Patent GB-671936-A (GB)
Title: Propyl and isopropyl methacrylate
IPC: C07C67/08
Filed: 1949-02-18
Abstract: n-Propyl and isopropyl methacrylate are obtained by reacting n- or iso-propanol with methacrylic acid in the presence of a polymerization inhibitor and of an azeotropic-forming liquid while removing the water of reaction by azeotropic distillation and then separating the propyl methacrylate from the reaction product by fractional distillation.  The fractional distillation is preferably effected under reduced pressure and it is desirable to add the polymerization inhibitor to the reaction mixture initially and before fractional distillation.  Specified azeotropic forming liquids are benzene, ethylene dichloride, chloroform, di-isopropyl and di-n-propyl ethers, and trichloroethylene.  The process may be carried out in the presence of a mineral acid or esterification catalyst.  In examples: (1) a mixture of isopropanol, hydroquinone, sulphuric acid, methacrylic acid and trichloroethylene, the latter being recovered from a previous preparation of isopropyl methacrylate and containing a small amount of water, isopropanol, and isopropyl methacrylate, is heated in a flask provided with a fractionating column surmounted by a reflux condenser and automatic separator to return the trichloroethylene rich phase of the condensate and reject the water-rich phase.  Distillation is continued until no more aqueous layer is rejected and the cooled reaction mixture is then washed with water and sodium hydroxide solution and after adding hydroquinone is fractionally distilled, under reduced pressure, to yield isopropyl methacrylate; (2) n-propyl methacrylate is obtained from n-propanol, hydroquinone, sulphuric acid, methacrylic acid and trichloroethylene using the procedure of (1); (3) and (4) isopropyl methacrylate is obtained as in (1) using trichloroethylene which is not stated to be recovered from a previous operation as the azeotropic-forming liquid.  It is stated that the process is not suitable for the conversion of methanol and ethanol into the methacrylates because the rejected aqueous layer of the condensed azeotrope with, for example, benzene or trichloroethylene entrainer, contains a large proportion of the alcohol.  Specification 490,007 is referred to.ALSO:n-Propyl and isopropyl methacrylate are obtained by reacting n or isopropanol with methacrylic acid in the presence of a polymerization inhibitor and of an azeotropic-forming liquid while removing the water of reaction by azeotropic distillation and then separating the propyl methacrylate from the reaction product by fractional distillation (see Group IV(b)).  Specified azeotropic-forming liquids are benzene, ethylene dichloride, chloroform, di-isopropyl and di-n-propyl ethers and trichloroethylene.  It is stated that when a system containing water, a propanol and an entrainer such as trichlorethylene is distilled a ternary azeotrope is formed which on condensation separates into two layers, the aqueous portion of which contains relatively little propanol.  Data showing the composition of the two layers in the case of water-n or iso-propanol-trichlorethylene ternary azeotropes is tabulated.  It is also stated that the propyl methacrylates do not form binary azeotropes with benzene or trichlorethylene or with the corresponding alcohols.