Diss. (sammanfattning) Stockholm : Kungliga Tekniska högskolan, 2006. / Härtill 5 uppsatser.

<p>Atom transfer radical polymerization (ATRP) has proven to be a powerful technique to obtain polymers with narrow polydispersities and controlled molecular weight. It also offers control over chain-ends. The technique is the most studied and utilized of thecontrolled/”living” radical polymerization techniques since a large number of monomerscan be polymerized under simple conditions. ATRP can be used to obtain polymer graftsfrom multifunctional substrates. The substrates can be either soluble (i. e. based ondendritic molecules) or insoluble (such as gold or silicon surfaces). The large number ofgrowing chains from the multifunctional substrates increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems, andsuppress side-reactions such as termination, the concentration of propagating radicalsmust be kept low. To elaborate such a system a soluble multifunctional substrate, based on 3-ethyl-3-(hydroxymethyl)oxetane, was synthesized. It was used as a macroinitiatorfor the atom transfer radical polymerisation of methyl acrylate (MA) mediated byCu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. Since mostsolid substrates are sensitive to the temperatures at which most ATRP polymerisations are performed, lowering the polymerization temperatures are preferred. ATRP at ambienttemperature is always more desirable since it also suppresses the formation of thermally formed polymer. The macroinitiator contained approximately 25 initiating sites, which well mimicked the conditions on a solid substrate. The polymers had low polydispersity and conversions as high as 65% were reached without loss of control. The solid substrateof choice was cellulose fibers that prior to this study not had been grafted through ATRP.As cellulose fibers a filter paper, Whatman 1, was used due to its high cellulose content.The hydroxyl groups on the surface was first reacted with 2-bromoisobutyryl bromidefollowed by grafting of MA. Essentially the same reaction conditions were used that hadbeen elaborated from the soluble substrate. The grafting yielded fibers that were very hydrophobic (contact angles>100°). By altering the sacrificial initiator-to-monomer ratiothe amount of polymer that was attached to the surface could be tailor. PMA with degreesof polymerization (DP’s) of 100, 200 and 300 were aimed. In order to control that thepolymerizations from the surface was indeed “living” a second layer of a hydrophilicmonomer, 2-hydroxymethyl methacrylate (HEMA), was grafted onto the surface. Thisdramatically changed the hydrophobic behavior of the fibers.</p> / QC 20100524

<p>The use of degradable biomedical materials has during the past decades indeed modernized medical science, finding applications in e.g. tissue engineering and drug delivery. The key question is to adapt the material with respect to mechanical properties, surface characteristics and degradation profile to suit the specific application. Degradation products are generally considered non-toxic and they are excreted from the human body. However, large amounts of hydroxy acids may induce a pH decrease and a subsequent inflammatory response at the implantation site.</p><p>In this study, macromolecular design and a combination of cross-linking and adjusted hydrophilicity are utilized as tools to control and tailor degradation rate and subsequent release of degradation products from biomedical polyester-ethers. A series of different homo- and copolymers of -caprolactone (CL) and 1,5-dioxepan-2-one (DXO) were synthesized and their hydrolytic degradation was monitored in phosphate buffer solution at pH 7.4 and 37 °C for up to 546 days. The various materials comprised linear DXO/CL triblock and multiblock copolymers, PCL linear homopolymer and porous structure, and random cross-linked homo- and copolymers of CL/DXO using 2,2’-bis-(ε-caprolactone-4-yl) propane (BCP) as a cross-linking agent.</p><p>The results showed that macromolecular engineering and controlled hydrophilicity of cross-linked networks were useful implements for customizing the release rate of acidic degradation products in order to prevent the formation of local acidic environments and thereby reduce the risk of inflammatory responses in the body.</p>

