Patent GB-848965-A (GB)
Title: Preparation of polyurethane foams
Inventor: MUELLER ERWIN
IPC: C08G18/54
Filed: 1958-05-16
Abstract: A process for the preparation of hydroxyl terminated polyhydroxy condensation compounds comprises the steps of (1) reacting an aryl primary or secondary amine with ethylene oxide or isopropylene oxide to form an aromatic compound of the general formula: <FORM:0848965/IV(a)/1> wherein R represents hydrogen or a methyl group, R, represents an alkyl, cycloalkyl, aryl or aralkyl radical, R11 represents an aryl radical and n is a whole number from 1 to 10, and (2) reacting the said aromatic compound with an aldehyde.  In a modification the arylamine is first condensed with formaldehyde and the resin obtained is reacted with ethylene oxide or isopropylene oxide.  The hydroxyl-terminated polyhydroxy compounds can then be reacted further with an organic polyisocyanate to give a polyurethane.  In this reaction the hydroxy compounds can be mixed with other compounds containing hydroxy groups such as polyesters, polyethers and polyacetals.  A cross-linking agent such as water, alkylene glycol, diamine or aminoalcohol may be reacted simultaneously or subsequently. Cellular products result by using water as the cross-linking agent, suitably in the presence of a tertiary amine.  In another modification the polyhydroxy compound is reacted with less than enough polyisocyanate to react with all the hydroxy groups (in the presence of a tertiary amine containing reactive groups, such as methyldiethanolamine and triethanolamine) and the hydroxy-terminated isocyanate-modified product is reacted with additional polyisocyanate and, if necessary, cross-linking agents. Aromatic amines specified are toluidine, xylidine, 2,6diethyl aniline, cyclohexyl toluidine, chloroaniline, 4-aminodiphenyl and its chlorination products, phenylene diamine, 4,41-diaminodiphenyl methane, triaminotriphenyl methane, alpha or beta naphthylamine, 1,5- and 1,8diaminonaphthalene, N-ethyl-, butyl or cyclohexylaniline, N,N1 - dimethyl - 4,41 - diaminodiphenylmethane, N-methylamino-a - or b -naphthylamine and N,N1-dimethyl-1,8-diaminonaphthalene. Suitable aldehydes are formaldehyde, chloral, benzaldehyde, butyraldehyde, acetaldehyde, furfural, alpha-ethyl-beta-propyl acrolein and 3-hydroxy-2-dimethyl propionaldehyde-1.  The polyisocyanates can be used as such or as dimers, masked compounds or as reaction of excess polyisocyanate with a polyhydric alcohol, polyester or polyether. The polyurethane products can be used as cellular polyurethanes, coatings, foils, tubes, tyres and castable items.  In typical examples (2) the reaction product of aniline and ethylene oxide is condensed with paraformaldehyde by heating in the presence of p-toluene sulphonic acid while distilling off water: (12) a foam is prepared by mixing a condensation product of tetra-oxyethyl aniline, paraformaldehyde and p-toluene sulphonic acid with a polyester from adipic acid, phthalic anhydride, oleicacid and trimethylol propane and adding a mixture of bis-(diethylaminoethyl)1 adipate and aqueous sodium salt of sulphonated castor oil; (16) a foam is prepared from the reactionproduct of tetra-oxyethyl aniline, N-methyl hydroxyethyl-aniline and paraformaldehyde (with the addition of phosphoric acid) by adding a mixture of dimethylbenzylamine, aqueous sodium salt of sulphonated castor oil and toluylene diisocyanate. Specification 842,420 is referred to.ALSO:Foamed polyurethanes are produced by reacting with polyisocyanates and water, (in the presence of a tertiary amine catalyst) polyhydroxy compounds obtained by (1) reacting an aryl primary or secondary amine with ethylene oxide or isopropylene oxide to form an aromatic compound of the general formula R11-N =[(CH2CHR-O)nH]2 or R11-NR1-(CH2CHR-O)nH wherein R represents hydrogen or a methyl group, R1 represents an alkyl, cycloalkyl aryl, or aralkyl radical, R11 represents an aryl radical and n is a whole number from 1 to 10, and (2) reacting the said aromatic compound with an aldehyde.  (In a modification the arylamine is first condensed with formaldehyde and the resin obtained is reacted with ethylene oxide or isopropylene oxide).  Other compounds containing hydroxyl groups such as polyesters, polyethers and polyaretals, and cross-linking agents such as alkylene glycols, diamines or aminoalcohols may be present in the reaction mixture.  In another modification excess polyhydroxy compound is reacted with the polyisocyanate (e.g. in the presence of methyl-diethanolamine or triethanolamine) and the hydroxy-containing product is reacted with additional polyisocyanate and, if necessary, cross-linking agents. Lists of suitable amines and aldehydes are given (see Group IV(a)). In typical examples (12) a foam is prepared by mixing a condensation product of tetra-oxyethyl aniline, paraformaldehyde and p-toluene sulphonic acid with a polyester from adipic acid, phthalic anhydride, oleic acid and trimethylolpropane, and adding a mixture of bis-(diethylaminoethyl) adipate and aqueous sodium salt of sulphonated castor oil; (16) a foam is prepared from the reaction product of tetra-oxyethyl aniline, N-methyl hydroxyethyl aniline and paraformaldehyde (in the presence of phosphoric acid) by adding a mixture of dimethylbenzylamine, aqueous sodium salt of sulphonated castor oil and toluene diisocyanate.  Specification 842,420 is referred to.