Two-component high-solid polyurethane coating systems based on soy polyols

Soybean oil based polyols—soybean oil phosphate ester polyols (SOPEPs)—having varying hydroxyl content and viscosity were prepared as low cost and low-VOC polyols for coatings applications. These SOPEPs were used as the hydroxyl component of “two-component polyurethane (2K-PU)” coating compositions and their film properties were studied. Blends of commercial polyester polyol and SOPEP in varying proportions were also used to formulate PU coatings. Their film properties were studied and compared. We found that SOPEP can be used as the sole hydroxyl component or as the reactive diluent for polyester polyols in 2K-PU coating systems. SOPEP, is derived from a relatively inexpensive and renewable resource and the use of SOPEP can substantially reduce VOC and cost of PU coating formulations. Presented at the International Waterborne, High-Solids, and Powder Coatings Symposium, New Orleans, LA, February 2002.     

Novel coatings from soybean oil phosphate ester polyols

Novel coatings with excellent properties have been formulated from polyols derived from the renewable resource soybean oil. Partially and fully epoxidized soybean oils (ESBO) were converted to novel soybean oil phosphate ester polyols (SOPEP) which were successfully incorporated into solventborne and waterborne bake coatings. Thermally cured waterborne alkyd coatings were produced with improved coating adhesion, low volatile organic compounds (VOC), excellent impact resistance, good hardness, less severe curing conditions, and lower cost. Solventborne alkyd coatings gave similar results. Soybean oil phosphate ester polyols appear to offer the coatings industry a low cost route to tough, durable, environmentally compliant, high performance coatings. Presented at the 27th International Waterborne, High-Solids, and Powder Coatings Symposium, on March 1–3, 2000, in New Orleans, LA. 430 West Forest Avenue, Ypsilanti, MI 48197.     

PU/BA-HEMA互穿网络型聚合物的合成及性能

以异佛尔酮二异氰酸酯（IPDI）、二羟甲基丙酸（DMPA）为硬段,聚醚多元醇（N220）为软段,以丙烯酸丁酯（BA）和甲基丙烯酸羟乙酯（HEMA）改性,制备了水性聚氨酯（PU）分散液,测定了水分散液及其膜的物理性能和力学性能。结果表明,与未改性的PU水分散液相比,改性聚氨酯水分散液的粒径均有所增大,表面张力减小,力学性能和硬度提高。HEMA 的引入,形成了具有化学交联的核-壳互穿网络结构的聚合物,说明改性材料中分子链硬段与PA分子链具有较高的相容性。     

Seed oil based polyester polyols for coatings

The hydroformylation of seed oil based fatty acid methyl esters leads to aldehyde intermediates that can be hydrogenated to give novel seed oil based monomers. In this study, the seed oil based monomers were polymerized with low molecular weight diols to produce novel aliphatic polyester polyols with very low viscosities. The seed oil polyester polyols provide environmentally friendly (green) coating formulations with low volatile organic compound emissions which lead to coatings with superior physical properties, such as exceptional hydrolytic resistance and flexibility. From these polyester polyols, waterborne polyurethane dispersions were also developed with excellent stability resulting in coatings with superior physical properties (i.e., good toughness and abrasion resistance), and exceptional hydrolytic and acid resistance.     

Polyols and polyurethanes prepared from epoxidized soybean oil ring‐opened by polyhydroxy fatty acids with varying OH numbers

Bio‐based polyols from epoxidized soybean oil and different fatty acids were successfully prepared using a solvent‐free method in order to investigate the effect of the polyols' OH numbers on the thermal and mechanical properties of the polyurethanes prepared using them. Epoxidized soybean oil/epoxidized linseed oil was ring‐opened by methanol/glycol followed by saponification to prepare polyhydroxy fatty acids. These fatty acids and epoxidized soybean oil were then used for further solvent‐free ring‐opening reactions with DBU as catalyst, which facilitated the carboxylic ring‐opening. Gel permeation chromatography revealed that a molar ratio of carboxylic acid from polyhydroxy fatty aicds and epoxy group of 0.5 : 1 resulted in optimized polyols containing the smallest amounts of residual starting materials. The obtained polyols had varying OH numbers and the acquired polyurethane films were comprehensively characterized. With increasing OH number of the polyols the PUs displayed an increase in crosslinking density, glass transition temperature (T_g), tensile strength and Young's modulus, and a decrease in elongation and toughness. This work provides Supporting Information on the effect of OH number of polyols obtained via a solvent‐free ring‐opening method on the mechanical and thermal properties of polyurethanes, of particular interest when designing PU products for specific purposes. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41213.     

