Synthesis and characterization of transparent and high impact resistance polyurethane coatings based on polyester polyols and isocyanate trimers

A series of polyester polyols were synthesized by polycondensation reaction using adipic acid (AA), 1,4-cyclohexanedicarboxylic acid (1,4-CHDA), and 1,6-hexanediol (HDO), 1,4-cyclohexanedimethanol (1,4-CHDM) and trimethylol propane (TMP), in which the molar ratio of the reactants AA/1,4-CHDA was varied. These series of polyols were reacted with isophorone diisocyanate (IPDI) and hexamethylene diisocyanate (HDI), alone or in combination, to form polyurethane (PU) coatings.     

Cycloaliphatic polyester based high solids polyurethane coatings: I. The effect of difunctional alcohols

High-solids polyesters were synthesized with two cycloaliphatic diacids, 1,4- cyclohexanedicarboxylic acid (1,4-CHDA) and 1,3-cyclohexanedicarboxylic acid (1,3-CHDA); and with five diols, 1,4-cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), hydroxypivalyl hydroxypivalate (HPHP), 2-butyl-2-ethyl-1, 3-propanediol (BEPD), and 1,6-hexanediol (HD). The viscosity of the polyesters was dependent on the structures of diols. The viscosity of polyesters is lower with the diol HD, intermediate with BEPD and HPHP, and higher with the diols CHDM and NPG. The polyesters were crosslinked with hexamethylene diisocyanate isocyanurate (HDI isocyanurate) affording polyurethane coatings. The mechanical properties, tensile properties, fracture toughness, and viscoelastic properties were investigated for the polyurethane films with five different diols. The cyclohexyl structure of the CHDM provides the polyurethane with rigidity which is manifested in high tensile modulus, hardness, and fracture toughness. In contrast, the linear diol, 1,6-hexanediol provides polyurethane with very high flexibility, but these coatings suffer with respect to low hardness and tensile modulus. Polymers and Coatings Department, Fargo, ND 58105. 3401 Grays Ferry Avenue, Philadelphia, PA 19146.     

The effect of difunctional acids on the performance properties of polyurethane coatings

Hydroxyl-terminated polyesters are the most common polyols that are crosslinked through an isocyanate group. In this study, the polyester polyol resins were synthesized by using 1,4-cyclohexanedimethanol (1,4-CHDM) with the mixture of different diacids as 1,3-cyclohexanedicarboxylicacid (1,3-CHDA), 1,4-cyclohexanedicarboxylicacid (1,4-CHDA), isophthalic acid (IPA), adipic acid (AA), and azelaic acid (AZA). The solubility and viscosity of these polyester polyol resins were determined by using suitable solvent. All the polyester polyols were crosslinked with HDI isocyanurate and IPDI trimer to form polyurethane coating films. These films were evaluated for their mechanical, thermal, and chemical resistance properties. The studies on film characteristics reveal that the cycloaliphatic diacids afforded polyurethane with greater performance properties than that of aromatic and linear aliphatic diacids.     

Fully biobased polyester polyols derived from renewable resources toward preparation of polyurethane and their application for coatings

Renewable resources such as isosorbide and dimer acid were used to prepare fully biobased polyester polyols and polyurethane (PU) coatings. The structural features of polyester polyols were studied by end-group analysis and spectroscopic methods. Then polyols were utilized in the preparation of PU coatings by reacting with diisocyanate. The prepared PU coatings were tested for both mechanical and chemical testings, which involved gloss, cross-cut adhesion, pencil hardness, anticorrosion performance by immersion and Tafel plot methods, and chemical resistance against water, solvent, and acid media. The prepared PUs were also tested for their thermal stability using a thermogravimetric analyzer and surface morphology by a scanning electron microscopy. Tested mechanical properties, chemical resistance, and thermal stability results demonstrated that the renewable sources used in the preparation of PU coatings can be good substitutes over petroleum resources. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47558.     

