Urethane Oil Research Articles

Synthesis and Antimicrobial Activity of Metal-Containing Linseed Oil-Based Waterborne Urethane Oil Wood Coatings

In this study, the antimicrobial agents of mono(hydroxyethoxyethyl)phthalate (M(HEEP)2) with different metal of M = Zn, Mn, Pb, and Ca were synthesized from diethylene glycol (DEG), phthalic anhydride (PA), and divalent metal acetates including calcium acetate, zinc acetate, manganese acetate, and lead acetate, respectively. The waterborne urethane oil (WUO) dispersions synthesized from linseed oil, diisocyanates (hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI)), dimethylolpropionic acid at NCO/OH molars of 0.9, by acetone processing method were described as in our previous report. The M(HEEP)2 antimicrobial agents as well as the commercial nanosilver powder were added into WUO dispersions as the antimicrobial coatings. The effects of various antimicrobial agents and dosages (0.0, 0.2, 0.6, 0.8, 1.0, 2.0, and 4.0 phr) on antimicrobial activity of WUO films against gram-negative bacterium of Escherichia coli, gram-positive bacterium of Staphylococcus aureus, brown-rot fungus of Gloeophyllum trabeum, and white-rot fungus of Lenzites betulina were assessed. In addition, the film properties of the best antimicrobial WUO coatings were also examined. The results showed that the antimicrobial agents of mono(hydroxyethoxyethyl) phthalate M(HEEP)2 (M = Zn, Mn, Pb, and Ca) powders should certainly be synthesized by FTIR, 1H-NMR, 13C-NMR, and energy-dispersive X-ray spectroscopy (EDS) identifications and the yields of them were 43–55%. The results also revealed that the WUO film synthesizing with HDI films containing Zn(HEEP)2 of 2.0 phr and Pb(HEEP)2 of 0.4 phr had the best antibacterial activity for E. coli and S. aureus, respectively. The IPDI films containing Zn(HEEP)2 of 1.0 phr had the best antibacterial activity for both E. coli and S. aureus. For antifungal activity, the WUO film synthesizing with HDI films containing Pb(HEEP)2 of 0.8 phr and Zn(HEEP)2 of 2.0 phr as well as IPDI films containing Mn(HEEP)2 of 0.2 phr and Zn(HEEP)2 of 4.0 phr had the best performances against G. trabeum and L. betulina, respectively. Comparing with commercial nanoAg powder, the Zn(HEEP)2 and Pb(HEEP)2 had a superior antifungal efficiency for G. trabeum and L. betulina, while it had a slightly inferior efficiency in the antibacterial activity for E. coli and S. aureus. On the properties of WUO films, adding metal-containing antimicrobial agents could slightly enhance the thermal stability, but lowered the gloss of all films, however, the Tg value increased for HDI film and decreased for IPDI film. In addition to this, they had no significant difference in the film properties including hardness, impact resistance, bending resistance, adhesion, mass retention, and light-fastness between the WUO films with and without adding antimicrobial agents.

Synthesis of Linseed Oil-Based Waterborne Urethane Oil Wood Coatings.

The linseed oil glyceride (LOG) was synthesized by using a transesterification process with a glycerol/linseed oil molar ratio of 1.0. The waterborne urethane oil (WUO) wood coating was prepared by acetone process. First, dimethylolpropionic acid was reacted with hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI), followed by adding LOG at various NCO/OH molars of 0.7, 0.8, and 0.9, respectively, and the COOH-containing prepolymer was obtained. Then, the ionomer which was prepared by neutralizing prepolymer with trimethylamine, was dispersed by adding deionized water, and the water–acetone dispersion was obtained. Finally, the acetone was removed by vacuum distillation. In the whole synthesized process, the LOG and COOH-containing prepolymer could be steadily synthesized by FTIR analysis, and the weight-average molecular weight and polydispersity of COOH-containing prepolymer increased with an increase of NCO/OH molar ratios. During the water dispersion process of the ionomer acetone solution, the point of phase inversion was prolonged, meaning the solid content decreased with an increase of NCO/OH molar ratios. After acetone was removed, the color of WUO was milky-white, and it was weakly alkaline and possessed a pseudoplastic fluid behavior. The particle size of WUO increased with increasing of NCO/OH molar ratios, however, the storage stability was extended for HDI and shortened for IPDI synthesized with increasing of NCO/OH molar ratios.

