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Allylation of a lignin model phenol: a highly selective reaction under benign conditions towards a new thermoset resin platform
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0003-4226-8593
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center.ORCID iD: 0000-0002-8614-6291
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Perstorp AB, Sweden.
KTH, School of Chemical Science and Engineering (CHE), Fibre and Polymer Technology. KTH, School of Chemical Science and Engineering (CHE), Centres, Wallenberg Wood Science Center. Univ Autonoma Coahuila, Mexico.
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2016 (English)In: RSC Advances, E-ISSN 2046-2069, Vol. 6, no 98, p. 96281-96288Article in journal (Refereed) Published
Abstract [en]

The lack of aromatic material constituents derived from renewable resources poses a problem to meet the future demands of a more sustainable society. Lignin is the most abundant source of aromatic structures found in nature and is a highly interesting source for material applications. Development of controlled chemical modification routes of lignin structures are crucial in order to further develop this area. In this study allyl chloride is used to selectively modify a lignin phenol in the presence of other lignin functionalities, i.e. aliphatic hydroxyls and conjugated alkenes, under mild reaction conditions in quantitative yields. For this, coniferyl alcohol was used as a model compound in the present study. The modification was carried out in ethanol as the synthesis media. Studies on the effect of reaction time and temperature revealed optimum conditions allowing for a quantitative yield without any detectable levels of byproducts as studied with NMR, FT-IR and FT-Raman. The thermal stability of the formed product was determined to be up to at least 160 degrees C through DSC measurements. In addition, as a proof of concept, the use of the allylated monomer to form crosslinked films using free radical thiol-ene polymerization was demonstrated.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2016. Vol. 6, no 98, p. 96281-96288
National Category
Polymer Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-199018DOI: 10.1039/c6ra21447aISI: 000385633100109Scopus ID: 2-s2.0-84991578448OAI: oai:DiVA.org:kth-199018DiVA, id: diva2:1066754
Funder
Knut and Alice Wallenberg Foundation
Note

QC 20170119

Available from: 2017-01-19 Created: 2016-12-22 Last updated: 2022-09-15Bibliographically approved
In thesis
1. Thermoset resins using technical lignin as a base constituent
Open this publication in new window or tab >>Thermoset resins using technical lignin as a base constituent
2019 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The need to find sustainable paths for our society is imminent to tackle environmental concerns of today. The majority of all plastic materials are produced from crude oil but in the future a much larger portion must originate from renewable resources to address some of these problems. Aromatic molecules are often used when producing rigid and thermally stable polymeric materials but there are few natural sources for them. One is, however, the wood component lignin that is produced on a large scale from chemical pulping processes of biomass. Lignins aromatic structures could be an alternative for non-renewable aromatics in e.g. thermoset applications.

The heterogeneity of lignin does however present some problems in terms of e.g. dispersity, solubility, diverse functionality, and varying polymer backbone structure. To tackle these challenges, work-up of lignin and thorough characterization are important to be able to produce materials with predetermined, predictable, properties. Technical lignins have functional groups that can be utilized as chemical handles for further modifications required for different material systems e.g. phenols, aliphatic hydroxyls, and carboxylic acids.

This thesis focuses on how to utilize solvent fractionated, relatively well-characterized, LignoBoost Kraft lignin to produce thermoset resins by chemical modification and a crosslinking procedure. An efficient procedure to selectively allylate the phenolics, the most abundant functionality, of the lignin fractions has been developed and evaluated as well as a curing procedure using a thiol crosslinker and a thiol-ene reaction. The produced materials were analysed with regards to material properties, density, and morphology. The resins based on the selectively allylated lignin fractions were furthermore evaluated as a potential matrix for carbon fibre composites. It was shown that the material samples could be processed by pre-impregnating carbon fibres and form composite materials. The molecules of the lignin fraction were also used as core substrates in a ring-opening polymerization to produce functional star co-polymers. The procedure was evaluated and it could be shown that the lignin backbone was subjected to substantial structural changes of lignin inter-unit linkages.

Lignin being one of the few large resources of naturally occurring aromatics has a big potential to be used for material applications where rigidity and thermal stability is important. This thesis attempts to add a few pieces towards such a goal.

Abstract [sv]

Behovet av att hitta hållbara tillvägagångssätt för vårt samhälle ökar hela tiden för att bemöta dagens miljöutmaningar. Större delen av alla plastmaterial tillverkas idag av råolja men i framtiden måste en mycket större del produceras från förnyelsebara råvaror för att hantera några av dessa problem. Aromatiska molekyler används ofta vid tillverkning av styva och termiskt stabila material, dock finns det få naturliga källor för sådana. En är emellertid träkomponenten lignin som produceras i stor skala i kemisk massatillverkning. Lignins aromatiska strukturer kan vara ett alternativ för icke-förnyelsebara aromatiska molekylära byggstenar i t.ex. härdplastsapplikationer.

Lignins heterogenitet ger upphov till vissa problem i termer av t.ex. dispersitet, löslighet, olika funktionalitet och varierande polymerskelettstruktur. För att hantera dessa problem är upparbetning av lignin och noggrann karaktärisering viktigt för att material med förutbestämda och förutsägbara egenskaper ska kunna tillverkas. Tekniskt lignin har funktionella grupper som kan användas som kemiska handtag för modifieringar som krävs för användning i olika materialsystem.

Denna avhandling fokuserar på hur lösningsmedelsfraktionerad, relativt välkarakteriserad, LignoBoost Kraftlignin kan användas för att producera termiskt härdande hartser genom kemisk modifiering och tvärbindning. Ett effektivt sätt att selektivt allylera ligninfraktionernas fenol-grupper, den vanligaste av de funktionella grupperna, har utvecklats och utvärderats såväl som en härdningsprocedur med hjälp av en tiol-tvärbindare och tiol-en-kemi. De producerade materialen analyserades med avseende på materialegenskaper, densitet och morfologi. Harts baserad på en av de selektivt allylerade ligninfraktionen undersöktes även som en potentiell matris för kolfiberkompositer. Det kunde påvisas att genom för-impregnering av kolfibrer kunde kompositmaterial tillverkas. Molekylerna i de olika ligninfraktionerna användes även som kärnor för att producera funktionella sampolymerer genom ringöppningspolymerisation. Det kunde påvisas att ligninets molekylära uppbyggnad blev kraftigt påverkat av tekniken då intramolekylära bindningar bröts upp.  

Lignin som tillhör en av de mycket få stora naturligt förekommande råvarorna för aromatiska strukturer har stor potential för användning i materialapplikationer där hög styvhet och termisk stabilitet är viktiga egenskaper. Den här avhandlingen försöker bidra med några pusselbitar mot ett sådant mål. 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2019. p. 57
Series
TRITA-CBH-FOU ; 2020:2
National Category
Polymer Technologies
Research subject
Fibre and Polymer Science
Identifiers
urn:nbn:se:kth:diva-265010 (URN)978-91-7873-402-3 (ISBN)
Public defence
2020-01-31, F3, Lindstedtsvägen 26, Stockholm, 14:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation
Note

QC 2019-12-12

Available from: 2019-12-12 Created: 2019-12-11 Last updated: 2022-06-26Bibliographically approved

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Jawerth, MarcusLawoko, MartinLundmark, StefanPérez-Berumen, Catalina MariaJohansson, Mats K G

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