Physical properties of water‐blown rigid polyurethane foams from vegetable oil‐based polyols

Fifty vegetable oil‐based polyols were characterized in terms of their hydroxyl number and their potential of replacing up to 50% of the petroleum‐based polyol in waterborne rigid polyurethane foam applications was evaluated. Polyurethane foams were prepared by reacting isocyanates with polyols containing 50% of vegetable oil‐based polyols and 50% of petroleum‐based polyol and their thermal conductivity, density, and compressive strength were determined. The vegetable oil‐based polyols included epoxidized soybean oil reacted with acetol, commercial soybean oil polyols (soyoils), polyols derived from epoxidized soybean oil and diglycerides, etc. Most of the foams made with polyols containing 50% of vegetable oil‐based polyols were inferior to foams made from 100% petroleum‐based polyol. However, foams made with polyols containing 50% hydroxy soybean oil, epoxidized soybean oil reacted with acetol, and oxidized epoxidized diglyceride of soybean oil not only had superior thermal conductivity, but also better density and compressive strength properties than had foams made from 100% petroleum polyol. Although the epoxidized soybean oil did not have any hydroxyl functional group to react with isocyanate, when used in 50 : 50 blend with the petroleum‐based polyol the resulting polyurethane foams had density versus compressive properties similar to polyurethane foams made from 100% petroleum‐based polyol. The density and compressive strength of foams were affected by the hydroxyl number of polyols, but the thermal conductivity of foams was not. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Sea Buckthorn Oil Tocopherol Extraction's By‐Product Utilization in Green Synthesis of Polyurethane Coating

The focus of the present study is to utilize a by‐product obtained during extraction of tocopherols, a valuable vitamin E compound, from sea buckthorn (SBT) oil and in doing so find a reliable alternative to petrochemical based polyols. Bio‐based polyurethane (PU) is prepared by using SBT oil based fatty acid methyl ester polyesteramide polyols (SBTPEP) with toluene diisocyanate (TDI). The fatty acid methyl ester is converted to the corresponding fatty amide by reaction with diethanolamine. The formed fatty amide is then esterified with phthalic anhydride to synthesize polyesteramide polyol. Characterization techniques used to evaluate polyesteramide polyol are Fourier‐transform infrared spectroscopy (FTIR) and NMR. The cured PU coating is also put through various mechanical tests to analyze the physical properties. The cured PU coating shows good surface and mechanical properties. It shows a gloss value of 87.4 and passes impact, adhesion, and chemical resistance tests. It is hydrophobic which is evident from its contact angle of 100.2°. It has good thermal stability which is evident by its glass transition temperature of 53.9 °C. Use of phthalic anhydride contributes to the bio‐based characteristics of synthesized PU. Practical Application: The present study presents a synthesis route which has minimal dependence on hazardous feedstock by utilization of green feedstock. The results obtained from physical and mechanical evaluations favor the use of this PU formulation in the coating sector. The adhesion and impact strength test results show potential application in the industrial sector coatings where the applied coat must be able to withstand high levels of physical stress and strain. The presence of aromatic rings and oil‐based moiety, that is the fatty acid hydrocarbon chain, contributes to the hydrophobic nature of the PU coating. Hydrophobic coatings have tremendous application in various fields such as marine coatings, automotive, electronics, and decorative coatings. These are potential fields of application for the synthesized green PU coating obtained from tocopherol extraction by‐products.     