Organic–inorganic hybrid linseed oil‐based urethane oil wood coatings

ABSTRACTTo prepare alkoxysilane‐functionalized urethane oil (AFUO) using linseed oil, 3‐aminopropyltriethoxysilane (APTES) was first reacted with diisocyanate to obtain an NCO‐terminating oligomer. The reaction was continued by adding linseed oil glyceride to form an AFUO prepolymer. The auto‐oxidative drying coating was obtained after adding a metal dryer to the AFUO prepolymer. Urethane oil (UO) coating, as a control, was obtained by the same procedure as that for AFUO, but without containing alkoxysilane‐functional groups in the formation. Siloxane hybrid urethane oil (SHUO) wood coatings were prepared by mixing tetraethyl orthosilicate (TEOS) solutions, as an external crosslinking agent by sol–gel process, with the AFUO and UO coatings. We found that introducing of APTES into the molecular chains of the UO coating resulted in a film with superior impact and abrasion resistance, and it is the most efficient process to enhance the UO films. The addition of TEOS into AFUO coatings shortened the curing time and further improved the crosslinking density of the AFUO films; however, the physical properties like impact resistance, bending resistance, and gloss were even worse than AFUO films. Mixing of TEOS and UO coating also shorten the curing time and improved the heat resistance, lightfastness, and hardness of the UO coating. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017, 134, 44562.

Styrenated urethane oil synthesis via CuAAC “click” chemistry approach

Abstract In this study, a novel route for the modification of sunflower oil-based partial triglycerides with styrene (St) was described. For this purpose, in the first step, copolymers of St and 4-chloromethyl styrene (P(St-co-CMS)) were synthesized by free radical polymerization (FRP) and controlled/living radical polymerization (nitroxide mediated radical polymerization (NMRP)) methods. In the second step, chloro groups of these samples were transformed into azido groups by using NaN3/DMF and then azido groups were coupled with propargyl alcohol to achieve hydroxyl functional polystyrene chain (PSt-OH) via Cu(I)-catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) “click” chemistry approach. Finally, alcohol groups of PSt-OH and the partial glyceride (PG) were combined by the reaction with toluene 2,4-diisocyanate (TDI). As a result, styrenated urethane oil (PG-TDI-PSt) was obtained as an oil-based binder. The structures were determined by FT-IR, 1H NMR and GPC analyses, and film properties of the products were examined according to the related standards. (PG-TDI-PSt) gave good film properties, and therefore could be considered as an applicable oil-based binder.

Abstract 1604: Treatment with Pequi (Caryocar brasiliense Camb) fruit pulp oil decrease the DNA damage caused by chemical carcinogenesis in experimental model of lung cancer.

Abstract Background: It is well known that a daily consumption of foods that are rich in antioxidants prevents the oxidative damage caused by reactive species (ROS), including DNA damage, and can reduce the risk of cancer, atherosclerosis and other degenerative diseases. The pulp of Caryocar brasiliense Camb, most known as pequi, is a Brazilian fruit that has high levels of antoxidants properties, such as vitamin C, carotenoids, phenolic compounds like flavonoids, saponins and tannins, and essential oils. The aim of this study was to evaluate the action of the pequi oil in the DNA damage in experimental model of lung cancer induced by the urethane. Material and Methods: Male BALB/c mice (n=14) received by gavage 0,5μL/mg/day of pequi oil (CBC oil) during 75 days. After 15 days of the beginning of the gavage, 10 of these animals received two doses of 1,5g/kg intraperitoneal of urethane (Urethane + CBC oil). Urethane animals (n=4) were only submitted to two doses of 1,5g/kg intraperitoneal of urethane (urethane group). After these 75 days, lung tissues were submitted to histological and biochemical analysis by comet assay method to evaluated the DNA damage. The DNA damage was quantificate by image analysis. Results: The lung parenchyma from the urethane groups without oil and with oil showed neoplasic formations induced by the chemical carcinogenesis in contrast with oil control group. The image analysis of the comet assay showed a statistical significant diminish of the DNA damage cells in the urethane oil group when compared with urethane control group (p=0.001). The decreased DNA damage was very similar that we obtained in the oil control group. Conclusion: We conclude that the different antioxidant components found in the pequi oil diminish the DNA damage in the mouse lung after chemical carcinogenesis, suggesting that this type of strategies may have a greater impact in lung cancer treatment. Financial Support: FAPESP, CNPq Citation Format: {Authors}. {Abstract title} [abstract]. In: Proceedings of the 103rd Annual Meeting of the American Association for Cancer Research; 2012 Mar 31-Apr 4; Chicago, IL. Philadelphia (PA): AACR; Cancer Res 2012;72(8 Suppl):Abstract nr 1604. doi:1538-7445.AM2012-1604

