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European Patent Office © Publication Number: 0 026 547 A1 Office Europeen Des Brevets Europaisch.es Patentamt European Patent Office © Publication number: 0 026 547 A1 Office europeen des brevets © EUROPEAN PATENT APPLICATION © Application number: 80200911.8 © Int. CI.3: C 07 F 3/00 C 07 C 31/30, C 07 C 29/68 © Date of filing: 26.09.80 //C08G65/28, C07C41/03, B01J31/02 © Priority: 27.09.79 US 79497 © Applicant: UNION CARBIDE CORPORATION 270, Park Avenue New York, N.Y. 10017(US) © Date of publication of application: 08.04.81 Bulletin 81/14 @ Inventor: McCain, James Herndon 1987 Parkwood Road © Designated Contracting States: Charleston West Virginia 25314(US) BE DE FR GB IT NL SE © Inventor: Foster, Donald Joseph 603 39th Street, S.E. Charleston West Virginia 25304(US) © Representative: Urbanus, Henricus Maria, Ir. et al, c/o Vereenigde Octrooibureaux Nieuwe Parklaan 107 NL-2587 BP 's-Gravenhage(NL) © Process for the preparation of basic salts of alkaline earth metals and basic salts obtained by this process. (57) A process is provided for the preparation of soluble basic salts of alkaline earth metals that are catalytically active in the oxyalkylation reaction of alcohols, polyols and phenols which comprises reacting an alkaline earth metal material selected from the group consisting of calcium, strontium, and barium and mixtures of the same with a lower monohydric alcohol having 1 to 7 carbon atoms at a temperature at which the reaction proceeds to form a lower alcohol metal alkoxide, mixing a polyol or a higher monohydric alcohol having at least 4 carbon atoms with the lower alcohol-alkaline earth metal alkoxide reaction product and removing the lower alcohol therefrom. <* in to o D. lil Croydon Printing Company Ltd. BACKGROUND OF THE INVENTION: This invention relates to the preparation of compositions which are catalytically active for the pre- paration of condensation reaction products of an epoxide and organic compounds having an active hydrogen with a restricted molecular weight distribution and reduced by-products. A variety of products such as surfactants, functional fluids, glycol ethers, polyols, and the like are commercially prepared by the condensation reaction of epoxides with organic compounds having an active hydrogen, generally in the presence of an alkaline or acidic catalyst. The types of products prepared and properties thereof depend on the active hydrogen compound, the epoxide, and the number of moles of epoxide employed as well as the catalyst, a mixture of condensation products species being obtained containing different molecular proportions of epoxide. Thus, the reaction products generally obtained have a wide range of molecular weights and of molecular distribution of the - epoxide units. It is generally desirable to restrict the molecular distribution of the mixture to adjacent analogues of the desired product, insofar as possible, but this is quite difficult to control. Acidic catalysts tend to give a narrower molecular distribution than alkaline catalysts, but also contribute to the formation of undesired by-products. Thus, alkaline catalysts are generally used as the more efficient type of catalyst,but the molecular distribution in the resulting products are more diffuse. - Heretofore, several methods have been suggested for providing reaction products of an active hydrogen com- pound and epoxides having a narrower range of molecular weights and molecular distribution of the epoxide units, or which reduce or eliminate the production of undesirable poly(ethylene) glycol and cyclic and straight chain ether by-products. For example, in U.S. Patent 4,112,231 to Weibull et al. it is disclosed that the use of certain neutral inorganic fluoborate and perchlorate salts will catalyze the reaction of epoxides with active hydrogen compounds to give products having a narrower molecular distribution and a larger proportion of desired species; in U.S. Patent No. 3,682,849 to Smith et al improved ethoxylated derivatives of Cll - C18 alcohols are prepared by removing unreacted alcohol and lower ethoxylates from the conventionally produced ethoxylate mixture using vapor phase separation techniques; in U.S. Patent 2,870,220 to Carter, a two-stage process is disclosed for preparing monoalkyl ethers of ethylene glycol and polyethylene glycols of more restricted molecular weight range wherein an alkanol and ethylene oxide are reacted in the presence of an acidic catalyst during the first stage and'then in the second-stage, after removal of acid catalyst and unreacted alkanol, reacting the mixture with ethylene oxide in the presence of an alkali metal alcoholate of the initial alkanol; and in U.K. Patent 1,501,327 to » Laemmle et al is disclosed a method of preparing mono- and poly-glycol ethers substantially free of undesired alkylene glycols by-products which involves heating a reaction mixture containing an alkylene oxide and an alcohol in the presence of a catalyst containing alkali or alkaline earth cations wherein some or all of the catalyst is an anhydrous high boiling liquid residue prepared by concentrating the liquid residue left from the same or different etherification