Патент USA US3023234код для вставки
I United- ‘States Patent '0 " "ice 3,023,224 Patented Feb. 27, 1962 2 1 As initial materials there are suitable polyhalogen 3,023,224 DEHYDROHALOGENATION 0F POLY ‘ HALOGENHYDRIN ETHERS Ferdinand Meyer, Mannheim, and Kurt Demmler, Lud wlgshaven (Rhine), Germany, assignors to Badische Anilln- 8: Soda-Fabrik Aktiengesellschaft, Ludwigs hafen (Rhine), Germany vNo Drawing. Filed Apr; 23, 1956, Ser. No. 579,760v _ 1 Claim. (Cl. 260-348.6) This invention relates to an improved process for the production of epoxy ethers from polyhalogenhydrin ethers of saturated aliphatic polyhydric alcohols.‘ ' hydrin ethers of polyhydric aliphatic saturated alcohols, such asv glycerine, butane-triol, pentaerythritol, tri methylol propane, trimethylol ethers, hexamethylol ‘ethers of melamine, sorbitol, dipentaerythritol and hexanetriol. The polyhalogenhydrin ethers for example polybrom hydrin_ or 'polychlorhydrin ethers of these polyhydric alcohols are known and may be prepared in the usual way, as for example by etheri?cation‘ by the action of 10 corresponding amounts of epoxychlorhydrin or dichlor hydrin or the corresponding brom-compounds on all or only part of the hydroxyl groups of the polyhydric alco hol in the presence of.a catalyst, as for example boron tri?uoride. Suitable polyhalogenhydrin ethers are espe Epoxy ethers have heretofore been obtained by treat ing monohalogenhydrin ethers of monohydric or poly 15 cially those which contain more than 2, as for example 2.1 to 3, halogenhydrin ether groups. hydric alcohols with ‘aqueous solutions of compounds having a strong basic action, as for example caustic alkali or alkaline earth solutions, at reduced or normal, Monohydric alcohols which. are suitable as solvents and dissolve both the initial polyhalogenhydrin ether and the epoxy compound formed are chie?y the saturated temperature, and extracting the reaction mixture with selective solvents, such as ether, hydrocarbons or carbon 20 primary, secondary or tertiary aliphatic alcohols, in par ticular those of a medium number of carbon atoms, espe tetrachloride. This method cannot beused however in the ‘case of . halogenhydrin ethers of polyhydric alcohols which con tain more‘ than ‘one halogenhydrin ether group because -- cially with 4 to 8 carbon atoms. Suitable alcohols ‘are for example normal butanol, normal amyl alcohol, secondary n-amyl alcohol, tertiary in this case the quality of the end product is consider 25 amyl alcohol and ethylhexanol. The alcohols ‘should only take up small amounts'of water, preferably 2 to ably reduced by reason of hydrolysis and/or polymeriza 10% of weight, at the working temperatures. They may tion of the epoxy compounds. ‘For the dehydrohalo therefore be separated well from the aqueous mother genation of such halogenhydrin ethers there have there liquor. The alcohols may also be used in admixture fore been developed processes in which the splittingoil is carried out with solid caustic soda 30 with each other or with an addition of other vwater-in soluble organic solvents, as for example aromatic hy alkali salts of amphoteric oxides, as drocarbons, such as benzene or toluene. These water alkali aluminate, silicate or zincate, insoluble organic solvents should be indifferent, i.e. they solvents which take up at least small should not react under the reaction conditions either with amounts of water being used as diluents. This method of working is also unsatisfactory because relatively large 35 the initial materials or with the end products. of hydrogen halide in acetone or with for‘ example‘ solid dioxane or organic amounts of solvent are required to carry it out and the * The dehydrohalogenation of the polyhalogenhydrin separation of the solid inorganic salts makes necessary I -- ethers according to this invention is preferably effected by introducing an amount of an aqueous concentrated. a further working operation; 'moreover‘the quality of solution of a strong inorganic base which is at least The object of this invention is to providev a process 40 equivalent to that required for binding the amount of the compounds prepared 'i‘s‘not‘ entirely Satisfactory. for the production of polyepoxy ethers of polyhydric hydrogen halide split off, preferably a somewhat larger alcohols in which the above-mentioned disadvantages are avoided and the poly-epoxy ethers are obtained in a good of the halogenhydrin ether in the inonohydric alcohol amount, as for