Cette thèse est dédiée à l'élaboration de matériaux poreux par polymérisation d'émulsion concentrées à partir de polymères issus de la biomasse. La méthodologie polyHIPE a été adaptée pour mettre en œuvre un sous-produit de l'industrie papetière : la liqueur noire Kraft. Des matériaux poreux et possédant une structure interne modulable par les paramètres d'émulsification, ont été obtenus. / This project is dedicated to the synthesis of porous materials from biopolymers via an emulsion-templated polymerisation. The polyHIPE synthesis was adaptated to the physico-chemical properties of the main by-product of the paper industry : the Kraft black liquor. Porous material was obtained and their morphological caracteristics can be modulated through the emulsification parameters.

O uso de recursos florestais e madeireiros como cargas em matrizes poliméricas pode originar novos materiais com forte apelo ecológico e econômico. Dentre os resíduos do processamento mecânico e químico da madeira, há uma série de materiais de fácil acesso que podem ser manipulados a partir de certas técnicas de biorrefinaria, tais como a madeira, a casca de madeira, as pinhas (frutos do pinus), as acículas (folhas do pinus), a lignina residual (processo kraft) e o lodo de papel derivadas do processo químico de polpação celulósica. Tais matérias primas foram incorporadas em espumas rígidas e semi-rígidas de poliuretano (PU) processadas pelo método da expansão livre, utilizando-se uma mistura de óleo de mamona e glicerina loira como biopoliol, com vistas a obtenção de espumas quimicamente estáveis e ecologicamente corretas. A compatibilidade de algumas dessas cargas no sistema PU foi testada mediante reações induzidas na presença de isocianato e catalisador. As espumas PU foram caracterizadas por meio de técnicas de microscopia e espectroscopia, além de ensaios mecânicos, térmicos, higroscópicos, óticos, de resistência a chamas e de resistência à radiação UV. Por fim, foi avaliado o efeito de expansões sob confinamento nas propriedades morfológicas, mecânicas e térmicas do PU puro e de uma espuma carregada PU/madeira As espumas apresentaram estabilidade química e a inserção das cargas no PU puro possibilitou a obtenção de espumas com células homogêneas, melhor desempenho higroscópico, níveis similares de condutividade térmica e flamabilidade, além de maior brilho e diferentes padrões de cor. A farinha de madeira apresentou a maior afinidade com o sistema PU, seguida pela lignina kraft, resultando em espumas carregadas com células menores, mais arredondadas e com maior teor de células fechadas, além de espumas com maiores estabilidades térmica e dimensional. Todas as espumas apresentaram fotodegradações similares, marcadas por uma cor alaranjada, acompanhada por uma acentuada perda de brilho. As espumas carregadas naturalmente mais escuras foram mais resistentes à fotodegradação por serem capazes de causar um efeito contrário ao da descoloração natural do PU quando sujeito aos raios UV. O confinamento diminuiu o diâmetro médio de células da espuma PU/madeira e a anisotropia do PU puro, levando a formação de células mais homogêneas, marcadas por números de arestas rompidas e de células abertas aparentemente menores, que resultaram em maiores densidades aparentes e melhores propriedades mecânicas para espumas preparadas a 50% de confinamento e menor condutividade térmica para as espumas confinadas a 70%. / The use of forestry and wood-based resources as fillers in polymer matrices may originate new materials with strong environmental and economic appeals. Among the wastes from chemical and mechanical processing of wood, there are many materials readily available, which can be handled through biorrefinary techniques, like wood flour, wood bark, pine cones (fruits), pine needles (leaves), residual lignin (e.g. from kraft process) and paper sludge, the last two from the chemical processing of cellulosic pulp. In this thesis, such raw materials were incorporated into rigid and semi-rigid polyurethane (PU) foams prepared by the free-rising pouring method, using a mixture of castor oil and crude glycerin as a bio-based polyol in order to achieve chemically stable and eco-friendly foams. Compatibility of the fillers with the PU system was evaluated using induced reactions in the presence of isocyanate and catalyst. The PU foams were characterized by microscopy and spectroscopy techniques, as well as mechanical, thermal, hygroscopic, optical, flame resistance and UV radiation resistance tests. And the effect of rising under confinement on the morphological, mechanical and thermal properties of neat PU and wood/PU foam composites was also investigated The foams presented chemical stability and the addition of fillers into PU yielded foams with more homogeneous cells, better hygroscopic performance, similar thermal conductivities and flammabilities, as well as higher specular glosses and different colorimetric patterns. The wood flour presented the highest affinity with the PU system, followed by kraft lignin, resulting in foam composites with smaller and more rounded cells, with higher closed-cells content, and increased thermal and dimensional stabilities. All foams presented similar photodegradation behavior characterized by an orange color and a significant loss in specular gloss. The foam composites, being naturally darker, were more resistant to photodegradation, since they had an opposite effect related to natural discoloration under UV radiation. The confinement decreased cell diameter for the wood filled PU foam and the anisotropy index for neat PU foam, yielding more homogeneous cells, with fewer broken edges and open-cells, with greater apparent densities and better mechanical properties for foams prepared at 50% confinement and lower thermal conductivity for foams confined at 70%.

