We present new acrylic monomers, polymers and coatings derived directly from abundant naturally available terpenes via facile, green and catalytic approaches.

Electrically conductive composites consisting of carbon nanotubes (CNTs) in a poly(2,6‐dimethyl‐1,4‐phenylene ether)/polystyrene (PPE/PS) blend are prepared by latex technology. The latter consists of 4 steps: preparation of an aqueous dispersion of CNTs, mixing with a polymer latex, solvent removal by freeze–drying and processing. In the first route, PPE/PS blend latexes are directly used to prepare nanocomposites by latex technology. The CNT/PPE/PS composites display an increased glass transition temperature compared to unfilled material and a percolation threshold as low as 0.3 wt% of CNTs. Secondly, CNT/PS masterbatches prepared by latex technology are mixed with PS/PPE blend pellets by extrusion. This approach constitutes a potential first step towards an industrially viable process.

The effect of annealing on the phase composition, molecular mobility and water absorption in linear and branched polyamide 46, poly(tetramethylene adipamide) - PA46, was studied by DSC, H-1 and H-2 solid-state NMR. A series of samples with varying amount of long-chain branches was synthesized for this study. The branches as well as a higher molecular weight of branched PA46 cause a decrease in crystallization rate as it follows from a lower crystallization temperature. 1H NMR transverse magnetization relaxation (T-2 relaxation) experiments show that, at temperatures well above T-g, the amount of low mobile chain segments (rigid fraction) in all injection-molded samples equals 60-63%. This value is close to the crystallinity of linear PA46 as measured by WAXD. Although chain branches hardly affect the amount of the rigid fraction in injection-molded samples, molecular mobility in the crystalline phase of branched PA46 is lower than that in linear PA46, suggesting a more perfect crystalline structure in branched PA46 due to slower crystallization. 12.5 h annealing at 260 degrees C causes a large increase in the amount of the rigid fraction in linear PA46, whereas WAXD crystallinity only slightly increases upon annealing. The increase in the rigid fraction is largely caused by immobilization of the amorphous phase due to chains rearrangements resulting in stronger hydrogen bonds between amide groups in the amorphous phase. The amount of the rigid fraction in annealed samples is smaller in samples with higher amount of branches, and molecular mobility in the rigid and soft fractions is larger. This suggests that chain branches hamper chain rearrangements both in the crystalline and the amorphous phases during annealing of PA46. This results in a less ordered structure in the crystalline and the amorphous phases in annealed branched PA46. The amount of absorbed water decreases upon increasing amount of branches in injection-molded samples and upon annealing. H-2 NMR experiments for PA46 saturated with D2O show that the mobility of absorbed water is strongly hindered as compared to pure water. Below ambient temperatures, mobility of water in PA46 is characterized by a very broad distribution of molecular motions. The mobility of water molecules gradually decreases upon sample cooling from ambient temperature to -40 degrees C. The majority of water molecules is immobilized below -40 degrees C. The results of the present study suggest that water uptake by PA46 is mainly determined by the strength of hydrogen bonds between amide groups in the amorphous phase, which is largely affected by the crystallization rate and annealing at elevated temperatures. (C) 2014 Elsevier Ltd. All rights reserved.

In this work we describe a possibly new generation of (powder) coating resins of the polycarbonate or poly(ester-co-carbonate) type, synthesized from epoxides like cyclohexene oxide (CHO), anhydrides like phthalic anhydride (PA) and carbon dioxide (CO2) by chain growth polymerization, catalyzed by a chromium-Salophen complex and using dimethylaminopyridine (DMAP) as a co-catalyst. The molecular structures of the polymers produced were characterized and especially MALDI-ToF-MS yielded important information on the end-groups and other functional groups which are crucial for the curing chemistry of these resins. One special type of copolycarbonate in this study carried pendent vinyl groups, introduced by copolymerization of CHO and CO2 with 4-vinylcyclohexene oxide (VCHO). This copolycarbonate was first casted from solution, after which the polymer film was successfully cured with a trithiol compound by UV- or thermally induced radical curing chemistry. These cured coatings showed a good acetone resistance (≥75 double rubs) and reversed impact toughness. A powder coating evaluation of this CHO/VCHO-based copolycarbonate showed excellent processability, high pencil hardness (6-8H), value zero in a Gitterschnitt test on aluminum, reasonable appearance in a 'PCI-smoothness test' (value 2–3) and good acetone resistance (≥75 double rubs). Most probably due to a too high Tg (85–104 °C) of the cured coating the reverse impact resistance was poor. A similar powder coating evaluation of a poly(ester-co-carbonate) based on CHO, PA and CO2 showed less promising results due to poor flow properties and foaming above 140 °C.