Preparation and Properties of Urethane Oil from Jatropha Oil

In this study, jatropha oil was reacted with glycerol and toluene diisocyanate to obtain urethane oil at hydroxyl to isocyanate ratio of 1:0.8 with methanol acting as a blocking agent. The prepared urethane oil was characterized for molecular weight and its properties were determined and compared with those of the linseed oil-modified and commercial urethane oils. It was found that the jatropha-modified urethane oil was a yellowish viscous liquid with a number-average molecular weight of 2,673. The urethane oil prepared from jatropha oil took longer time to dry than the linseed oil-modified and commercial urethane oils. Results showed that the film properties of the jatropha-modified urethane oil were comparable to those of the commercial urethane oil. The film exhibited good hardness, excellent flexibility and adhesion, and high impact strength. Additionally, it also showed excellent water resistance but only fair alkali resistance.

Preparation of Urethane Oils from Microwave-Assisted Glycolyzed Products of Waste PET Bottles

Abstract Post-consumer PET bottles were depolymerized with propylene glycol at a weight ratio between PET and glycol of 37.5 : 62.5 under microwave energy at irradiation power of 600 watt, using zinc acetate as a catalyst. The glycolyzed product, consisting of oligomeric diols with a hydroxyl value of 253 mg KOH/g, was obtained. Analysis of the glycolyzed product by GPC indicated that it consists of compounds with a number-average molecular weight of 2265. The glycolyzed product was further reacted with linseed oil and toluene diisocyanate to obtain urethane oil at hydroxyl to isocyanate ratio of 1 : 0.8 with methanol acting as a blocking agent. It was found that the obtained urethane oil was a transparent yellowish liquid with low viscosity. The prepared urethane oil was characterized for molecular weight and its properties were determined and compared with those of the conventional and commercial urethane oils. Results showed that the properties of waste PET bottles-based urethane oil were comparable to those of the commercial urethane oil.

Synthesis and properties of alkoxysilane-functionalized urethane oil/titania hybrid films

In this study, alkoxysilane-functionalized urethane oil/titania (AFUO/titania) hybrid films were synthesized by sol–gel method. For this purpose, alkoxysilane-functionalized urethane oil (AFUO) was first produced by the reaction of 3-aminopropyltriethoxysilane (APES) and partial glyceride (PG) mixture with toluene diisocyanate (TDI). Then, this intermediate was further reacted with titanium isopropoxide (TIP) by sol–gel process in thin films applied on a glass substrate. TIP content of the hybrid films were varied in the range of 5–20 wt.% in order to investigate optimum amount of TIP in view of film properties. The characterization of the hybrid films were done by FTIR, DSC, TGA and SEM analyses. FTIR and DSC analyses indicated the existence of Ti–O–Si bond. Film properties for coating purposes such as flexibility, adhesion, hardness, water, alkali and acid resistances were determined. Hybrid composite films showed better film properties in comparison with classical urethane oil.