<p>The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin.</p><p>Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.</p><p> </p><p>The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.</p><p> </p><p>The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.</p><p> </p><p>The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.</p>

The aim of this project is to investigate the possibilities of minimizing the sulphur content in Kraft lignin. Kraft lignin contains about 1.5 to 3% sulphur. The sulphur is believed to be present in lignin as inorganic sulphur, as elemental sulphur, as adsorbed polysulphide and/or as organically bound sulphur. For the determination of these different types of sulphur components, different approaches and methods were used. For the determination of inorganic sulphur, lignin was washed with water at pH 6 and pH 2 and the wash waters were analysed with ion chromatography (IC). For the determination of total sulphur content in the lignin, two methods were used; Schöniger combustion followed by ion chromatography (IC) and wet digestion followed by inductively coupled plasma (ICP). The elemental sulphur content in water-extracted lignin was determined after n-pentane extraction. ICP analysis was performed on the washed lignin. Calcium present in the lignin may bind polysulphides and thus be a source of the observed sulphur. The lignin was thus ion-exchanged to remove any calcium. To further investigate how the sulphur content in lignin can be decreased, two different types of reactions were performed on lignin; oxidation and reduction. The oxidation reactions were made in sodium hydroxide with oxygen at different temperatures and time on both original and water-extracted lignin. The reduction reactions were made on water-extracted lignin with Raney nickel in three different solvent systems: methanol: water, acetone: water and sodium hydroxide.   The original lignin contained 2.6% sulphur as determined by ICP. Washing lowered the content to 1.85% sulphur. By n-pentane extraction the elemental sulphur was lowered to a level of 1.82% sulphur, which was considered to be organically bound sulphur. Neither the ion exchange nor the oxidation lowered the sulphur content significantly.   The reduction reactions successfully the organically bound sulphur from 1.82% to a level of 0.54%.   The relative distribution of the sulphur content in the studied softwood lignin was as follows: about 29% as inorganic sulphur, about 1% as elemental sulphur and approximately 70% as organically bound sulphur, of which 49% could be removed by Raney nickel.

