Sustainable Aromatic Aliphatic Polyesters and Polyurethanes Prepared from Vanillin-Derived Diols via Green Catalysis.

The design and preparation of polymers by using biobased chemicals is regarded as an important strategy towards a sustainable polymer chemistry. Herein, two aromatic diols, 4-(hydroxymethyl)-2-methoxyphenol and 2-(4-(hydroxymethyl)-2-methoxyphenoxy)ethanol, have been prepared in good yields through the direct reduction of vanillin and hydroxyethylated vanillin (4-(2-hydroxyethoxy)-3-methoxybenzaldehyde) using NaBH4, respectively. The diols were submitted to traditional polycondensation and polyaddition with acyl chlorides and diisocyanatos, and serials of new polyesters and polyurethanes were prepared in high yields with moderate molecular weight ranging from 17,000 to 40,000 g mol-1. Their structures were characterized by 1H NMR, 13C NMR and FTIR, and their thermal properties were studied by TGA and differential scanning calorimetry (DSC), indicating that the as-prepared polyesters and polyurethanes have Tg in the range of 16.2 to 81.2 °C and 11.6 to 80.4 °C, respectively.

Rapid Ring-Opening Metathesis Polymerization of Monomers Obtained from Biomass-Derived Furfuryl Amines and Maleic Anhydride.

Well-controlled and extremely rapid ring-opening metathesis polymerization of unusual oxanorbornene lactam esters by Grubbs third-generation catalyst is used to prepare a range of bio-based homo- and copolymers. Bio-derived oxanorbornene lactam monomers were prepared at room temperature from maleic anhydride and secondary furfuryl amines by using a 100 % atom economical, tandem Diels-Alder lactamization reaction, followed by esterification. Several of the resulting homo- and copolymers show good control over polymer molecular weight and have narrow molecular weight distributions.

Resin Swelling in Mixed Solvents Analysed using Hansen Solubility Parameter Space.

The swelling of resins (Merrifield and HypoGel 200) in mixtures of two solvents was generally found not to vary linearly with the relative amount of each solvent in the mixture. Hansen solubility parameter (HSP) space could be used to define high, medium and low swelling regions for each resin. The variation of resin swelling with binary solvent composition could then be explained based on the HSP parameters of the two solvents and the way in which the line connecting the points corresponding to the two pure solvents bisected the swelling region for the resin. The applicability of the methodology was demonstrated by showing that an appropriate mixture of two green solvents was more effective for solid-phase peptide synthesis on Merrifield resin than use of either individual solvent and could completely replace the use of traditional polar aprotic and chlorinated solvents for this application. It was also shown that the high resin swelling area of Merrifield resin can be used to predict mixtures of green solvents that will dissolve linear, unfunctionalised polystyrene.

Vanillin derived a carbonate dialdehyde and a carbonate diol: novel platform monomers for sustainable polymers synthesis.

Vanillin has been regarded as one of the important biomass-based platform chemicals for aromatic polymers synthesis. Herein, novel symmetric bis(4-formyl-2-methoxyphenyl)carbonate (BFMC) and bis(4-(hydroxymethyl)-2-methoxyphenyl)carbonate (BHMC) polymeric monomers have been synthesized in high yields using vanillin as a raw chemical, which have been submitted for polymer synthesis via well-established polymeric strategies. A new class of poly(carbonate ester)s oligomers with amide moieties in their side chain can be prepared by using the BFMC as one of monomers via the Passerini three compound reaction (3CR). A new class of poly(carbonate ester)s oligomers and poly(carbonate urethane)s can be prepared via reactions between BHMC with dicarboxylic acid chlorides and diisocyanates, respectively. Their structure have been confirmed by 1H NMR, 13C NMR and FTIR, and the gel permeation chromatograph (GPC) analysis shows that the Mn of poly(carbonate ester)s oligomers ranges from 3100 to 7900 with PDI between 1.31 and 1.65, and the Mn of poly(carbonate urethane)s ranges from 16 400 to 24 400 with PDI ranging from 1.36 to 2.17. The DSC analysis shows that the poly(carbonate ester)s oligomers have relative low T g ranging from 37.4 to 74.1 °C, and the poly(carbonate urethane)s have T g ranging from 97.3 to 138.3 °C, mainly correlating to the structure of dicarboxylic acid chlorides and diisocyanates used.

Necessary conditions for a maximum likelihood estimate to become asymptotically unbiased and attain the Cramer-Rao lower bound. II. Range and depth localization of a sound source in an ocean waveguide.

Analytic expressions for the first order bias and second order covariance of a maximum-likelihood estimate (MLE) are applied to the problem of localizing an acoustic source in range and depth in a shallow water waveguide with a vertical hydrophone array. These expressions are then used to determine necessary conditions on sample size, or equivalently signal-to-noise ratio (SNR), for the localization MLE to become asymptotically unbiased and attain minimum variance as expressed by the Cramer-Rao lower bound (CRLB). These analytic expressions can be applied in a similar fashion to any ocean-acoustic inverse problem involving random data. Both deterministic and completely randomized signals embedded in independent and additive waveguide noise are investigated. As the energy ratio of received signal to additive noise (SANR) descends to the lower operational range of a typical passive localization system, source range and depth estimates exhibit significant biases and have variances that can exceed the CRLB by orders of magnitude. The spatial structure of the bias suggests that acoustic range and depth estimates tend to converge around particular range and depth cells for moderate SANR values.