United States Patent Office Patented July 11, 1967
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3,330,782 United States Patent Office Patented July 11, 1967 1. 2 employ the classical Williamson ether synthesis, for ex 3,330,782 ample: BETA-(N,N-DEMETHYLAMINO)ALKYL ETHERS AS CATALYSTS FOR ISOCYANATE REACTIONS (CH3)2NCHCH2Cl -- NaOCECHN (CH3)2 Fedor Poppelsdorf, Charleston, W. Va., assignor to Union Carbide Corporation, a corporation of New York OCH2CH2N(CH3)2) -- NaCl even No Drawing. Filed Nov. 12, 1963, Ser. No. 323,148 This method can be employed to produce bis(2-(N,N- 19 Claims. (C. 260-2.5) dimethylamino) - 1 - methylethyl]ether and 2-(N,N-di methylamino)ethyl 2 - (N,N-dimethylamino)-1-methyl The invention relates to catalysts for the reaction of or ethyl ether, as reported by Fakstrop et al., Acta Chemica ganic isocyanates with active hydrogen-containing com Scandinavica 7, pages 134-139 (1953). pounds. In one aspect, the invention relates to the use of 0 The process of the invention is preferably employed in certain tertiary amine ethers as catalysts for the reaction the reaction of organic polyisocyanates with composi of organic isocyanates with active hydrogen-containing tions having at least 2 active hydrogen atoms, although compounds. In another aspect, the invention relates to monofunctional reactants can be employed, for example, the production of polymeric reaction products by the re 5 in the production of compositions useful as plasticizers action of organic polyisocyanates with active hydrogen and in organic syntheses. Among the organic isocyanates containing compounds. that can be employed in the invention are monoisocy Tertiary amines as a class generally show catalytic ac anates such as phenyl isocyanate, tolyl isocyanates, benzyl tivity for the reaction or organic isocyanates with active isocyanate, xylyl isocyanates, hexyl isocyanate, and other hydrogen-containing compounds. For example, see "Part 20 aromatic and aliphatic isocyanates. Preferred isocyanates IV. Kinetics and Catalysis of Reactions' of Saunders et for use in the process of the invention are organic poly al. "Polyurethanes: Chemistry and Technology-Part I. isocyanates. Illustrative polyisocyanates include, among Chemistry,” Interscience Publishers. However, there are others, 2,4- and 2,6-tolylene diisocyanate, 3,3'-tolidene only a few tertiary amines that have attained commercial 4,4'-diisocyanate, isocyanates produced by phosgenation importance as catalysts for the reaction of organic isocy 25 of the condensation products of formaldehyde and vari anates with active hydrogen-containing compounds. The ous aromatic amines such as bis(3-methyl-4-isocyanato most active of such tertiary amine catalysts are 1,4-di phenyl)methane, bis(4-isocyanatophenyl)methane, and azabicyclo[2.2.2]octane and N,N,N',N'-tetramethyl-1,3- isocyanates disclosed in U.S. Patent No. 2,683,730, and butanediamine. U.S. Patent 2,941,967 discloses the use of the like. Additional polyisocyanates that are usefui in the certain tertiary amines that contain ether oxygen as cat 30 invention include 1,5-naphthalene diisocyanate, xylylene alysts in polyurethane foams. These tertiary amine ethers diisocyanates, 1,3-phenylene diisocyanate, tris(4-isocyana have not attained commercial importance as catalysts in tophenyl)methane, chlorophenylene diisocyanates, hexa the polyurethane industry because their catalytic power in methylene diisocyanate, bis(3-isocyanatopropoxy)ethane, accelerating the isocyanate-active hydrogen reaction is and many others. Other organic monoisocyanates and substantially weaker than, for instance, the two amines 35 polyisocyanates than can be employed in the process of mentioned above which have attained such commercial the invention are disclosed in the literature, for example, importance. in an article by Siefken, Annalen 562, pages 75-135 In accordance with the present invention it has been (1949), in U.S. Patents 3,093,451 and 3,084,177 and in discovered that a certain class of tertiary amine ethers the Saunders et al. text (cited above). The aromatic display surprising and unexpected strength in accelerating 40 polyisocyanates are particularly useful in the invention, the isocyanate-active hydrogen reaction. The tertiary especially the tolylene diisocyanates and the polyisocy amine ethers which are employed in the invention are the anates produced by phosgenation of the condensation bisbeta-(N,N-dimethylamino) alkyl ethers wherein the products of aniline and formaldehyde. alkyl is either ethyl or propyl. Accordingly, the process of In the process of the invention one or more organic the invention comprises reacting an organic isocyanate 45 isocyanates are reacted with one or more active hydro with an active hydrogen-containing compound in the gen-containing compounds. The active hydrogen com presence of a catalytic quantity of a bis beta-(N,N-di pounds contemplated are those which contain reactive hy methylamino) alkyll ether wherein said alkyl is either drogen as determined by the procedure described by Zere ethyl or propyl. witinoff, J. Am. Chem. Soc., 49, page 3181 (1927). The bisbeta-(N,N-dimethylamino) alkyl