O uso de recursos florestais e madeireiros como cargas em matrizes poliméricas pode originar novos materiais com forte apelo ecológico e econômico. Dentre os resíduos do processamento mecânico e químico da madeira, há uma série de materiais de fácil acesso que podem ser manipulados a partir de certas técnicas de biorrefinaria, tais como a madeira, a casca de madeira, as pinhas (frutos do pinus), as acículas (folhas do pinus), a lignina residual (processo kraft) e o lodo de papel derivadas do processo químico de polpação celulósica. Tais matérias primas foram incorporadas em espumas rígidas e semi-rígidas de poliuretano (PU) processadas pelo método da expansão livre, utilizando-se uma mistura de óleo de mamona e glicerina loira como biopoliol, com vistas a obtenção de espumas quimicamente estáveis e ecologicamente corretas. A compatibilidade de algumas dessas cargas no sistema PU foi testada mediante reações induzidas na presença de isocianato e catalisador. As espumas PU foram caracterizadas por meio de técnicas de microscopia e espectroscopia, além de ensaios mecânicos, térmicos, higroscópicos, óticos, de resistência a chamas e de resistência à radiação UV. Por fim, foi avaliado o efeito de expansões sob confinamento nas propriedades morfológicas, mecânicas e térmicas do PU puro e de uma espuma carregada PU/madeira As espumas apresentaram estabilidade química e a inserção das cargas no PU puro possibilitou a obtenção de espumas com células homogêneas, melhor desempenho higroscópico, níveis similares de condutividade térmica e flamabilidade, além de maior brilho e diferentes padrões de cor. A farinha de madeira apresentou a maior afinidade com o sistema PU, seguida pela lignina kraft, resultando em espumas carregadas com células menores, mais arredondadas e com maior teor de células fechadas, além de espumas com maiores estabilidades térmica e dimensional. Todas as espumas apresentaram fotodegradações similares, marcadas por uma cor alaranjada, acompanhada por uma acentuada perda de brilho. As espumas carregadas naturalmente mais escuras foram mais resistentes à fotodegradação por serem capazes de causar um efeito contrário ao da descoloração natural do PU quando sujeito aos raios UV. O confinamento diminuiu o diâmetro médio de células da espuma PU/madeira e a anisotropia do PU puro, levando a formação de células mais homogêneas, marcadas por números de arestas rompidas e de células abertas aparentemente menores, que resultaram em maiores densidades aparentes e melhores propriedades mecânicas para espumas preparadas a 50% de confinamento e menor condutividade térmica para as espumas confinadas a 70%. / The use of forestry and wood-based resources as fillers in polymer matrices may originate new materials with strong environmental and economic appeals. Among the wastes from chemical and mechanical processing of wood, there are many materials readily available, which can be handled through biorrefinary techniques, like wood flour, wood bark, pine cones (fruits), pine needles (leaves), residual lignin (e.g. from kraft process) and paper sludge, the last two from the chemical processing of cellulosic pulp. In this thesis, such raw materials were incorporated into rigid and semi-rigid polyurethane (PU) foams prepared by the free-rising pouring method, using a mixture of castor oil and crude glycerin as a bio-based polyol in order to achieve chemically stable and eco-friendly foams. Compatibility of the fillers with the PU system was evaluated using induced reactions in the presence of isocyanate and catalyst. The PU foams were characterized by microscopy and spectroscopy techniques, as well as mechanical, thermal, hygroscopic, optical, flame resistance and UV radiation resistance tests. And the effect of rising under confinement on the morphological, mechanical and thermal properties of neat PU and wood/PU foam composites was also investigated The foams presented chemical stability and the addition of fillers into PU yielded foams with more homogeneous cells, better hygroscopic performance, similar thermal conductivities and flammabilities, as well as higher specular glosses and different colorimetric patterns. The wood flour presented the highest affinity with the PU system, followed by kraft lignin, resulting in foam composites with smaller and more rounded cells, with higher closed-cells content, and increased thermal and dimensional stabilities. All foams presented similar photodegradation behavior characterized by an orange color and a significant loss in specular gloss. The foam composites, being naturally darker, were more resistant to photodegradation, since they had an opposite effect related to natural discoloration under UV radiation. The confinement decreased cell diameter for the wood filled PU foam and the anisotropy index for neat PU foam, yielding more homogeneous cells, with fewer broken edges and open-cells, with greater apparent densities and better mechanical properties for foams prepared at 50% confinement and lower thermal conductivity for foams confined at 70%.