Two bicyclic carbohydrate-based diols, 2,3:4,5-di-O-methylene-galactitol (Galx) or 2,4:3,5-di-O-methylene-D-mannitol (Manx), were introduced into the backbone of poly(butylene terephthalate) using the solid-state modification technique (SSM). The resulting copolyesters had a unique block-like chemical microstructure that endows them with superior thermal properties when compared with their random counterparts obtained by melt copolymerization. The materials prepared by SSM displayed higher melting points, crystallization temperatures, and crystallinity due to the presence of long PBT sequences in the copolyester. The glass-transition temperatures also increased upon incorporation of the bicyclic comonomers, this effect being more pronounced for Manx units. The melting points of these block like copolyesters decreased after melting due to the occurrence of randomization, but they remained higher than those of copolyesters prepared from the melt. SSM was demonstrated to be a very suitable technique for the incorporation of rigid monomers into the amorphous phase of PBT, leading to bio-based non-random copolyesters with remarkable thermal properties.

The electrical conductivity of graphene, multi-wall carbon nanotubes, carbon black nanopowders and graphite powder is characterized using paper-like films and by means of powder compression. The large difference in surface area of these materials results in different packing density and number of contact spots, influencing the macroscopic conductivity of the compacts during powder compression. The results are compared with the percolation threshold and final conductivity of polypropylene (PP) composites, using latex technology for the incorporation of the carbon fillers in the polymer. Even though the PP composites produced in this work exhibit percolation thresholds as low as 0.3wt.%, the final conductivity for all the composites is below 1.5S/m. Reasons why the high value of ∼103S/m, which is obtained for graphene- and nanotube-based paper films or graphite compacts, is not reached for the composites are investigated.

In this work, two series of PDMS-modified poly(styrene-alt-maleic anhydride)s (PSMA) were prepared by the partial imidization of their anhydride groups with mono-functional, amine-terminated polydimethyl siloxanes (PDMS-NH2) with two different molecular weights. Subsequently, surfactant-free artificial latexes were prepared and characterized and applied onto cotton fabric. The water contact angle values of the coated cotton fabric indicate the formation of hydrophobic surfaces, with static contact angles varying from 119° to 142° depending on the PDMS loading and PDMS molecular weight. Coatings of the prepared copolymers on cotton fabric are highly durable, as shown by washing studies with a standard soap solution. The properties of these water-based surfactant-free latexes can be tuned easily by changing the composition of the polymers, i.e. mol% of imidization, ammonolysis and cross-linking.

Novel polyesters from 2,5-furandicarboxylic acid or 2,5-dimethyl-furandicarboxylate and 2,3-butanediol have been synthesized via bulk polycondensation catalyzed by titanium (IV) n-butoxide, tin (IV) ethylhexanoate, or zirconium (IV) butoxide. The polymers were analyzed by size exclusion chromatography, nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy (FTIR), matrix-assisted laser ionization-desorption time-of-flight mass spectrometry, electrospray ionization time-of-flight mass spectrometry, electrospray ionization quadruple time-of-flight mass spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Fully bio-based polyesters with number average molecular weights ranging from 2 to 7 kg/mol were obtained which can be suitable for coating applications. The analysis of their thermal properties proved that these polyesters are thermally stable up to 270-300 degrees C, whereas their glass transition temperature (T-g) values were found between 70 and 110 degrees C. Furthermore, a material was prepared with a molecular weight of 13 kg/mol, with a T-g of 113 degrees C. This high T-g would make this material possibly suitable for hot-fill applications. (C) 2012 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 890-898

