) high ene-density copolymers result in much lower extracted sol fractions and high T(g) values as a result of a more dense and homogeneous crosslinked network. The thiol-ene system evaluated in this contribution serve as model example for the sustainable use of naturally occurring 1,2-disubstituted alkenes in making semisynthetic polymeric materials in high conversions with a range of properties.

Keyword
thiol-ene photopolymerization, unsaturated macrolactones, renewable resoruces, networks
National Category
Polymer Chemistry
Identifiers
urn:nbn:se:kth:diva-40431 (URN)10.1002/pola.24940 (DOI)000298478300002 ()2-s2.0-82255181237 (Scopus ID)
Note
Updated from submitted to published. QC 20120127Available from: 2011-09-15 Created: 2011-09-15 Last updated: 2017-12-08Bibliographically approved
3. Thiol-ene coupling kinetics of D-limonene: a versatile 'non-click' free-radical reaction involving a natural terpene
Open this publication in new window or tab >>Thiol-ene coupling kinetics of D-limonene: a versatile 'non-click' free-radical reaction involving a natural terpene
2013 (English)In: RSC Advances, ISSN 2046-2069, E-ISSN 2046-2069, Vol. 3, no 27, 11021-11034 p.Article in journal (Refereed) Published
Abstract [en]

The free-radical photoinduced thiol-ene reaction between D-limonene, as renewable diolefinic substrate, and two mono-/tri-functional thiols (iso-tridecyl 3-mercaptopropionate and trimethylolpropane tris(3-mercaptopropionate)), has been investigated kinetically to define a relationship between alkene structure and reactivity. Separate thiol-ene solutions of the appropriate thiol in d-chloroform, supplemented with 1.0 wt% of DMPA (Irgacure 651), were subjected to polychromatic UV-irradiation and the chemical changes monitored discontinuously via H-1 NMR spectroscopy to quantify double bond conversion. The kinetic concentration profiles were modeled analytically and simulated in the application software COPASI for parameter estimation and to verify if the experimental data explained a suggested mechanistic scheme. Empirical results demonstrate that the external vinylidene bond of limonene reacts about 6.5 times faster with thiol than the internal trisubstituted 1-methyl-cyclohexene unsaturation. The selectivity observed for the two unsaturations was successfully explained by means of a simplified steady-state equation derived from the sequential reaction mechanism accounting for propagation and chain-transfer elementary steps with estimated rate coefficients. Kinetic modeling results attribute the difference in selectivity partially to steric impediments controlling thiyl-radical insertion onto the double bonds and predominantly to differences in relative energy between the two tertiary insertion carbon radical intermediates. The rate-limiting step was identified as the third chain-transfer hydrogen-abstraction reaction promoted by the second insertion carbon radical intermediate. High thiol-ene conversions were obtained in a timely fashion without major influence of secondary reactions demonstrating the suitability of this reaction for network forming purposes. The mechanistic and kinetic information collected can be used as a quantitative predictive tool to assess the potential use of D-limonene in thiol-ene network forming systems involving multifunctional alkyl ester 3-mercaptopropionates.

Place, publisher, year, edition, pages
RSC Publishing, 2013
Keyword
Carbon-Centered Radicals, Acrylate Photopolymerizations, Unsaturated-Compounds, Vinyl Mechanisms, Thiyl Radicals, Cross-Linking, Chemistry, Polymerization, Termination, Copolymers
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-124738 (URN)10.1039/c3ra40696b (DOI)000320467500059 ()2-s2.0-84881446388 (Scopus ID)
Funder
Swedish Research Council, 621-2007-5723
Note

QC 20130730

Available from: 2013-07-30 Created: 2013-07-29 Last updated: 2017-12-06Bibliographically approved
4. Utilizing Thiol-Ene Coupling Kinetics in the Design of Renewable Thermosed Resins based on D-Limonene and Polyfunctional Thiols
Open this publication in new window or tab >>Utilizing Thiol-Ene Coupling Kinetics in the Design of Renewable Thermosed Resins based on D-Limonene and Polyfunctional Thiols
(English)Manuscript (preprint) (Other academic)
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-129548 (URN)
Note

QS 2013

Available from: 2013-10-02 Created: 2013-10-02 Last updated: 2013-10-02Bibliographically approved

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