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.

The main drawback of conventional chemotherapeutics is their non-specific distribution in the body which causes serious side effects to healthy cells. As a consequence, the drug concentration reaching the tumor is reduced, resulting in suboptimal therapeutic efficacy. The discovery that polymer-based nanomaterials can be used for controlled drug delivery systems offers well-defined reservoirs for a wide spectrum of pharmaceutical agents, with the ability to reduce the toxic response. The most widely explored polymeric nanocarriers, including biodegradable polymers, amphiphilic copolymers and polymers that form unimolecular micelles, are discussed in this brief chapter.

A biomimetic, facile approach to cellulose modification is the utilisation of self-adsorbing, naturally occurring biopolymers, such as the hemicellulose xyloglucan (XG). Herein, XG-block-poly(sulfobetaine methacrylate) (XG-b-PSBMA) zwitterionic block copolymers have been prepared and assessed for their ability to adsorb to cellulose, specifically cellulose nanofibrils (CNF). The polymers were synthesised using reversible addition-fragmentation chain-transfer (RAFT) polymerisation, employing an XG macromolecular RAFT agent (XG-RAFT), polymerising a sulfobetaine methacrylate (SBMA) under aqueous conditions. The incorporation of the XG block shifted the upper critical solution temperature (UCST) values to higher temperatures (20 and 30 °C) compared with the PSBMA homopolymers (17 and 22 °C) and the transition was also broadened. The adsorption of the polymers to a CNF surface was monitored using quartz crystal microbalance with dissipation monitoring (QCM-D), showing that the XG block enhanced the adsorption of the zwitterionic polymer. The formation of CNF-composite films was achieved utilising a facile vacuum filtration methodology, and the targeted compositions were confirmed by FT-IR and TGA analyses. The films exhibited high degrees of swelling in water, which were investigated at two different temperatures, 5 and 60 °C (below and above the polymer USCT values). These results highlight the advantage of using an XG block for the biomimetic modification of cellulose to form new cellulose-composite materials such as super-absorbing films.

Surface discharge behavior of modified oil-impregnated paper (OIP) with nanoparticles (NPs), has been investigated under AC voltage with superimposed impulses. Surface Partial Discharges (PD) can develop at an oil-paper interface and lead to its degradation. Modified paper, made from fibers with adsorbed nanoparticles, can affect the partial discharge behavior of a paper in combination with oil at the interface between oil and fibers. Papers with two different concentrations (2 wt% and 6 wt%) of silica (SiO2), and paper with silanized zinc oxide (ZnO) nanoparticles (1 wt%) have been studied. Papers with SiO2 NPs showed lower impulse-induced surface PD activity. However, thorough purification during the production of SiO2 filled papers was necessary to achieve a good performance. With less purification, paper with 2 wt% of SiO2 did not show such significant improvements. Paper with 6 wt% of SiO2 NPs showed a large number of AC surface PDs, but low influence of impulse voltage on subsequent PD. Papers containing 1 wt% of silanized ZnO showed reduced relative permittivity, but no significant difference in surface PD behavior. The effect of high lignin content in Kraft paper has also been studied. Paper with higher lignin content showed better surface PD characteristics under the impulse. Paper with low concentrations of pure SiO2 NPs, and paper with high lignin content thus appear good candidates for further studies to improve the surface PD behavior of OIP.

Polyethylene composites based on metal oxide nanoparticles are emerging materials for use in the insulation of extruded HVDC cables. The short-term electrical performance of these materials is adequate, but their stability for extended service needs to be assessed. This study is focussed on the capacity of the nanoparticles to adsorb polar species (water, dicumyl peroxide and byproducts from peroxide-vulcanisation, acetophenone and cumyl alcohol) that have an impact on the electrical conductivity of nanocomposites, the oxidative stability by adsorption of phenolic antioxidants on the nanoparticles and the potential transfer of catalytic impurities from the nanoparticles to the polymer. The adsorption of water, dicumyl peroxide, acetophenone, cumyl alcohol and Irganox 1076 (phenolic antioxidant) on pristine and coated (hydrophobic silanes and poly(lauryl methacrylate)) Al2O3, MgO and ZnO particles ranging from 25 nm to 2 gm was assessed. Composites based on low-density polyethylene and the particles mentioned (<= 12 wt.%) were prepared, the degree of adsorption of Irganox 1076 onto the particles was assessed by OIT measurements, and the release of volatile species at elevated temperature was assessed by TG. The concentration of moisture adsorbed on the particles at 25 degrees C increased linearly with both increasing hydroxyl group concentration on the particle surfaces and increasing relative humidity. Dicumyl peroxide showed no adsorption on any of the nanoparticles. Acetophenone and cumyl alcohol showed a linear increase in adsorption with increasing concentration of hydroxyl groups, but the quantities were much smaller than those of water. Irganox 1076 adsorbed only onto the uncoated nanoparticles. Uncoated ZnO nanoparticles that contained ionic species promoted radical formation and a lowering of the OIT. This study showed that carefully coated pure metal oxide nano particles are not likely to adsorb phenolic antioxidants or dicumyl peroxide, but that they have the capacity to adsorb moisture and polar byproducts from peroxide vulcanisation, and that they will not introduce destabilizing ionic species into the polymer matrix. Low contents of dry, equiaxed ZnO and MgO particles strongly retarded the release of volatile species at temperatures above 300 degrees C.