Lignosulphonates are by‐products from the sulphite pulping process for the manufacture ofspecialty dissolving pulps and paper. During the liberation of the cellulose, the lignin isfractionated and solubilised through covalent addition of sulphonic acid groups at variouspositions in the structure. The formed sulphonated lignin, lignosulphonate is then furtherisolated and refined. The amphiphilic nature of lignosulphonates has enabled them to be used as additives to varioussuspensions to improve their dispersion and stability. The by far largest utilisation oflignosulphonates is as dispersants in concrete. Here, lignosulphonates act by dispersing cementparticles to prevent flocculation, un‐even particle distribution and reduced strengthdevelopment. The dispersion is achieved through steric and electrostatic repulsion of the cementparticles by the lignosulphonate polymer. This behaviour is intimately linked with the overallsize and amount of charged groups in the dispersing polymer. Traditional modifications oflignosulphonates have been limited to removal of sugars, filtration and fractionation. Thesemodifications are not sufficient for utilisation of lignosulphonates in high‐strength concrete. Heresynthetic dispersants and superplasticisers are used which are considerably more efficient evenat low dosages. To compete with these, additional modifications of lignosulphonates are likely tobe necessary. The molecular weight and functional group composition have been identified anddescribed as the most interesting parameters that can be modified. Currently, no suitable method exists to increase the molecular weight of lignosulphonates.Oxidation by the natural radical initiating enzyme laccase is an interesting tool to achieve suchmodifications. In this thesis several aspects of the mechanism through which this enzyme reactswith lignin and lignosulphonate structures have been elucidated through model compoundstudies. Further studies showed that laccase alone was a highly efficient tool for increasing themolecular weight of commercial lignosulphonates at low dosages and in short incubation times.Immobilisation of the laccase to a solid support to enable re‐utilisation was also investigated. Modification of functional group composition of lignosulphonates was achieved throughozonolysis and the Fenton’s reagent, a mixture of hydrogen peroxide and iron(II)acetate.Introduction of charged carboxylic groups was achieved through opening of the benzyl rings oflignosulphonates. It was found that a two‐stage process consisting of laccase oxidation followedby ozonolysis was an efficient technique to create a polymer enriched with carboxylic acidgroups with a sufficient molecular size. Oxidation by the Fenton’s reagent was shown to yield similar modifications as the combinedlaccase/ozonolysis treatment albeit with less pronounced results but with a large level of controlthrough variation of a number of reaction parameters. The Fenton’s reagent can therefore be aninteresting alternative to the aforementioned two‐stage treatment. These modifications are interesting for large‐scale applications not only because of theirsimplicity in terms of reaction parameters but also because of the ubiquity of the used enzymeand the chemicals in the pulp and paper industry. / QC 20110427

Various technical lignins, e.g. industrial Softwood Kraft lignin (SKL), are now largely available while they are generally underutilized due to their heterogeneous and complicated structures and/or the poor properties. SKL has here been modified by physical, chemical and biochemical methods for preparation of lignin microspheres, phenol substitution in phenol-formaldehyde (PF) resin preparation and preparation of highly efficient fertilizers. Physically, a brand-new slow and exhaustive solution evaporation process was developed for the highly efficient and productive preparation of microsphere structures. Highly homogenous SKL hollow microspheres were obtained and for the first time, urea encapsulating SKL microspheres were similarly prepared which could be an excellent controlled release urea fertilizer. Chemically, Mannich reaction (one type of amination) was deeply investigated by including for the first time an LC-MS study of vanillin reaction, resulting in the establishment of a fast and reliable lignin reactivity (for phenol substation in PF resin) quantification method. In addition, SKL was functionalized using the Mannich reaction or esterification, leading to an improved hydrophobicity and compatibility for blending with polylactic acid (PLA). Using dip-coating technique for the first time, PLA-functionalised SKL-coated urea pellets were prepared, leading expectedly to a highly efficient urea fertilizer with simultaneous controlled- and slow- release and biological stabilization effects. Biochemically, SKL was demethylated via incubation with different laccase-mediator combinations, which in principle will increase its reactivity in PF resin preparation. However, polymerization occurred which would decrease the reactivity.  The overall effects need to be further investigated. Conclusively, broader or larger scale SKL applications can expectedly be realized after the development of SKL modifications tailored towards the optimum desired structures and properties. / <p>QC 170912</p>

Biotemplating is the art of using a biological structure as a scaffold which is decorated with a functional material. In this fashion the structures will gain new functionalities and biotemplating offers a simple route of mass-producing mesoscopic material with new interesting properties. Biological structures are abundant and come in a great variety of elaborate and due to their natural origin they could be more suitable for interaction with biological systems than wholly synthetic materials. Conducting polymers are a novel class of material which was developed just 40 years ago and are well suited for interaction with biological material due to their organic composition. Furthermore the electronic properties of the conducting polymers can be tuned giving rise to dynamic control of the behavior of the material. Self-assembly processes are interesting since they do not require complicated or energy demanding processing conditions. This is particularly important as most biological materials are unstable at elevated temperatures or harsh environments. The main aim of this thesis is to show the possibility of using self-assembly to decorate a conducting polymer onto various biotemplates. Due to the intrinsic variety in charge, size and structure between the available natural scaffolds it is difficult, if not impossible, to find a universal method. In this thesis we show how biotemplating can be used to create new hybrid materials by self-assembling a conducting polymer with biological structures based on DNA, protein, lipids and cellulose, and in this fashion create material with novel optical and electronic properties.

