The effects of the structure and molecular weight of the macrodiol on the properties polyurethane anionic adhesives

Polyurethane anionic adhesives were synthesized as waterborne polyurethane dispersions (PUDs) by modified dispersing procedure, using isophorone diisocyanate, dimethylol propionic acid, ethylenediamine as a chain extender and a range of soft segments with various macrodiols proportions. The soft segment was formed by replacing poly(propylene glycol) (PPG) as polyether polyol with polycarbonate diol (PCD), as polyester polyol. The effect of the macrodiols proportions of soft segment on the thermal properties of polyurethane films was measured by thermogravimetry analyses (TGA) and differential scanning calorimetry (DSC) methods. The infrared spectroscopy (FTIR) was used for evaluating the degree of phase separation. The results showed that phase separation between hard and soft segments of poly(ester-urethane) is more significant than of poly(ether-urethane). The phase separation degree of polyurethane dispersion significantly affected the glass transition temperature (T-g) and film properties. While the phase separation degree increased, T-g proportionally decreased, but the hardness and gloss of the dried films increased, as expected. However, thermal stability was influenced by the molecular weight of used polyols and chemical structure of the polyols, and it was described by the effect of oxygen content, and interaction between the soft and hard segment, and the soft segment composition. The soft segment can be achieved with a proper selection, in order to fine-tune the performance of waterborne polyurethane dispersion, considering certain practical application. (C) 2012 Elsevier Ltd. All rights reserved

Synthesis and properties of novel star-shaped polyesters based on l-lactide and castor oil

The topology of biodegradable polyesters can be adjusted by incorporating multifunctional polyols into the polyester backbone to obtain branched polymers. The aim of this study was to prepare the biodegradable-branched polyester polyols based on l-lactide and castor oil using the trifluoromethanesulfonic acid as a catalyst. FTIR and H-1 NMR spectroscopy measurements were used to estimate the molecular structure of the novel materials. The polyester polyol was synthesized by core-first method which involves a polymerization of l-lactide by using a castor oil as multifunctional initiator. Molar masses estimated by gel permeation chromatography and vapor pressure osmometry were in good correlation with calculated values based on hydroxyl number of obtained polymers. DSC measurements confirmed high crystallinity degree of the synthesized material. It was assessed that the molar masses of obtained polymers-influenced glass transition temperature significantly. The thermal stability was investigated by TG analysis, and the results have shown the dependence of weight loss on the arm length of the star-shaped polyesters. The thermal stability of star-shaped polyesters significantly decreased with degradation of polyester polyol obtained in acid solution

The waterborne polyurethane dispersions based on polycarbonate diol: Effect of ionic content

Three water-based polyurethane dispersions (PUD) were synthesized by modified dispersing procedure using polycarbonate diol (PCD), isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), triethylamine (TEA) and ethylenediamine (EDA). The ionic group content in the polyurethane-ionomer structure was varied by changing the amount of the internal emulsifier, DMPA (4.5, 7.5 and 10 wt.% to the prepolymer weight). The expected structures of obtained materials were confirmed by FTIR spectroscopy. The effect of the DMPA content on the thermal properties of polyurethane films was measured by TGA, DTA, DSC and DMTA methods. Increased DMPA amounts result in the higher hard segment contents and in the increase of the weight loss corresponding to the degradation of the hard segments. The reduction of hard segment content led to the elevated temperature of decomposition and to the decrease of the glass transition temperature and thermoplasticity. The atomic force microscopy (AFM), results indicated that phase separation between hard and soft segment of PUD with higher DMPA content is more significant than of PUD with lower DMPA content. The physico-mechanical properties, such as hardness, adhesion test and gloss of the dried films were also determined considering the effect of DMPA content on coating properties. (C) 2012 Elsevier B.V. All rights reserved

Preparation and characterization of waterborne polyurethane/silica hybrid dispersions from castor oil polyols obtained by glycolysis poly (ethylene terephthalate) waste