Preparation and properties of eco-friendly two pack PU coatings based on renewable source (sorbitol) and its property improvement by nano ZnO

Today most of the coating formulations are based on petroleum sources, which are limited. Therefore, it is necessary to use any eco-friendly renewable source for making polymers, as they are renewable and may be non-hazardous, easily available and cheaper. In the present work we selected sorbitol as a renewable source, which is derived from naturally occurring polymer, i.e., cellulose. The technology of converting cellulose to sorbitol is well established. Hence we directly utilized sorbitol in the preparation of polyester polyols. These polyols were synthesized with the help of sorbitol, 1,2,3,6-tetrahydro phthalic anhydride, adipic acid, diethylene glycol and zinc acetate (catalyst). The synthesized polyols were characterized for their acid value, hydroxyl value, molecular weight, IR spectroscopy, etc. The polyol is further used in polyurethane coatings after reacting with polyisocyanates. For further improvement in properties, these coatings were prepared by adding nano sized ZnO. This ZnO was prepared in the laboratory and characterized for its size by SEM. The prepared PU coatings were analyzed for their coating properties such as gloss, scratch resistance, flexibility, impact test, chemical properties and anticorrosive properties.     

Synthesis and application of novel UV-curable hyperbranched methacrylates from renewable natural tannic acid

With a view to developing high performance UV curable coatings with high renewable contents, acrylated epoxidized soybean oil (AESO) was combined with a novel kind of biorenewable tannic acid-based hyperbranched methacrylates (TAHAs). The TAHAs were synthesized by ring-opening reaction of glycidyl methacrylate (GMA), glycidyl ester of Versatic acid (CE10) and natural tannic acid (TA). The epoxy groups of GMA and CE10 were involved in the ring-opening reaction with the hydroxyl groups of TA while residual methacrylate groups can carry out photopolymerization. By controlling the ratio of GMA and CE10, TAHAs with varying degree of methacrylate groups have been prepared. The synthesized TAHAs were formulated into acrylated epoxidized soybean oil (AESO) based UV curable coatings to produce the biorenewable materials based UV curable coatings. The effects of TAHAs on AESO coated film properties of pendulum hardness, flexibility and adhesion were investigated. Mechanical properties, thermal properties and biodegradability of the cured films were also evaluated. With the incorporation of TAHAs, the hardness, adhesion, tensile strength of the cured coating films were remarkably improved, which were attributed to the unique structure of hyperbranched methacrylates. Meanwhile, the biorenewable content was not greatly decreased due to the biorenewable character of tannic acid in TAHAs. These results showed that TAHAs as efficient toughening agents could produce UV-curable coatings of balanced coating performance with reasonably high biorenewable content. Moreover, the environment degradability of AESO-based cured films was also enhanced after the addition of TAHAs.     

Effects of unsaturation and different ring-opening methods on the properties of vegetable oil-based polyurethane coatings

A variety of vegetable oil-based, waterborne polyurethane dispersions have been successfully synthesized from different vegetable oil polyols exhibiting almost constant hydroxyl functionalities of 2.7 OH groups per molecule. The vegetable oil polyols, which have been prepared from vegetable oils with different fatty acid compositions (peanut, corn, soybean, and linseed oil), range in residual degree of unsaturation from 0.4 to 3.5 carbon–carbon double bonds per triglyceride molecule. The effects of residual unsaturation on the thermal and mechanical properties of the resulting polyurethane films have been investigated by dynamic mechanical analysis, differential scanning calorimetry, and thermal gravimetric analysis. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) has been used to accurately determine the molecular weight and mass distribution of the vegetable oil polyols. Higher residual unsaturation results in polyurethane films with increased break strength, Young's modulus, and toughness. This work has isolated the effect of unsaturation on vegetable oil-based polyurethane films, which has been neglected in previous studies. The effect of different oxirane ring opening methods (methanol, butanol, acetic acid, and hydrochloric acid) on the properties of the coatings has also been examined.     