The interest for polymeric nanocomposites has rapidly grown during the last decades, fuelled by the great potential and superior properties of nanoparticles (NPs). The production volumes of commercial NPs have increased exponentially during the last ten years, and the quality has been significantly improved. The aim of this study was to design polymer grafted commercially available metal-oxide NPs, and graphene oxide (GO), to develop isotropic (homogeneous) and anisotropic (heterogeneous) polymer nanocomposites for dielectric applications. The motivation was to formulate functional insulation materials for compact components in future power-grid systems using high-voltage direct-current (HVDC) or high-voltage alternating-current (HVAC), and to fabricate responsive sensor materials for monitoring e.g. temperature and voltage fluctuations in so called “Smart Grids”. Aluminium oxide (Al2O3), zinc oxide (ZnO) and reduced GO (rGO) NPs were modified with sparse polymer grafts via a controlled “covalent route” and were mixed with silicone (PDMS) or polyethylene matrices (EBA and LDPE) commonly used in HV-cable systems. The graft length and the graft-to-matrix compatibility were tailored to obtain nanocomposites with various self-assembled NP-morphologies, including well-dispersed, connected and phase-separated structures. The graft length was used to adjust the inter-particle distance of nanocomposites with continuous morphologies or connected (percolated) NPs. It was found that nanocomposites with percolated NPs and short inter-particle distances exhibited 10-100 times higher conductivity than the unfilled (neat) polymer, or displayed a rapid non-linear increase in conductivity (~1 million times) with increasingelectric field, while well-dispersed NPs with long inter-particle distances exhibited 10-100 times lower conductivity (i.e. higher resistivity) as an effect of their trapping of charge carriers. These tunable and functional properties are desirable for HV-insulation, field-grading applications, and flexible electronics. In addition it was shown that GO modified with dense polymer grafts via a “physisorption route” formed suspensions with liquid crystals, or matrix-free GO-composites with well-dispersed GO in isotropic or nematic states. These materials were reinforced by the GO, and exhibited elevated glass transition temperatures and a rapid thermo-responsive shape-memory effect, and are thus proposed to have a great potential as sensor materials and responsive separation membranes. / Intresset för polymera nanokompositer har snabbt ökat under de senaste decennierna, drivet av den stora potentialen och de överlägsna egenskaperna hos nanopartiklar (NPs). Produktionsvolymerna för kommersiella NP har ökat exponentiellt under de senaste tio åren, och kvaliteten har förbättrats avsevärt. Syftet med denna studie var att polymer-ympa kommersiellt tillgängliga metalloxid-NPs, och grafenoxid (GO), för att designa isotropa (homogena) och anisotropa (heterogena) polymera nanokompositer för dielektriska tillämpningar. Motiveringen var att formulera funktionella isoleringsmaterial för kompakta komponenter i framtida kraftnätssystem som använder högspänd likström (HVDC) eller högspänd växelström (HVAC), samt att tillverka responsiva sensormaterial för övervakning av t.ex. temperatur- and spänningsvariationer i så kallade "Smart Grids". Aluminiumoxid (Al2O3), zinkoxid (ZnO) och reducerad GO (rGO) NPs modifierades med glesa polymerympar via en kontrollerad "kovalent väg" och blandades med silikon (PDMS) eller polyeten matriser (EBA och LDPE) som är vanliga i HV-kabelsystem. Ymplängden och ymp-till-matrix kompatibiliteten skräddarsyddes för att erhålla nanokompositer med olika självordnande NP-morfologier, inklusive väldispergerade, länkade och fasseparerade strukturer. Ymplängden användes för att justera partikelavståndet i nanokompositer med förbundna morfologier eller länkade NPs. Man fann att nanokompositer med länkade NPs och korta interpartikelavstånd uppvisade 10-100 gånger högre konduktivitet än den ofyllda (rena) polymeren, eller erhöll en snabb icke-linjär ökning i konduktivitet (~1 miljon gånger) med ökande elektriskt fält, medan väldispergerade NPs med långa interpartikelavstånd uppvisade 10-100 gånger lägre ledningsförmåga (dvs. högre resistivitet) som en effekt av deras infångande av laddningsbärare. Dessa inställbara och funktionella egenskaper är önskvärda för HV-isolering, fältstyrande applikationer och flexibel elektronik. Dessutom visades att GO, som modifierats med täta polymerympar via en "fysisorptionsväg", bildade suspensioner med flytande kristaller, eller matrisfria GO-kompositer med väldispergerad GO i isotropa eller nematiska tillstånd. Dessa material armerades av GO och uppvisade förhöjda glastransitionstemperaturer och en snabb värmeresponsiv form-minneseffekt, och föreslås därigenom ha en stor potential som sensor-material och responsiva separationsmembran. / <p>QC 20170323</p>

