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Rosin polymer–grafted lignin composites were prepared via “grafting from” atom transfer radical polymerization (ATRP) with the aid of 2‐bromoisobutyryl ester‐modified lignin as macroinitiators. Three different monomers derived from dehydroabietic acid (DA) were used for execution of grafting from ATRP, while DA was separately attached onto lignin by a simple esterification reaction. Kinetic studies indicated controlled and “living” characteristics of all monomer polymerizations. Thermal studies indicated that rosin polymer–grafted lignin composites exhibited glass transition temperatures in a broad temperature range from ∼20 to 100°C. The grafting of both DA and rosin polymers significantly enhanced hydrophobicity of lignin. Static contact angle measurement of water droplets showed ∼90° for all these rosin modified lignin composites. X‐ray photoelectron spectroscopy demonstrated that the surface of rosin–lignin composites was dominated with chemical compositions originating from the hydrocarbon rich rosin moiety. The impartation of hydrophobicity of rosin into lignin provided excellent water resistance of this class of renewable polymers, as all rosin‐modified lignin composites showed water uptake below 1.0 wt %. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011

We report novel robust resin acid-derived antimicrobial agents that exhibit excellent antimicrobial activities against a broad spectrum of bacteria (6 Gram-positive and 7 Gram-negative) with selective lysis of microbial membranes over mammalian membranes. Our results indicate that hydrophobicity and unique structures of resin acids can be determining factors in dictating the antimicrobial activity.

Two series of graft copolymers, cellulose-g-poly(n-butyl acrylate-co-dehydroabietic ethyl methacrylate) (Cell-g-P(BA-co-DAEMA))and cellulose-g-poly(lauryl methacrylate-co-dehydroabietic ethyl methacrylate) (Cell-g-P(LMA-co-DAEMA)), were prepared by "grafting from" atom transfer radical polymerization (ATRP). In these novel graft copolymers, cellulose, DAEMA (derived from rosin), and LMA (derived from fatty acids) are all sourced from renewable natural resources. The "grafting from" ATRP strategy allows the preparation of high molecular weight graft copolymers consisting of a cellulose main chain with acrylate copolymer side chains. By manipulating the monomer ratios in the P(BA-co-DAEMA)and P(LMA-co-DAEMA) side chains, graft copolymers with varying glass transition temperatures (À50-60 C) were obtained. Tensile stress-strain and creep compliance testing were employed to characterize mechanical properties. These novel graft copolymers did not exhibit linear elastic properties above about 1% strain, but they did manifest remarkable elasticity at strains of 500% or more. These results suggest that these cellulose-based, acrylate side-chain polymers are potential candidates for service as thermoplastic elastomers materials in applications requiring high elasticity without rupture at high strains.

We have carried out the synthesis of side-chain rosin-ester-structured poly(ε-caprolactone) (PCL) through a combination of ring-opening polymerization and click chemistry. Rosin structures are shown to be effectively incorporated into each repeat unit of caprolactone. This simple and versatile methodology does not require sophisticated purification of raw renewable biomass from nature. The rosin properties have been successfully imparted to the PCL polymers. The bulky hydrophenanthrene group of rosin increases the glass-transition temperature of PCL by >100 °C, whereas the hydrocarbon nature of rosin structures provides PCL excellent hydrophobicity with contact angle very similar to polystyrene and very low water uptake. The rosin-containing PCL graft copolymers exhibit full degradability and good biocompatibility. This study illustrates a general strategy to prepare a new class of renewable hydrocarbon-rich degradable biopolymers.

Lignin-grafted copolymers, namely lignin-graft-poly(methyl methacrylate-co-butyl acrylate) (lignin-g-P(MMA-co-BA)), are synthesized via "grafting from" atom transfer radical polymerization (ATRP) with the aid of lignin-based macroinitiators. By manipulating the monomer feed ratios of MMA/BA, grafted copolymers with tunable glass transition temperatures (-10-40 °C) are obtained. These copolymers are evaluated as sustainable thermoplastic elastomers (TPEs). The results suggest that the mechanical properties of these TPEs lignin-g-P(MMA-co-BA) copolymers are improved significantly by comparing with those of linear P(MMA-co-BA) copolymer counterparts, and the elastic strain recovery is nearly 70%. Lignin-g-P(MMA-co-BA) copolymers exhibit high absorption in the range of the UV spectrum, which might allow for applications in UV-blocking coatings.

Well-defined polymers derived from biomass feedstock (e.g., soybean oil, rosin acid, and furfural) were successfully prepared by metal-free atom transfer radical polymerization (ATRP). In the presence of photoredox catalysts and UV irradiation, three biomass-based methacrylate monomers were efficiently polymerized with good control over molecular weight and dispersity. NMR and MALDI-TOF MS confirmed high fidelity of chain end groups originated from initiators. Furthermore, block copolymers from these monomers were also achieved through chain extension by metal-free ATRP.

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