Polyurethane Dispersions Based on Interesterification Product of Fish and Linseed Oil

Alkyd and styrenated alkyd resins based on fish oil and their interesterifications with linseed oil were synthesized. The various properties of fish oil, such as its iodine value, acid value, saponification value and moisture content were determined. The interesterification product of fish oil and linseed oil can be used to partially replace the commercially available linseed oil alkyd resin. Alkyd resin and styrenated alkyd resin were modified with 2,2 dimethylolpropionic acid to introduce acid functionality and then sequentially reacted with isophorone diisocyanate, neutralized with amine, chain extended with ethylenediamine and dispersed in water to form a polyurethane dispersion. The newly synthesized resins and polyurethane dispersions were studied for coating properties such as scratch hardness, adhesion, flexibility, impact, solvent and chemical resistance. The polyurethane dispersions exhibited superior coating properties to those of their respective alkyds and styrenated alkyds.     

植物油基聚酯酰胺多元醇的合成及其在水性聚氨酯中的应用

以菜籽油和二乙醇胺为原料制备了脂肪醇酰胺混合多元醇RDEA，进一步和己二酸等原料反应合成了系列的聚酯酰胺多元醇，并对两类多元醇进行了表征。以聚酯酰胺多元醇、二羟甲基丙酸、异佛尔酮二异氰酸酯、苯乙烯和丙烯酸丁酯等原料合成了水性聚氨酯脲（PUU）分散液及聚氨酯脲-乙烯基聚合物（PUA）复合水分散液，并对其流变性能及稳定性进行了研究。     

软段含离子基团的阴离子型水性聚氨酯胶粘剂的研究(Ⅰ)——软段结构的影响

以含有不同离子基团的聚酯多元醇为软段,采用丙酮法合成了一系列水性聚氨酯乳液。研究了不同离子基团的聚酯多元醇和不同软段结构对其干膜物理机械性能和吸水率的影响。     

可再生聚酯多元醇的合成及其在聚氨酯材料中的应用

采用油酸为主要原料合成了羟值为236mgKOH／g、酸值为2．8mgKOH／g的可再生聚酯多元醇,并以此聚酯多元醇为原料制备了聚氨酯硬质泡沫。研究了该聚酯多元醇用量对泡沫发泡和力学性能的影响。结果表明,随着聚酯多元醇加入量的增加,形成聚氨酯硬质泡沫的反应速度增加;与纯聚醚多元醇制备的聚氨酯硬质泡沫相比,加入20％～30％的该聚酯多元醇制备的聚氨酯泡沫的尺寸稳定性和压缩强度增加。     

Synthesis,characterization, and comparison of polyurethane dispersions based on highly versatile anionomer,ATBS, and conventional DMPA

Polyurethane dispersions (PUDs) are one such class of coatings that comply well with stringent VOC regulations. In this study, PUDs were prepared as aqueous dispersions using a new highly versatile crosslinkable anionomer, 2-acrylamido 2 methylpropanesulfonic acid (ATBS), which is commercially available, yet not explored by the coating industry. The influence of this novel anionomer on the performance properties of polyurethane resins was evaluated by comparing performance/properties of this newly synthesized PUD with dispersion based on conventional anionomer, DMPA. Analyses of their physico-chemical and thermo-mechanical properties revealed that PUD based on ATBS showed comparatively much better thermal, mechanical, and chemical and coating properties than the PUD based on DMPA anionomer.     

水性环氧丙烯酸酯乳液涂层成膜性能

采用细乳液聚合法制备了环氧丙烯酸酯复合乳液,考察了固化温度、固化时间及磷酸酯乳化剂含量对环氧丙烯酸酯复合涂膜性能的影响,结果表明环氧丙烯酸酯复合乳胶粒子呈均匀的球形结构,且平均粒径分布在150 nm左右。当固化温度为120℃、固化时间为2 h、磷酸酯乳化剂含量为3%时,涂层的耐腐蚀性较好。研究了复合乳液的成膜过程和防腐蚀机理,通过复合乳液与金属底材形成致密的钝化膜,阻隔水分子和无机离子的浸入,提高了涂层的防腐性能。     