In this article, we report the modification of poly(styrene-alt-maleic anhydride) (PSMA) with monofunctional amine-terminated poly(dimethyl siloxane) (PDMSNH2) by thermal imidization, followed by the preparation and characterization of a surfactant-free artificial latex thereof and application of this latex onto cotton fabric. The imidization reaction was monitored by NMR and attenuated total reflection Fourier transform infrared (ATRFTIR) spectroscopy. 1,2-Cyclohexyldicarboxylic anhydride was chosen as a model compound for the PSMA copolymer; this allowed a more detailed characterization by NMR and ATRFTIR spectroscopy. After the PSMA/PDMSNH2 imidization reached completion, a fraction of the anhydrides were ammonolyzed. In this way, a self-emulsifying latex with an average particle diameter of approximately 145 nm and a ? potential of -56 mV was obtained. It was found that the PDMS-modified PSMA latex in which 30 mol% of the initial amount of anhydride groups were previously imidized by using PDMS-NH2 and a fraction of the anhydrides were ammonolyzed with 0.3 eq. of NH3 (PSMA30) was stable in the pH range 410. The water contact angle values of the latex-coated cotton textile fabric indicated a hydrophobized surface, with a static contact angle of 135.7 degrees +/- 1.2 degrees. The washing studies with a standard soap solution of the cotton samples with or without crosslinker showed that the crosslinked PSMA30 offered a good coating durability to the cotton. This waterborne resin based on surfactant-free latices displayed promising properties for coating applications and seemed to be very suitable for the hydrophobization of polar surfaces. (c) 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012

Graphene was produced from graphite powder using the three best known water-based conversion approaches. The first two are based on chemical oxidation methods, only differing in the reduction process, either by the use of hydrazine or by thermal expansion, respectively. The third one is based on long-term ultrasonic exfoliation. Water/surfactant solutions were prepared with these three nanofillers and latex technology was applied for the preparation of conductive graphene/polystyrene composites, with well-dispersed graphene platelets. Microscopic studies showed that both reduction processes lead to agglomeration/wrinkling of the nanoplatelets, even though they yield composites with high conductivity and low percolation threshold. Although mechanical ultrasound exfoliation of graphite produces less defective multi-layer graphene, these platelets have a smaller lateral size and their composites exhibit a higher percolation threshold.

In this study, two novel, bio-based, amorphous polyester diols, namely poly(1,2-dimethylethylene adipate) (PDMEA) and poly(1,2-dimethylethylene succinate) (PDMES) are used to prepare thermoplastic poly(urethane urea)s (TPUUs). Interestingly, the TPUUs based on PDMEA show similar thermal and mechanical properties as their counterparts based on poly(1,2-propylene glycol). By decreasing the hard segment length, the flow temperature (Tfl) of the TPUUs decreases. The Tfl values of the 3U series are around 170 degrees C, which is below their degradation temperatures. The methyl groups adjacent to the ester groups in PDMEA and PDMES may hinder the hydrolysis of the polyester soft segments in the TPUUs.

Microwave irradiation was used for the amidation of a nitrile with an amine with a freshly prepared zirconium-based heterogeneous catalyst. Microwave irradiation selectively heats the catalyst which enhances its activity as compared to conventional heating. The difference between microwave heating and conventional heating disappears when Zr(OH)(4) is used instead of ZrO2, indicating a microwave-induced shift in the hydrolysis equilibrium, i.e. the distribution of ZrO2, ZrO(OH)(2) and Zr(OH)(4), of the zirconium-based catalyst. The catalyst efficiently catalyzes the amidation of valeronitrile with n-hexylamine with conventional as well as with microwave heating. Zr(OH)(4) was also used for the polymerization of 6-aminocapronitrile using conventional and microwave heating. With both heating methods a relatively low molecular weight polymer with a M-n of 4000 g/mol was obtained in a sealed vessel, due to the presence of water and ammonia. A post-polymerization step under microwave irradiation, with active removal of water and ammonia shifts M-n to 10000 g/mol. Pressure decrease to facilitate water removal resulted in products with higher molecular weights. A pressure reduction to 50 Pa and operation in an argon atmosphere at 230 degrees C resulted in nylon-6 with a M-n of 65000 in rather short reaction times. Lower pressures led to end-biting and evaporation of the volatile epsilon-caprolactam at 230 degrees C. As a consequence the resulting product has than a much lower molecular weight. The combination of a heterogeneous zirconium based catalyst and microwave heating is promising for process intensification for nylon-6 production.