Linking of oligoesters hydrolysis to polyurethane coatings

The hydrolytic stability of a series of oligoesters comprised of three and four different monomers was evaluated. The hydroxyl terminal oligoesters were prepared from adipic acid (AA) and isophthalic acid (IPA), with six different diols and one triol, which included: 1,4‐butanediol, 1,5‐pentanediol, 1,6‐hexanediol, neopentyl glycol, 2‐methyl‐1,3‐propanediol, trimethylolpropane, and 2‐butene‐1,4‐diol. The hydroxyl terminated oligoesters were reacted with phenyl isocyanate to form telechelic urethane groups. Hydrolysis rate constants were obtained from plots of acid number vs. time. It was observed that ternary oligoester systems had lower hydrolysis rates than quaternary systems. In addition to investigating the hydrolytic stability of the synthesized oligoesters, polyurethane coatings were produced by reacting the hydroxyl‐terminated oligoesters with an aliphatic polyisocyanate (1,6‐hexanediisocyanate trimer). Model oliogester hydrolysis was then correlated to the weatherability of a crosslinked polyurethane film. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40198.     

Synthesis and characterization of waterborne polyurethane dispersion from glycolyzed products of waste polyethylene terephthalate used as soft and hard segment

Waste polyethylene terephthalate (PET) bottles were collected, cleaned and then depolymerized by glycolysis with neopentyl glycol (NPG) and dipropylene glycol (DPG), in the presence of N-butyl titanate catalyst. The product, named glycolyzed oligoesters, obtained through the depolymerization, were employed respectively in hard segment and soft segment in the synthesis of novel waterborne polyurethane dispersions (PUDs) via a simple and environmentally benign process. In addition, a polyurethane dispersion without glycolyzed oligoesters was synthesized as a comparison. The bulk structure of PET glycolyzed oligoesters and PUDs films were characterized by Fourier transform infrared spectroscopy (FT-IR), H-nuclear magnetic resonance (¹H NMR) and Gel permeation chromatography (GPC). The results illustrated that glycolyzed oligoesters were successfully introduced into the hard and soft segment of the polyurethanes. Furthermore, differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to investigate the thermal properties of the PET glycolyzed oligoesters and PUDs films. The results showed that the thermal resistance of waterborne polyurethanes obtained with glycolyzed oligoesters increased due to lower degrees of phase separation. X-ray diffraction indicated that all synthesized polyurethanes exhibited reduced degrees of orientation. Due to the balance between hard-/soft-segment of the waterborne polyurethane dispersions, the formulations containing glycolyzed oligoesters within the hard segment sections of the polyurethanes provided the best performance.     

Preparation and characterization of waterborne polyurethane containing PET waste/PPG as soft segment

Soft drinks poly(ethylene terephthalate) (PET) bottles were depolymerized by glycolysis using a 1 : 3 molar ratio of PET repeating unit to glycols like neopentyl glycol (NPG) and dipropylene glycol (DPG). Further, a series of waterborne polyurethanes (WPUs) was synthesized using pure polypropylene glycol (PPG), and glycolyzed oligoesters/PPG blends in different molar ratios as soft segment. Thermal property of WPU was tested by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Moreover, viscosity and particle size of WPU were also investigated. The results show that introduction of a certain amount of glycolyzed oligoester to soft segment makes the degree of hard‐soft domain microphase separation smaller, and can also improve thermal stability of WPU. Furthermore, WPUs synthesised from glycolyzed oligoesters and PPG blends possess larger particle size, better particle size distribution, relative lower and more stable viscosity. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42757.     

Synthesis and characterization of saturated and unsaturated copolyesters based on bis-1,4-(dicarboxymethoxy) benzene

Saturated copolyester were prepared by copolyesterification of bis-1,4-(dicarboxymethoxy) benzene and phthalic anhydride with diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-butane diol, 1,2-propane diol, and 1,6-hexamethylene glycol. Also, unsaturated copolyesters were prepared by copolyesterification of bis-1,4-(dicarboxymethoxy) benzene and maleic anhydride with the same glycols. All the copolyester resins obtained have been characterized and unsaturated copolyesters in the form of films were determined. IR and ¹H-NMR spectroscopy were used for both qualitative and quantitative analysis of the copolyesters resins and their hydrolyzate products, after curing with styrene. © 1992 John Wiley & Sons, Inc.     