二乙醇胺开环环氧大豆油制备大豆多元醇及其性能表征

以大豆油、冰乙酸和过氧化氢为原料,硫酸为催化剂,合成了不同环氧值的环氧大豆油。再由合成的环氧大豆油与二乙醇胺在四氟硼酸作催化剂的条件下．通过开环加成反应制备了羟基值分别为261mgKOH／g、285mgKOH／g、312mgKOH／g、340mgKOH／g的4种大豆多元醇。用滴定法测定多元醇羟值,用傅立叶变换红外光谱、差示扫描量热法、热重分析法对多元醇进行了分析和表征。结果表明4种多元醇的熔点和热稳定性都随多元醇羟值增大而增大。     

聚苯胺颗粒对水性环氧树脂涂层防腐性能的影响

以盐酸为掺杂剂、过硫酸铵为氧化剂、咪唑类离子液体为稳定剂,采用化学氧化聚合法合成了导电聚苯胺(PANI)颗粒,将其分散到水性环氧树脂(ER)中制成聚苯胺水性环氧防腐涂层,研究了聚苯胺颗粒对涂层防腐性能和机械性能的影响。结果表明,添加聚苯胺显著提高了水性环氧涂层的阻隔性能,信号频率f=0.01 Hz时,PANI/ER涂层的阻抗(|Z|f=0.01Hz)均高于纯ER涂层。添加5.0wt% PANI时ER涂层阻隔性能最好,浸泡0~168 h时|Z|f=0.01Hz稳定在约8.0×108 Ω?cm2,浸泡168 h后|Z|f=0.01Hz=7.5×108 Ω?cm2,远高于ER和其它PANI/ER体系。中性盐雾实验结果表明,聚苯胺赋予了涂层钝化腐蚀的能力,显著提高了涂层的防腐性能,且其添加量越高,防腐性能越好。弯曲和冲击实验结果表明,涂层的机械性能随聚苯胺含量增加先上升后降低,当聚苯胺添加量不超过5.0wt%时,涂层的机械性能优异,附着力和韧性均较好;PANI添加量增至7.0wt%时,ER涂层的脆性明显变大,机械性能下降。聚苯胺在水性环氧体系中的最宜添加量为5.0wt%,此时涂层的机械性能良好,综合防腐性能最优。     

Study of hexafunctional polyol in high solids air-drying alkyd: Improved film performance

A series of high solid alkyd polymers from soya oil fatty acid (SOFA) and dehydrated castor oil fatty acid (DCOFA) combinations with varying percentage of dipentaerythritol (DPE, a hexafunctional polyol) have been synthesized and characterized for their physicochemical, optical, thermal and mechanical properties. For the study purpose the polymers were prepared at 80% solids in mineral turpentine oil (MTO) keeping the oil length constant. The curing behavior of the alkyds was studied using FT-IR and DSC. Increasing DPE content in resin backbone was found to increase gloss and hardness. The gloss improvement was also supported well by atomic force microscopy (AFM) pictures. Results of 500 h of QUV exposure revealed higher gloss retention for DPE-based systems. When compared for the anticorrosive properties, the EIS spectrum reveals that alkyd film containing 100% DPE has the higher value of impedance.     

Network structure and properties of polyurethanes from soybean oil

Vegetable oils are very heterogeneous materials with a wide distribution of triacylglycerol structures and double‐bond contents. The hydrogenation of epoxidized soybean oil (ESO) produces polyols having a functionality distribution related to that of soybean oil. Therefore, these polyols are convenient substances for studying the impact of structural heterogeneity on network formation and properties. Polyols of hydroxyl numbers ranging from 225 to 82 mg KOH/g and weight‐average functionalities ranging from 4.4 to 2.7 were obtained by the variation of the time of hydrogenation of ESO. An analysis of the functionality distribution in polyols shows that gel points with diisocyanates vary from 54 to 76% conversion. The molecular weights of the network chains of polyurethanes prepared from these polyols and diphenyl methane diisocyanate varied from 688 to 1993. Polyols with hydroxyl numbers above 200 mg KOH/g gave glassy polymers, whereas those below that value gave rubbers. The heterogeneity of polyols had a negative effect on the elastic properties only at low crosslinking densities. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007