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To prepare water-borne polyurethane dispersions (PUD) from novel renewable-based, asymmetric bifunctional building blocks, it is important to understand the reactivity and regio-selectivity differences between the various functional groups and reagents, respectively. This paper firstly describes the mutual reactivity and regio-selectivity of biomass-derived, asymmetric 1,4:3,6-dianhydro-D-glucitol (isosorbide, IS) and ethyl ester L-lysine diisocyanate (EELDI) in polyurethane (PU) syntheses. The regio-selectivities of the endo- and the exo-OH functional groups of IS and the primary e-NCO and the secondary a-NCO of EELDI were found to have only minor consequences for the formation of NCO-terminated PU prepolymers. In addition, a model study of IS, dimethylolpropionic acid (DMPA), EELDI and a dimer fatty acid-based diisocyanate (DDI) in their respective PU reactions revealed the reaction rate differences between these four compounds. Surprisingly, a comparatively low reaction rate of DMPA was observed. For the PU prepolymers synthesized from the four mentioned components, an enrichment in DMPA near the polymer chain ends may thus be expected. Finally, PU dispersions prepared from these four-component prepolymers showed a good storage stability. The relatively small particle size at a low DMPA content and a high EELDI and IS content is predominantly regarded as the result of the hydrophilicity of EELDI, IS and possibly the enhanced DMPA concentration near the chain ends of the PU prepolymer.

The chain extension process of renewable waterborne polyurethane dispersions (WBPUDs) prepared from a dimer fatty acid-based diisocyanate (DDI) and isosorbide (IS), using dimethylolpropionic acid (DMPA) as the internal dispersing agent, was investigated. Ethylene diamine (EDA), adipic dihydrazide (ADH) and water were evaluated as chain extenders. Other variables such as the chain extension temperature, the sequence of addition of the chain extender with respect to the dispersion step and the utilization of a catalyst (triethylamine, TEA) were investigated as well. It was found that EDA extended the NCO-functional prepolymer chains at both 30 and 50 °C, independent of the moment of its addition. A limited extent of chain extension by ADH was observed, which was thought to be caused by the low solubility of ADH in the solvent 2-butanone, used for the prepolymer synthesis. ADH chain extension only took place after removal of the 2-butanone. Water chain extension was observed at temperatures ranging from 50 °C to 70 °C. A good balance was found at 50 °C, where a stable dispersion with a relatively high molecular weight, a small particle size and a narrow particle size distribution were obtained. The usage of TEA during the dispersion process promoted the water chain extension reaction, however, at the cost of dispersion stability. An increased DMPA level has shown to improve the dispersion stability. Dispersion-cast poly(urethane urea) films were found to be thermally stable up to 249 °C (5 wt% mass loss) and had Tg values around room temperature.

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. © 2013 Elsevier B.V. All rights reserved.

In this article, we report the modification of poly(styrene-alt-maleic anhydride) (PSMA) with monofunctional amine-terminated poly(dimethyl siloxane) (PDMS-NH2) 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 (ATR-FTIR) spectroscopy. 1,2-Cyclohexyldicarboxylic anhydride was chosen as a model compound for the PSMA copolymer; this allowed a more detailed characterization by NMR and ATR-FTIR spectroscopy. After the PSMA/PDMS-NH2 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 ζ 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 4-10. The water contact angle values of the latex-coated cotton textile fabric indicated a hydrophobized surface, with a static contact angle of 135.7°Â± 1.2°. 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. © 2012 Wiley Periodicals, Inc.

We have successfully obtained surfactant-free latexes from anhydride-containing polymers, including poly(styrene-alt-maleic anhydride) (PSMA), maleinized polybutadiene (PBDMA), and poly(octadecene-alt-maleic anhydride) (POMA). Here we report barrier and adhesion properties of the coatings made from these surfactant-free latexes, which were crosslinked with adipic acid dihydrazide (ADH). The barrier property of these coatings was studied with electrochemical impedance spectroscopy in NaCl solutions on pretreated aluminum substrates. PSMA and PBDMA-based coatings demonstrated good barrier property, indicated by the absence of corrosion after 1-month immersion in NaCl solutions, which was comparable to that of a commercially available polyester coating. The polyester coating, however, was found to hydrolytically degrade when immersed in a NaCl solution, which was not observed for our latex-based coatings. The POMA-based coating showed inferior barrier property on un-pretreated aluminum, likely due to inhomogeneous film formation and poor adhesion to the substrate, but the adhesion could be improved by an alkali pretreatment of the substrate. In comparison, PBDMA and PSMA-based coatings showed much better adhesion toward the aluminum substrates. The anti-corrosion behavior appeared to be closely related to both the barrier and adhesion properties of the coatings on the metal substrate. © 2008 Elsevier B.V. All rights reserved

Due to limited fossil resources and an increased need for environmentally friendly, sustainable technologies, the importance of using renewable feedstocks in the paint and coatings area will increase in the decades to come. This paper highlights some of the perspectives in this area. Alkyd resins for high-solid paints and reactive diluents, completely based on commercially available renewable resources, were prepared and characterized. Alkyd resins based on sucrose and unsaturated fatty acids or oils showed a low intrinsic viscosity, making them suitable to be used in high-solid alkyd paints. Reactive diluents based on similar starting materials showed excellent properties with regard to thinning behavior and effect on drying characteristics. Powder coating polyester resins were synthesized, starting from isosorbide and diacids. Polyester resins with glass transition temperatures up to 70°C were obtained. Incorporation of small amounts of other diols and trifunctional components was found to improve color and coating properties. In order to create completely renewable resin systems, the development of renewable drying agents for alkyds and crosslinkers for powder coatings is in progress.