Synthesis of urethane oils from palm oil and waste PET bottles

AbstractWaste PET bottles were depolymerized by propylene glycol at a weight ratio of PET to propylene glycol of 37.5 : 62.5, using zinc acetate as a catalyst. The glycolyzed product, consisting of oligomeric diols with a number–average molecular weight range of 240–1107, was obtained. It was further reacted with palm oil and tolylene diisocyanate to obtain urethane oils at hydroxyl to isocyanate ratios from 1 : 1 to 1 : 0.8, with and without methanol acting as a blocking agent. It was found that all the synthesized urethane oils were yellowish transparent liquids of low molecular weights. A lower isocyanate content or the presence of a blocking agent resulted in higher viscosity, higher molecular weight, and shorter drying time. The films of all synthesized urethane oils exhibited good hardness, excellent flexibility, and high impact strength. They also showed excellent water resistance, good acid resistance but only fair alkali resistance. Moreover, these prepared urethane oils had better adhesion compared with those of the commercial urethane oil. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007

The usage of linseed oil‐based polyurethanes as a rheological modifier

AbstractSome oil‐based urethanes (urethane oils) were prepared from linseed oil, glycerol, and two types of diisocyanates, hexamethyle diisocyanate (HMDI) and 4,4′‐ diphenylmethane diisocyanate (MDI). These urethane oils were used as a rheological modifier in solvent‐based coatings. For this purpose the mixture prepared from urethane oil and alkyd resin (AR‐UO) was investigated in view of flow properties. Time dependence of AR‐UO was investigated by using the hysteresis loop method. None of the samples showed thixotropic flow behavior. The flow type was decided after calculation of the ratio of viscosity at low shear rate to viscosity at high shear rate. The results showed that HMDI‐based samples had the smallest viscosity ratio and increasing the amount of aromatic structure caused increasing shear thinning behavior. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1032–1035, 2005

Flow behavior of oil-modified polymer solutions

In this study, the flow behavior of urethane oils prepared with different reactant ratios was determined. For this purpose, in the first step, the viscosities of polymer solutions were determined at different temperatures. Then, Bingham, Power-law and Casson models were tested to express the relationship between τ and γ. Under test conditions, toluene diisocyanate (TDI)-based polymer solutions behaved as non-Newtonian fluids, whereas the polymer solution prepared from poly(1,4-butandiol) tolylene 2,4-diisocyanate terminated prepolymer (PBTDI)-based samples behaved as Newtonian fluids. Additionally, Andrade and Erickson’s equations were tested for investigating the viscosity–temperature and viscosity–concentration relationships, respectively. It was showed that, these equations were available for all polymer solutions. After comparing all results with those of comparative sample we suggested that, the polymer solution prepared from the sample containing high ratio of TDI, could be used in the high solid coating formulation for industrial application.

Synthesis of urethane oils from waste poly(ethylene terephthalate) bottles

AbstractWaste poly(ethylene terephthalate) (PET) bottles were glycolyzed by propylene glycol (PG) at a weight ratio of PET to PG of 37.5 : 62.5 using zinc acetate as a catalyst. The glycolyzed product, consisting of oligomeric diols with a number‐average molecular weight range of 458–844, was obtained. It was further reacted with soybean oil and toluene diisocyanate to obtain urethane oils at hydroxyl to isocyanate ratios from 1 : 1 to 1 : 0.7, with and without methanol acting as a blocking agent. All the synthesized urethane oils were yellowish, transparent, low‐viscosity liquids of low molecular weights. A lower diisocyanate content and the presence of a blocking agent resulted in higher viscosity, higher molecular weight, and shorter drying time. The films of all synthesized urethane oils exhibited good hardness and adhesion. They also showed excellent water and acid resistance but only fair alkali resistance. However, these prepared urethane oils had lower flexibility and poorer wear resistance compared to those of the commercial urethane oil. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3040–3045, 2004

Study of film properties of some urethane oils

In this study, sunflower oil-based urethane oils were obtained from three kinds of isocyanate components: toluene diisocyanate (TDI), hexamethylene diisocyanate (HMDI) and poly(1,4-butandiol) toluene 2,4-diisocyanate (PBTDI) terminated prepolymer. The polymers were prepared at four different ratios of isocyanate component/oil. Sunflower and linseed oil alkyd resin samples were also prepared as the comparative samples. The results suggest that the viscosity and the film properties of urethane oils depend on the amount and type of isocyanate component.

