Synthesis Of Urethanes Research Articles

Urethane Synthesis in the Presence of Organic Acid Catalysts-A Computational Study.

A general mechanism for catalytic urethane formation in the presence of acid catalysts, dimethyl hydrogen phosphate (DMHP), methanesulfonic acid (MSA), and trifluoromethanesulfonic acid (TFMSA), has been studied using theoretical methods. The reaction of phenyl isocyanate (PhNCO) and butan-1-ol (BuOH) has been selected to describe the energetic and structural features of the catalyst-free urethane formation. The catalytic activities of DMHP, MSA, and TFMSA have been compared by adding them to the PhNCO-BuOH model system. The thermodynamic properties of the reactions were computed by using the G3MP2BHandHLYP composite method. It was revealed that in the presence of trifluoromethanesulfonic acid, the activation energy was the lowest within the studied set of catalysts. The achieved results indicate that acids can be successfully employed in urethane synthesis and the mechanism was described.

Stoichiometric reaction and catalytic effect of 2-dimethylaminoethanol in urethane formation.

A computational study of the stoichiometric reaction and catalytic effect of 2-dimethylaminoethanol (DMEA) in urethane formation was performed. DMEA, besides its catalytic tertiary amine site, contains a hydroxyl group that can react with isocyanates and thus, it can affect the synthesis of polyurethane. In the catalytic system, the reaction between phenyl isocyanate and butan-1-ol, involving DMEA as a catalyst, was investigated. Meanwhile, for the competitive stoichiometric process, the reaction between phenyl isocyanate and DMEA was also considered. Both reactions were investigated by using the G3MP2BHandHLYP composite method and acetonitrile was chosen as the solvent. It was revealed that both pathways (catalytic and stoichiometric processes) are similar thermodynamically, but the catalytic reaction is preferred kinetically, which indicates the applicability of DMEA in urethane synthesis.

Effect of morpholine, and 4-methylmorpholine on urethane formation: a computational study

A theoretical study of urethane formation through the reaction of phenyl isocyanate and butan-1-ol was carried out, without and in the presence of morpholine, and 4-methylmorpholine catalysts. The reaction with and without catalysts was studied at BHandHLYP/6-31G(d) and G3MP2BHandHLYP levels of theories. The reaction mechanism in the presence of catalysts differs significantly from the catalyst-free case and includes seven steps. The catalyst-free system was investigated along with the catalytic process, the geometries were optimized, and the corresponding thermodynamic properties were calculated. Calculated reactant complexes were compared with crystal structures of morpholine, and 4-methylmorpholine complexed with diols found in the literature. The structures were strikingly similar and thus, the validity of the proposed and studied general organocatalytic reaction mechanism was partially verified. Meanwhile, an irregularity in the energy profile occurred due to the zwitterionic nature of an intermediate. To handle the irregularity, a correction was implemented which handles the appearance of a zwitterionic structure and the corresponding energetic properties. The results showed that morpholine is less effective catalyst compared to 4-methylmorpholine, which can be associated with the difference in their PA (1523.95 and 963.07 kJ/mol, respectively). The current results prove the important role of amine catalysts in urethane synthesis which can be applied in polyurethane catalyst design and development.

Electrostatically Enhanced 3- and 4-Pyridyl Borate Salt Nucleophiles and Bases.

A variety of electrostatically enhanced 3- and 4-pyridylborate salt catalysts are reported and show significant improvement over an activated noncharged neutral control compound. Their nucleophilicity in a stoichiometric SN2 reaction and catalytic performance in a urethane synthesis are evaluated along with three methods for rapidly evaluating the basicity of these species. That is, qualitative titrations in CH2Cl2 and CHCl3 were carried out, two separate solution-state IR studies in CCl4 and CDCl3 are reported, and the proton affinities of the anionic components of the salts were computed. Charge differences between the anion and its protonated zwitterionic conjugate acid are evaluated along with the highest occupied molecular orbitals of the anions in relationship to some of the surprising reactivity findings that were observed in the two kinetic studies.

Urethane formation in the presence of 2,2-dimorpholinodiethylether (DMDEE) and 1,4-dimethylpiperazine (DMP) – A combined experimental and theoretical study

The reaction of phenyl isocyanate (PhNCO) and butan-1-ol (BuOH) in acetonitrile without and in the presence of two amine catalysts, 2,2-dimorpholinodiethylether (DMDEE) and 1,4-dimethylpiperazine (DMP), has been studied, using computational and experimental tools. Kinetic investigation of the alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile was examined as well. The same reaction was investigated by using density functional theory and composite methods (BHandHLYP/6-31G(d) and G3MP2BHandHLYP) in combination with the SMD implicit solvent model. The results showed that the barrier height of the reaction significantly decreased (>120 kJ/mol) in the presence of catalysts. The computed and measured thermodynamic properties were in good agreement with each other. This proves the important role of amine catalysts in urethane synthesis.

