Patent GB-971901-A (GB)
Title: Improvements in organic esters and in lubricants consisting of or containing them
Inventor: CRITCHLEY STUART WALTER
IPC: C07C69/74
Filed: 1959-11-11
Abstract: Fully esterified liquid complex ester compositions are prepared by reacting in one or more stages (a) a saturated aliphatic non-hydroxylated mono-carboxylic acid with 1-18 carbon atoms, or an aromatic non-hydroxylated mono-carboxylic acid with 7-15 carbon atoms not containing any unsaturated nuclear substituent or a mixture thereof, (b) a saturated aliphatic polyhydric alcohol with 5-15 carbon atoms with no hydrogen atom attached to any carbon atom in a -2 position with respect to any hydroxyl group of the formula <FORM:0971901/C1/1> wherein R2 is alkyl with 2-4 carbon atoms or CH2OR3 wherein R3 is hydrogen or completes a di- or tripentaerythritol molecule and (c) a saturated aliphatic non-hydroxylated dicarboxylic acid with 4-14 carbon atoms or a mixture thereof. Specified polyols are 1,1,1 trimethylol propane pentaerythritol, di- and tri-pentaerythritol but polyols of formula <FORM:0971901/C1/2> such as neopentyl glycol may be admixed with the specified polyols.  The esterification may be effected as a one stage process where all three components are refluxed together, a two stage process where the alcohol (b) is partially esterified with the monocarboxylic acid (a) and then heated with the dicarboxylic acid (c) or a three stage process where part of the alcohol (b) is reacted with the mono-acid (a) and the remainder of (b) reacted with the di-acid (c) and the partial esters refluxed together. The preferred proportions of a:b:c are 2-20:2:0.25-1.5 and the above reactions may be carried out in the presence of an esterification catalyst e.g. p-toluene sulphonic acid, sodium bisulphate, potassium pyrosulphate, a tetraalkyl titanate, titanium tetrachloride or a molecular sieve and a water entrainer such as benzene or toluene may be added. The preferred reactants are (a) a saturated straight chain fatty acid with 7-10 carbon atoms or a mixture thereof, (b) 1:1:1 trimethylol propane and (c) sebacic acid. The esters may be used as lubricants or may be blended with neutral simple esters and used as lubricants. Specified monocarboxylic acids are capric, n-valeric, isovaleric, enanthic, caprylic, pelargonic, propionic and benzoic while specified dicarboxylic acids are adipic, sebacic and azelaic. Specifications 892,943 and 894,639 are referred to.ALSO:Fully esterified liquid complex ester compositions are prepared by reacting in one or more stages (a) a saturated aliphatic non-hydroxylated mono-carboxylic acid with 1-18 carbon atoms, or an aromatic non-hydroxylated mono-carboxylic acid with 7-15 carbon atoms not containing any unsaturated nuclear substituent or a mixture thereof, (b) a saturated aliphatic polyhydric alcohol with 5-15 carbon atoms with no hydrogen atom attached to any carbon atom in a -2 position with respect to any hydroxyl group of the formula <FORM:0971901/C3/1> wherein R2 is alkyl with 2-4 carbon atoms or CH2OR3 wherein R3 is hydrogen or completes a di- or tripentaerythritol molecule and (c) a saturated aliphatic non-hydroxylated dicarboxylic acid with 4-14 carbon atoms or a mixture thereof. Specified polyols are 1,1,1 trimethylol propane pentaerythritol, di- and tripentaerythritol but polyols of formula <FORM:0971901/C3/2> such as neopentyl glycol may be admixed with the specified polyols. The esterification may be effected as a one stage process where all three components are refluxed together, a two stage process where the alcohol (b) is partially esterified with the monocarboxylic acid (a) and then heated with the dicarboxylic acid (c) or a three stage process where part of the alcohol (b) is reacted with the mono-acid (a) and the remainder of (b) reacted with the di-acid (c) and the partial esters refluxed together. The preferred proportions of a:b:c: are 2-20:2:0.25-1.5 and the above reactions may be carried out in the presence of an esterification catalyst e.g. p-toluene sulphonic acid, sodium bisulphate, potassium pyrosulphate, a tetraalkyl titanate, titanium tetrachloride or a molecular sieve and a water entrainer such as benzene or toluene may be added. The preferred reactants are (a) a saturated straight chain fatty acid with 7-10 carbon atoms or a mixture thereof, (b) 1:1:1 trimethylol propane and (c) sebacic acid. The esters may be used as lubricants or may be blended with neutral simple esters and, possibly, anti-oxidants (e.g. phenothiazine, phenyl-alpha-naphthylamine of 5-ethyl-10, 10-diphenyl-phenazasilane and used as lubricants. Specified monocarboxylic acids are capric, n-valeric, isovaleric, enanthic, caprylic, pelargonic, propionic and benzoic while specified dicarboxylic acids are adipic, sebacic and azelaic. Specifications 892,943 and 894,639 are referred to.ALSO:A lubricant blend comprises two components, one component being one or more fully esterified liquid complex ester compositions prepared by reacting in one or more stages: (a) a saturated aliphatic non-hydroxylated monocarboxylic with 1-18 carbon atoms or an aromatic nonhydroxylated monocarboxylic acid with 7 to 15 carbon atoms and not containing any unsaturated nuclear substituent or a mixture thereof, (b) a saturated aliphatic polyol with 5 to 15 carbon atoms, having no hydrogen attached to any carbon in a 2-position with respect to any hydroxyl group and of formula <FORM:0971901/C4-C5/1> wherein R1 and R2 are alkyl with 1 to 4 carbon atoms, or R1 is methylol and R2 is alkyl with 2 to 4 carbon atoms or -CH2OR3 (wherein R3 is hydrogen or completes di- or tri-pentaerythritol) and (c) a saturated aliphatic nonhydroxylated dicarboxylic acid with 4-14 carbon atoms or a mixture thereof and the other component being (1) one or more liquid fully esterified simple esters of a saturated aliphatic polyhydric primary alcohol or a mixture thereof with a saturated aliphatic or aromatic non-hydroxylated monocarboxylic acid or a mixture thereof, or (2) a simple ester with an alcohol as in (1) with a saturated aliphatic or aromatic non-hydroxylated polycarboxylic acid or a mixture thereof, or (3) a mixture of simple esters of types (1) and (2) so that the relative proportions of the two components is such that the viscosity is from 3 to 15 centistokes at 210 DEG F.  Specified polyhydric alcohols are 1,1,1-trimethylolpropane pentaerythritol, di- and tri-pentaerythritol or a mixture of neopentyl glycol with 1,1,1-trimethylolpropane. Specified monocarboxylic acids are capric, n-valeric, isovaleric, enanthic, caprylic, pelargonic, propionic and benzoic while specified dicarboxylic acids are adipic sebacic and azelaic.  The preferred complex ester is prepared by reacting (d) a saturated straight chain fatty acid of 7-10 carbon atoms or a mixture thereof, (e) 1,1,1-trimethylol propane and (f) sebacic acid. Specifications 892,943 and 894,639 are referred to