Pinene-Based Oxidative Synthetic Toolbox for Scalable Polyester Synthesis.

Generation of renewable polymers is a long-standing goal toward reaching a more sustainable society, but building blocks in biomass can be incompatible with desired polymerization type, hampering the full implementation potential of biomaterials. Herein, we show how conceptually simple oxidative transformations can be used to unlock the inherent reactivity of terpene synthons in generating polyesters by two different mechanisms starting from the same α-pinene substrate. In the first pathway, α-pinene was oxidized into the bicyclic verbanone-based lactone and subsequently polymerized into star-shaped polymers via ring-opening polymerization, resulting in a biobased semicrystalline polyester with tunable glass transition and melting temperatures. In a second pathway, polyesters were synthesized via polycondensation, utilizing the diol 1-(1'-hydroxyethyl)-3-(2'-hydroxy-ethyl)-2,2-dimethylcyclobutane (HHDC) synthesized by oxidative cleavage of the double bond of α-pinene, together with unsaturated biobased diesters such as dimethyl maleate (DMM) and dimethyl itaconate (DMI). The resulting families of terpene-based polyesters were thereafter successfully cross-linked by either transetherification, utilizing the terminal hydroxyl groups of the synthesized verbanone-based materials, or by UV irradiation, utilizing the unsaturation provided by the DMM or DMI moieties within the HHDC-based copolymers. This work highlights the potential to apply an oxidative toolbox to valorize inert terpene metabolites enabling generation of biosourced polyesters and coatings thereof by complementary mechanisms.

A Retro-biosynthesis-Based Route to Generate Pinene-Derived Polyesters.

Significantly increased production of biobased polymers is a prerequisite to replace petroleum-based materials towards reaching a circular bioeconomy. However, many renewable building blocks from wood and other plant material are not directly amenable for polymerization, due to their inert backbones and/or lack of functional group compatibility with the desired polymerization type. Based on a retro-biosynthetic analysis of polyesters, a chemoenzymatic route from (-)-α-pinene towards a verbanone-based lactone, which is further used in ring-opening polymerization, is presented. Generated pinene-derived polyesters showed elevated degradation and glass transition temperatures, compared with poly(ϵ-decalactone), which lacks a ring structure in its backbone. Semirational enzyme engineering of the cyclohexanone monooxygenase from Acinetobacter calcoaceticus enabled the biosynthesis of the key lactone intermediate for the targeted polyester. As a proof of principle, one enzyme variant identified from screening in a microtiter plate was used in biocatalytic upscaling, which afforded the bicyclic lactone in 39 % conversion in shake flask scale reactions.

Polycaprolactone Nanocomposites Reinforced with Cellulose Nanocrystals Surface-Modified via Covalent Grafting or Physisorption: A Comparative Study.

In the present work, cellulose nanocrystals (CNCs) have been surface-modified either via covalent grafting or through physisorption of poly(n-butyl methacrylate) (PBMA) and employed as reinforcement in PCL. Covalent grafting was achieved by surface-initiated atom transfer radical polymerization (SI-ATRP). Two approaches were utilized for the physisorption: using either micelles of poly(dimethyl aminoethyl methacrylate)-block-poly(n-butyl methacrylate) (PDMAEMA-b-PBMA) or latex nanoparticles of poly(dimethyl aminoethyl methacrylate-co-methacrylic acid)-block-poly(n-butyl methacrylate) (P(DMAEMA-co-MAA)-b-PBMA). Block copolymers (PDMAEMA-b-PBMA)s were obtained by ATRP and subsequently micellized. Latex nanoparticles were produced via reversible addition-fragmentation chain-transfer (RAFT) mediated surfactant-free emulsion polymerization, employing polymer-induced self-assembly (PISA) for the particle formation. For a reliable comparison, the amounts of micelles/latex particles adsorbed and the amount of polymer grafted onto the CNCs were kept similar. Two different chain lengths of PBMA were targeted, below and above the critical molecular weight for chain entanglement of PBMA (Mn,c ∼ 56 000 g mol-1). Poly(ε-caprolactone) (PCL) nanocomposites reinforced with unmodified and modified CNCs in different weight percentages (0.5, 1, and 3 wt %) were prepared via melt extrusion. The resulting composites were evaluated by UV-vis, scanning electron microscopy (SEM), thermal gravimetric analysis (TGA), and tensile testing. All materials resulted in higher transparency, greater thermal stability, and stronger mechanical properties than unfilled PCL and nanocomposites containing unmodified CNCs. The degradation temperature of PCL reinforced with grafted CNCs was higher than that of micelle-modified CNCs, and the latter was higher than that of latex-adsorbed CNCs with a long PBMA chain length. The results clearly indicate that covalent grafting is superior to physisorption with regard to thermal and mechanical properties of the final nanocomposite. This unique study is of great value for the future design of CNC-based nanocomposites with tailored properties.

