GB1002190A - Esters of ester acids, their production and use - Google Patents

Abstract

Allyl esters of mono-glycol bis-(polycarboxylate) ester acids of the formula HO2CRCO2ZO2CRCO2H, wherein each R represents the residue of an internal anhydride of an aliphatic or mono-benzenoid di- or tri-carboxylic acid having a 5 or 6 membered anhydride ring system and of the formula <FORM:1002190/C3/1> and Z represents the residue of an alkylene glycol or polyalkylene ether glycol of the formula HOZOH, are prepared by reacting said ester acid with allyl chloride in the presence of a tertiary amine in a molecular proportion at least equal to the molecular proportion of allyl chloride theoretically consumed during the reaction. It is preferred that Z be the residue of an alpha-omega glycol or of a polyethylene ether glycol of the formula HO(CH2CH2O)nOH, wherein n has an average value of 2 to 45. The reaction is preferably carried out under substantially anhydrous conditions at between ambient temperature and 90 DEG C. in the absence or presence of an inert diluent or solvent and with a 10% molar excess of allyl chloride over the ester acid. The symmetrical ester acid reactants may be prepared by reacting two molecular proportions of an anhydride of the formula <FORM:1002190/C3/2> with substantially one molecular proportion of an alkylene glycol or polyalkylene ether glycol of the formula HOZOH. The reaction is normally performed under substantially anhydrous conditions in the absence or presence of an inert solvent for the ester acid product and preferably in the presence of an amine. Preferred amines are the tertiary amines which may remain in the reaction mixture for subsequent use in the process of the invention. Asymmetrical ester acid reactants may be prepared by reacting equimolar proportions of glycol and anhydride and subsequently reacting the monoester so obtained with a different anhydride. Specified polyalkylene ether glycols include those obtained by polymerization of ethylene oxide, propylene oxide, butylene oxide or epichlorohydrin and by polymerizing a mixture of alkylene oxides.ALSO:Allyl esters of mono-glycol bis-(polycarboxylate) ester acids of the formula HO2CRCO2ZO2CRCO2H wherein each R represents the residue of an internal anhydride of an aliphatic or monobenzenoid di- or tri-carboxylic acid having a 5 or 6-membered anhydride ring system and of the formula <FORM:1002190/C2/1> and Z represents the residue of an alkylene glycol or polyalkylene ether glycol of the formula HOZOH, are prepared by reacting said ester acid with allyl chloride in the presence of a tertiary amine in a molecular proportion at least equal to the molecular proportion of allyl chloride theoretically consumed during the reaction. It is preferred that Z represents the residue of an alpha-omega glycol or a polyethylene ether glycol of the formula HO(CH2CH2O)nOH, wherein n has an average value of from 2 to 45. The reaction is preferably carried out under substantially anhydrous conditions at between ambient temperature and 90 DEG C. in the absence or presence of an inert diluent or solvent and with a 10% molar excess of allyl chloride over the ester acid. The symmetrical ester acid reactants may be prepared by reacting two molecularproportions of an anhydride of the formula <FORM:1002190/C2/2> with substantially one molecular proportion of an alkylene glycol or polyalkylene ether glycol of the formula HOZOH. The reaction is normally performed under substantially anhydrous conditions in the absence or presence of an inert solvent for the ester acid product and preferably in the presence of an amine. Preferred amines are the tertiary amines which may remain in the reaction mixture for subsequent use in the process of the invention. Asymmetrical ester acid reactants may be prepared by reacting equimolecular proportions of glycol and anhydride and subsequently reacting the monoester so obtained with a different anhydride.