Patent GB-972772-A (GB)
Title: Improvements in or relating to the manufacture of polyurethanes
Inventor: CHAPMAN JOHN FREDERICK
IPC: C08G18/50
Filed: 1960-02-12
Abstract: Polyurethane reaction products are obtained by interaction of an organic polyisocyanate and a polyether which contains two or more hydroxyl groups and at least two tertiary amino groups of which the N atoms are each directly attached to aromatic carbon atoms.  The N may be attached to the same or different substituted or unsubstituted aromatic hydrocarbon radicals, e.g. phenyl, mono-, di-, or tri-alkyl phenyl where each alkyl contains 1-8 C atoms, benzyl phenyl alkyl substituted benzyl-phenyl, or halogen substituted radicals such as chlorphenyl or benzyl chlorphenyl. The polyethers may be the reaction products of 1:2 alkylene, e.g. ethylene, butylene, or propylene, or mixtures, oxides with compounds containing at least two primary or secondary aromatic amino groups or one primary and one tertiary aromatic amino group e.g. o-, m-, or p-phenylene diamine, 2:4- and 2:6-diaminotoluene, 4:41 diaminodiphenylmethane and other aniline-formaldehyde reaction products 4-aminodiphenylamine, N:N-diethyl-p-phenylene diamine, 2:4:6-triaminotoluene, 2:4:41-triamino diphenylmethane, and 4:41 diaminodiphenylamine, or mixtures.  From 1 to 10 mol. proportions alkylene oxide for each equivalent proportion of H in the amino groups are used at 70-130 DEG C. and 0-50 p.s.i.g. to form polyethers of average mol. wt. 350-1200. The reaction is in aqueous or alcoholic solution in the presence of KOH and water or alcohol is subsequently distilled off.  Where KOH is used the reaction mixture is neutralised by acid, e.g. glacial acetic or CO2, and the formed salt filtered.  The reaction may be effected in stages with the same or different alkylene oxide, e.g. mono-, di-, tri-, or tetrab -hydroxyl ethyl-2:4-diaminotoluene may be the intermediate, which is further reacted, Isocyanates are hexamethylene diisocyanate. tolylene-2:4-, tolylene-2:6-, diphenyl methane-4:41-, 3 methyldiphenylmethane-4:41-, m- and p-phenylene-, chlorophenylene-2:4-, naphthalene-1:5-, diphenyl-4:41-diisocyanates, 4:41-diisocyanato-3:31-dimethyldiphenyl, diphenyl ether diisocyanate, dicyclohexylmethane diisocyanate, 2:4:6-triisocyanatotoluene, 2:4:41-triisocyanatodiphenyl ether, polyisocyanates obtained by reacting excess diisocyanate with trimethylol propane and uretedione dimers, isocyanurate polymers of tolylene-2:4-diisocyanate, or mixtures of polyisocyanates obtained by phosgenation of reaction products of formaldehyde with aniline or o-toluidine.  The polyurethanes may be rigid or flexible, and solid or cellular form. Foamed polyurethanes are formed by reacting polyether and polyisocyanate with up to 20% water, 1-100% of low boiling (-40 to 50 DEG C.) organic liquid blowing agent may also be added, e.g. halogen substituted hydrocarbons particularly containing at least one F atom and a number are exemplified.  The reaction mixture may include not more than an equal weight of polyhydric alcohols, containing 2 or more OH groups and one or more aliphatic N groups, which are listed. Exemplified tertiary amine or organo metallic catalysts may be present, as well as other listed additives.  In examples: (1) a resin is prepared by stirring water, tri-(b -chloroethyl) phosphate, the reaction product of ethylene oxide and cetyl/oleyl alcohol mixture, aqueous dimethylbenzylamine lactate solution, and polyether.  This polyether is prepared by reacting diaminodiphenylmethane in a pressure vessel at 100-120 DEG C. with ethylene oxide and KOH.  The resin is reacted with 4:41-diisocyanatodiphenyl methane to form polyurethane. (3) A resin from oxypropylated tolylene diamine, polysiloxane-polyoxyalkylene block copolymer, and trichloromonofluoromethane is reacted with a mixture of tolylene-2:4- and 2:6-diisocyanates, and (5) dibutyl tin dilaurate catalyst may be used. (6) and (10) Oxypropylated-4:41-diaminodiphenyl methane is reacted as in (1) with, or without, triethanolamine.  (13) and (15) are similar to (1) but start from oxyethylated tolylene diamine and the reaction product of ethylene oxide and octyl cresol respectively. Specification 848,965 also is referred to.