Patent GB-767747-A (GB)
Title: Plasticized polyvinyl halide compositions
IPC: C08K5/11
Filed: 1954-07-08
Abstract: A polyvinyl halide is plasticised with a mixed monomeric or polymeric ester of adipic acid, ethylene glycol or a polyethylene glycol and an aliphatic monohydric alcohol.  The ester has a formula <FORM:0767747/IV(a)/1> where R is an alkyl radical of 1-6 carbon atoms, R1 is an ethylene or oxyethylene radical and n is 1 or more but is sufficiently low to give the ester a molecular weight of below 1000.  The monomeric ester or polyester may be made: (a) by reacting the acid chloride of a monoalkyl adipate with a glycol, (b) by esterifying a monoalkyl adipate with a glycol, (c) by reacting adipic acid with a glycol to form a glycol adipate followed by esterification with the monohydric alcohol or (d) by effecting ester-interchange between a glycol and a dialkyl adipate in presence of a catalyst, e.g. sulphuric acid, paratoluene sulphonic acid, calcium oxide or litharge.  In examples (1)-(3) ethylene glycol bis-(isobutyl adipate), ethylene glycol bis-(ethyl adipate) are prepared (see Group IV (b)).  (4) Adipic acid is esterified with diethylene glycol and the product heated with ethyl alcohol to yield a mixture of diethylene glycol bis-(ethyl adipate) and higher polyesters.  (5) A polyester is made by reacting di-isobutyl adipate with ethylene glycol in presence of sulphuric acid and decolourising carbon whilst distilling off isobutyl alcohol.  (6) A polyester is made by reacting a mixture of mono-ethyl adipate, diethyl adipate and ethylene glycol.  (7) A polyester is made by reacting di-n-propyl adipate with ethylene glycol.  (8) Compositions are made comprising polyvinyl chloride, a plasticiser, basic lead carbonate and stearic acid, the plasticiser being a monomeric or polymeric ester as made in Examples (1)-(7) alone or in combination with dioctyl phthalate, epoxidized soya bean oil or tricresyl phosphate.ALSO:A mixed ester of adipic acid, ethylene glycol or a polyethylene glycol and an aliphatic monohydric alcohol has a formula ROOC(CH2)4COO-[-R1OCO(CH2)4 COO-]-nR where R is an alkyl radical of 1-6 carbon atoms, R1 is an ethylene or oxyethylene radical and n is 1 or more but sufficiently low to give the ester a molecular weight of below 1000.  The ester may be made:-(a) by reacting the acid chloride of a monoalkyl adipate with a glycol, (b) by esterifying a mono-alkyl adipate with a glycol, (c) by reacting adipic acid with a glycol to form a glycol adipate followed by esterification with the monohydric alcohol or (d) by effecting ester-interchange between a glycol and a dialkyl adipate in presence of a catalyst, e.g. sulphuric acid, para-toluene sulphonic acid, calcium oxide or litharge.  In examples: (1) ethylene glycol bis-(isobutyl adipate) is made by heating the acid chloride of mono-isobutyl adipate with ethylene glycol, adding xylene and maintaining the mixture at reflux and then washing the reacting mixture with water and sodium carbonate and removing the xylene by distillation.  (2) Ethylene glycol bis-(ethyl adipate) is made in similar manner.  (3) Polyethylene glycol bis-(ethyl adipate) is made by heating in presence of xylene and quinoline the acid chloride of monoethyl adipate with a mixture of ethylene-, diethylene-, tri-ethylene and higher polyethylene-glycols, allowing the reaction mixture to separate into two layers, adding water to the lower layer, extracting the lower layer with benzene and adding the benzene extract to the previously separated oil layer.  The combined extracts are then washed with hydrochloric acid and water and the solvents and water removed by distillation to obtain the ester. (4)-(11) Polymeric polyesters of adipic acid, ethylene or a polyethylene glycol and a monohydric alcohol are prepared and the use of the monomeric and polymeric esters for plasticizing polyvinyl chloride is described (see Group IV (a)].  Mixed esters (a) from dimethyl, diethyl or dibutyl phthalate and ethylene glycol and (b) from diisobutyl diglycollate and ethylene glycol are referred to for comparison purposes.