Castor oil polyols (COLs) have been synthesized from glycolyzed oligoester polyol in order to produce waterborne polyurethane (WPU)/silica hybrid dispersions. Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of poly(ethylene glycol) ( PEG 400), in the presence of zinc acetate as catalyst. The obtained glycolyzed products were reacted with castor oil (CO) to attain castor oil polyols by the process of transesterification. Five castor oil polyols were used with hydroxyl values of 255, 275, 326, 366 and 426 mg KOH g(-1). Several castor oil-based, polyurethane/ silica hybrid dispersions having soft segment content of 39.6% to 28.2% and two concentrations of SiO2 nanoparticles (0.5 and 1.0) have been prepared. The incorporation effect of SiO2 nanoparticles into the PU matrix and the hydroxyl functionality of the COLs on the thermal and mechanical properties of resulting polyurethane films has been examined by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TG) and measurement of the mechanical properties. The degree of phase separation (DPS) between oxide nanoparticles and hard segment, and particle size in the polyurethane, depends to some extent on nanosilica content and the hydroxyl functionality of the polyols employed in the polyurethane preparation process. Thermal stability of obtained hybrid materials depends on the hydroxyl functionality of the COLs and nanosilica content. The T-10 and T-50% (the temperature where 10 and 50% weight loss occurred) of WPU films decreased with the rise of OH functionality of castor oil polyols, caused by the increase of hard segment content. Glass transition temperature increased with increasing OH functionality and SiO2 content. The hardness, adhesion and gloss quality of the polyurethane films were also determined with a view to assessing the effect of mole ratios of PET to glycol in glycolyzed products, the hydroxyl functionality and the SiO2 content. (C) 2016 Elsevier Ltd. All rights reserved

Synthesis and properties biobased waterborne polyurethanes from glycolysis product of PET waste and poly(caprolactone) diol

Novel biobased poly(ester-urethane)s (PUDs) were synthesized by solvent free homogeneous solution polymerization of poly(caprolactone) diol (PCL), castor oil-based polyols (COLs), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI) and 1,4-butane diol (BD) as the chain extender. The polyurethane dispersions were prepared by adding required amount of triethylamine (TEA) and water. In this Work, castor oil-based polyols have been synthesized using the depolymerized oligoester obtained from glycolysis of PET waste with poly(ethylene glycol) (PEG 400) and castor oil. The effects of the soft segments content on the thermal and coatings properties of resulting polyurethane films have been examined by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and measurement of the coatings properties. Phase separation of polyurethane shows a strong correlation with crystallization behaviour of the polyurethane prepared. It is established that all PUD samples containing PCL as a part soft segment with different molar ratio of castor-oil polyol are crystallisable polymers. The results from XRD analysis have showed that highest degree of crystallinity (23 and 22%) is reached in polyurethanes based on the largest content PCL diol (CPU77 and CPU73). The thermal stability of samples based on (COL/PCL molar ratio 0.25:0.75) possesses the best thermal properties but less values hardness coatings which can be ascribed to a decrease of the hard segment i.e. DMPA content in polyurethane dispersions. The long-term stability of polyurethane dispersions has been investigated using UV vis spectroscopy. The physico-mechanical properties such as hardness adhesion test and gloss of the dried films have also been determined considering the effect of soft segment content on coating properties. (C) 2016 Elsevier B.V. All rights reserved

Glycolyzed poly(ethylene terephthalate) waste and castor oil-based polyols for waterborne polyurethane adhesives containing hexamethoxymethyl melamine