ethers that 50 Among the various classes of compounds that contain re are employed in the process of the invention are bis(2-(N, active hydrogen are alcohols, water, amines, ureas, ure N - dimethylamino)ethyl ether, bis(2-(N,N-dimethyl thanes, phenols, thiols, carboxylic acids, and the like. The amino)-1-methyl-ethyl ether, and 2-(N,N-dimethyl preferred active hydrogen-containing reactants are water amino)ethyl 2 - (N,N-dimethylamino) - 1 - methylethyl and primary and secondary alcohols. Since urethanes, ether. The preferred tertiary amine ether is bis(2-(N,N- 55 amines, and ureas are produced when an isocyanate is dimethylamino)ethyl ether. reacted with an alcohol and water, urethanes, amines, and Bis(2-(N,N-dimethylamino)ethyl ether can be pro ureas are also preferred reactants. The amines are also duced by the reaction of bis(2-chloroethyl) ether with very useful reactants in many cases, for example, when the excess dimethylamine. This synthesis is reported in the process of the invention is employed to produce an amine literature, for instance, by Marxer et al., K. Helv. Chim. 60 cured elastomer. Acta 34,924 (1951) and by Hromataka et al., Monatsh. A large variety of alcohols can be used in the inven 84, 349 (1953). Another route to this compound is to tion. For instance, alkanols such as methanol, ethanol, 3,330,782 3 4. 2-propanol, butanol, 2-ethylhexanol, and many other deserve particular mention are the alkylene oxide adducts alkanols. The preferred alcohols for use in the invention of aniline or substituted-aniline/formaldehyde conden are the polyols, for instance, one or more polyols from sation products. the following classes of compositions: A further class of polyols which can be employed are (a) Hydroxyl-terminated polyesters and polyester the non-reducing sugars, the non-reducing Sugar deriva ethers; tives, and more preferably, the alkylene oxide adducts (b) Polyhydroxyalkanes and alkylene oxide adducts thereof wherein the alkylene oxides have from 2 to 4 thereof; carbon atoms. Among the non-reducing Sugars and Sugar (c) Triakanolamines and alkylene oxide adducts derivatives contemplated are sucrose, alkyl glycosides thereof; such as methyl glucoside, ethyl glucoside, and the like, (d) Alcohols derived from mono- and polyamines by polyol glycosides such as ethylene glycol glucoside, addition of alkylene oxides; propylene glycol glucoside, glycerol glucoside, 1,2,6-hex (e) Non-reducing sugar and sugar derivatives and anetriol glucoside, and the like. alkylene oxide adducts thereof; A still further useful class of polyols are the alkylene (f) Alkylene oxide adducts of aromatic amine/phenol/ oxide adducts of polyphenols wherein the alkylene oxides aldehyde ternary condensation products; have from 2 to 4 carbon atoms. Among the polyphenols (g) Alkylene oxide adducts of phosphorus and poly which are contemplated are found, for example, bis phosphorus acids, and various hydroxyl-terminated phos phenol A, bisphenol F, condensation products of phenol phites and phosphonates; and formaldehyde, more particularly the novolac resins, (h) Alkylene oxide adducts of polyphenols; 20 condensation products of various phenolic compounds (i) Polytetramethylene glycols; and acrolein, the simplest members of this class being (j) Functional glycerides, such as castor oil; the 1,1,3-tris(hydroxyphenyl)propanes, condensation (k) Hydroxyl-containing polymers; and the like. products of various phenolic compounds and glyoxal, Illustrative hydroxyl-terminated polyesters are those glutaraldehyde, and other dialdehydes, the simplest mem which are prepared by polymerizing a lactone (pref bers of this class being the 1,1,2,2-tetrakis(hydroxy erably, an epsilon-caprolactone) in the presence of an phenyl)ethanes, and the like. active hydrogen-containing starter as disclosed in U.S. Another desirable class of polyols are the alkylene Patents 2,914,556; 2,890,208; 2,878,236; and 2,977,385. oxide adducts, preferably the ethylene oxide, 1,2-epoxy Polyesters from adipic acid and diols such as ethylene propane, epoxybutane, and mixutres thereof, adducts of glycol, propylene glycol, diethylene glycol, dipropylene 30 aromatic amine/phenol/aldehyde ternary condensation glycol, and the like, and triols such as 1,1,1-trimethylol products. The ternary condensation products are pre propane, 1,2,6-hexanetriol, glycerol, and others, are also pared by condensing an aromatic amine, for instance useful. Copolymers of lactones and alkylene oxides such aniline, toluidine, or the like, a phenol such as phenol, as those described in U.S. Patent 2,962,524, can also be cresol, or the like, and an aldehyde preferably formalde used with good results. hyde, at elevated temperatures in the range of, for ex Illustrative polyhydroxyalkanes include, among others ample, from 60° C. to 180° C. The condensation product ethylene glycol, propylene glycol, 1,3-dihydroxypropane, is then recovered and reacted with alkylene oxide, using 1,3-dihydroxybutane, 1,4-dihydroxybutane, 1,4-, 1,5-, a basic catalyst (e.g., potassium hydroxide) if desired, to and 1,6-dihydroxyhexane, 1,2-, 1,3-, 1,5-, 1,6-, and 1,8- produce the polyols.