Experimental and Theoretical Study of Cyclic Amine Catalysed Urethane Formation

The alcoholysis of phenyl isocyanate (PhNCO) using stoichiometric butan-1-ol (BuOH) in acetonitrile in the presence of different cyclic amine catalysts was examined using a combined kinetic and mechanistic approach. The molecular mechanism of urethane formation without and in the presence of cyclic amine catalysts was studied using the G3MP2BHandHLYP composite method in combination with the SMD implicit solvent model. It was found that the energetics of the model reaction significantly decreased in the presence of catalysts. The computed and measured thermodynamic properties were in good agreement with each other. The results prove that amine catalysts are important in urethane synthesis. Based on the previous and current results, the design of new catalysts will be possible in the near future.

Rapeseed oil gallate-amide-urethane coating material: Synthesis and evaluation of coating properties

Abstract The present manuscript describes the synthesis of urethane (ROGAU) coating material from Rapeseed oil (RO), Gallic acid (GA) and Toluylene-2,4-diisocyanate [TDI], for the first time. The reaction was accomplished in the following steps: (i) amidation of RO, producing diol fatty amide, HERA, followed by (ii) gallation reaction of HERA with GA, resulting in RO-based gallate amide (ROGA). The structural elucidation by FTIR and NMR confirmed the insertion of amide and ester moieties in the ROGA backbone. To add applicational value to ROGA, it was then derivatized by urethanation reaction with TDI to develop ambient temperature-cured ROGAU, as a corrosion protective coating material. ROGAU coatings were scratch resistant, well-adherent, and flexible to a considerable extent and showed good corrosion resistance performance toward saline medium (3.5 wt% NaCl). ROGAU coatings can be safely used up to 200°C.

New Thermal Latent Catalyst Using Titanium and Organic Ligand for Urethane Polymerization.

New thermal-latent metal catalyst such as tetrakis (lauorate) titanium (LPTi) was designed and synthesized based on a lauroyl peroxide and titanium. The synthetic method is simple with one step reaction. LPTi structure was confirmed by FT-IR analysis, also nano-sized structure of LPTi confirmed using SEM-EDX. LPTi is thermal-latent metal catalyst including titanium that not only promotes urethane synthesis reaction but also increases the dissociation rate of blocked isocyanate. As a result of quantitative analysis of NCO (%) through back titration, when LPTi was added, NCO (%) increased from 2.34% to 3.24%. LPTi can be used as an excellent catalyst for urethane reaction by reducing the polymerization time by about 30% compared to no catalyst. LPTi can be applied to the electronic polymer synthesis.

Synthesis of amino alcohols, cyclic urea, urethanes, and cyclic carbonates and tandem one-pot conversion of an epoxide to urethanes using a Zn–Zr bimetallic oxide catalyst

The one-pot tandem synthesis of urethanes directly from an epoxide, with urea in solvent-free condition using Zn2ZrOx is demonstrated. The catalyst exhibits excellent activity in cyclic urea, urethane, and cyclic carbonate production in neat conditions.

Chemical Reaction of Carbon Dioxide with Bisepoxides for Synthesis of Organic Cyclic Dicarbonates at Ambient Pressure for Polyhydroxy Urethane Synthesis

The synthesis of multifunctional cyclic carbonates starting from different epoxides will most likely be an important step to open an alternative way for an isocyanate-free formation of linear and c...

Synthesis of Urethanes Using Carbon Dioxide as Raw Material

Synthesis of Urethanes Using Carbon Dioxide as Raw Material

Development of epoxy-urethane hybrid coatings via non-isocyanate route

Non-isocyanate route of urethane synthesis based on reaction of cyclic carbonated compound with amines is well known. Taking inspiration from this, we have synthesized a monomer containing urethane linkage through the reaction of propylene carbonate with ethylene diamine. This monomer was further reacted with commercial epoxy polymer to obtain hybrid epoxy-urethane adduct. Synthesized adduct was then cured with various structural amines such as isophorone diamine (IPDA), Jeffamine T-403 and diaminodiphenyl methane (DDM). The resultant epoxy-urethane hybrid coatings were characterized for mechanical, chemical, thermal and anticorrosive properties. The hybrid coatings exhibited at par mechanical, chemical and corrosion resistance as compared to that of commercial epoxy coatings. DSC and TGA analysis revealed that glass transition temperature, thermal stability and char yield of hybrid coatings was higher than that of commercial epoxy coatings.