Effect of difunctional acids on the physicochemical,thermal, and mechanical properties of polyester polyol‐based polyurethane coatings

Polyester polyol (PP)‐based polyurethanes (PUs) consisting of two difunctional acids [1,4‐cyclohexanedicarboxylic acid (CHDA) and 1,6‐adipic acid (AA)] and also two diols [1,4‐cyclohexanedimethanol (CHDM) and 1,6‐hexanediol (HDO)] were synthesized by a two‐step procedure with a variable feed ratio of CHDA to AA but fixed ratio of CHDM and HDO. The prepared PPs and/or PUs were characterized by Fourier transform infrared spectroscopy, X‐ray diffraction spectroscopy, and atomic force microscopy. The effects of difunctional acids on the thermal, mechanical, and dynamic mechanical thermal properties of PPs or PU films were investigated by thermogravimetry analysis, differential thermogravimetry and dynamic mechanical thermal analysis. The results show that PP exhibits a lowest viscosity with the mole fraction of CHDA and AA at 3 : 7 whereas it delivers a lowest melting point with the mole fraction at 9 : 1. After PPs being cross‐linked by isocyanate trimers, the impact resistance, shear strength and glass transition temperature increase the mixed‐acid formulations with increasing the content of CHDA. In detail, the resultant PU almost simultaneously exhibits the best mechanical and thermal properties when the mole fraction of CHDA and AA is kept constant at 9 : 1, thus giving rise to a high glass transition temperature of 56.4°C and a onset decomposition temperature of 350°C, and also delivering a balanced toughness and hardness with an impact resistance of 100 J/g and storage modulus as high as 10⁹ Pa. This path for synthesis of PP‐based PU provides a design tool for high performance polymer coatings. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41246.     

车身反光贴用聚氨酯胶粘剂的研制

以结晶性聚酯多元醇、直链二醇扩链剂、异氰酸酯和纳米助剂等为主要原料,制备出一种高粘接强度、耐老化性能优良的车身反光贴用PU(聚氨酯)胶粘剂。分析了聚酯多元醇的种类及其Mr(相对分子质量)、扩链剂、异氰酸酯、纳米助剂和催化剂等对PU胶粘剂性能的影响。结果表明:当结晶性聚酯多元醇为Mr=3 000的聚己二酸-1,4-丁二醇酯、扩链剂为1,6-己二醇(HDO)、异氰酸酯为1,6-己二异氰酸酯(HDI)、催化剂为有机铋类(BiCAT 8108)且w(催化剂)=0.03%(相对于反应物总质量而言)、n(聚酯多元醇)∶n(扩链剂)=1∶0.3和w(气相白炭黑)=0.2%～0.3%(相对于反应物总质量而言)时,PU胶粘剂的综合性能相对最好。     

Biobased step-growth polymers in powder coating applications

Co- and terpolyesters based on 1,4:3,6-dianhydro-d-glucitol (isosorbide), 1,4:3,6-dianhydro-l-iditol (isoidide) and succinic acid were evaluated for their applicability in solvent-cast and powder coatings. These biobased polyesters have functionalities and T_g values in the appropriate range for such applications and were cross-linked using conventional curing agents. Introduction of poly-functional monomers such as glycerol and citric acid led to coatings with enhanced performance with respect to mechanical and chemical resistance, compared to formulations based on linear polymers. The curing behavior of these systems was investigated with DSC and rheological experiments. Formulations containing citric acid-modified polyester resins showed rapid curing, probably facilitated by anhydride formation at the chain ends. Hydroxy- as well as carboxylic acid-functional 1,4:3,6-dianhydrohexitol-based polyesters proved to be suitable materials for coating applications with respect to solvent resistance, impact resistance and hardness, with performance comparable to commercially available systems. Accelerated weathering experiments showed that functional groups such as hydroxyl groups, carboxylic acids, anhydrides and peroxides are formed during UV-exposure. The weathered coatings have reduced impact stability. On the other hand, the appearance of the coatings does not change significantly. Isosorbide-based coating systems appear to have similar weathering resistance as conventional terephthalic acid-based poly(ester urethane) coatings.     