O uso de recursos florestais e madeireiros como cargas em matrizes poliméricas pode originar novos materiais com forte apelo ecológico e econômico. Dentre os resíduos do processamento mecânico e químico da madeira, há uma série de materiais de fácil acesso que podem ser manipulados a partir de certas técnicas de biorrefinaria, tais como a madeira, a casca de madeira, as pinhas (frutos do pinus), as acículas (folhas do pinus), a lignina residual (processo kraft) e o lodo de papel derivadas do processo químico de polpação celulósica. Tais matérias primas foram incorporadas em espumas rígidas e semi-rígidas de poliuretano (PU) processadas pelo método da expansão livre, utilizando-se uma mistura de óleo de mamona e glicerina loira como biopoliol, com vistas a obtenção de espumas quimicamente estáveis e ecologicamente corretas. A compatibilidade de algumas dessas cargas no sistema PU foi testada mediante reações induzidas na presença de isocianato e catalisador. As espumas PU foram caracterizadas por meio de técnicas de microscopia e espectroscopia, além de ensaios mecânicos, térmicos, higroscópicos, óticos, de resistência a chamas e de resistência à radiação UV. Por fim, foi avaliado o efeito de expansões sob confinamento nas propriedades morfológicas, mecânicas e térmicas do PU puro e de uma espuma carregada PU/madeira As espumas apresentaram estabilidade química e a inserção das cargas no PU puro possibilitou a obtenção de espumas com células homogêneas, melhor desempenho higroscópico, níveis similares de condutividade térmica e flamabilidade, além de maior brilho e diferentes padrões de cor. A farinha de madeira apresentou a maior afinidade com o sistema PU, seguida pela lignina kraft, resultando em espumas carregadas com células menores, mais arredondadas e com maior teor de células fechadas, além de espumas com maiores estabilidades térmica e dimensional. Todas as espumas apresentaram fotodegradações similares, marcadas por uma cor alaranjada, acompanhada por uma acentuada perda de brilho. As espumas carregadas naturalmente mais escuras foram mais resistentes à fotodegradação por serem capazes de causar um efeito contrário ao da descoloração natural do PU quando sujeito aos raios UV. O confinamento diminuiu o diâmetro médio de células da espuma PU/madeira e a anisotropia do PU puro, levando a formação de células mais homogêneas, marcadas por números de arestas rompidas e de células abertas aparentemente menores, que resultaram em maiores densidades aparentes e melhores propriedades mecânicas para espumas preparadas a 50% de confinamento e menor condutividade térmica para as espumas confinadas a 70%. / The use of forestry and wood-based resources as fillers in polymer matrices may originate new materials with strong environmental and economic appeals. Among the wastes from chemical and mechanical processing of wood, there are many materials readily available, which can be handled through biorrefinary techniques, like wood flour, wood bark, pine cones (fruits), pine needles (leaves), residual lignin (e.g. from kraft process) and paper sludge, the last two from the chemical processing of cellulosic pulp. In this thesis, such raw materials were incorporated into rigid and semi-rigid polyurethane (PU) foams prepared by the free-rising pouring method, using a mixture of castor oil and crude glycerin as a bio-based polyol in order to achieve chemically stable and eco-friendly foams. Compatibility of the fillers with the PU system was evaluated using induced reactions in the presence of isocyanate and catalyst. The PU foams were characterized by microscopy and spectroscopy techniques, as well as mechanical, thermal, hygroscopic, optical, flame resistance and UV radiation resistance tests. And the effect of rising under confinement on the morphological, mechanical and thermal properties of neat PU and wood/PU foam composites was also investigated The foams presented chemical stability and the addition of fillers into PU yielded foams with more homogeneous cells, better hygroscopic performance, similar thermal conductivities and flammabilities, as well as higher specular glosses and different colorimetric patterns. The wood flour presented the highest affinity with the PU system, followed by kraft lignin, resulting in foam composites with smaller and more rounded cells, with higher closed-cells content, and increased thermal and dimensional stabilities. All foams presented similar photodegradation behavior characterized by an orange color and a significant loss in specular gloss. The foam composites, being naturally darker, were more resistant to photodegradation, since they had an opposite effect related to natural discoloration under UV radiation. The confinement decreased cell diameter for the wood filled PU foam and the anisotropy index for neat PU foam, yielding more homogeneous cells, with fewer broken edges and open-cells, with greater apparent densities and better mechanical properties for foams prepared at 50% confinement and lower thermal conductivity for foams confined at 70%.

