Patent GB-1121953-A (GB)
Title: Novel carbocyclic phosphonic acid compounds
Inventor: FAULKNER RAYMOND NOEL
IPC: C07F9/38
Filed: 1966-10-05
Abstract: The flotation tendencies of pigments in paints, particularly alkyd paints, are inhibited by incorporating therein, preferably at the milling stage, a phosphonic compound of the formula <FORM:1121953/C3/1> wherein Z is OH or halogen, Y is a -COOR radical wherein R is either (i) C1-C4 alkyl or (ii) a (CH2CH2O)n-R1 radical wherein R1 is either C1-C4 alkyl or C(O)R11 wherein R11 is C1-C4 alkyl and n is 1 or 2.  Specified pigments are titanium dioxide, phthalocyanine blue and arylamide yellow and the alkyd resin may be a long oil linseed (or medium oil)/ phthalic/pentaerythritol alkyd. The paint may be a stoving lacquer in which an alkyd resin, e.g. a castor/phthalic/glycerol alkyd is used in conjunction with an amino resin, e.g. an unmodified butylated melamine formaldehyde resin and in this case the phosphonic compound is added (as a solution in ethylene glycol ethyl ether) to the latter before mixing with the alkyd resin. The paints may be made up in xylol or white spirit and may contain cobalt and lead naphthenates.ALSO:The invention comprises carbocyclic compounds of the general formula <FORM:1121953/C2/1> wherein Z is a halogen atom or a hydroxyl radical and Y is COOR, wherein R is either (I) C1-C4 alkyl or (II) a (CH2-CH2-O)n-R1 radical, wherein R1 is either C1-C4 alkyl or is a -C(O)R11 radical, wherein R11 is C1-C4 alkyl, and n is 1 or 2.  They may be obtained by the Diels-Alder reaction of a vinyl phosphonic acid halide, e.g. chloride, with an appropriate sorbic acid ester, e.g. by heating a vinyl phosphonic acid halide, in the absence of oxygen and water, with a sorbic acid ester of the formula CH3-CH=CH-CH=CH-COOR and, if desired, hydrolysing any acid halide groups in the product to the corresponding acid.  The reaction is preferably carried out under an atmosphere of nitrogen and preferably at 140 DEG  to 150 DEG  C.  The radical Y is preferably -COOCH3, -COOCH2CH2OC(O)CH3 or -COO(CH2CH2O)2C4H9. The products are useful for inhibiting the flotation tendencies of pigments in paints, particularly alkyd paints.  Acetoxy ethyl sorbate is prepared by refluxing b -acetoxy ethanol and sorbic acid in the presence of xylene and concentrated H2SO4 and sulphur (Example 2) and diethylene glycol monobutyl ether sorbate, <FORM:1121953/C2/2> is prepared similarly from diethylene glycol monobutyl ether and sorbic acid (Example 3).ALSO:Glass panels are coated with a paint prepared from nutile titanium dioxide, a long oil linseed/phthalic/pentacrythritol alkyd, a small amount of a flotation inhibitor comprising a methyl sorbate-vinyl phosphonic acid adduct dissolved in ethylene glycol ethyl ether, and xylol or white spirit, with the addition, after ball milling, of cobalt and lead naphthenates.  Aluminium is coated with a paint prepared from a phthalocyanine blue tinted titanium dioxide alkyd paint containing as flotation inhibitor a small amount of an acetoxy ethyl sorbate/vinyl phosphonic acid adduct added at the milling stage.  The flotation inhibitors have the formulae:- <FORM:1121953/B1-B2/1> wherein Z is OH and Y is -COOCH3 and -COOCH2CH2OC(O)CH3 respectively.