Novel Nanocomposites of Poly(lauryl methacrylate)-Grafted Al2O3 Nanoparticles in LDPE.

Aluminum oxide nanoparticles (NPs) were surface-modified by poly(lauryl methacrylate) (PLMA) using surface-initiated atom-transfer radical polymerization (SI-ATRP) of lauryl methacrylate. Nanocomposites were obtained by mixing the grafted NPs in a low-density polyethylene (LDPE) matrix in different ratios. First, the NPs were silanized with different aminosilanes, (3-aminopropyl)triethoxysilane, and 3-aminopropyl(diethoxy)methylsilane (APDMS). Subsequently, α-BiB, an initiator for SI-ATRP, was attached to the amino groups, showing higher immobilization ratios for APDMS and confirming that fewer self-condensation reactions between silanes took place. In a third step SI-ATRP of LMA at different times was performed to render PLMA-grafted NPs (NP-PLMAs), showing good control of the polymerization. Reactions were conducted for 20 to 60 min, obtaining a range of molecular weights between 23 000 and 83 000 g/mol, as confirmed by size-exclusion chromoatography of the cleaved grafts. Nanocomposites of NP-PLMAs at low loadings in LDPE were prepared by extrusion. At low loadings, 0.5 wt % of inorganic content, the second yield point, storage, and loss moduli increased significantly, suggesting an improved interphase as an effect of the PLMA grafts. These observations were also confirmed by an increase in transparency of the nanocomposite films. At higher loadings, 1 wt % of inorganics, the increasing amount of PLMA gave rise to the formation of small aggregates, which may explain the loss of mechanical properties. Finally, dielectric measurements were performed, showing a decrease in tan δ values for LDPE-NP-PLMAs, as compared to the nanocomposites containing unmodified NP, thus indicating an improved interphase between the NPs and LDPE.

Physical tuning of cellulose-polymer interactions utilizing cationic block copolymers based on PCL and quaternized PDMAEMA.

In this work, the objective was to synthesize and evaluate the properties of a compatibilizer based on poly(ε-caprolactone) aimed at tuning the surface properties of cellulose fibers used in fiber-reinforced biocomposites. The compatibilizer is an amphiphilic block copolymer consisting of two different blocks which have different functions. One block is cationic, quaternized poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) and can therefore electrostatically attach to anionic reinforcing materials such as cellulose-based fibers/fibrils under mild conditions in water. The other block consists of poly(ε-caprolactone) (PCL) which can decrease the surface energy of a cellulose surface and also has the ability to form physical entanglements with a PCL surface thereby improving the interfacial adhesion. Atom Transfer Radical Polymerization (ATRP) and Ring-Opening Polymerization (ROP) were used to synthesize three block copolymers with the same length of the cationic PDMAEMA block but with different lengths of the PCL blocks. The block copolymers form cationic micelles in water which can adsorb to anionic surfaces such as silicon oxide and cellulose-model surfaces. After heat treatment, the contact angles of water on the treated surfaces increased significantly, and contact angles close to those of pure PCL were obtained for the block copolymers with longer PCL blocks. AFM force measurements showed a clear entangling behavior between the block copolymers and a PCL surface at about 60 °C, which is important for the formation of an adhesive interface in the final biocomposites. This demonstrates that this type of amphiphilic block copolymer can be used to improve interactions in biocomposites between anionic reinforcing materials such as cellulose-based fibers/fibrils and less polar matrices such as PCL.