RISE Bioeconomy is working with the biorefinery concept. That is, for the company, to utilize all wood derivatives in effective processes, resulting in unique products. RISE Bioeconomy is investigating the possibilities of producing holocellulose through an oxidative delignification process of wood, using peracetic acid (PAA). The product, high-purity holocellulose, can be used for the production of for example cellulose nanofibers, a product that in recent years have increased in interest. The PAA-delignification process relies on oxidative treatment with peracetic acid, where the lignin is solubilized in water through the formation of carboxylic groups in the lignin, yielding cellulose of very low lignin content and minimal degradation of the cellulose. In addition to the holocellulose, a solution containing water, acetic acid, salts and highly oxidized lignin is obtained. The PAA-delignification has yet only been performed in lab-scale, however, the aim is to scale up the process. There has not yet been any further utilization of the oxidized lignin and it has been proposed that esterification of the carboxylic groups with an alcohol is a possible valorization route. Due to the up-scaling of the PAA-delignification, it is of large interest to find a valorization route for the lignin by-product to fulfill the biorefinery concept. This master thesis focuses on evaluating esterification of an oxidized lignin, with the aim to propose a process suitable for up-scaling. The lab trials for the PAA-delignification of wood yielded limited amounts of lignin and due to difficulties while isolating this lignin, it was not partially characterized until months into the project. Therefore, model compounds were initially used to evaluate the process setup. Compounds with muconic acid type structures are some of the expected products from PAA-delignification of wood and muconic acid was therefore used as a model compound. In addition to this, vanillic acid was used to represent the phenolic lignin compounds. Gas Chromatography/Mass Spectrometry (GC/MS) analysis of the vanillic acid esterification was shown to be a suitable method for analyzing the conversion of this reaction. Due to the difficulties with the analysis of the model compounds, no results regarding the reaction procedures were obtained. As a “proof-of-concept”, a kraft lignin was oxidized, isolated and then esterified. Two different methods of esterification were performed, with and without a molecular sieve. It was assumed that the amount of carboxylic groups would increase after oxidation and decrease after a successful esterification. The amount of carboxylic groups after each process was analyzed with Phosphorus Nuclear Magnetic Resonance (31P-NMR). For the process without molecular sieve, the 31P-NMR analysis indicated that esterification of the lignin had occurred, to a limited extent. This was confirmed by Fourier Transform Infrared Spectrometry (FTIR). The process with molecular sieve showed no indication of esterification of the lignin. The project did prove the concept of esterifying an oxidized lignin and led to several different proposals for further work in the area. Due to the very wide scope of this project and several unexpected obstacles, this project did not fully answer the research questions given.

An experimental study on the effect of fuel mixing on the products resulting from hydrothermal liquefaction (HTL) was conducted. The feedstocks used were kraft lignin (KL), GROT (GT) and microalgae cultivated in wastewater (MA). Three sets of mixtures were prepared, each containing two types of feedstocks with a 1:1 ratio: KLGT, MAKL, and MAGT. The experiments were performed using a pilot-scale continuous HTL-system. Elemental analysis CHNO and thermogravimetric analysis were used to determine the ultimate and proximate composition of the samples. Scanning electron microscopy with energy dispersive spectroscopy (SEM/EDS) was used to further analyse the elemental distribution on the hydrochars’ surface. The co-liquefaction effect (CE) was evaluated by comparing the experimental results found for the mixtures with the theoretical values calculated as the average of the respective pure components. The results showed that the yield of light oil was not significantly affected for any mixture. However, the mixtures containing KL showed a lower yield of heavy oil than the predicted value, while a higher yield was found for MAGT. All heavy oils had higher carbon content than