Telechelic polyesters of ethane diol and adipic or sebacic acid by means of bismuth carboxylates as non-toxic catalysts

Dimethyladipate or dimethylsebacate were polycondensed with an excess of 1,2-ethane diol in bulk using two different temperature/time programs. Bismuth(III)n-hexanoate (BiHex₃), tin(II)2-ethylhexanoate (SnOct₂) and titanium tetrabutoxide were used as catalysts. Only the bismuth catalyst yielded clean telechelic polyesters having two ethylene glycol endgroups. With SnOct₂ cyclic oligoesters were obtained as byproducts. Ti(OBu)₄ yielded OH-terminated linear chains containing large amounts of diethylene glycol units (detectable up to three ether groups per chain). Furthermore, small amounts of cycles were also formed. Acid-catalyzed polycondensations of ethylene glycol with sebacic acid gave low yields of low oligomers, part of which contained diethylene glycol units.     

Synthesis and physical properties of H12MDI-based polyurethane resins

This paper described the synthesis of four types of polyurethanes by using diisocyanato dicyclohexylmethane (H₁₂MDI) as the hard segment and poly hexamethylene carbonate diol, polybutylene adipate diol, poly(hexamethylene diol/neopentyl glycol)-based copolyester diol, or poly hexamethylene diol/hexamethylene carbonate)-based copolyester/carbonate diol as the corresponding soft segment. The spectral analysis, thermal studies (differential scanning calorimetry and dynamic mechanical analysis), tensile strength-elongation relationship, and water vapor permeability of these samples were investigated. The results of these studies showed that the phase separation extent of the four types of polyurethanes displayed the following order: ESBA (polybutylene adipate-based polyurethane) > ECHH (co-polyester / carbonate-based polyurethane) > ESHN (copolyester diol-based polyurethane) > CAHC (polyhexamethylene carbonate-based polyurethane). The water vapor permeability of the cast films increased with the increase of the phase separation extent, in which the polyester-based polyurethane (sample ESBA) displayed the highest water vapor permeability. In terms of tensile strength-elongation property, the polycarbonate diol based polyurethane displayed higher tensile strength but lower elongation than polyester-based polyurethanes.     

Dilute gelling systems: copolymers of styrene and glycol dimethacrylates

Gelation properties of the copolymers of styrene with various proportions of ¹⁴C labelled ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and polyethylene glycol (MW = 400) dimethacrylate have been studied. The thermal copolymerizations were carried out in 15% (v/v) solution in toluene. The rates of polymerization were found to increase with larger proportions of dimethacrylate cross-linking agents. The conversion at the gel point was surprisingly constant over a wide range of crosslinker concentration. The fraction of crosslinker saturated at both ends was found to increase in the order ethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate and polyethylene glycol 400 dimethacrylate. The proportion of completely reacted crosslinker increased only slowly with conversion. At very high concentrations of crosslinker, the onset of inhomogeneity was observed as described previously by Storey³ and Dusek¹⁸.     

Moisture-cured polyurethane based on polyester and polycarbonate polyols

Moisture-cured polyurethanes were prepared by reacting toluene diisocyanate and sebacic acid-based hydroxy esters such as ethylene glycol sebacate, propylene glycol sebacate, diethylene glycol sebacate, and polyester polyols such as poly(ethylene glycol sebacate), poly(propylene glycol sebacate), poly(diethylene glycol sebacate), and poly(butane diol sebacate). The effect of molecular weight of the esters on film properties and the catalytic effect of 3–5% triethylamine, triethanolamine, and 2-diethylaminoethanol on curing of such films were investigated. Polyurethanes were also prepared using a blend of poly(butane diol carbonate) polyol with polyester polyols. Best polyurethane compositions were obtained when sebacic acid-based polyester polyols were blended with poly(butane diol carbonate) polyol in the ratio of 3:2. These polyurethanes show good tensile strength (120–215 kg/cm²) and elongation (340–460%) properties, having high melting points (247–268°C) and good resistance to solvents and chemicals. Moreover, they are colorless and transparent.     

Synthesis and study of properties of new oligoesters based on soybean oil as potential poly(vinyl chloride) plasticizers

New compounds as potential poly(vinyl chloride) plasticizers based on soybean oil and oligoesters of adipic acid and different glycols by one-pot transesterification are synthesized. In the first step of the plasticizer synthesis oligoesters of adipic acid and diethylene glycol, triethylene glycol, or dipropylene glycol are synthesized, and then in situ in the second step, a defined amount of soybean oil is introduced. By degradation of soybean oil with oligoesters, and transesterification reaction, different compounds are obtained. Their physicochemical properties are determined by NMR, SEC, DSC, TGA, and volatility analyses. The properties of synthesized plasticizers are compared with commercial products: monomeric (DEHP) and aliphatic oligoster of adipic acid and 1,3-butanediol (H-1).     

