Patent GB-980110-A (GB)
Title: Fluorine-containing organic aluminium compounds
Inventor: NAM BILLIE
IPC: C07F5/06
Filed: 1962-05-28
Abstract: The invention comprises organic aluminium compounds obtained by heating an aluminium alkoxide with at least one organic hydroxy compound and at least one carboxylic acid, at least one of the hydroxy compounds or carboxylic acids containing at least one -CF2- group. Suitable alkoxides for use as starting materials are, for example, the ethoxide, propoxide, isopropoxide, butoxide, sec.-butoxide and phenoxide. Suitable fluorinated hydroxy compounds are, for example, 1,1,5-trihydroperfluoro-n-pentanol, 1,1,9 - trihydroperfluoro - n - nonanol, 1,1,11 - trihydroperfluoroundecanol, 1,1 - dihydroperfluoro - n - butanol, 1,1 - dihydroperfluoroethanol, 1 - (3 - trifluoromethyl - 4 - fluorophenyl) - ethanol, 1 - (o - trifluoromethylfluorophenyl) - 2 - propanol, 2,2 - difluoroethanol, 2 - (tetrafluoroethoxy) - ethanol and 1 - (perfluoropropyl) - 1 - methylethanol.  Other halogens and other groups such as amide and ester groups may be present in the hydroxy compounds. Suitable fluorinated carboxylic acids are, for example, perfluorobutyric acid, perfluoroactanoic acid, perfluoroacetic acid, difluoroacetic acid, difluoropropionic acid, difluorobutyric acid, 5-hydroxyperfluoro valeric acid, perfluorocaproic acid, perfluorodecanoic acid, 2,2,3,3 - tetrafluorocyclobutanecarboxylic acid and perfluorocyclohexane carboxylic acid. Dibasic fluorinated acids may also be used. Non-fluorinated hydroxy compounds which may be used include, for example, methanol, ethanol, propanol, iso-propanol, butanol, octanols, nonanol, decanol, stearyl alcohol, oleyl alcohol, cetyl alcohol, lauryl alcohol, geraniol cyclohexanol, benzyl alcohol, furfuryl alcoho and phenols and also polyhydroxy compounds such as glycols, glycerol, polyethylene glycols, and methylol phenols. Non-fluorinated carboxylic acids used may be aliphatic or aromatic and include acetic, propionic, butyric, octoic, nonanoic, decanoic, oleic, linoleic, stearic and ricinoleic acids. Dicarboxylic acids and carboxylic acids derived from naturally occuring fats and oils may also be used.  Examples are given of the preparation of aluminium compounds from (a) aluminium sec.-butoxide, 1,1,11 - H - eicosafluoroundecanol and 2 - ethylhexoic acid; (b) aluminium sec.-butoxide, 1,1,11 - H - eicosafluoroundecanol, 3,5,5-trimethyl hexanol and 2-ethyl hexoic acid; and (c) aluminium sec.-butoxide, 1,1,11-H-eicosafluoroundecanol and naphthenic acid.ALSO:The invention comprises organic aluminium compounds obtained by the heating of an aluminium alkoxide with at least one organic hydroxy compound and at least one carboxylic acid, optionally in the presence of water, at least one of the hydroxy compounds or carboxylic acids containing at least one - CH2=-group. The products may be compounds of the formulae (where aluminium butoxide is the starting material):- <FORM:0980110/C3/1> <FORM:0980110/C3/2> <FORM:0980110/C3/3> in which ROH is the hydroxy compound and R1COOH the carboxylic acid used.  ROH may be a non-fluoroniated compound and may be aliphatic aromatic or heterocyclic and may be, for example, polyoxy alkylene alcohols such as hydroxy-ended polymers or copolymers of olefine oxides. Non-fluorinated acids which may be used are aliphatic or aromatic. Fluorinated hydroxy compounds which may be used are, for example, 1,1,5-trihydro-perfluoro-n-pentanol, 1,1,9 - trihydro - perfluoro - n - nonanol, 1,1,11 - trihydroperfluoroundecanol, 1,1 - dihydroperfluoro - n - butanol, 1,1 - dihydro - perfluoro - ethanol, 1 - (3 - trifluoromethyl - 4 - fluorophenyl) - ethanol 1 - (o - trifluoromethyl - fluorophenyl) - 2 - propanol, 2 - (tetrafluoroethoxy) - ethanol and phenols, and ariliphatic alcohols containing trifluoro-methyl, pentafluoro-ethyl and heptafluoropropyl groups attached to the aromatic ring. Other hydroxy compounds which may be used include hydroxy esters and amides of fluorinated acids and hydroxyl-group containing derivatives of fluorinated isocyanates. Suitable fluorinated carboxylic acids containing a -CF2-group include perfluoroalkanoic acids, difluoroalkanoic acids, 5-hydroxyperfluoro valeric acid, 2,2,3,3 - tetrafluorocyclobutane - carboxylic acid and perfluorocyclohexane carboxylic acid. Fluorinated dicarboxylic acids may also be used.  The new products may be used for the formation of polyurethane foams.  The foams are prepared from organic polyisocyanates, hydroxyl group-containing polymers containing at least two isocyanate-reactive groups per molecule, water and/or a low-boiling liquid and one of the new aluminium compounds. Suitable isocyanate-reactive groups are carboxylic, amino and hydroxy groups and suitable compounds containing these are polyesters, polyesteramides and polyethers.  The polyesters or polyesteramides may be made from dicarboxylic acids and polyhydric alcohols with, if necessary, diamines or amino alcohols. Other suitable compounds are those prepared from starting materials containing more than two groups selected from hydroxyl, carboxyl, and secondary or primary amino, e.g. diethanolamine, trimesic acid, dihydroxystearic acid and tricarballylic acid.  The polyesters used may be polymers and copolymers of cyclic oxides. The polyesters generally have a molecular weight of 200-5000 and the polyethers 200-6000.  Suitable polyisocyanates are aliphatic, aromatic or cycloaliphatic. Low-boiling liquids which may be used in the formation of the polymethane foams are fluorinated alkanes, fluorinated-chloro-alkanes or unsubstituted hydrocarbons.  The polymethane foams may be prepared using conventional additives and fillers.