Synthesis of urethane—acrylic multi-block copolymers via electrochemically mediated ATRP

AbstractThe electrochemically mediated atom transfer radical polymerisation (

Development of Poly (Ester Amide-Urethanes) from De-saturated Thevetia peruviana Seed Oil-FAMEs

This study present the synthesis of eco - friendly poly(ester amide - urethane) coating from Thevetia peruviana seed oil (TPSO). FT - IR, 1 H NMR and 13 C NMR spectral analyses were used in confirming the structure of compounds. Physico - chemical properties of desaturated N,N' - bis (2 hydroxyethyl) Thevetia peruviana seed oil fatty amide (DHETA), poly(ester amide) (PESA) and poly(ester amide urethanes) (PESA U), as well as chemical resistance, antibacterial studies and thermal analysis of PESAU were also examined. Aims: To evaluate the thermal stability and antibacterial activities of PESAU. Study Design: Extraction of seed oil from the air - dried seedlings of Thevetia peruviana seeds and preparation of polyol through urea fractionation. Followed by urethane synthesis using 4,4'

The preparation of UV-cured superhydrophobic cotton fabric surfaces by electrospinning method

Electrospinning was used for the coating of the polyurethane/silica hybrid solutions on the cotton fabric surface. An ultraviolet curing process was performed on the collector by an ultraviolet lamp positioned inside the electrospinning cabin. In order to investigate the effect of fluorinated, silane-functionalized urethane (inorganic part) content on the water-repellency; five different fluorinated concentrations (10%, 20%, 30%, 40%, and 50% by weight) were used. The disappearance of isocyanate peaks during the silane-functionalized urethane synthesis was observed by Fourier transform infrared spectroscopy. Surface morphology and elemental analysis of the coated cotton fabric surfaces was investigated by scanning electron microscopy and energy dispersive spectroscopy analysis respectively. Water-repellency was evaluated by contact angle measurements. A sample that contained 50% inorganic part showed a contact angle of 154.5°. Samples were thermally characterized by differential scanning calorimetry. Glass transition temperature of the synthesized hybrid polymer increased with increasing inorganic part ratio. Additionally, abrasion resistance and crease recovery angle tests were performed to evaluate the effect of fluorinated part percentage on the mechanical and comfort properties of fabrics.

Efficient green synthesis of bis(cyclic carbonate)poly(dimethylsiloxane) derivative using CO2 addition: a novel precursor for synthesis of urethanes

Poly(dimethyl siloxane), PDMS, with terminal cyclic carbonate groups was prepared by cycloaddition of carbon dioxide to epoxy rings using tetra alkyl-ammonium bromide as a catalyst under efficient and mild conditions.

ChemInform Abstract: Palladium-Mediated Synthesis of Urethanes from Amines, Carbon Dioxide, and Cyclic Diolefins.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

ChemInform Abstract: Synthesis of Urethanes and Azidocarbonyls of the 1,2,3-Triazole Series.

ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Hydroxyl‐terminated poly(urethane acrylate) as a soft liner in dental applications: Synthesis and characterization

AbstractHydroxyl‐terminated poly(urethane acrylate)s were synthesized for use in biomedical applications. Acrylate end capping via an interesterification reaction was successfully achieved with methacryloyl chloride addition to the hydroxyl ends of the polyurethane at low temperatures. 2,4‐Toluene diisocyanate, 1,6‐hexane diisocyanate, and methylene diphenyl diisocyanate were used as diisocyanates for urethane synthesis, and they were end‐capped with methyl methacrylate and hydroxyethyl methacrylate. The nature of the monomers that we used had an effect on the thermal and morphological properties that were interpreted in terms of the level of hydrogen bonding and the degree of phase separation. The synthesized polymers were characterized by NMR, Fourier transform infrared/attenuated total reflectance spectroscopy, differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography. The number‐average molecular weights of the poly(urethane acrylate)s were 2500–6000 g/mol. To use the polymer as a soft‐liner material in denture applications, the residual isocyanate should not exist. In this study, we showed that a prepolymer without residual isocyanate could be synthesized. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Frontal free‐radical copolymerization of urethane–acrylates

AbstractWe report the first synthesis of urethane–acrylate copolymers via free‐radical frontal polymerization. In a typical run, the appropriate amounts of the reactants (urethane–acrylate macromonomer and 2‐hydroxyethyl acrylate) and initiator (ammonium persulfate) were dissolved in dimethyl sulfoxide. Frontal polymerization was initiated by the heating of the wall of the tube with a soldering iron, and the resultant hot fronts were allowed to self‐propagate throughout the reaction vessel. Once it was initiated, no further energy was required for the polymerization to occur. The dependence of the front velocity and front temperature on the initiator concentration was investigated. The front temperatures were between 55 and 65 °C, depending on the persulfate concentration. Thermogravimetric analysis indicated that the urethane–acrylate copolymers had higher thermal stability than pure frontally prepared polyurethane. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3018–3024, 2006