Synthesis of Urethane Oil Varnishes from Waste Poly(ethylene terephthalate)

Waste poly(ethylene terephthalate) was depolymerized by glycolysis to obtain hydroxyl-terminated oligomers. The effect of depolymerization temperature, the type of glycol and the amount of catalyst on the yield and the composition of the products were studied. The hydroxyl-terminated oligomers obtained from the glycolysis of poly(ethylene terephthalate) were used in the synthesis of urethane oils. The physical properties of urethane oils were compared with a commercial product.

Chemoenzymatic synthesis of urethane oil based on special functional group oil

A two-step chemoenzymatic synthesis of urethane oil, consisting of a lipase-catalyzed transesterification of castor oil with n-butanol and a reaction of the resulting precursor (partial esters) with different diisocyanates, was studied. The effect of the type of lipase, alcohol chain length, solvent, and temperature in the transesterification step was examined. Urethane oils were characterized by IR, 1 H-NMR, and GPC techniques. The film properties were also tested. The composition varies with time in the transesterification step. Conversions were faster and more complete using lipozyme, where yields to 75% could be achieved. Enzyme activity increases with increase in the log P value of the solvent. The degree of transesterification and composition of the precursor have influence on the molecular weight and film properties of urethane oils. A good correlation was observed between the scratch resistance and monoglyceride percentage of the precursor of the respective urethane oils.

Chemoenzymatic synthesis and characterization of urethane oils for surface coatings

Two-step chemoenzymatic synthesis of urethane oils has been studied. Initially, the partial esters were prepared by lipase-catalyzed transesterification of soybean and linseed oils with n-butanol. Partial esters were further reacted with different diisocyanates to obtain urethane oils. The composition of the partial esters was varied with reaction time in the transesterification step. Among all the lipases, the lipozyme was found to be the most suitable lipase for the transesterification reaction, yielding 80–85%. All of the urethane oils were of low molecular weights irrespective of the type of oil used in their preparation. Urethane oils, based on MDI, exhibited the best scratch resistance. All of the urethane oils showed good acid and alkali resistance and excellent solvent resistance. These oils also satisfactorily passed the impact resistance and the flexibility tests.

Gel permeation chromatographic method for monitoring the transesterification reaction in a two-step chemoenzymatic synthesis of urethane oil based on vegetable oils

Urethane oils (isocyanate-modified vegetable oils) are used in decorative paints and protective coating formulations. A gel permeation chromatographic method using tetrahydrofuran as mobile phase, an Ultra-Styragel column, a refractive index detector and polystyrene standards has been developed for monitoring the formation of precursor (partial esters) in the first step of a two-step chemoenzymatic synthesis of urethane oil and for the subsequent molecular mass determination of the final product. The method allows the simultaneous determination of precursor and the starting material in the first step and thereby permits the optimization of reaction parameters in the second step to yield urethane oil of the desired molecular mass.

Studies on biocide release and performance of novel anti‐fungal paints

The controlled release of an isothiazolone fungicide, C9211 (4,5‐dichloro‐2‐(n‐octyl)‐3(2H)‐isothiazolone) from a urethane oil paint is described. Leaching experiments showed that the amount of C9211 in the leachates was proportional to the loading in the paint. Paints containing 8% C9211 in the undercoat but none in the topcoat released C9211 in the same amounts as paints containing 4% C9211 in both undercoat and topcoat and the field performance of both paint combinations were identical. These results indicate that the C9211 is able to migrate through the urethane oil matrix replenishing any lost from the surface and thus giving effective antifungal control as long as biocide remains in the bulk of the paint.

Urethane oils and alkyds

Urethane polymers may be separated into three main types, which are briefly outlined here, but for the purpose of this article only the third section is relevant:

Synthesis of Urethane Oils from C18 Fatty Isocyanates

AbstractFor preparing mixed ester‐urethane oils 2,2,‐dimethyl‐1,3‐dioxolane‐4‐methanol was reacted with linseed, safflower or tall oil and the corresponding fatty isocyanates to form the mono‐ester and mono‐urethanes respectively. These were then reacted with fatty isocyanates and fatty acids respectively to give the desired products in yields of 90% or better. The products varied from viscous liquids to waxy yellow solids according to the increasing number of urethane groups.