Patent GB-987715-A (GB)
Title: Organic aluminium compounds and their use in the preparation of polyurethane foams
IPC: C07F5/06
Filed: 1962-10-12
Abstract: An organic aluminium compound is produced by heating an aluminium alkoxide or phenoxide with at least one hydroxy compound and at least one carboxylic acid, at least the later stages of heating being carried out above 140 DEG  C., characterized in that there is present at least one monohydroxy compound or one mono carboxylic acid containing a secondary or tertiary amino group.  For each mole of aluminium alkoxide used there may be used 0.5-1.5 moles in all of hydroxy compounds, 0.5-15 moles in all of carboxylic acids.  Organic phosphates or phosphonic or sulphonic acids may also be present. The products may have the following structures <FORM:0987715/C2/1> and <FORM:0987715/C2/2> where A and A1 are hydrocarbon or substituted hydrocarbon radicals.  The products may be partially or totally converted to quaternary ammonium compounds by treatment with a compound RY where R is a hydrocarbon radical or substituted hydrocarbon radical and Y is an acid radical.  Aluminium alkoxides specified are: aluminium iso-propoxide, isobutoxide, ethoxide, propoxide and sec.-butoxide.  Monohydroxy compounds containing secondary or tertiary amino groups specified are of the structure <FORM:0987715/C2/3> where R is a substituted or unsubstituted hydrocarbon radical, R1 is H or a substituted or unsubstituted hydrocarbon radical or R and R1 together with the nitrogen atom make up a heterocyclic ring and X is a divalent organic radical.  Examples of R and R1 are:  hydrocarbon radicals which may be substituted with cyano groups or chlorine atoms. Examples of heterocyclic rings are piperidine and morpholine. Examples of X are hydrocarbon radicals and groups of the following formulae <FORM:0987715/C2/4> Carboxylic acids containing secondary or tertiary amino groups specified are: sarcosine nicotinic acid, piperidine-4-carboxylic acid, serine, methionine, p-N,N-dimethylamino benzoic acid and N,N-dimethylaminopropionic acid. Other hydroxy compounds specified are alkanols, alkenols, cycloalkanols, cycloalkenols, aralkanols, furfuryl, polyoxyalkylene glycols, alkylene glycols, and substituted derivatives thereof. Other carboxylic acids specified are saturated and unsaturated mono- and di-carboxylic acids. Hydroxy and carboxy compounds may also be derived from natural oils.  Compounds RY specified are methyl iodide, dimethyl sulphate and benzyl chloride. In examples aluminium secondary butoxide was reacted with 2-ethylhexoic acid and N - hydroxypropyl di-n-butylamine (7), N-2-hydroxypropyl diisopropylamine (9) or N,N-di-(2-hydroxypropyl)-cetylamine.ALSO:An organic aluminium compound is produced by heating together an aluminium alkoxide or phenoxide, a carboxylic acid and a polyalkylene glycol or other hydroxy compound characterized in that there is present at least one monocarboxylic acid or at least one hydroxy compound containing a secondary or tertiary amino group.  For each mole of aluminium alkoxide there may be used 0.5-1.5 moles in all of hydroxy compounds and 0.5-1.5 moles in all of carboxylic acids. The products may have the following structures: <FORM:0987715/C3/1> <FORM:0987715/C3/2> and <FORM:0987715/C3/3> where A is the residue of the polyglycol or alcohol and A1 is the residue of the carboxylic acid.  The products may be partially or totally converted to quaternary ammonium compounds by treatment with a compound RY, where R is a substituted or unsubstituted hydrocarbon and Y is an acid radical.  Aluminium alkoxides specified are the isopropoxide, isobutoxide, ethoxide, propoxide and sec-butoxide.  Monohydroxy compounds containing secondary or tertiary amino groups specified are of the structure: <FORM:0987715/C3/4> where R is a substituted or unsubstituted hydrocarbon radical, R1 is H or a substituted or unsubstituted hydrocarbon radical or R and R1 together with the nitrogen atom make a heterocyclic ring, and X is a divalent organic radical.  Examples of R and R1 specified are alkyl, cyanoalkyl, cycloalkyl, aryl, chloroaryl, and aralkyl groups.  Examples of heterocyclic rings are piperidine and morpholine.  Examples of X are alkylene, cycloalkylene and arylene radicals and radicals of the structure: <FORM:0987715/C3/5> and <FORM:0987715/C3/6> Carboxylic acids containing secondary or tertiary amino groups specified are: sarcosine, nicotinic acid, piperidine-4-carboxylic acid, serine, methionine, p-N,N-dimethylaminobenzoic acid and N,N-dimethylaminopropionic acid. Polyoxyalkylene glycols specified are polyoxyethylene glycol and polyoxypropylene glycol. Other hydroxy compounds specified are alkanols, alkenols, cycloalkanols, aralkanols, furfuryl alcohol, alkylene glycols and glycerol. Other carboxylic acids specified are saturated and unsaturated mono- and dicarboxylic acids. Hydroxy and carboxy compounds may be derived from natural oils.  Compounds RY specified are methyl iodide, dimethyl sulphate and benzyl chloride.  In Examples, aluminium secondary butoxide was treated (1) with an isooctanol/propylene oxide adduct, nonanol, N-2-hydroxypropyl morpholine and 2-ethylhexoic acid and (11) with an isooctanol/propylene oxide adduct, a methanol/ethylene oxide adduct, nonanol and N-2-hydroxypropyl-di-(2-phenylethyl) amine.  In Examples (2) and (3), the product from (1) was treated with methyl iodide.  Polyurethane foams may be produced by reacting an organic polyisocyanate with a polymer containing at least 2 hydroxyl groups per molecule in the presence of 0.1-2% of the products of the invention as surface-active agents.  Foaming may be caused by the addition of 1-10% water or 1-100% of a low boiling point liquid, e.g. a fluorinated hydrocarbon or halohydrocarbon.  The polyhydroxy compounds may be polyesters or polyesteramides or polyethers having terminal secondary hydroxyl groups, e.g. polymers of propylene and butylene oxides.  Other additives may be: catalysts, e.g. tertiary amines and organo-metallic compounds; surface-active agents; flame retardants; colouring matter, fillers, colour stabilizers, whitening agents and antioxidants. The polyurethanes may be flexible or rigid and may be used for surface coatings, sheets, shaped articles and adhesive surfaces. In Examples (4), (5) and (6), a tolylene-2,4 and 2,6-diisocyanate mixture is reacted with an oxypropylated glycerol in the presence of 4-dimethylaminopyridine, stannous octoate and the products of Examples (1), (2) and (3) above. In Example (8) the surface-active agent is derived from aluminium secondary butoxide, N - 2 - hydroxypropyl - di - n - butylamine, nonanol and 2-ethyl hexoic acid.