Isocyanates reactions forming isocyanate

The water-isocyanate reaction forming carbon dioxide is commonly used to form open-cell flexible foams. Trichlorofluoromethane (TCFM) is a physical blowing agent relying on heat from the urethane reaction exotherm to boil this is used to form rigid closed-cell foams and most self-skinned moulded products. There is considerable concern over the effect of fluorocarbons on the Earth s ozone layer, and suitable replacements are actively being sought. 

Further reaction of the active hydrogens on nitrogen in the urethane groups (3) can occur with additional isocyanate (1) at higher temperatures to cause formation of aHophanate stmctures. The active hydrogens in urea groups can also react with additional isocyanate to form disubstituted ureas which can stiU further react with isocyanate to form biurets (13). 

A variety of olefins or aromatic compounds having electron-donating substituents are known to undergo C—H iasertion reactions with isocyanates to form amides (36,37). Many of these reactions are known to iavolve cycHc iatermediates. 

Isocyanates iasert iato RO and RN bonds. CycHc ethers, such as oxiranes, are known to undergo reactions with isocyanates to form 2-oxa2oHdinones ia high yield (38—40). 

A large number of Diels-Alder-type reactions, involving both aromatic and sulfonyl isocyanates, have been reported. Heterodienes having high electron density ate found to add to isocyanates to form sis membered heterocycles as shown in Figure 2 (48—50). 

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

Similarly, thioalcohols and thiophenols react with isocyanates to form thiocarbamates. Although these reactions are generally found to be much slower than that of the corresponding alcohol, alkoxide catalysts have successfully been used to provide moderate levels of rate enhancement (68). 

Industrially, polyurethane flexible foam manufacturers combine a version of the carbamate-forming reaction and the amine—isocyanate reaction to provide both density reduction and elastic modulus increases. The overall scheme involves the reaction of one mole of water with one mole of isocyanate to produce a carbamic acid intermediate. The carbamic acid intermediate spontaneously loses carbon dioxide to yield a primary amine which reacts with a second mole of isocyanate to yield a substituted urea. 

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. 

V-Phenylsuccinimide [83-25-0] (succanil) is obtained in essentially quantitative yield by heating equivalent amounts of succinic acid and aniline at 140—150°C (25). The reaction of a primary aromatic amine with phosgene leads to formation of an arylcarbamoyl chloride, that when heated loses hydrogen chloride to form an isocyanate. Commercially important isocyanates are obtained from aromatic primary diamines. 

AH of the amine hydrogens are replaced when MDA or PMDA reacts with epoxides to form amine based polyols. These polyols can be used in reactions with isocyanates to form urethanes or with additional epoxide to form cross-linked thermo set resins. 

The water reaction evolves carbon dioxide and is to be avoided with solid elastomers but is important in the manufacture of foams. These reactions cause chain extension and by the formation of urea and urethane linkages they provide sites for cross-linking, since these groups can react with free isocyanate or terminal isocyanate groups to form biuret or allophanate linkages respectively (Figure 27.5). 

An isocyanate 2 formed by a Curtius rearrangement can undergo various subsequent reactions, depending on the reaction conditions. In aqueous solution the isocyanate reacts with water to give a carbaminic acid 6, which immediately decarboxylates to yield an amine 3. When alcohol is used as solvent, the isocyanate reacts to a carbamate 7 ... 

Isocyanates react with carboxylic acids to form amides, ureas, anhydrides, and carbon dioxide, depending on reaction conditions and the structure of the starting materials (Scheme 4.13). Aliphatic isocyanates more readily give amides. Aromatic isocyanates tend to react with carboxylic acids to first generate anhydrides and ureas, which at elevated temperatures (ca. 160°C) may further react to give amides. In practice, the isocyanate reaction with carboxylic acid is rarely utilized deliberately but can be an unwanted side reaction resulting from residual C02H functionality in polyester polyols. 

Impurities in CL have also been destroyed by oxidation with ozone22 followed by distillation. Ozonation treatment of waste CL leaves no ionic impurities. However, the most commonly used oxidizing agents are potassium permanganate, perboric acid, perborate, and potassium bromate. Treatment of CL with these oxidizing agents is carried out in a neutral medium at 40-60°C. Strongly alkaline or acidic conditions accelerate the oxidation of CL to form isocyanates. Hie undesirable oxidation reaction is fast above pH 7 because of the reaction with isocyanate to form carbamic acid salts, which shifts the equilibrium to form additional isocyanate. 

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...

Subsequent experiments on the same system aimed to determine the stability of the isocyanate species and to measure the reactivity of the Pd(lll) model catalyst for the CO + NO reaction.125 When exposing the sample to different CO/NO ratios (2 and 1.5) at room temperature, peaks were obtained which corresponded to threefold NO, atop NO, and threefold CO, with the higher CO/NO ratio leading to a greater amount of CO binding. When the samples were flashed to 650 K and cooled back to 300 K in the presence of the reaction mixtures, isocyanate was formed. However, as is apparent from Figure 10.25, an increase in the CO/NO ratio strongly favored isocyanate formation. 

Reactions with Isocyanates. The reaction of alcohols with isocyanates to form carbamates is well known and similar reactions with poly(vinyl alcohol) would be expected. Until recently, the only available reaction conditions were to use a heterogeneous reaction mixture or to run the reaction in a poor solvent for poly(vinyl alcohol). The best poly(vinyl alcohol) solvents, water and formaide derivatives, react rapidly with isocyanates. Nevertheless, several such reactions have been run in the past and we will cite only a few of them. A potentially photosensitive polymer was made by the reaction of allyl isocyanate with poly(vinyl alcohol) (57) and several workers have crosslinked poly(vinyl alcohol) with hexamethylene diisocyanate (58.59). 

Isocyanates are capable of co-reacting to form dimers, oligomers and polymers. For example, aromatic isocyanates will readily dimerize when heated, although the presence of a substituent ortho to the -NCO group reduces this tendency. For example, toluene diisocyanate (TDI) is less susceptible to dimer formation than diphenylmethane diisocyanate (MDI). The dimerization reaction is reversible, with dissociation being complete above 200 °C. It is unusual for aliphatic isocyanates to form dimers, but they will readily form trimers, as do aromatic isocyanates. The polymerization of aromatic isocyanates is known, but requires the use of metallic sodium in DMF. 

It should be noted that isocyanates react with DMF to form bicychc ureas or isocyanurates (Chadwick and Cleveland, 1981). DMF is an unsuitable solvent for wood isocyanate reactions because of these side reactions. 

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