<p>QC 20150323</p>

Atom transfer radical polymerization (ATRP) has proven to be a powerful technique to obtain polymers with narrow polydispersities and controlled molecular weight. It also offers control over chain-ends. The technique is the most studied and utilized of thecontrolled/”living” radical polymerization techniques since a large number of monomerscan be polymerized under simple conditions. ATRP can be used to obtain polymer graftsfrom multifunctional substrates. The substrates can be either soluble (i. e. based ondendritic molecules) or insoluble (such as gold or silicon surfaces). The large number ofgrowing chains from the multifunctional substrates increases the probability of inter-and intramolecular reactions. In order to control these kinds of polymerizing systems, andsuppress side-reactions such as termination, the concentration of propagating radicalsmust be kept low. To elaborate such a system a soluble multifunctional substrate, based on 3-ethyl-3-(hydroxymethyl)oxetane, was synthesized. It was used as a macroinitiatorfor the atom transfer radical polymerisation of methyl acrylate (MA) mediated byCu(I)Br and tris(2-(dimethylamino)ethyl)amine (Me6-TREN) in ethyl acetate at room temperature. This yielded a co-polymer with a dendritic-linear architecture. Since mostsolid substrates are sensitive to the temperatures at which most ATRP polymerisations are performed, lowering the polymerization temperatures are preferred. ATRP at ambienttemperature is always more desirable since it also suppresses the formation of thermally formed polymer. The macroinitiator contained approximately 25 initiating sites, which well mimicked the conditions on a solid substrate. The polymers had low polydispersity and conversions as high as 65% were reached without loss of control. The solid substrateof choice was cellulose fibers that prior to this study not had been grafted through ATRP.As cellulose fibers a filter paper, Whatman 1, was used due to its high cellulose content.The hydroxyl groups on the surface was first reacted with 2-bromoisobutyryl bromidefollowed by grafting of MA. Essentially the same reaction conditions were used that hadbeen elaborated from the soluble substrate. The grafting yielded fibers that were very hydrophobic (contact angles&gt;100°). By altering the sacrificial initiator-to-monomer ratiothe amount of polymer that was attached to the surface could be tailor. PMA with degreesof polymerization (DP’s) of 100, 200 and 300 were aimed. In order to control that thepolymerizations from the surface was indeed “living” a second layer of a hydrophilicmonomer, 2-hydroxymethyl methacrylate (HEMA), was grafted onto the surface. Thisdramatically changed the hydrophobic behavior of the fibers. / QC 20100524