expected from the predicted values. Every mixture had a significantly larger yield of hydrochar than what was expected. The increased yield of hydrochar for KLGT was insufficient to compensate for the loss of heavy oil and thus the overall product yield was decrease showing antagonistic interactions in the mixture. The hydrochar from MAGT had the highest ash content, and upon closer inspection with SEM/EDS it showed a much larger phosphorus content than any other hydrochar, even compared to the predicted value. This suggests that an interaction between MA and GROT causes the hydrochar to bind more contaminants and enables it to collect more ash than what would have been achieved from liquefying the components individually. Thus, MAGT showed synergetic effects overall, MAKL had increased carbon recovery but at the cost of heavy oil yield making in a poor choice for HTL, and KLGT showed antagonistic effects in the form of lower yield of biocrude and overall recovery of products. The study highlights that co-liquefaction can potentially have a larger impact on the hydrochar than it does on the biocrude, and that evaluation of hydrochar should be included when examining co-liquefaction

The market is in great need of more environmentally friendly alternatives to fossil-based composite materials to obtain a more sustainable future. Lignin is the second most common biopolymer and is a byproduct in the pulping and paper industry. Fractionation of lignin has made it possible to receive lignin with narrow dispersity and low molecular weight, which is suitable for further applications. Modification of lignin structure yields new reactive sites that can be tailored for specific needs. Because of the aromatic structure of lignin, it is a promising renewable resource for production of thermosets. In this project Kraft lignin is sequentially solvent-fractionated and modified in an allylation process with allyl chloride. The allylated lignin is reacted with a cross-linking agent and used to impregnate carbon fibre mats. The resin-coated material is then cured at 125 oC to achieve a composite material. The project also encompasses characterization of the chemical structure of lignin in the different fractions. The morphology and adhesive properties of the lignin as well as the carbon fibres and the composite material was investigated. Although the production of composite material from lignin and carbon fibres were accomplished, bubble formation in the resin was a problem for all composite samples that were prepared, whether it was during solvent evaporation or during curing. By performing the addition of resin to carbon fibre mats in multiple steps, where pressure is added after the first applied layer, it is suggested that complete adhesion to the carbon fibre can be achieved, whilst maintaining adequate resin to carbon fibre ratio. / Marknaden är i stort behov av mer miljövänliga alternativ till fossilbaserade kompositmaterial för att kunna erhålla en mer hållbar framtid. Lignin är den näst vanligaste aromatiska biopolymeren och framställs som en biprodukt i pappersindustrin. Fraktionering av lignin har gjort det möjligt att erhålla lignin med låg dispersitet och molekylvikt vilket är lämpligt för vidare applikationer. Modifiering av lignins struktur ger upphov till nya reaktiva grupper som kan anpassas för ens behov. Den aromatiska strukturen som lignin besitter resulterar i en lovande förnybar resurs för produktion av härdplast. I detta projekt är Kraft lignin sekventiellt fraktionerat med lösningsmedel och modifierat med hjälp av en allyleringsprocess i närvaro av allylklorid. Det allylerade ligninet reagerar med en tvärbindare och används vidare för att impregnera kolfiber. De impregnerade kolfibermattorna härdades i ugn vid 125 oC för att erhålla kompositmaterial. Projektet omfattar även karaktärisering av den kemiska strukturen i lignin från de olika fraktionerna. Morfologin och vidhäftningsförmåga av lignin, kolfiber och likaså kompositmaterialet undersöktes. Ett kompositmaterial bestående av kolfiber och lignin erhölls med framgång under projektets gång, dock var bubbelbildning ett stort problem under förångningen av lösningsmedel och även under härdningsprocessen. Addition av harts till kolfibermattorna i flera steg, där tryck är adderat efter det första lagret har blivit applicerat, anses vara en lovande metod för att en hög vidhäftningsgrad ska kunna erhållas. Detta medan ett adekvat förhållande mellan harts och kolfiber upprätthålls.

