High Oxygen Barrier Polyester from 3,3'-Bifuran-5,5'-dicarboxylic Acid.

An exceptional oxygen barrier polyester prepared from a new biomass-derived monomer, 3,3'-bifuran-5,5'-dicarboxylic acid, is reported. When exposed to air, the furan-based polyester cross-links and gains O2 permeability 2 orders of magnitude lower than initially, resulting in performance comparable to the best polymers in this class, such as ethylene-vinyl alcohol copolymers. The cross-links hinder the crystallization of amorphous samples, also rendering them insoluble. The process was observable via UV-vis measurements, which showed a gradual increase of absorbance between wavelengths of 320 and 520 nm in free-standing films. The structural trigger bringing about these changes appears subtle: the polyester containing 5,5'-disubstituted 3,3'-bifuran moieties cross-linked, whereas the polyester with 5,5'-disubstituted 2,2'-bifuran moieties was inert. The 3,3'-bifuran-based polyester is effectively a semicrystalline thermoplastic, which is slowly converted into a cross-linked material with intriguing material properties once sufficiently exposed to ambient air.

Renewable Furfural-Based Polyesters Bearing Sulfur-Bridged Difuran Moieties with High Oxygen Barrier Properties.

With the goal of achieving high barrier with bio-based materials, for example, for packaging applications, a series of novel furfural-based polyesters bearing sulfide-bridged difuran dicarboxylic acid units with high oxygen barrier properties were synthesized and characterized. For the novel poly(alkylene sulfanediyldifuranoate)s, a 11.2-1.9× higher barrier improvement factor compared to amorphous poly(ethylene terephthalate) was observed which places the novel polyesters in the top class among previously reported 2,5-furandicarboxylic acid (FDCA) and 2,2'-bifuran-based polyesters. Titanium-catalyzed polycondensation reactions between the novel synthesized monomer, dimethyl 5,5'-sulfanediyldi(furan-2-carboxylate), and four different diols, ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,5-pentanediol, afforded difuran polyesters with high intrinsic viscosities (0.76-0.90 dL/g). These polyesters had good thermal stability, decomposing at 342-363 and 328-570 °C under nitrogen and air, respectively, which allowed processing them into free-standing films via melt-pressing. In tensile testing of the film specimens, tensile moduli in the range of 0.4-2.6 GPa were recorded, with higher values observed for the polyesters with shorter diol units. Interestingly, besides the low oxygen permeability, the renewable sulfide-bridged furan monomer also endowed the polyesters with slight UV shielding effect, with cutoff wavelengths of ca. 350 nm, in contrast to FDCA-based polyesters, which lack significant UV light absorption at over 300 nm.

Online betting intensity is linked with Extraversion and Conscientiousness.

INTRODUCTION: Extraversion and Conscientiousness are well-studied personality traits associated with reward processing and goal prioritization, respectively, and bear on individual differences in financial risk-taking. Using unique large datasets, we investigated the link between these traits and male online gamblers' actual betting participation and intensity. METHOD: We combined datasets containing online horse betting data (during 2015-2016) from the Finnish monopoly betting company, administrative registry data from Statistics Finland, and personality trait measures from the Finnish Defence Forces corresponding to Extraversion and Conscientiousness as defined in the five-factor model. We modelled associations between these traits and betting participation (n = 471,968) and intensity (n = 11,217) among male horse bettors (age = 36-53). RESULTS: Controlling for demographics and IQ, individuals scoring high on Conscientiousness (or Extraversion) were less (or more) likely to bet and less (or more) intensive bettors-even when personality was measured 16-34 years before betting occurred. One SD personality score increase represented an annual decrease (Conscientiousness) or increase (Extraversion) of €570-754 in spending. CONCLUSIONS: Extraversion and Conscientiousness are implicated in real-life financial behavior with tangible consequences for individuals. These effects are stronger than for many known demographic variables used in gambling studies and persist up to 34 years after personality has been measured.

Does Losing on a Previous Betting Day Predict How Long it Takes to Return to the Next Session of Online Horse Race Betting?

This study examined how recent losses predict the frequency of play in online betting. Previous studies have suggested that players tend to decrease betting volume and consequently take on less risk after a losing session. We used a daily panel of actual gambling data and survival regression to investigate how incurring losses predicts the duration to the next betting day. Our main findings were that, after a losing betting day, a bettor typically abstained from betting for a 27% longer time than after a day he or she broke even. Further, we found that either untypically high wins or loses significantly predicted the amount of time to the next gambling event. This study adds to the gambling literature by presenting evidence on a reduction in betting activity following a losing session.

Utilizing Furfural-Based Bifuran Diester as Monomer and Comonomer for High-Performance Bioplastics: Properties of Poly(butylene furanoate), Poly(butylene bifuranoate), and Their Copolyesters.

Two homopolyesters and a series of novel random copolyesters were synthesized from two bio-based diacid esters, dimethyl 2,5-furandicarboxylate, a well-known renewable monomer, and dimethyl 2,2'-bifuran-5,5'-dicarboxylate, a more uncommon diacid based on biochemical furfural. Compared to homopolyesters poly(butylene furanoate) (PBF) and poly(butylene bifuranoate) (PBBf), their random copolyesters differed dramatically in that their melting temperatures were either lowered significantly or they showed no crystallinity at all. However, the thermal stabilities of the homopolyesters and the copolyesters were comparable. Based on tensile tests from amorphous film specimens, it was concluded that the elastic moduli, tensile strengths, and elongation at break values for all copolyesters were similar as well, irrespective of the furan:bifuran molar ratio. Tensile moduli of approximately 2 GPa and tensile strengths up to 66 MPa were observed for amorphous film specimens prepared from the copolyesters. However, copolymerizing bifuran units into PBF allowed the glass transition temperature to be increased by increasing the amount of bifuran units. Besides enhancing the glass transition temperatures, the bifuran units also conferred the copolyesters with significant UV absorbance. This combined with the highly amorphous nature of the copolyesters allowed them to be melt-pressed into highly transparent films with very low ultraviolet light transmission. It was also found that furan-bifuran copolyesters could be as effective, or better, oxygen barrier materials as neat PBF or PBBf, which themselves were found superior to common barrier polyesters such as PET.

UV-Blocking Synthetic Biopolymer from Biomass-Based Bifuran Diester and Ethylene Glycol.

A furan-based synthetic biopolymer composed of a bifuran monomer and ethylene glycol was synthesized through melt polycondensation, and the resulting polyester was found to have promising thermal and mechanical properties. The bifuran monomer, dimethyl 2,2'-bifuran-5,5'-dicarboxylate, was prepared using a palladium-catalyzed, phosphine ligand-free direct coupling protocol. A titanium-catalyzed polycondensation procedure was found effective at polymerizing the bifuran monomer with ethylene glycol. The prepared bifuran polyester exhibited several intriguing properties including high tensile modulus. In addition, the bifuran monomer furnished the polyester with a relatively high glass transition temperature. Films prepared from the new polyester also had excellent oxygen and water barrier properties, which were found to be superior to those of poly(ethylene terephthalate). Moreover, the novel polyester also has good ultraviolet radiation blocking properties.