Preparation and surface properties of silicone-modified polyester-based polyurethane coats

A series of novel silicone-modified polyesters (SPE) were prepared by substituting part of diol with low molecular weight hydroxyl-terminated poly(dimenthylsiloxane) (PDMS). Then, isophorone diisoclanate (IPDI) as hard segments and 1,4-butanediol as chain extender were added to SPE to prepare a silicone-modified polyurethane (SPU). The effects of the type of diol, diacid, and hydroxyl-terminated PDMS, and the amount of hydroxyl-terminated PDMS on the preparation and surface properties of SPU were investigated. It was found that the amount of PDMS incorporated into a polyester chain was relatively higher when 1,6-hexanediol (HDO) and 1,10-decandiol (DDO) were used as diol and the PDMS with lower molecular weight was used as organosilicone compound. Consequently, the SPU coats with HDO as diol, adipic acid (AA) as diacid, and short chain PDMS as silicone segment had the lowest surface-free energy since it had the highest and most homogeneous distribution of silicone segments at its top layer surfaces.     

Influence of cycloaliphatic compounds on the properties of polyurethane coatings

A series of polyester polyol resin was synthesized by using 1,4-cyclohexanedimethanol (1,4-CHDM) and three different diacids: 1,3-cyclohexanedicarboxylic acid (1,3-CHDA), isophthalic acid (IPA) and adipic acid (AA). The solubility and viscosity of the polyester polyols were determined by using methyl ethyl ketone (MEK). All the polyester polyols were crosslinked with hexamethylene diisocyanate (HDI) isocyanurate to form polyurethane coating films. These films were evaluated for their mechanical and chemical resistance properties. Studies on the film characteristics revealed that the polyurethane films based on cycloaliphatic diacid generally showed comparatively better performance properties than the polyurethane film based on aromatic and linear aliphatic diacids in general.     

Degradable polyurethane based on star-shaped polyester polyols (trimethylolpropane and ɛ-caprolactone) for marine antifouling

The star-shaped polyester polyols based on initiators (trimethylolpropane or pentaerythritol) and ɛ-caprolactone were prepared by polycondensation reaction. The degradable polyurethane (PU) films were prepared by mixing star-shaped polyester polyols and crosslinker agent (hexamethylene diisocyanate trimer). The hydrolytic degradation and water absorption experiments demonstrated that the PU films could erode in artificial sea water, which were controlled by varying the ratios of ɛ-caprolactone/trimethylolpropane and the arm number of star-shaped polyester polyols. The mechanical properties of PU films and coatings increased with decreasing the ratios of ɛ-caprolactone/trimethylolpropane and increasing the arm number of star-shaped polyester polyols. The surfaces of PU films and coatings kept eroding, which were revealed by scanning electron microscopy. The copper ion release rates from PU coatings reached steady state at about 31 days. The marine field tests of PU coatings demonstrated that the degradable PU coatings based on star-shaped polyester polyols were effective coatings for marine antifouling.     

纳米SiO_2改性PU的合成与性能研究

以异佛尔酮二异氰酸酯(IPDI)、聚酯二元醇(PCD、PCL)、环氧树脂(EP)和1,4-丁二醇等为主要原料,纳米SiO2为改性剂,二月桂酸二丁基锡(DBTDL)为催化剂,成功合成了纳米SiO2改性聚氨酯(PU)。结果表明:纳米SiO2的加入,提高了PU的热稳定性、致密性、耐水性、硬度及耐黄变等性能;当w(纳米SiO2)=1.5%(相对于单体总质量而言)时,改性PU的综合性能较好。     

Novel polyurethane polyols for waterborne and high solids coatings

Recently developed oligomeric β-hydroxyalkyl urethane polyols are finding application as modifiers and crosslinkers for waterborne and high solids coatings. In waterborne coatings, urethane polyols can be used as modifiers for acrylic, polyester or alkyd melamine resin crosslinked coatings to replace the cosolvent. In high solids coatings, polyurethane polyols are being employed to raise the application solids, increase film hardness and water resistance, and exterior durability.

There are also applications for polyurethane diols as resin intermediates and in the preparation of blocked isocyanate crosslinkers. β-Hydroxyalkyl urethane diol or polyols can be prepared by an isocyanate reaction with a diol, such as 1,2-propylene glycol, but also by non-isocyanate processes. The non-isocyanate routes to urethanes can utilize carbon monoxide, carbon dioxide, urea or organic carbonates as a carbonyl source for the carbamic acid ester.