Photopolymerization of hydroxypropyl acrylate and tetraethylene glycol dimethacrylate initiated by uranyl ion

Uranyl nitrate, acetate, sulfate, and dibutyl phosphate were used in solution for the photoinitiation of homopolymerization and copolymerization of hydroxypropyl acrylate and tetraethylene glycol dimethacrylate. Solvents used included water, water-ethylene glycol mixtures, and dimethylformamide. Polymer yields in excess of 90% can readily be obtained by exposing solutions containing 0.014M UO₂²⁺ to light from a tungsten bulb for 1 hr. The rigidity of the polymers varied directly, the affinity for water in-versely, with the concentration of tetraethylene glycol dimethacrylate in the monomer mixture. Poly(hydroxypropy1 acrylate) contained 52% water and poly(tetraethy1ene glycol dimethacrylate) 34% water, a t equilibrium.     

Biodegradable polymers based on renewable resources VIII. Environmental and enzymatic degradability of copolycarbonates containing 1,4 : 3,6‐dianhydrohexitols

Environmental and enzymatic degradations were investigated on a series of copolycarbonates consisting of equimolar amounts of 1,4 : 3,6‐dianhydrohexitols (1,4 : 3,6‐dianhydro‐D ‐glucitol (1a) and 1,4 : 3,6‐dianhydro‐D ‐mannitol (1b)) and alkylene diols (1,4‐butanediol, 1,6‐hexanediol, 1,8‐octanediol, and 1,10‐decanediol) or oligo(ethylene glycol)s (di‐, tri‐, and tetraethylene glycols). Fourteen different copolycarbonates with number average molecular weights in the range of 1.1–4.2 × 10⁴ were prepared by solution polycondensation as described in our previous article. Biodegradability of the copolycarbonates was assessed by soil burial degradation tests in composted soil at 27 °C and by enzymatic degradation tests in a phosphate buffer solution at 37 °C. In general, biodegradability of the copolycarbonates increased with increasing chain lengths of the methylene groups of alkylene diols or of the oxyethylene groups of the oligo(ethylene glycol)s. SEM observations of the film surfaces of polymers recovered from soil burial indicated that the copolycarbonates were degraded by microorganisms in soil. In enzymatic degradation, the copolycarbonates containing alkylene diol components showed high degradability with Pseudomonas sp. lipase, whereas the copolycarbonates containing oligo(ethylene glycol) components were not degraded at all. The enzymatic degradability of the copolycarbonates is discussed with reference to the geometrical structure around the carbonate linkages and the microstructure and hydrophobicity of the polymer chains. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1679–1687, 2005     

丙烯海松酸酯改性水性聚氨酯乳液及性能的研究

以松香和丙烯酸为原料,经Diels—Alder加成反应制备丙烯海松酸（RA）;RA与新戊二醇经缩聚反应制备端羟基丙烯海松酸新戊二醇酯（ANGE）。以ANGE、异佛尔酮二异氰酸酯（IPDI）、聚酯二元醇（PBA）和二羟甲基丙酸（DMPA）为主要原料,通过顸聚体法制备了固含量为33％～35％的ANGE改性水性聚氨酯乳液（WPUA）。讨论了ANGE含量（N）、R值（-NCO／—OH的物质的量比）及DMPA含量对WPUA乳液及胶膜性能的影响。试验结果表明：当N〈3／4时,可以制备稳定的WPUA乳液,且随着ANGE含量的增加,WPUA胶膜的力争陛能及耐7KI}生明显提高;当R=1．8,DMPA含量为5％时．WPUA乳液及胶膜的综合性能较好。     

Model esterification of neopentyl glycol and trimethylol propane with 1,4-tert-butyl benzoic acid

The esterification kinetics of difunctional neopentyl glycol and trifunctional trimethylol propane with monofunctional 1,4-tert-butyl benzoic acid was studied in the melt phase at 200°C in the presence of a metal catalyst. The rate of conversion was monitored via titrations and by determination of the relative concentrations of products and reactants using HPLC with a UV detector. A small but significant positive substitution effect was found for neopentyl glycol (K_DA = 1.15) and none was found for trimethylol propane. The reaction rate constant of neopentyl glycol with the acid is about 40% higher than that of trimethylol propane with the acid. A second-order overall reaction order was used to compute the rate constants.     