pro- cess after removal of the glycol ether product from the reaction mixture. There has also been suggested basic compounds of alkali and alkaline earth metals that have been used, for example, in the polymerization of alkaline oxides (see U.S. Patent 3,100,750 to Bailey, Jr. et al.) and the preparation of nonionic surfactants having special properties (see U.S. Patent 4,134,854 to Milligan). To the best of our know- ledge, however, none of the processes or special catalysts disclosed in the art are completely satisfactory in that they require multi-stage procedures or special acid- resistant equipment, give undesirable by-products or simply do not provide sufficient control over the molecular weight distribution. It would be highly desirable, therefore, to develop a process for the preparation of compositions which are catalytically active in the reaction of an epoxide with an organic compound having an active hydrogen wherein such reaction could be more readily carried out to prepare products that have a narrow molecular weight distribution of anologue species and contain only small amounts, at most, of undesirable by-products. SUMMARY OF THE INVENTION Various soluble basic salts of alkaline earth metals have been described in our copending application Serial No. as being effective catalysts for the preparation of condensation reaction products of an epoxide and an organic compound having an active hydrogen compound. The instant invention is directed to the novel method for the preparation of a class of catalysts which are extremely effective for the preparation of oxyalkylation reaction products having a narrower molecular weight distribution and reduced amount of undesirable by-products. In accordance with the present invention there is provided a process for the preparation of soluble basic salts of alkaline earth metals that are catalytically active in the oxyalkylation reaction of alcohols, polyols and phenols which comprises reacting an alkaline earth metal material selected from the group consisting of calcium, stron- tium, and barium and mixtures of the same with a lower mono- hydric aliphatic alcohol having 1 to 7 carbon atoms at a temperature at which the reaction proceeds to form a lower alcohol metal alkoxide; mixing a polyol or a higher monohydric alcohol having at least 4 carbon atoms with the lower alcohol- alkaline earth metal alkoxide reaction product and removing the lower alcohol from the reaction mixture of higher alcohol or polyol and lower alcohol metal alkoxide. It has been discovered that the basic salts of alkaline earth metals herein described not only catalyze the reaction of a monohydric alcohol, polyol, or alkyl phenol and an epoxide'but also favor a narrower molecular distribution, i.e., a more limited range of molecular species and a larger proportion of the desired species in the reaction product. Moreover, the oxyalkylation reaction can be carried out in a single stage without the need for special acid- resistant equipment and the products produced thereby have been found, in general, to contain only small amounts of undesired poly(alkylene) glycol and ether by-products. DESCRIPTION OF THE INVENTION In the process of the invention an alkaline earth metal material selected from the group consisting of calcium, strontium, barium and mixtures of the same is reacted with a lower monohydric alcohol having 1 to 7 carbon atoms to form the alkaline earth metal alkoxide; mixing a polyol or a mono- hydric alcohol having at least 4 carbon atoms with the lower alcohol alkaline earth metal alkoxide, and removing the lower monohydric alcohol from the reaction mixture. The calcium, strontium, and barium containing materials suitable for use in accordance with the process of the invention may be any metal containing material which will react with water to give the corresponding metal hydroxide and another reaction product. Exemplary of such suitable materials are calcium, strontium, and barium metals, calcium, strontium, and barium hydrides, and calcium, strontium, and barium acetylides. The lower monohydric alcohols which can be used are primary, secondary or tertiary aliphatic alcohols hav- ing 1 to 7 carbon atoms and preferably 1 to 4 carbon atoms which are branched or straight chain. Exemplary of pre- ferred alcohols are methanol, ethanol, n-propanol, iso- propanol, n-butanol,, and iso-butanol. Also suitable are n-pentanol, 2-pentanol, 3-pentanol, n-hexanol and the like. Suitable higher monohydric alcohols having at least 4 carbon atoms that may be used in accordance with the inven- tion can be primary and secondary aliphatic alcohols which are straight or branched chain having at least 4 and preferably from 8 to about 30 or more carbon atoms. Exemplary of such primary straight chain alcohols are n-octanol, nonanol, decano undecanol, dodecanol, tridecanol, tetradecanol, penta- decanol, hexadecanol, and octadecanol; and of such branched chain or secondary alcohols are 2-ethylhexanol, isooctanol, secoctanol, and isodecanol. Particularly suitable are linear and branched primary alcohols and alcohol mixtures such as produced by the "Oxo" reaction of normal C3-C2p olefins.
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