It is possible to split these urethanes to the isocyanate, but interest has concentrated on using the urethane intermediates directly in coating applications without going through the isocyanate. The structures reported are bis-hydroxyalkyl urethane intermediates and derivatives of these compounds.     

Synthesis and properties of novel water‐dispersible polyisocyanates

A series of novel water‐dispersible polyisocyanates (WDPs) were synthesized with hexamethylene diisocyanate isoxyanurates (HDI trimer), dimethylol butanoic acid (DMBA), polyethylene glycol monomethyl ether (MPEG‐600) and 1,4‐cyclohexanedimethanol (CHDM) as materials. Two‐component waterborne polyurethane (2K‐WPU) films based on WDPs were prepared and characterized by ultraviolet‐visible spectrophotometer, thermogravimetric analyzer (TGA), scanning electron microscopy (SEM), and surface contact angle measurement. The effects of molar ratios of DMBA/MPEG and CHDM/MPEG and their amounts on properties of WDPs including the water dispersibility, storage stability, films hardness, and water resistance were also investigated. The results showed that the introduction of CHDM could efficiently improve the storage stability, the hardness and water resistance of 2K‐WPU films due to the rigid cyclic structure and hydrophobicity property of CHDM. It was found that WDPs had excellent storage stability, and the 2K‐WPU displayed short tack‐free times, high hardness, good water resistance, excellent surface appearance and gloss with 3:7:3 of the molar ratio of DMBA/MPEG/CHDM. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44735.     

Effect of dicarboxylic acids on the performance properties of polyurethane dispersions

A series of low molecular weight linear polyester polyols were synthesized by using various diacids, neopentyl glycol, as a diol, and a trimethylol propane, as a branching monomer. Polyurethane dispersions were prepared primarily from isophorone diisocyanate, polyester polyol, and dimethylol propionic acid, as potential ionic center for water dispersibility, and were subsequently chain extended with ethylene diamine. The effect of polyester polyols based on variable diacids, on the physico‐chemical and thermal properties of polyurethane dispersions were evaluated by hardness, flexibility, impact resistance, solvent resistance, thermogravimetric analysis, and differential scanning calorimetry. Particle size was evaluated by particle size analyzer. It was observed that the number of alkylene groups present in the polyester polyol soft segment in addition to its molecular weight had a pronounced effect on the particle size, physico‐chemical, and thermal properties. With a proper selection of the soft segment, it is possible to fine‐tune properties of aqueous polyurethane dispersion coatings with respect to the final application. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

TIPA/BDO扩链的聚氨酯弹性体力学性能的研究

以聚酯(PEA、PEPA)或聚醚(PTMG)和TDI为原料合成聚氨酯(PU)预聚体,用三异丙醇胺(TIPA)和1,4-丁二醇(BDO)的混合物作扩链剂制备PU弹性体。讨论了软段相对分子质量、弹性体交联点相对分子质量和扩链剂的种类对PU弹性体性能的影响。结果表明,PU弹性体的硬度、拉伸强度、300%模量和撕裂强度随软段相对分子质量的增加而下降,而伸长率和冲击弹性随软段相对分子质量的增加而增加;交联点相对分子质量为6600时,PTMG2000为软段的PU弹性体的拉伸强度最高,达到28.44MPa;与TMP/BDO扩链的聚酯型PU弹性体相比,TIPA/BDO扩链的弹性体的拉伸强度、伸长率和撕裂强度均较高,而硬度、300%模量和冲击弹性差异不大。     

Preparation and characterization of high-solid polyurethane coating systems based on vegetable oil derived polyols

A series of bio-based polyols with high functionality and low viscosity were synthesized from 5 different vegetable oils (refined or crude). Their chemical structures and the distribution of oligomers in these polyols (known as Liprol™) were characterized. Liprol structures varied due to the fatty acid profile of the starting oils and their overall degree of unsaturation, along with the extent of oligomerization during their formation. These polyols were then used as starting materials for the production of high-solid content polyurethane (PU) coatings, by reacting them with commercial petrochemical derived diisocyanate and other additives. All of the PU coatings obtained had a bio-based content of around 60% and showed good thermo-mechanical and mechanical properties. NuLin^® flax PU, made from oil with the highest linolenic acid content, had the highest glass transition temperature, high contact angle with water, good abrasion resistance and Shore hardness, low degree of solvent swelling and formed highly cross-linked networks.     

