Amines isocyanate reactions

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. 

Open times of two-component urethanes can vary widely, depending on the level of catalyst. Reaction times can vary from 90 s to over 8 h. Dibutyltin dilaurate is the most common catalyst employed to catalyze the urethane reaction. This is normally added to the polyol side. A tertiary amine may also be added in small amounts. Tin catalysts do not catalyze the amine/isocyanate reaction very well. Acids, such as 2-ethyl hexanoic acid, may be employed to catalyze the amine/isocyanate reaction where needed. 

In this section isocyanate-based polyurea foams ja-oduced by the reaction of the water-isocyanate or amine-isocyanate reactions will be described. Urea-formaldehyde foams will be excluded. The isocyanate-based urea-linkage formation is shown by the following model reactions ... 

Priester et al (141) have found a method of controlling the amine-isocyanate reaction by using substituted-amine-terminated polyethers, and they obtained high-resiliency polyurea foams by this method. Ashida et al (81) prepared low-density flexible polyurea foams by using a primary-amine-terminated polyether (Jefhunine D-2000, Texaco Chemical). 

This paper will describe the reactions of ketene aminals, 1, more highly activated electron-rich alkenes, with isocyanates to again afford amide products. We shall initially discuss the chemistry of the ketene aminal/isocyanate reaction, the preparation of these activated monomers and sane properties of solution-derived model "hard segments". 

Absorption bands at 1320, 1580, and 1920 cm are observed in the spectra of product II. The attribution of the absorption bands made above suggests that sodium carbamates, sodium carbonate, and partially amines are formed on contact with water. To demonstrate the presence of amine in the filtrate, the following experiment was performed 2,4-TDI was added to the product II product III resulting from this reaction was washed with CCI4 and dried, and the IR spec-tnun was obtained. In the product III spectrum the 1620 cm absorption band disappeared the 1550,1640, and 3300 cm bands appeared and the 1320 and 1580 cm bands remained the same. It is concluded that for isocyanate interaction in strong bases (concentration of more than 20%), the carbamates formed in reaction (a) decompose more slowly [reaction (b)] than the amine—isocyanate [reaction (c)]. 

Keywords Additives Aliphatic Aliphatic isocyanates Amine-isocyanate reaction Aromatic isocyanates Blocked isocyanates Chain extenders Construction (application in) Glass transition temperature Hydroxyl-isocyanate reactions Hot melt reactive PU Isocyanates MDl Moisture curing PU One-component PU Packaging (application in) Plastic and composites (application in) Polyester Polyether polyols Polyisocyanates Sealants Silane PU hybrids TDI Testing of PU adhesives testing of PU sealants Testing standards TPU thermoplastic PU Transportation (application in) Two-component PU Water-borne PU... 

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. 

Alkylation of the protected azetidinyl bromide 61 with the anion from m-trifluormethyl-phenol gives ether 62. Removal of the N-(alpha-methylbenzyl)- protecting group by catalytic hydrogenation gives the secondary amine 63. Reaction of that compound with methyl isocyanate gives the anticonvulsant urea fluzinamide (64) [14]. 

I. S. Bechara, The Mechanism of Tin-Amine Synergism in the Catalysis of Isocyanate Reaction with Alcohols, in Urethane Chemistry and Applications, ACS Symposium Series 172, K. N. Edwards, (Ed.), American Chemical Society, Washington, DC, 1981. 

Ammonia and primary and secondary amines can be added to isocyanates to give substituted ureas. Isothiocyanates give thioureas. This is an excellent method for the preparation of ureas and thioureas, and these compounds are often used as derivatives for primary and secondary amines. Isocyanic acid (HNCO) also gives the reaction usually its salts (e.g., NaNCO) are used. Wohler s famous synthesis of urea involved the addition of ammonia to a salt of this acid. "... 

If the ring nitrogen atom forms a secondary amine, its reaction with aryl isocyanate can yield substituted ureas and this transformation is strongly related to a N-acylation. In this respect, a publication by Saczewski and Nasal <1995APH237> should be mentioned here these authors described the transformation of 119 with a number of arylisocyanates to the urea 120 in medium to high yields (49-82%) (Scheme 17). 

Kaldor [49 i, 55] demonstrated the advantages of applying solid-supported scavengers to the preparation of parallel arrays in a multi-step fashion. In these studies he examined the clean-up of multiple amine alkylation and acylation reactions using a variety of immobilized electrophilic and nucleophilic scavenger reagents including an amine, isocyanate, aldehyde and acid chloride (Tab. 2.1). 

De Mello et al. have constructed a so-called pSYNTAS (miniaturized synthesis and total analysis system). The system was used to perform an Ugi-type reaction to form several a-aminoacetamides from amines, isocyanates and formaldehyde in the presence of water (Scheme 25) [56-58]. The reported system consists of a glass/silicon nanoreactor [59] in connection to a TOF-MS for the real-time online analysis of the reaction stream. Reactions were conducted in the 600 nl volume chip under continuous flow of 20-2 pl/min flow rate. Reduced flow rates resulted in increased outputs. The analyzed outlet flow showed high yields of the desired products with small quantities of starting materials and intermediates (no exact yields were reported). 

Tertiary amines catalyze the homopolymerization of epoxy resins in the presence of hydroxyl groups, a condition which generally exists since most commercial resins contain varying amounts of hydroxyl functionality (B-68MI11501). The efficiency of the catalyst depends on its basicity and steric requirements (B-67MI11501) in the way already discussed for amine-catalyzed isocyanate reactions. A number of heterocyclic amines have been used as catalytic curatives pyridine, pyrazine, iV,A-dimethylpiperazine, (V-methylmorpholine and DABCO. Mild heat is usually required to achieve optimum performance which, however, is limited due to the low molecular weight polymers obtained by this type of cure. 

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