Reactions of isocyanates

Isocyanates will react with all compounds containing hydrogen atoms attached to a nitrogen atom [2]. There are four basic reactions chemists employ to make polyurethanes. The reaction of isocyanates with hydroxyl groups to produce urethane is the primary reaction. The reaction of isocyanates with amines yields urea and the reactions of isocyanates with urea and urethane produce biurets and allophanates, respectively. 

When a mixture of KF and K[OCN] in cylinders of brass gauze (within a copper reactor) was treated with a F /N mixture at 50-55 C, the principal products were CF3OF, NFj and KF, with small amounts of COF and CO 3 being formed [2220]. However, the analogous reaction with Ag[OCN] produces COFj as the principal reaction product, along with 

The alkali metal fluorides, KF, CsF or NaF, catalyse the polymerisation of gaseous chloroisocyanate, CINCO, but COFj is formed as a by-product of the reaction, according to [805]  

Indeed, FNCO is unstable at room temperature, even in the gas phase, and its reactions and decompositions generally produce COF 3, either as one of the main products, or as a by-product [749a]. 

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A comprehensive review of reactions of isocyanates and 1,3-dipolar compounds has been previously pubhshed (51). The example shown illustrates the reaction of azides and isocyanates to yield tetrazoles (14,R = alkyl or aryl, R = aryl or sulfonyl) (52,53). 

Addition Polymers. The most commonly referenced reaction of isocyanates iavolves their addition to polyhydroxyl, polyamine, or polycarboxyhc acid compounds to yield addition polymers. Due to the wide diversity of raw material characteristics and the broad range of functionahty, polyurethane polymers having a wide range of processiag and performance characteristics are available. 

The reaction of isocyanates with alcohols to form carbamates is catalyzed by amines and a variety of organometaHic compounds. 

Conversely, the rate of reaction of isocyanates with amines to yield ureas is both rapid and quantitative. Much has been written concerning the reaction... 

Primary cycloaUphatic amines react with phosgene to form isocyanates. Reaction of isocyanates with primary and secondary amines forms ureas. Dehydration of ureas or dehydrosulfuri2ation of thioureas results in carhodiimides. The nucleophilicity that deterrnines rapid amine reactivity with acid chlorides and isocyanates also promotes epoxide ring opening to form hydroxyalkyl- and dihydroxyalkylaniines. Michael addition to acrylonitrile yields stable cyanoethylcycloalkylarnines. 

The fillers used in urethane formulations are similar to those used in sihcones calcium carbonate, talc, clays, and siUca are among the most common. On account of the undesirable reaction of isocyanates with water, fillers used in urethane formulations must be dry. 

In the manufacture of highly resident flexible foams and thermoset RIM elastomers, graft or polymer polyols are used. Graft polyols are dispersions of free-radical-polymerized mixtures of acrylonitrile and styrene partially grafted to a polyol. Polymer polyols are available from BASF, Dow, and Union Carbide. In situ polyaddition reaction of isocyanates with amines in a polyol substrate produces PHD (polyhamstoff dispersion) polyols, which are marketed by Bayer (21). In addition, blending of polyether polyols with diethanolamine, followed by reaction with TDI, also affords a urethane/urea dispersion. The polymer or PHD-type polyols increase the load bearing properties and stiffness of flexible foams. Interreactive dispersion polyols are also used in RIM appHcations where elastomers of high modulus, low thermal coefficient of expansion, and improved paintabiUty are needed. 

Because of their great versatility there continues to be a steady stream of developments of polymers made by reaction of isocyanates. In addition to the materials discussed in this chapter there are, to name but three, the polyureas, the polyoxazolidinones and polybenzoxazinediones. 

Fig, 17. (a) Isocyanate-terminated polyurethane prepolymer synthesis, (b) Moisture cure of isocyanate-terminated polyurethane prepolymers, (c) Side reactions of isocyanate-terminated polyurethane prepolymers. 

The reaction of isocyanates with enamines disubstituted at the -carbon gives -amino- -lactams (107,108). Thus the enamine (16) reacted exothermally with phenylisocyanate to give (33) dimethyl-l-phenyl-4-dimethylamino-2-acetidinone (157), which was converted by acid hydrolysis to 2-formyl-2-methyl propionanilide (158). 

The synthesis of 5-aminothiazoles via the reaction of isocyanate derivatives with aminomalononitrile p-toluenesulfonate (AMNT) has been investigated. It was found that AMNT 12 reacted with alkyl and aryl isothiocyanates in l-methyl-2-pyrrolidine (NMP) to furnish 5-amino-2-(alkylamino)-4-cyanothiazoles (13a) and 5-amino-2-(arylamino)-4-cyanothiazoles (13b-c) in 44-81 % yields. " ... 