Cellulose is a natural material that can be used both in its original form and as a building block for creating new types of materials. This work focused on regenerated cellulose (RC) and cellulose acetate butyrate (CAB) in which the hydroxyls on the cellulose backbone were substituted with ester groups. In this work both RC and CAB were formed as free-standing films via initial dissolution and characterized with respect to their structural and morphological aspects, as well as some other material properties. Cellulose pulp was dissolved in cold aqueous alkali urea solution and regenerated in either alcohols or esters to form RC films. Variations of commercially available CAB were dissolved in acetone and solvent cast to form CAB films.This work strove to understand the structural relations of cellulose-based films, the fundamental principles of these materials and how they affect the material properties. This work examined the effect of the polarity of the regeneration liquid on the crystallinity and on other material properties of dried RC films (Papers I and III). This work also investigated the variation in degree of substitution of butyrate and the variation in molecular weight of commercially available CAB and how those could affect the microstructural order of a solvent cast film to the degree that a measurable change in material properties could be observed (Paper II). This was done via structural analysisusing solid-state nuclear magnetic resonance (ss-NMR), x-ray diffraction (XRD), and temperature-modulated differential scanning calorimetry (TOPEM DSC), on RC and CAB films. The qualitative concept of “film formability” was used in this work to determine the practical film properties (related to the ease of handling a film) based on subjective observations.Both the RC films and the CAB films were transparent, with some variations. The CAB films were more fragile than the RC films, even when theCAB films were almost triple the RC films’ thickness. The RC films could be bent considerably, even sharply folded, whereas the CAB films were only slightly bendable before they snapped.The crystallinity of the RC films varied with the regeneration liquid used,and an increase in crystallinity was observed in the following order: EtOH &lt;n-PrOH &lt; MeAc &lt; EtFm. By controlling the crystallinity of the RC films, some material properties could be tuned accordingly, and in that the advantages of the material can be predicted and used to their fullest. For the CAB films, boththeir crystallinity and microstructural order increased with increasing molecular weight and increasing number of hydroxyl groups along the iibackbone. The microstructural order of the films could be tailored accordingly, although less clearly than for the RC films.By using cellulose-based polymers in a film-making process, the ease withwhich the material can be handled could be investigated and informationvaluable for product development could be obtained. This thesis advances our knowledge of the variations in properties caused by structural elementsin cellulose-based films. / Cellulosa är ett naturligt material som kan användas både som det är och som en byggsten för nya, helt andra typer av material. Det här arbetet fokuserade på regenererad cellulosa (RC), och cellulosa acetat butyrat (CAB), där cellulosan agerar som ryggrad där hydroxylgrupperna delvis är substituerade med estergrupper. Både RC och CAB är i det här arbetet efter upplösning formade som tunna filmer, och analyserade med avseende på strukturella och morfologiska aspekter samt materialegenskaper. Cellulosamassa löstes upp med kall vattenbaserad alkalisk urealösning och regenererades med antingen etanol, normal propanol, metylacetat eller etylformat för att forma RC-filmer. Olika varianter av kommersiellt tillgängliga CAB löstes upp i aceton och gjöts för att forma CAB-filmer. Det här arbetet syftade till att förstå strukturen i cellulosabaserade filmer, de fundamentala principerna kring materialet och hur de påverkar materialegenskaperna. Effekten av regenereringsvätskans polaritet på kristalliniteten och andra materialegenskaper på torkade RC-filmer studerades (Artikel I och III). I arbetet undersöktes också hur variationen i grad av butyratsubstitution och variation av molekylvikt för kommersiellt tillgängliga CAB påverkade den strukturella ordningen i lösningsmedelsgjutna filmer, till den grad att en märkbar skillnad i materialegenskaper kunde observeras (Artikel II). Det är gjort genom analyser av filmerna med fastfas kärnmagnetisk resonans (ss-NMR), röntgendiffraktion (XRD) och temperaturmodifierad differentiell svepkalorimetri (TOPEM DSC) på RC- och CAB-filmer. En kvalitativ term ”Filmformbarhet” användes i arbetet för att avgöra de praktiska filmegenskaperna (som relaterar till hur lätthanterlig filmen var) med subjektiva observationer. Både RC-filmer och CAB-filmer var transparenta, med lite variation. CABfilmerna var skörare än RC-filmerna, även om de förstnämnda var nästan tre gånger tjockare. RC-filmerna kunde böjas och till och med vikas skarpt, medan CAB-filmerna bara var något böjbara innan de sprack, med stor variation beroende på vilken CAB som användes. Kristalliniteten hos RC-filmerna varierade med regenereringsvätskan och en ökande kristallinitet observerades i följande ordning: EtOH&lt;nPrOH&lt;MeAc&lt;EtFm. Genom att styra kristalliniteten hos RC-filmerna kunde även några materialegenskaper varieras, och med det kunde fördelarna med materialet förutses och utnyttjas till fullo. För CAB-filmerna kunde både kristalliniteten och mikrostrukturordningen ökas med ökad molekylvikt och ökat antal hydroxylgrupper längs polymerens ryggrad, och ordningen i filmerna kunde därmed skräddarsys efter önskemål, även om det gav mindre effekt än vad det gjorde för RC-filmerna. Genom att använda cellulosa-baserade polymerer som material i filmtillverkning kunde hanterbarheten av materialen undersökas, och information som är värdefull för produktutveckling kunde hittas. Därför bidrar den här avhandlingen med kunskap kring egenskapsvariationers beroende av strukturella element i cellulosabaserade filmer. / <p>Vid tidpunkten för framläggningen av avhandlingen var följande delarbete opublicerat: delarbete 3 (inskickat).</p><p>At the time of the defence the following paper was unpublished: paper 3 (submitted).</p>