Toward an alternative compatibilizer for PLA/cellulose composites: grafting of xyloglucan with PLA.

Poly(L-lactic acid) (PLLA) chains were grafted on xyloglucan substrates via ring-opening polymerization of the L-lactide monomer. Different parameters such as the nature of the substrate (native or modified xyloglucan) and the substrate/monomer ratios were varied in the synthesis to achieve different lengths of the grafted chains. A range of experimental techniques including infrared spectroscopy and nuclear magnetic resonance were used to characterize the final product. Thermal analysis showed that the glass transition temperature of xyloglucan was decreased from 252 °C to 216 °C following the grafting of PLLA. The grafting of less hydrophilic chains from xyloglucan also affected the interaction with water: the PLLA-grafted xyloglucan was insoluble in water and the moisture uptake could be decreased by about 30%. Xyloglucan adsorbs strongly to cellulose; therefore such a graft copolymer may improve the compatibility between cellulose fibers and PLLA. The PLLA-grafted xyloglucan may be useful as a novel compatibilizer in fiber-reinforced PLLA composites.

Hard and flexible nanocomposite coatings using nanoclay-filled hyperbranched polymers.

The combination of hardness, scratch resistance, and flexibility is a highly desired feature in many coating applications. The aim of this study is to achieve this through the introduction of an unmodified nanoclay, montmorillonite (Na(+)MMT), in a polymer resin based on the hyperbranched polyester Boltorn H30. Smooth and transparent films were prepared from both the neat and the nanoparticle-filled hyperbranched resins. X-ray diffraction (XRD) and transmission electron microscopy (TEM) corroborated a mainly exfoliated structure in the nanocomposite films, which was also supported by results from dynamic mechanical analysis (DMA). Furthermore, DMA measurements showed a 9-16 degrees C increase in Tg and a higher storage modulus-above and below the T(g)-both indications of a more cross-linked network, for the clay-containing film. Thermogravimetric analysis (TGA) demonstrated the influence of the nanofiller on the thermal properties of the nanocomposites, where a shift upward of the decomposition temperature in oxygen atmosphere is attributed to the improved barrier properties of the nanoparticle-filled materials. Conventional coating characterization methods demonstrated an increase in the surface hardness, scratch resistance and flexibility, with the introduction of clay, and all coatings exhibited excellent chemical resistance and adhesion.

Enzymatic one-pot route to telechelic polypentadecalactone epoxide: synthesis, UV curing, and characterization.

In an enzymatic one-pot procedure immobilized lipase B from Candida antarctica was used to synthesize semicrystalline diepoxy functional macromonomers based on glycidol, pentadecalactone, and adipic acid. By changing the stoichiometry of the building blocks, macromonomers of controlled molecular weight from 1400 to 2700 g mol(-1) could be afforded. The enzyme-catalyzed reaction went to completion (conversion >or=95%) within 24 h at 60 degrees C. After removal of the enzyme, the produced macromonomers were used for photopolymerization without any purification. The macromonomers readily copolymerized cationically with a cycloaliphatic diepoxide (Cyracure UVR-6110; CA-dE) to high conversion. The cross-linked copolymers formed a durable film with a degree of crystallinity depending on the macromonomer size and amount of CA-dE used, without CA-dE the macromonomers homopolymerized only to a low degree. Combined with CA-dE conversions of 85-90% were determined by FT-Raman spectroscopy. The films became more durable once reinforced with CA-dE, increasing the cross-link density and reducing the crystallinity of the PDL segments in the films.