Preparation of polyurethane wood adhesives by polyols formulated with polyester polyols based on castor oil

The aim of this work was the synthesis of polyester polyols from renewable sources as one of the important compounds of polymeric polyurethane (PU) adhesives. The polyester polyols were synthesized by condensation polymerization of different dicarboxylic acids with castor oil and the reaction conditions were in agreement with green chemistry principles. The preparation of PU wood adhesives was carried out by the reaction of each obtained polyester polyol with 4, 4′-diphenylmethane diisocyanate (MDI). The adhesive performance was improved by mixing the obtained polyester polyols with polypropylene glycol (PPG 400) and butanediol (BD). Different NCO/OH ratios were used to obtain adhesives with appropriate properties. The structures of the synthesized polyesters and adhesives were characterized by FTIR, thermogravimetric analysis (TGA) and lap shear strength values were also determined in various conditions such as cold water, hot water, acid and alkali solutions.     

High Tg and tough poly(butylene 2,5-thiophenedicarboxylate-co-1,4-cyclohexanedimethylene 2,5-thiophenedicarboxylate)s: Synthesis and characterization

The purpose of this study was to enhance the glass-transition temperature of poly(butylene 2,5-thiophenedicarboxylate) (PBTF). A series of poly(butylene-co-1,4-cyclohexanedimethylene 2,5-thiophenedicarboxylate)s (PBCTFs) were synthesized from 2,5-thiophenedicarboxylic acid, 1,4-cyclohexanedimethanol (CHDM), and 1,4-butanediol. CHDM can increase the chain rigidity and lead the β relaxation temperature shift to lower temperature. Consequently, PBCTFs showed not only the high glass-transition temperature, but also high elongations at break. PBTF was a crystalline polyester. However, differential scanning calorimetry and wide-angle X-ray diffraction results suggested PBCTFs were amorphous polyesters. Thermogravimetric analysis results indicated the thermal stability of copolyesters was gradually enhanced with increasing the CHDM content. When the CHDM content was 95 mol %, PBCTF95 exhibited high glass-transition temperature (69.2 °C), tensile strength (44.4 MPa), and elongation at break (205%). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48634.     

Synthesis of flame retardant polyester‐urethanes and their applications in nanoclay composites and coatings

This paper describes the synthesis of phosphorus‐containing polyester‐urethanes and their applications in nanoclay composites and coatings. Polyester was prepared by the reaction of bis(bisphenol‐A) monophenyl phosphonate, maleic anhydride and phthalic anhydride. The polyester was reacted with various diols such as ethylene glycol, diethylene glycol and propylene glycol to obtain polyester polyols. Synthesized polyester polyols were characterized by chemical analysis and instrumental analysis and was used further to react with different isocyanates to develop polyester‐urethanes. The synthesized polyester‐urethanes were blended with organo‐modified montmorillonite nanoclay (1 wt%, 3 wt% and 5 wt%) and were cast in a mold and coated on mild steel panels. The thermal stability of neat polyester‐urethane and the nanoclay composites was determined by thermogravimetric analysis. The flame retardant properties of cast films and their composites were determined by the limiting oxygen index and UL‐94 test methods. The physical and mechanical properties of coatings such as pot life, drying properties, scratch hardness, pencil hardness, impact resistance, adhesion and flexibility were investigated. The chemical resistance properties of the coatings were also determined in different reagents. The data reveal that the polyester‐urethane nanoclay composites with 3 wt% clay hold promise for use in effective flame retardant coatings. © 2013 Society of Chemical Industry     

软段对水性聚氨酯木器涂料性能的影响

合成了系列水性聚氨酯乳液,研究了低聚物多元醇种类及分子量不同对水性聚氨酯涂料性能的影响。结果表明:聚酯型水性聚氨酯随着软段分子量的增大结晶程度增加,机械强度和硬度较聚醚型高,耐水性较好;结构规整,易结晶的软段合成出的聚氨酯树脂力学性能和耐水性能都较好;而有机硅氧烷改性可以提高聚氨酯材料的耐水性。