Effects of environmentally benign solvents in the agarose gel electrolytes on dye-sensitized solar cells

The ionic agarose gel electrolytes are prepared by using environmental benign solvents and co-solvents to improve the agarose solubility and capacities of the additives for dye-sensitized solar cells. The effects of single solvents (dimethyl sulfoxide (DMSO), propylene carbonate (PC), propylene glycol, triethylene glycol, and tetraethylene glycol) and DMSO-based co-solvents are examined on the conductivities, diffusion coefficients of triiodide, and energy conversion efficiencies. The highest conductivity, 14.2 mS cm⁻¹, and the highest diffusion coefficient of triiodide, 2.7 × 10⁻⁶ cm² s⁻¹, are achieved for the electrolyte containing the co-solvent of 80 vol.% PC and 20 vol.% DMSO. The environmental benign co-solvent such as DMSO/PC can significantly increase the conversion efficiency to 3.4% with agarose compared to pure MPII with agarose (1.4%), while retaining ∼80% of the energy conversion efficiencies of the reference cell without agarose under the illumination at AM 1.5, 100 mW cm⁻².     

Studies on the kinetics of free-radical bulk polymerization of multifunctional acrylates by dynamic differential scanning calorimetry

The course and kinetics of nonisothermal bulk polymerization of multifunctional acrylates were studied by dynamic differential scanning calorimetry (DSC). Measurements were carried out for four straight-chain monomers, diethylene glycol diacrylate (DEGDA), triethylene glycol diacrylate (TEGDA), tetraethylene glycol diacrylate (TTGDA), and poly(ethylene glycol)diacrylate (PEGDA) (mol. wt. 600), to study the effect of the backbone chain length, atmosphere, and type of initiator on the crosslinking kinetics. 4,4′-Azobis(4-cyanovaleric acid) (1.0%, w/w) was used as a free-radical initiator. From the dynamic scanning of polymerization of DEGDA at five heating rates (2–30°C/min), the average heat of polymerization (ΔH_p) was found to be 524.2 J/g. An activation energy of 108.8 kJ/mol and preexponential factor 5.34 × 10¹² s^?1 were obtained from the Arrhenius plot, In dα/dt. The rate of polymerization was found manyfold greater at 20–60% conversion than at the initial stage (2–8% conversion). Polymerization was studied under both nitrogen and air atmosphere. The results corresponded well with the theory of oxygen inhibition. Different types of initiators, e.g., 4,4′-azobis(4-cyanovaleric acid) (ABCVA), 2,2′-azobisisobutyronitrile (AIBN), and benzoyl peroxide (BPO) were used for polymerization and ABCVA was found to be the most efficient among all. © 1995 John Wiley & Sons, Inc.     

Polybutadiene/polyhedral oligomeric silsesquioxane nanohybrid: investigation of various reactants in polyesterification reaction

Nano‐sized polyhedral oligomeric silsesquioxane (POSS) diol or ethylene glycol (EG) as diol monomer was incorporated into hydroxyl‐terminated polybutadiene (HTPBD) chain in the presence of fumaryl or thionyl chloride as extenders. Using these polyesterification reactions, two fumarate‐based polyesters and two polyester sulfites were synthesized. Each couple of polyesters and polyester sulfites includes a linear (diol:EG) and a nanohybrid macromer (diol:POSS). Full structural characterization was performed using Fourier transform infrared, ¹H NMR and ¹³C NMR spectroscopies. Gel permeation chromatography was undertaken to study polyesterification mechanisms by deconvolution of the obtained traces. Finally, differential scanning calorimetry, thermogravimetric analysis and cell culture were performed to evaluate the structure–property relationship for the synthesized macromers in comparison with unreacted HTPBD. © 2016 Society of Chemical Industry     

Rheological and thermal properties of glycidyl azide polyol‐based energetic thermoplastic polyurethane elastomers

