Patent GB-882642-A (GB)
Title: Esters of 2,2,4,4-tetraalkylcyclobutane-1,3-diols
IPC: C08K5/12
Filed: 1960-03-31
Abstract: Esters derived from cyclobutane diol and having the formula <FORM:0882642/III/1> wherein each R is a methyl or ethyl group and R1 is an alkyl group having 1 to 12 carbon atoms, are lubricants of high thermal and hydrolytic stability.  A suitable composition comprises 2, 2, 4, 4-tetramethylcyclobutane-1, 3-diol dipelargonate (96%), tricresyl phosphate (3%), and phenothiazine (1%).  Another specified composition comprises 2,2,4,4-tetramethylcyclobutane1, 3-diol bis (2-ethyl hexanoate) (98%), phosphorus acid (0,07%), and 2, 6-ditertiarybutyl-p-cresol (1,93%).  A third composition comprises bis (2-ethylhexyl) sebacate (50%) and tetramethylcyclobutane-1, 3-diol dipelargonate (50%).  For the preparation of the esters (see Group IV(b)).  Specification 767,455 is referred to.ALSO:Esters derived from cyclobutane diol and having the formula <FORM:0882642/IV (a)/1> wherein each R is a methyl or ethyl group and R1 is an alkyl group having 1 to 12 carbon atoms, have utility as plasticizers for cellulose esters.  In Example 11, cellulose acetate butyrate (80 parts) and 2,2,4,4-tetramethylcyclobutane-1,3-diol bis (2-ethyl hexanoate) are mixed on heated rolls, extruded into sheets, and then granulated and moulded. 2,2,4,4-tetraethylcyclobutane-1,3-diol dipelargonate is also specified as a plasticizer which is compatible with cellulose acetate butyrate.  Examples 12 and 13 relate to similar subject-matter.  For the preparation of the plasticizers-(see Group IV(b)).  Specification 767,455 is referred to.ALSO:Esters of the formula <FORM:0882642/IV (b)/1> wherein each R is a methyl or ethyl group and R1 is an alkyl group having 1 to 12 carbon atoms, are prepared by reacting the appropriate 2,2,4,4-tetra-alkyl-cyclobutane-1,3-diol with an alkanoic acid having 2 to 13 carbon atoms.  The esterification can also be carried out using a carboxylic acid chloride or anhydride. In example 1, a solution in toluene of 2,2,4,4-tetramethyl-cyclobutane-1,3-diol and 2-ethylhexanoic acid is refluxed (base temperature about 195 DEG C.) with azeotropic removal of water.  The mixture is then washed with sodium bicarbonate solution, dried over sodium sulphate, and stripped of low boilers under vacuum 2,2,4,4-tetramethylcyclobutane - 1, 3 - diol bis (2 - ethyl - hexanoate) is isolated from the product by molecular distillation.  In Example 3, the same ester is prepared using 2-ethylhexanoic anhydride, together with zinc chloride as catalyst.  Example 2 describes the preparation tetramethylcyclobutane diol diacetate.  Example 5 describes the preparation of 2,4-dimethyl-2,4-diethylcyclobutane-1,3-diol dipelargonate by reacting the appropriate diol with pelargonic acid.  In Example 14, a solution in pyridine of tetramethylcyclobutane-1,3-diol is reacted with butryl chloride to give tetramethylcyclobutane-1,3-diol monobutyrate.  This monoester is then reacted with dodecanoyl chloride to give tetramethylcyclobutane-1,3-diol butyrate dodecanate. These diesters have use as lubricants (Group III) and as plasticisers for cellulose esters (Group IV (a)).  Specificatio 767,455 is referred to.