Herein, we report a novel class of latex particles composed of a hemicellulose, xyloglucan (XG), and poly(methyl methacrylate) (PMMA), specially designed to enable a biomimetic modification of cellulose. The formation of the latex particles was achieved utilizing reversible addition-fragmentation chain transfer (RAFT) mediated surfactant-free emulsion polymerization employing XG as a hydrophilic macromolecular RAFT agent (macroRAFT). In an initial step, XG was functionalized at the reducing chain end to bear a dithioester. This XG macroRAFT was subsequently utilized in water and chain extended with methyl methacrylate (MMA) as hydrophobic monomer, inspired by a polymerization-induced self-assembly (PISA) process. This yielded latex nanoparticles with a hydrophobic PMMA core stabilized by the hydrophilic XG chains at the corona. The molar mass of PMMA targeted was varied, resulting in a series of stable latex particles with hydrophobic PMMA content between 22 and 68 wt % of the total solids content (5-10%). The XG-PMMA nanoparticles were subsequently adsorbed to a neutral cellulose substrate (filter paper), and the modified surfaces were analyzed by FT-IR and SEM analyses. The adsorption of the latex particles was also investigated by quartz crystal microbalance with dissipation monitoring (QCM-D), where the nanoparticles were adsorbed to negatively charged model cellulose surfaces. The surfaces were analyzed by atomic force microscopy (AFM) and contact angle (CA) measurements. QCM-D experiments showed that more mass was adsorbed to the surfaces with increasing molar mass of the PMMA present. AFM of the surfaces after adsorption showed discrete particles, which were no longer present after annealing (160 °C, 1 h) and the roughness (Rq) of the surfaces had also decreased by at least half. Interestingly, after annealing, the surfaces did not all become more hydrophobic, as monitored by CA measurements, indicating that the surface roughness was an important factor to consider when evaluating the surface properties following particle adsorption. This novel class of latex nanoparticles provides an excellent platform for cellulose modification via physical adsorption. The utilization of XG as the anchoring molecule to cellulose provides a versatile methodology, as it does not rely on electrostatic interactions for the physical adsorption, enabling a wide range of cellulose substrates to be modified, including neutral sources such as cotton and bacterial nanocellulose, leading to new and advanced materials.

The photoinduced controlled radical polymerisation (CRP) technique has been utilised to graft methyl acrylate (MA) and di(ethylene glycol) ethyl ether acrylate (DEGA) from filter paper. Grafting of MA was performed from alpha-bromoisobutyryl bromide functionalised papers. The amount of polymer grafted on the surface could be regulated by modifying the target DP of the reaction. SEC of cleaved linear polymer grafts showed that the grafting from filter papers proceeded with different kinetics compared to polymerisation from a free initiator added to the reaction mixture, resulting in higher dispersity. Furthermore, filter papers were polymerised with a-chloro-epsilon-caprolactone by surface-initiated ring opening polymerisation, yielding linear grafts containing initiating functions through-out the main chain. This functionality was subsequently utilised for the photoinduced CRP grafting of DEGA, yielding a graft-on-graft structure, which resulted in a thermoresponsive cellulose surface.

Redox-sensitive hyperbranched dendritic-linear polymers (HBDLPs) were prepared and stabilized individually as unimolecular micelles with diameters in the range 25–40 nm. The high molecular weight (500–950 kDa), core–shell amphiphilic structures were synthesized through a combination of self-condensing vinyl copolymerization (SCVCP) and atom transfer radical polymerization (ATRP). Cleavable disulfide bonds were introduced, either in the backbone, or in pendant groups, of the hyperbranched core of the HBDLPs. By triggered reductive degradation, the HBDLPs showed up to a 7-fold decrease in molecular weight, and the extent of degradation was tuned by the amount of incorporated disulfides. The HBDLP with pendant disulfide-linked functionalities in the hyperbranched core was readily postfunctionalized with a hydrophobic dye, as a mimic for a drug. An instant release of the dye was observed as a response to a reductive environment similar to the one present intracellularly. The proposed strategy shows a facile route to highly stable unimolecular micelles, which attractively exhibit redox-responsive degradation and cargo release properties.

Histamine functionalized block copolymers based on poly(allyl glycidyl ether)-b-poly(ethylene oxide) (PAGE-b-PEO) were prepared with different ratios of histamine and octyl or benzyl groups using UV-initiated thiol-ene click chemistry. At neutral pH, the histamine units are uncharged and hydrophobic, while in acidic environments, such as in the endosome, lysosomes, or extracellular sites of tumours, the histamine groups are positively charged and hydrophilic. pH responsible polymer drug delivery systems is a promising route to site specific delivery of drugs and offers the potential to avoid side effects of systemic treatment. Our detailed in vitro experiments of the efficacy of drug delivery and the intracellular localization characteristics of this library of NPs in 2D and 3D cultures of breast cancer revealed that the 50% histamine-modified polymer loaded with DOX exhibited rapid accumulation in the nucleus of free DOX within 2 h. Confocal studies showed enhanced mitochondrial localization and lysosomal escape when compared to controls. From these combined studies, it was shown that by accurately tuning the structure of the initial block copolymers, the resulting self-assembled NPs can be designed to exploit histamine as an endosomal escape trigger and the octyl/benzyl units give rise to a hydrophobic core resulting in highly efficacious drug delivery systems (DDS) with control over intracellular localization. Optimization and rational control of the intracellular localization of both DDS and the parent drug can give nanomedicines a substantial increase in efficacy and should be explored in future studies.