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.

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.

High glass transition temperature (Tg) thiol-ene networks (TENs) based on poly(limonene carbonate)s (PLCs), derived from orange oils and of potential degradability are described here. PLCs with moderate molecular weight were prepared by copolymerization of limonene oxide with CO2 and subsequent breakdown reactions. These PLCs were cured with multifunctional thiol monomers in the presence of thermal initiators via thiol-ene chemistry to generate poly(thioether-cocarbonate) networks. The thermal curing experiments were optimized by a kinetic study using real-time ATR-FTIR, in which a delayed gelation was observed. For the first time, an interesting "cage" effect was observed during the network formation initiated by DCP, in which the addition reactions of pendant isopropenyls on high molecular weight PLC chains were significantly enhanced by thiol-ene crosslinking at 160 degrees C. The resulting homogeneous TENs with high T(g)s (> 100 degrees C) and a wide range of thermomechanical properties, including rubbery moduli from 2.9 to 28.2 MPa, were obtained. The TENs also showed promising properties such as high transparency, good acetone resistance and high hardness, suggesting their potential application in coatings.

This study describes the formulation, curing, and characterization of solid polymer electrolytes (SPE) based on plasticized poly(ethylene glycol)-methacrylate, intended for use in structural batteries that utilizes carbon fibers as electrodes. The effect of crosslink density, salt concentration, and amount of plasticizer has been investigated. Adding a plasticizing solvent increases the overall performance of the SPE. Increased ionic conductivity and mechanical performance can be attained compared to similar systems without plasticizer. At ambient temperature, ionic conductivity (sigma) of 3.3 x 10(-5) Scm(-1), with a corresponding storage modulus (E) of 20 MPa are reached.

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.

Aromatic material constituents derived from renewable resources are attractive for new biobased polymer systems. Lignin, derived from lignocellulosic biomass, is the most abundant natural source of such structures. Technical lignins are, however, heterogeneous in both structure and polydispersity and require a refining to obtain a more reproducible material. In this paper the ethanol-soluble fraction of Lignoboost Kraft lignin is selectively allylated using allyl chloride by means of a mild and industrially scalable procedure. Analysis using 1H-, 31P-, and 2D HSQC NMR give a detailed structural description of lignin, providing evidence of its functionalization and that the suggested procedure is selective toward phenols with a conversion of at least 95%. The selectively modified lignin is subsequently cross-linked using thermally induced thiol-ene chemistry. FT-IR is utilized to confirm the cross-linking reaction, and DSC measurements determined the Tg of the thermosets to be 45-65 °C depending on reactive group stoichiometry. The potential of lignin as a constituent in a thermoset application is demonstrated and discussed.

For the realization of structural batteries, electrolytes where both higher ionic conductivity and stiffness are combined need to be developed. The present study describes the formation of a structural battery electrolyte (SBE) as a two phase system using reaction induced phase separation. A liquid electrolyte phase is combined with a stiff vinyl ester based thermoset matrix to form a SBE. The effect of monomer structure variations on the formed morphology and electrochemical and mechanical performance has been investigated. An ionic conductivity of 1.5 x 10(-4) S cm(-1), with a corresponding storage modulus (E') of 750 MPa, has been obtained under ambient conditions. The SBEs have been combined with carbon fibers to form a composite lamina and evaluated as a battery half-cell. Studies on the lamina revealed that both mechanical load transfer and ion transport are allowed between the carbon fibers and the electrolyte. These results pave the way for the preparation of structural batteries using carbon fibers as electrodes.

The present work describes the synthesis and characterization of fully biobased soft polymer networks for pressure sensitive adhesives applications. The incorporation of different sugars into fatty-acid-based monomers, made it possible to tailor the viscoelastic properties of the materials. Lipase catalysis allowed to afford monomers with varying hydroxyl content and epoxy-functionalities. Step-growth polymerization catalyzed by DBU resulted in soft-polyester networks through combination of the monomers with a biobased diacid. Rheological and adhesion studies were performed to elucidate the different viscoelastic and adhesive properties of the materials as a function of their composition.

In polymer nanocomposites, particle-polymer interactions influence the properties of the matrix polymer next to the particle surface, providing different physicochemical properties than in the bulk matrix. This region is often referred to as the interphase, but detailed characterization of its properties remains a challenge. Here we employ two atomic force microscopy (AFM) force methods, differing by a factor of about 15 in probing rate, to directly measure the surface nanomechanical properties of the transition region between filler particle and matrix over a controlled temperature range. The nanocomposite consists of poly(ethyl methacrylate) (PEMA) and poly(isobutyl methacrylate) (PiBMA) with a high concentration of hydrophobized silica nanoparticles. Both AFM methods demonstrate that the interphase region around a 40-nm-sized particle located on the surface of the nanocomposite could extend to 55–70 nm, and the interphase exhibits a gradient distribution in surface nanomechanical properties. However, the slower probing rate provides somewhat lower numerical values for the surface stiffness. The analysis of the local glass transition temperature (T_g) of the interphase and the polymer matrix provides evidence for reduced stiffness of the polymer matrix at high particle concentration, a feature that we attribute to selective adsorption. These findings provide new insight into understanding the microstructure and mechanical properties of nanocomposites, which is of importance for designing nanomaterials.