Epichlorohydrin reaction with amine

Schlack [2] and Castan [3,4] are credited with the earliest U.S. patents describing epoxy resin technology. Greenlee [5] further emphasized the use of bisphenols and their reaction with epichlorohydrin to yield diepoxides capable of reaction with crude tall oil resin acids to yield resins useful for coatings. The use of diepoxide resins that are cured with amines was reported by Whittier and Lawn [6] in a U.S. patent in 1956. 

Reaction with epichlorohydrin (the chloroepoxide shown below) followed by amine displacement puts in one of the side chains and nucleophilic substitution with morpholine on the ring completes the synthesis. 

Reaction with epichlorohydrin followed by amine displacement puts in one of the side ---------------------------------------------... 

PoIya.mines are condensation polymers containing nitrogen they are made by a variety of synthetic routes. Most of the commercial polyamines are made by reaction of epichlorohydrin with amines such as methylamine [25988-97-0] or dimethylamine [39660-17-8] (18,19). Branching can be increased by a dding small amounts of diamines such as ethylenediamine [42751-79-1]. A typical stmcture of this type of polyamine is stmcture (9). 

Compounds are prepared by a fairly standard sequence which consists of condensation of an appropriate phenol with epichlorohydrin in the presence of base. Attack of phenoxide can proceed by means of displacement of chlorine to give epoxide (45) directly. Alternatively, opening of the epoxide leads to anion 44 this last, then, displaces halogen on the adjacent carbon to lead to the same epoxide. Reaction of the epoxide with the appropriate amine then completes the synthesis. 

Epoxyfunctional siloxanes are also useful as softeners. These may be derived from polysiloxane (10.231) or from aminopolysiloxanes (10.232). Further possibilities are represented by the polyalkoxylated epoxyfunctional silicones (10.233) and polyalkoxylated aminofunctional silicones (10.234). However, it has been pointed out [485] that the reaction of epichlorohydrin with aminopolysiloxanes is not very specific, since primary and secondary amine groups are usually randomly epoxidised resulting in viscous products that... 

Figure 25.9 Epichlorohydrin can be used to activate the hydroxyl group of mPEG, creating an epoxy derivative. Reaction with amine-containing molecules yields secondary amine bonds.

The reaction of amines or tosylamide with epichlorohydrins gives mixtures of epimeric l,5-disubstituted-l,5-diazocane-3,7-diols (263) in 20-30% yields. The t-alkylamino-epoxides (264) can be isolated and dimerized in methanol solution a sterically demanding R group is essential (67T2123). The diols (263 R = Tos, R = Me) were converted to dichlorides and thence to the dienes (265) and (266) (67JOC2425). 

Synthesis Epoxy resins consisting ofglycidyl ether, ester and amines are generally prepared by the condensation reaction between diol, dibasic acid or amine and epichlorohydrin in the presence of sodium hydroxide with the elimination of hydrochloric acid. The commercially available epoxy resins are, however, made by the reaction of epichlorohydrin and bisphenol-A. Cashew nut shell liquid (CNSL)-based novolac epoxy resins have also been reported [342]. 

Another major group of epoxy monomers derived from epichlorohydrin is that comprising monomers synthesized with an aromatic amine, such as aniline (DGA), para-aminophenol (TGpAP) and methylene dianiline (TGMDA) - (Table 2.1 e, f, and g). The reaction of epichlorohydrin with an alcohol is more difficult. Liquid monomers based on butanediol, neo-pentylglycol, and polypropylene oxide (molar mass in the range of 500 g mol-1), are the most common. 

Eisleb noted the reaction of epichlorohydrin with secondary amines and subsequent dehyrogenation with caustic. 

Various aminoalkyl and alkylaminoalkyl halides react with starch in alkaline media and are readily available by the reaction of epichlorohydrin with primary, secondary, and tertiary amines and even aqueous ammonia. Prior to the reaction with starch, the quaternary ammonium compounds were either decomposed to free amines, or they reacted as amminium compounds to give cationic aminium starches. Cationic starches were produced by the reaction of starch with arylalky-laminoalkyl epoxides. In the presence of formaldehyde, inorganic ammonium salts provided the source of amino groups.1316... 

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