The purpose of this study was to investigate the effects of polyol on glycidyl azide polyol (GAP)‐based energetic thermoplastic polyurethane elastomers (ETPEs). Briefly, a series of GAP/polyol‐based ETPEs (GAP/polyol ETPEs) with different copolyol ratios and hard segment contents were synthesized using GAP‐diol with common polyol and 4,4‐methylenebis(phenylisocyanate)‐extended 1,5‐pentanediol as soft and hard segments, respectively, by solution polymerization in dimethylformamide. The three types of polyols used were poly(tetramethylene ether) glycol (PTMG), polycarbonate‐diol (PCL‐diol) and polycaprolactone‐diol (PCD‐diol). The synthesized GAP/polyol ETPEs were identified and characterized using Fourier transform infrared and ¹H NMR spectroscopy, differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and rheometric mechanical spectrometry. For GAP/PCL ETPEs with lower hard segment content, DSC results showed that the GAP segment failed to interact with either the PCL segment or PCL melting. In addition, the results of DMA showed that the presence of PCL segments in ETPEs improved the storage modulus below the melting temperature of the PCL block. Further, the crystalline PCL segments were attributed to reinforcing the ETPEs in a manner similar to that of the hard domain. As the hard segment content increased in the GAP/polyol ETPEs, both GAP/PTMG ETPEs and GAP/PCL ETPEs exhibited microphase separation transitions, while rheological experiments demonstrated a sudden decrease in complex viscosity in neighboring microphase separation transitions. © 2012 Society of Chemical Industry     

Fatty acid modified polyurethane dispersion for surface coatings: Effect of fatty acid content and ionic content

The higher molecular weight fatty acid modified polyurethane–urea dispersions (PUDs) were prepared with effective utilization of fatty acid and ionic emulsifier. The PUDs were prepared using oligomer of linoleic fatty acid, dimethylol propionic acid (DMPA), linear polyester diol, isophorone diisocyanate (IPDI), triethylamine (TEA) and ethylenediamine (EDA) by prepolymer mixing method. Resultant PUDs had so-called controlled branched polymer structures. To incorporate fatty acid residues in the backbone of the polyurethane two types of oligomers were used which were synthesized by esterifying linoleic acid and phthalic anhydride (PA) with different monomers having different hydroxyl functionality i.e. trimethylol propane (TMP), pentaerythritol and neopentyl glycol (NPG). The oligomers were mixed with linear polyester diol in different proportions and used as polyol part in prepolymer for PUDs. Various compositional variations such as type of oligomer, content of oligomer and ionic emulsifier were studied for stability and compatibility with water. The PUDs were also examined by FTIR, AFM, GPC, particle size analyzer, viscometer, TGA, DMA and tensile tester to analyze structures and properties. Chemical, water and corrosion resistances of the dried films were also evaluated to study the effect of oligomer content in modified PUDs. These properties are found to be significantly affected by the content and type of oligomer as well as ionic content in the polymer.     

UV curable,liquid diacrylate monomers based on (<Emphasis Type="Italic">cis,trans</Emphasis>)-1,3/1,4-cyclohexanedimethanol

Novel, liquid cycloaliphatic diacrylate monomers based on (cis,trans)-1,3/1,4-cyclohexanedimethanol have been synthesized for use in ultraviolet (UV)- and electron beam (EB)-cured coatings, inks, and adhesives. Diacrylate monomers prepared from this unique diol, and containing less than 15 wt% trans-1,4-cyclohexanedimethanol diacrylate, are liquid at room temperature and readily soluble in other acrylate monomers and oligomers (in contrast to diacrylates prepared from 1,4-cyclohexanedimethanol, which are solid). More importantly, UV-cured coatings based on (cis,trans)-1,3/1,4-cyclohexanedimethanol diacrylates (1,3/1,4-CHDMDA) show superior hardness, scratch resistance, and chemical resistance as compared to common diacrylate monomers used in the UV coating industry such as tripropylene glycol diacrylate, hexanediol diacrylate, dipropylene glycol diacrylate, and propoxylated neopentyl glycol diacrylate. Thus, this new monomer appears to be a promising material for enhancing the performance of radiation-cured coatings, inks, and adhesives applied to a variety of substrates, including plastic, paper, wood, metal, and glass. This paper will summarize the synthesis of liquid diacrylates from (cis,trans)-1,3/1,4-cyclohexanedimethanol, as well as the performance properties of the corresponding UV-cured coatings.     

Phenyl carbamate end-capped oligoesters: a model for hydrolytic stability of ester-based urethanes

A series of hydroxyl-terminated oligoesters were synthesized to determine the structural effects on the relative rates of hydrolysis in both acidic and alkaline media. Model compounds consisting of one diol and one dibasic acid were used because the simplicity of the chemical structure allowed for the analysis of individual effects. Linear, cycloaliphatic, and aromatic dibasic acids were used. The diacids were reacted with a series of linear and bulky diols. All hydroxyl-terminated oligoesters were end-capped with phenyl isocyanate. Three different stages were distinguished in the case of aliphatic oligoesters, while more bulky structures (cycloaliphatic and aromatics) only presented one or two stages. Hydrolysis rates showed a complex behavior where steric and anchimeric effects play a mutual role on initial hydrolysis rates.