A two-step chemoenzymatic process for the preparation of polyvinylphenols from phenolic acids (PAs), being abundant aromatic constituents found in agricultural biomass, was developed. In the first step, conversion of 4-hydroxycinnamic acid derivatives to the corresponding vinylphenols, mediated by a recombinant phenolic acid decarboxylase, was evaluated using a variety of bioprocessing technologies that include biphasic whole cell and cell free extract biotransformations, a combination of biocatalyst with adsorbent resins for in situ product recovery, and fixed bed reactors using immobilized whole cells. The best yield (90%) with a high space time yield of 4.83 g/l/h was the result of a combination of crude enzyme extracts of the recombinant Escherichia coli ( E. coli ) with water immiscible organic solvents such as toluene. In the second step, cationic and radical polymerizations were tested to produce polyvinylguaiacol (PVG) from vinyl phenols. Characterization of PVG by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and nanoindentation test are reported here for the first time. The feasibility of the chemoenzymatic process for the production of aromatic poly mers from biomass was demonstrated by the production of polymers from a mixture of ferulic acid (FA) and p -coumaric acid ( p CA), obtained from alkaline hydrolysis of corn bran. Interestingly, nanoindentation tests showed that both PVG and " mixed " PVG polymers showed significantly higher performances than a commercial polystyrene polymer.

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Polypropylene (PP) clay nanocomposites were injection‐molded using two different coupling agents based on maleic anhydride‐grafted PP (MA‐g‐PP) and two clay loadings. The morphological aspects of these materials were studied by depth profiling. Molecular chain and clay orientations were characterized using attenuated total reflectance‐infrared analysis and transmission electron microscopy (TEM). Both clay platelets and PP molecular chain orientations were found to decrease from the surface toward the core of the injection–molded specimens. Clay intercalation, characterized by both complementary X‐ray diffraction and TEM, was found to be significantly influenced by both the characteristics of the coupling agent used and the type of residual stresses generated at each layer across the thickness of the injection‐molded parts. The use of low‐molecular weight (Mw) MA‐g‐PP led to a uniform intercalation but with no further exfoliation. The use of higher molecular weight MA‐g‐PP led to a heterogeneous intercalation with some signs of exfoliation. The crystallization behavior of PP clay nanocomposites studied by differential scanning calorimetry showed an increase in the level of crystallinity from the surface to the core of the specimens; these results were also confirmed by scanning electron microscopy. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers

The aim of this work is to experimentally characterize the UV‐degradation process at both the surface and at different layers across the thickness of injection‐molded polypropylene (PP) matrix containing different amounts of nanosized montmorillonite (MMT) clay particles. These nanocomposite materials have been exposed to UV irradiations (λ = 320 nm) at different preset temperatures (25, 45, and 65°C) in the presence of oxygen and during different exposure times. The extent of such process at these layers was determined using both the FTIR spectroscopy and the wide‐angle X‐ray diffraction analyses. The micromechanical properties across the thickness have been characterized using the nanoindentation technique. The obtained results have indicated that the UV‐degradation process for the nanocomposite materials is much more intense than the one observed for the neat PP. Moreover, it has been noted that such degradation process is not uniform across the thickness of the exposed materials. Results obtained from the X‐ray analysis have shown an increase of the crystallinity of the polymer molecules at only the external surface of the exposed materials. This was confirmed using the nanoindentation test as an increase of the Young's modulus at this layer was noted. POLYM. ENG. SCI., 56:469–478, 2016. © 2016 Society of Plastics Engineers

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