Patent GB-815232-A (GB)
Title: Bifunctional products from oxo reaction
Filed: 1955-11-30
Abstract: Polyvinyl chloride resin compositions are plasticized with a compound of the formula: <FORM:0815232/IV (a)/1> in which both hydrogen atoms on one of the carbon atoms marked with an asterisk are replaced by two <FORM:0815232/IV (a)/2> groups, in which R and R11 represent n-butyl radicals (see Group IV (b)).ALSO:The invention comprises compounds having the formula <FORM:0815232/IV (b)/1> in which both hydrogen atoms on one of the carbon atoms marked with an asterisk are replaced by two <FORM:0815232/IV (b)/2> groups, R and R11 being alkyl radicals; a process for the production of a dimethylol derivative of an ester aldehyde that comprises reacting a cyclic diolefin with an aliphatic monocarboxylic or dicarboxylic acid to form an olefinic ester and treating the ester with carbon monoxide and hydrogen, in the presence of a cobalt carbonylation catalyst and at a temperature within the range 225-375 DEG  F. and a pressure within the range 1500 to 4500 p.s.i.g. to obtain an ester aldehyde and reacting the ester aldehyde with formaldehyde to produce the corresponding dimethylol derivative and a process for converting the dimethylol derivative to a triester by reaction with a monocarboxylic acid. Cyclic diolefins mentioned include cyclopentadiene, dicyclopentadiene, their homologues, vinyl cyclohexene, dipentene, limonene, terpinolene, terpinene and sylvestrene. Carboxylic acids specified for reaction with the diolefin include formic, acetic, propionic, capric, palmitic, isooctanoic, isodecanoic, isotridecanoic, adipic and sebacic acids.  The reaction between the acid and diolefin is preferably catalysed by condensation catalysts such as sulphuric and perchloric acids, boron trifluoride and the boron trifluoride - phosphoric acid complex.  Carbonylation catalysts mentioned include the naphthenate, stearate, oleate, acetate and oxide of cobalt.  An apparatus for carrying out the process is described with reference to a drawing (not shown).  In examples: an unsaturated ester is obtained by reacting formic acid with dicyclopentadiene in the presence of perchloric acid and is converted to an ester-aldehyde by heating with carbon monoxide and hydrogen using a cobalt oleate catalyst (I); in a similar process acetic acid is used instead of formic acid (II); in similar processes palmitic acid is employed instead of acetic acid using perchloric acid and a boron-trifluoride-phosphoric acid complex as catalyst in the first stage (III); the dimethylol derivative of the acetate of hydroxy-dihydro-dicyclopentadiene is obtained by treating with formaldehyde in an aqueous alcoholic potash solution the product obtained by oxonation of the acetate ester of hydroxy-dihydro-dicyclopentadiene (IV); and the dimethylol product of Example (IV) is converted to the valerate ester by heating with normal valeric acid and toluene sulphonic acid in toluene solution (V).  The conversion of portions of the crude aldehyde-esters obtained in Examples (I) and (II) to hydroxy esters by hydrogenation over a nickel catalyst and the hydrolysis of the hydroxy ester obtained in (I) to the corresponding cyclic dihydric alcohol are described.  The trivalerate ester obtained in (V) is employed as a plasticizer in polyvinyl chloride resin compositions (see Group IV (a)).