Lignin är en restprodukt från massaindustrin som har stor potential för vidareanvändning i bland annat materialutveckling. För att utreda möjliga användningsområden för ett specifikt lignin är det viktigt att ha kunskap om ligninets molekylstruktur och bindningar. 31P-NMR spektroskopi kan användas som analysmetod för kvantifiering av hydroxylgrupperna hos lignin. Vid användning av 31P-NMR spektroskopi måste ligninprovet först derivatiseras med ett derivatiserings-reagens innehållande fosfor. Till analyserna behövs en lämplig intern standard för att kunna beräkna halten av de olika strukturelementen i lignin. RISE Research Institutes of Sweden ville se om det gick att komplettera analyserna av lignins struktur med hjälp av ett nytt derivatiserings-reagens, DR(I) (2-chloro-1,3,2-dioxaphospholane). Tidigare har derivatiserings-reagenset DR(II) (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane) använts. Det nya derivatiserings-reagenset DR(I) har en liknande struktur men är en mindre molekyl och förväntades därför kunna analysera fler strukturelement som tidigare inte kunnat påvisas. Projektet har undersökt 10 olika interna standarder med DR(I) i syfte att hitta den bästa interna standarden. Den första som undersöktes är den som används med DR(II), N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine. Av de undersökta interna standarderna är tre tagna från tidigare litteratur och sex är tidigare helt obeprövade. Samtliga undersöktes både som blankprov och med ett utvalt barrveds-kraftlignin. N-hydroxy-1,8-naftalimid (intern standard 4) var bäst baslinjeupplöst men inte tillräckligt stabil för att kunna användas som intern standard. Bisfenol-A (intern standard 3) var den interna standard som var den mest stabila och alla stabilitetstest utfördes med denna interna standard som referens. Av de tidigare obeprövade interna standarderna är det endast N-hydroxysuccinimide (intern standard 5) som kan användas som intern standard, dock är den inte tillräckligt stabil. N-hydroxy-5-norborene-2,3-dicarboxylic acid imine (intern standard 1) ansågs vara den bäst lämpade interna standarden. Denna prövades med olika typer av kraftlignin; barrveds-kraftlignin, lövveds-kraftlignin samt ett blandlignin. Den undersöktes även med ”milled wood lignin”. För detta lignin var det uppenbart att den valda interna standarden inte var helt optimal. En annan intern standard med bättre baslinjeupplösning skulle vara ett bättre alternativ för ”milled wood lignin”. Relaxationstiden mättes även för intern standard 1 och de olika strukturerna i ligninet. RISE Research Institutes of Sweden kan använda DR(I) som komplement till den nuvarande analysen med DR(II) vid beräkning av mängden av de sekundära alifatiska grupperna. En uppdelning av de olika formerna (erythro och threo) av den vanligaste bindningen hos lignin, β-O-4-bindningen, går också att urskilja. Eftersom denna bindning bryts i sulfatmassaprocessen är signalen svag, vilket gör att en uppdelning av erythro och threo vid beräkningarna av hydroxylgrupperna inte är relevant. / Lignin is a residue from the pulp industry, which has great potential for further use, including material development. To investigate possible uses for a specific lignin, it is important to have knowledge of the lignin's molecular structure. 31P NMR spectroscopy can be used when quantifying the hydroxyl groups of lignin. When using 31P NMR spectroscopy, the lignin sample must be derivatized with a phosphorous reagent. The analysis requires an appropriate internal standard to calculate the amount of the different structural elements in lignin. RISE Research Institutes of Sweden wishes to complement the analyzes of lignin structures using a new derivatization reagent, DR(I) (2-chloro-1,3,2-dioxaphospholane). Previously, the derivatization reagent DR(II) (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane) has been used. The new derivatization reagent DR(I) has a similar structure but is a smaller molecule. In this report, 10 different internal standards have been examined with DR(I) to find the most suitable one. The first internal standard, N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine, was used with DR(II). Three internal standards were from articles and six were previously unexamined. All of these were first tested as blanks without lignin and then with a selected softwood lignin. N-hydroxy-1,8-naphthalimide (internal standard 4) showed the best resolution but was not stable enough to be used as an internal standard. Bisphenol A (internal standard 3) was the most stable derivatized internal standard and the stability tests were performed with this internal standard as a reference. Of the previously unexamined internal standards, N-hydroxysuccinimide (internal standard 5) was the only appropriate internal standard to use. However, it was not as stable as N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine (internal standard 1), which was found to be the most suitable internal standard. N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine (internal standard 1) was examined with different types of kraft lignin; softwood kraft lignin, hardwood kraft lignin and a mixture kraft lignin. N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine was also investigated with "milled wood lignin". For ”milled wood lignin” it became obvious that the resolution of the selected internal standard can be improved. Another internal standard that has not been examined in this report could be a better option. The relaxation time was also determined for N-hydroxy-5-norbornene-2,3-dicarboxylic acid imine and the different hydroxyl groups of lignin. RISE Research Institutes of Sweden can use DR(I) in analysis of kraft lignin as a complement to the currently used method with DR(II) for calculating the amount of secondary aliphatic groups. A differentiation of erythro and threo of the most common binding (β-O-4) can also be noted with these lignins with DR(I). Since this bond is broken to a large extent in the kraft process, the signal is week. This means that when calculating the hydroxyl groups, a separation of erythro and threo is not relevant.