Glycolysis of poly(ethylene terephthalate) (PET) waste using different molar ratio of poly(ethylene glycol) (PEG400), was used to produce saturated hydroxyl-functional polyester polyols with castor oil (CO) by transesterification process. The waterborne polyurethane (WBPU) adhesives were synthesized from these saturated polyester polyols, isophorone diisocyanate (IPDI), dimethylolpropionic acid (DMPA), and hexamethoxymethyl melamine (HMMM) as cross-linking agent by a conventional prepolymer process. The glycolyzed polyols and polyester polyos formations were characterized using Fourier transform infrared spectroscopy (FTIR) and the molecular weights were determined using gel permeation chromatography (GPC). The cross-linking reaction between WBPU and HMMM was verified using FfIR and H-1 NMR analysis. Thermal properties were investigated by thermogravimetric analysis (TG). Thermal stability of cross-linked WBPU significantly increased with decreasing castor oil content in the process of transesterification to obtain polyester polyol as a soft segment. The T-15% and T-50% (the temperature where 15 and 50% weight loss occurred) of WBPU increased with the decreasing of castor oil content in the obtained polyester polyols, caused by the steric hindrance of polyester polyol with higher castor oil content, in the process of cross-linking reactions with HMMM. The physico-mechanical properties of WBPU, such as hardness, adhesion test, and gloss of the dried films were also determined considering the effect of participation of HMMM in cross-linking reactions with polyurethane, on coating properties. (C) 2014 Elsevier B.V. All rights reserved

Glycolyzed products from PET waste and their application in synthesis of polyurethane dispersions

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis with different molar ratio of glycol, such as propylene glycol (PG), triethylene glycol (TEG) and poly(ethylene glycol) (PEG 400), in the presence of a zinc acetate catalyst. These glycolyzed products were characterized by hydroxyl value (HV) determinations. The obtained glycolyzed products were reacted with isophorone diisocyanate (IPDI), dimethylol propionic acid (DMPA), as potential ionic center for water dispersibility, and mixed with ethylene diamine (EDA) as extender chain to prepare polyurethane dispersions. The PET glycolyzed products and polyurethane formation were characterized using Fourier transform infrared spectroscopy (FTIR). The molecular masses distribution of oligoester polyol and polyurethane dispersions were determined by using gel permeation chromatography (G PC). The effect of different PET/glycol molar ratio, on the physico-mechanical properties, such as hardness, adhesion test and gloss of polyurethane films were investigated. Thermal properties were investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). It was observed that initial degradation temperatures were at about 200 degrees C, with two-or three degradation steps. The influence of different molar ratio PET/glycol on DTG curves showed stages that were not noticeable in the appropriate weight loss curves. Polyurethane dispersions which lower molar ratio of PET/glycol in glycolyzed products showed lower thermal stability due to the presence of a greater amount of aromaticity in polyester backbone led to materials with higher film hardness. The values for the film adherence and gloss were confirmed their excellent properties for potential application for coatings in civil engineering, metal or polymer industry. (C) 2011 Elsevier B.V. All rights reserved

Structural Differences Between Lignin Model Polymers Synthesized from Various Monomers

In a plant cell wall, lignin is synthesized from several monomeric precursors, combined in various ratios. The variation in monomer type and quantity enables multifunctional role of lignin in plants. Thus, it is important to know how different combinations of lignin monomers impact variability of bond types and local structural changes in the polymer. Lignin model polymers are a good model system for studies of relation between variations of the starting monomers and structural variations within the polymer. We synthesized lignin model polymers from three monomers, CF-based on coniferyl alcohol and ferulic acid in monomer proportions 5:1 and 10:1 (w/w), CP-based on coniferyl alcohol and -coumaric acid in proportion 10:1 (w/w) and CA-based on pure coniferyl alcohol. We studied structural modifications in the obtained polymers, by combining fluorescence microscopy and spectroscopy, FT-IR and Raman spectroscopy, in parallel with determination of polymers' molecular mass distribution. The differences in the low (w) region of the distribution curves of the 10:1 polymers in comparison with the CA polymer may be connected with the increased content of C=C bonds and decreased content of condensed structures, as observed in FT-IR spectra and indicated by the analysis of fluorescence spectra. The 5:1 CF polymer contains a different type of structure in comparison with the 10:1 CF polymers, reflected in its simpler (w) distribution, higher homogeneity of the fluorescence emitting structures and in the appearance of a new high-wavelength emission component. We propose that this component may originate from -conjugated chains, which are longer in this polymer. The results are a contribution to the understanding of the involvement of structural variations of lignin polymers in the cell wall structural plasticity