Reaction of Isocyanates with Water and Carboxylic Acids... 

Scheme 4.13 Reaction of isocyanates with water and carboxylic acids.

Alcohols, reaction of isocyanates with, 224-225 Alcoholysis, 69 Alicyclic dianhydrides, 297 Alignment coating, for liquid crystal devices, 269-270 Aliphatic AA-BB-type polyamides, synthesis of, 164-173 Aliphatic AB-type polyamides, 173-180 Aliphatic acids, 60... 

This system was slightly modified by R J. Flory, who placed the emphasis on the mechanisms of the polymerisation reactions. He reclassified polymerisations as step reactions or chain reactions corresponding approximately to condensation or addition in Carother s scheme, but not completely. A notable exception occurs with the synthesis of polyurethanes, which are formed by reaction of isocyanates with hydroxy compounds and follow step kinetics, but without the elimination of a small molecule from the respective units (Reaction 1.3). 

Lastly, of course, the main reaction of interest is the formation of urethane groups by reaction of isocyanate groups and hydroxy-groups of the polyester or polyether. Even these reactions do not exhaust the possibilities available to the highly reactive isocyanate group. It will then go on to react with the urethane links to form a structure known as an allophanate (see Reaction 4.13). 

Figure 25.2 Reaction of isocyanate and organic hydroxyl to form a urethane linkage...

Base-catalysed reactions of isocyanates, such as the title compound, with alcohols may be explosively violent in absence of diluting solvents. 

A straightforward preparation of pyrimidinones and pyrimidinethiones 45 involved reaction of isocyanates or isothiocyanates with the readily available starting material 44, which had previously been described by the same authors. A particularly interesting application was the use of sugar isothiocyanates to give nucleosides. Nucleophilic displacements of the sulfur groups in the products were also reported <06EJO634>. 

An improved procedure for preparing urea derivatives involves reaction of isocyanates or isothiocyanates with 4(5)-aminoimidazole (25 R = H) in tetrahydrofuran solution [92JCS(P1)2779]. A THF solution of 4(5)-aminoimidazole (25 R=H) generated in situ and then treated with the appropriate reagent gave either lV-imidazole-4-yl-AT-phenylurea (56 X = 0) (32%) or AT-imidazoM-yl-A/ -phenylthiourea (56 X = S) (21%). 

A Tracer Study of the Reaction of Isocyanates with Carboxylic Acids. J. 

For the reaction of isocyanate with active hydrogen compounds, tertiary amines or tin compounds act on... 

Recently, poly(vinyl alcohol)-isocyanate reactions have been run successfully in dimethylsulfoxide solutions by several lab- oratories, including ours. While there are reports of solvent derived products from the reactions of isocyanates in DMSO (60), these reactions do not seem to pose a problem in the reaction with poly(vinyl alcohol). This solvent has been used to react PVA with methoxymethyl isocyanate (61.62) and a series of isocyanates including methyl, ethyl, isopropyl, phenyl and 1-naphthyl (63). This reaction is illustrated in Equation 17 where R is... 

K. Schwetlick, R. Noack, F. Stebner, Three Fundamental Mechanisms of Base-Catalysed Reactions of Isocyanates with Hydrogen-Acidic Compounds , J. Chem. Soc., Perk. Trans. 2 1994, 599 - 608. 

The synthesis of the oligomers involved the known reaction of isocyanates and cyanamide (Nl CN). For example, N-cyano-N -phenyl urea has been synthesized from phenyl isocyanate and an aqueous alkaline solution of cyanamide in high yield.(3) Recently, similar reactions were used to prepare various di-N-cyanourea compounds from diisocyanates. ( 1) These monomers were also synthesized directly by reacting diisocyanates with cyanamide at melt temperatures. 

Saka and Yakake (1993) chemically modified wood samples with 3-isocyanatopropyl-triethoxysilane (IPTES) (Figure 7.9c). Wood was impregnated with acetone solutions of IPTES of different concentrations. Where the wood had been pre-swollen by treating with pyridine vaponr, a maximnm WPG of 27 % was obtained, whereas without pre-swelling of the cell wall a WPG of only 7 % was obtained. Pyridine also serves as a catalyst for the reaction of isocyanate with wood. SEM-EDXA showed the presence of silicon in the cell walls of the treated wood. Becanse of the lower WPG obtained without cell wall swelling, ASEs of the order of 20 % were obtained, compared to about 60 % when swelling of the cell wall was used prior to reaction. 

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