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The rheological behavior of two series of aliphatic hyperbranched (HB) polyesters, based on 2,2-bis(hydroxymethyl)propionic acid (bis-MPA) and di-trimethylol propane (Di-TMP) as a tetrafunctional core, was studied. The effect of the size (pseudo-generation number, from second to eight) and structure on the melt rheological properties was investigated for a series of hydroxyl-terminated HB polyesters. In addition, the influence of the nature and degree of modification of the terminal OH groups in a series of fourth-generation polyesters end-capped with short and long alkyl chains and some aryl groups on the rheological properties was analyzed. The time–temperature superposition procedure was applied for the construction of master curves and for the analysis of the rheological properties of HB polyesters. The data obtained from WLF analysis of the HB polyesters showed that the values of the thermal coefficient of expansion of free volume αf and the fractional free volume at the glass transition temperature, fg, increase with increasing size of the HB polyesters. It was shown that the modified HB polyesters exhibited lower Tg and TG′=G″ temperatures, above which viscous became dominant over elastic behavior. From an analysis of the master curves of the modified HB polyesters, it was observed that with increasing degree of modification, both storage and loss modules and complex dynamic viscosity and apparent energy for viscoelastic relaxation decrease, because of reduced intermolecular hydrogen interactions. They do not exhibit a plateau of rubbery behavior, which confirms that no entanglements are present and that the molar masses are below the critical molar mass. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41479.

Urethane acrylate resins based on partially modified aliphatic hyperbranched polyesters (HBP) have been synthesized. HBP of the second and the third generation were synthesized from 2,2-bis(hydroxymethyl)propionic acid and di-trimethylol propane. The modification of certain amount of OH end-groups was carried out with soybean fatty acids. The urethane acrylates with different degrees of acrylation have been obtained by reaction of partially modified HBP and different amounts of NCO adduct which had been previously obtained by reaction of equimolar amounts of isophorone diisocyanate and 2-hydroxyethyl acrylate. The synthesized samples were characterized by FT-IR, 1 H and 13 C NMR and GPC. The rheological properties of uncured samples and mechanical and thermal properties of UV cured urethane acrylates diluted with 20 wt.% hexanediol diacrylate were examined. The modification of OH end-groups with soybean fatty acids causes a rapid decrease in viscosity of HBP. The examined properties of urethane acrylates depend on the degree of acrylation. After irradiating, the additional cross-linking, which is caused by reaction of double bonds from unsaturated fatty acids, has also important effect on the properties of cured samples.

Three series of hyperbranched urethane-acrylates (HB-UA), based on aliphatic hyperbranched polyesters and polyethyleneglycol acrylate, were prepared and evaluated for use in UV-curable coatings. UV-curing kinetics were monitored by FT-IR spectroscopy. The thermal and mechanical properties of UV-cured HB-UA were investigated by means of differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) and correlated to the mechanical properties of coatings (hardness and flexibility). These new HB-UA's are very reactive and did not show oxygen inhibition. Obtained coatings have good mechanical properties and solvent resistance.

The synthesis, characterization and UV-curing of hyperbranched urethaneacrylates (HB-UA) were investigated in this study. They were evaluated as oli-gomers in model UV curable coatings. HB-UAs were synthesized by reaction of an aliphatic hyperbranched polyester of the second generation (HBRG2) and an isocyanate adduct, obtained by the reaction of isophoronediisocyana-te and different hydroxy alkyl acrylates. Their thermal properties and viscosities depend on the degree of modification of HBRG2 and the type of hydroxy alkyl acrylate used. The introduction of a flexible alkoxylated spacer between the HBP core and acrylate end groups reduces steric hindrance by moving the cross linkable acrylate groups away from the HBP core and increase its reactivity. Due to the presence of abstractable H-atoms in the ?-position to the ether links, HB-UAs based on poly(ethylene oxide) monoacrylate are very reactive and do not show oxygen inhibition. The obtained coatings combine a high cross linking density with flexible segments between the cross links, which results in a good compromise between hardness and flexibility and have the potential to be used in different UV-curing applications.

The aim of this study was to investigate the influence of different components of interpenetrating polymer networks (IPNs) on their behavior in dual curing automotive applications. Dual curing is one of possible ways to obtain fast curing, scratch resistant coatings for use in OEM and car refinish applications. Dual curing systems, upon hardening, represent interpenetrating networks (IPNs) [1] . IPN's were obtained using novel acrylate-terminated hyperbranched polyester with high functionality and compared to classical 2-pack polyurethane clear coat. In our previous manuscript [1] we investigated the influence of the acrylated hyperbranched polyester (HBP(A)) content in dual curing systems. In this article we studied the influence of the reactive diluent on dual curing compositions. To this end, we have chosen IPN with 50/50 weigth ratio of polyurethane (PU) and polyacrylic (PA) component. In order to determine more clearly the role of the HBP(A) in one IPN HBP(A) was changed with hexane diol diacrylate (HDDA), keeping the same ratio with EHA. The IPNs were characterized by dynamic-mechanical analysis (DMA), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The mechanical properties of the IPNs were also investigated. The IPN with HDDA as reactive diluent, had the best performance. IPN with HBP(A) had the highest glass transition temperature Tg and the highest crosslink density, but it did not have the highest hardness.

A series of acrylate functionalized samples based on hyperbranched hydroxy-terminated polyesters with different molecular weights and different degrees of acrylation were synthesized. The obtained urethane acrylates were slightly yellow viscose liquids. Their composition was characterized by FTIR and 1H-NMR spectroscopy and their molecular weights were measured by GPC. All the synthesized samples were diluted with 25 wt.% 1,4-butanediol dimethacrylate (BDDM). The rheological properties of the uncured samples and the dynamic mechanical properties of the UV cured samples were examined. All the samples exhibit Newtonian behavior, which indicates the absence of physical entanglements in these polymers. The viscosity increases with increasing number of acrylic groups permolecule. The glass transition temperature of the UV cured samples increases with increasing the number of acrylic groups permolecule. The value of the storage modulus in the rubber-elastic plateau and the cross-link density increase with increasing number of acrylic groups permolecule. The formed networks are inhomogeneous and the residual unsaturation is the highest in the samples with the largest number of acrylic groups per molecule.