Patent GB-1001837-A (GB)
Title: Organic aluminium compounds
Inventor: BROOKS JOHN LANGSHAW
IPC: C07F9/02
Filed: 1963-01-01
Abstract: The invention comprises organic aluminoxanes in which some of the aluminium atoms are replaced by " hetero " atoms selected from copper, magnesium, zinc, cadmium, germanium, zirconium, titanium, tin, lead, vanadium, antimony, tantalum, bismuth, molybdenum, manganese, iron, cobalt, nickel, boron and phosphorus.  They are obtained by heating an aluminium alkoxide or phenoxide with at least one organic hydroxy compound, at least one carboxylic acid and at least one compound containing the hetero atom linked to an organic radical through oxygen or a -COO- radical, at least the later stages of the heating being carried out at a temperature exceeding 140 DEG C. Suitable aluminium compounds in use as starting materials are, for example, the ethoxide, propoxide, isopropoxide, butoxide and phenoxide. Suitable hydroxy compounds for use in the manufacture of the required compounds are alkanols, oleyl alcohol, cetyl alcohol, geraniol, cyclohexanol, benzyl alcohol, furfuryl alcohol, substituted benzyl alcohols, phenol and substituted phenols, polyoxyalkylene alcohols such as hydroxy-ended polymers or copolymers of cyclic oxides, ethylene glycol, propylene glycol, di-, tri- or tetraethylene glycols, glycerol or methylol phenols. Suitable carboxylic acids are, for example, acetic, propionic, butyric, octoic, nonanoic, decanoic, oleic, linoleic, stearic, ricinoleic, malonic, succinic, adipic and glutamic acids. Hydroxyl compounds and carboxylic acids derived from naturally occurring fats and oils may also be used.  The hydroxyl compounds and carboxylic acids may contain amino groups.  Suitable organic compounds containing the metallic hetero atoms include alkoxides and carboxylic acid salts.  Suitable organic compounds containing boron or phosphorus are, for example, trialkyl borates, dialkyl alkyl boronates, dialkyl alkyl phosphonates, trialkyl phosphites, trialkyl phosphates and dialkyl hydrogen phosphonates. The products may have a cyclic, linear or co-ordinated structure depending on the proportions of starting materials used.  The aluminoxanes of the invention are useful as surfactant additives for use in the manufacture of foamed cellular polyurethane materials by the reaction of organic polyisocyanates and polymers containing at least two hudroxy groups per molecule under such conditions that a foam-forming gas is generated.  The polymers containing at least two hydroxyl groups per molecule include linear and branched polyesters, polyethers and polyesteramides.  Suitable organic polyisocyanates include aliphatic and aromatic di- and tri-isocyanates.  The foam-forming gas may be carbon dioxide generated by the reaction of some of the polyisocyanate with water which has been added to the mixture or it may be generated by incorporating in the mixture a suitable low boiling liquid which on heating will volatilize to give the foam-forming gas.  In addition to one of the aluminoxanes of the invention, there may also be present in the mixture catalysts, e.g. tertiary amines or soluble heavy metal compounds, surface-ative agents, flame-retardants, plasticizers, fillers or antioxidants. The aluminoxane is normally used in the foam-forming mixture in an amount of 0.01-10% by weight.  In the Examples: (a) a reaction product of isooctanol and propylene oxide (N.Wr. 850) is added to aluminium secbutoxide; nonarol and methoxypolyethylene glycol are added and after heating 2-ethyl hexoic acid and lead octoate are added to give an aluminoxane containing lead; (b) similar reactions were carried out to obtain aluminoxanes containing zinc, tin, titanium, zirconium, boron and phosphorus; (c) the products of Examples (a) and (b) above are added to an oxypropylated glycerol (approx. mol. wt. 3000), and to the mixture are added tolylene diisocyanates and aqueous solutions of dimethyl-amino pyridine and stannous octoate; a low density flexible foam is formed.ALSO:The invention comprises organic aluminoxanes which contain in addition to aluminium atoms one or more "hetero" atoms selected from copper, magnesium, zinc, cadmium, germanium-zirconium, titanium, tin, lead, vanadium, antimony, tantalum, bismuth, molybdenum, manganese, iron, cobalt, nickel, boron and phosphones. The aluminoxanes are defined as having structures of alternate oxygen and aluminium atoms with one or more of the aluminium atoms being replaced by one or more of the "hetero" atoms and may be of cyclic, linear or co-ordinate structure.  The aluminoxanes of the invention may be obtained by heating an aluminium alkoxide or phenoxide with an organic hydroxy compound, a carboxylic acid and a compound containing the hetero atom linked to an organic radical through oxygen or a -COO- radical, at least the later stages of the heating being carried out at a temperature exceeding 140 DEG C.  Suitable starting aluminium compounds are, for example, the ethoxide, propoxide, butoxide and phenoxide.  The alcohols or phenols used include, for example, alkanols, oleyl alcohol, cetyl alcohol, geraniol, cyclohexanol, benzyl alcohol, furfuryl alcohol, substituted benzyl alcohols, phenol and substituted phenols, glycols, polyethylene glycols, glycerol and methylol phenols.  Suitable carboxylic acids are, for example, acetic, propionic, butyric, octoic, nonanoic, decanoic, oleic, linoleic, stearic, ricinoleic, malonic, succinic, adipic and glutaric acids.  Hydroxy compounds and acids derived from naturally occurring fats and waxes may also be used.  A proportion of the carboxylic acid may be replaced by an organic sulphonic acid, a phosphoric acid or an acid phosphate ester. The hydroxy compounds or carboxylic acids used may contain amino groups, e.g. N-2-hydroxypropyl-di-n-butylamine, N-hydroxypropyl - di - (2 - phenylethyl) - amine, N - 2 - hydroxypropylmorpholine, N-hydroxyethyldiethylamine, sarcosine, nicotinic acid, piperidine-4-carboxylic acid, serine, methionine and N,N - dimethylaminopropionic acid.  Suitable organic compounds containing the metallic hetero-atoms include alkoxides and carboxylic acid salts, e.g. titanium tetraisopropoxide, zirconium tetra-n-butoxide, vanadium tri-n-butoxide, zinc octoate, lead acetate, lead octoate, cadmium propionate, stannous octoate and cupric acetate.  Examples of suitable compounds containing non-metallic hetero-atoms include trialkyl borates, dialkyl alkyl boronates, dialkyl alkyl phosphonates, trialkyl phosphites, trialkyl phosphates and dialkyl hydrogen phosphonates.