example up to 20% excess, to a solution serving as solvent at temperatures of —20° to +30° , A further object is a process according to which the 45 C., care being taken for a good and thorough mixing until the end of the reaction. The amount of alcoholic hydrin compounds of polyhydric aliphatic alcohols with solvent is preferably chosen so high that a good and a plurality of halogenhydrin ether groups are converted thorough mixing of the solution with the aqueous alkali into the corresponding epoxy ethers and the latter may solution is ensured. This can readily be ascertained by be separated from the reaction mixture in the simplest a small preliminary test. In general solvent additions 50 of 33 to 66%, with reference tothe amount of halogen Another‘object of the invention resides in the use of hydrin ether used, are used. . a hitherto unemployed aqueous solution of an agent bind As inorganic bases, which are used in aqueous solu ing hydrogen halide for the dehydrohalogenation of yield with a high epoxy value. manner. , tion in concentrations of, for example, 25 to 60%, prefer alcohols containing a plurality halogenhydrin ether groups 55 ably 35 to 55% there may be mentioned in particular sodium hydroxide and potassium hydroxide. Surpris and a new solvent for this reaction which dissolves both ingly no hydrolysis or polymerization of the epoxy com both the halogenhydrin ether and also the epoxy ether pounds, once they have been formed, takes place. After formed, but is itself immiscible with water or only partly separation of the aqueous phase, the epoxy ethers are miscible therewith. We have now found that the said objects are achieved 60 obtained by distilling o?" the alcohol, if desired after washing with water or saturated salt solution, as for and polyepoxy ethers of polyhydric saturated aliphatic example sodium chloride solution. alcohols are obtained in good yields by carrying out the The following examples will further illustrate this in dehydrohalogenation of polyhalogenhydrin ethers espe halogenhydrin ethers of polyhydric saturated aliphatic cially polychlorhydrin ethers of aliphatic saturated poly vention but the invention is not restricted to these ex inorganic bases in the presence of an aliphatic mono Example 1 hydric alcohols with aqueous concentrated solutions of 65 amples. The parts speci?ed are parts by weight. hydric alcohol which is only moderately soluble or in soluble in water but which dissolves the resultant epoxy ether and the halogenhydrin ether used as initial ma terial, at temperatures of -20° C. to +30° C. advanta geously at --5° C. to +20“ 0., in particular at_—5° C. to +10° C. 370 parts of the chlorhydrin ether of glycerine, which has been obtained from glycerine and epichlorhydron in the mol ratio of 1:3 with boron tri?uoride as catalyst, are dissolved in 150 parts of butanol, cooled to -5° C. and while stirring vigorously 262 parts of a 45% 3 3,023,224; ' 4 caustic soda solution are slowly added so that the tem 10° C. to 15° C. 700 parts of a 45% caustic soda solu perature does not exceed 0° C. When all the caustic tion are added during the course of an hour. When soda solution has been run. in, the whole is stirred for all the caustic soda solutionhas been run in, the Whole about 3 hours further at 0° C. to —5° C; and then, is stirred for another 2 hours. Then 425 parts of water for more rapid phase separation, 50 parts of. toluene“ and: are added and the aqueousmother liquor separated from 200 parts of water are added. The phases are separated. the organic‘ liquids. The solvent is then removed in and the aqueous layer is repeatedly‘ extracted with 100' vacuo. There remain 670 parts. of apale yellow colored, parts of a mixture of butanol and toluene. in equal pro— liquid of low viscosity which has an epoxy value of 0.63 portions. From the non-aqueous phase combined with and a chlorine content- of 10.6%,. ' the extracts, the solvent is distilled o? in vacuo, ?nallyv 10 What we claim is: in a boiling waterbath, and- as a residue 260 parts are .In a method of producing polyepoxy- ethers from poly obtained which after ?ltration is an almost colorless, halogenhydrin ethers of saturated aliphatic polyhydric clear, thin liquid. The ?ltratehas an epoxy value oi alcohols selected from the group consisting of glycerine, 0.73. The substance still contains 10.5% of chlorine and? butane-triol, and‘ pentaerythritol by dehydrohalogenation has a mean molecular weight of 283 (ebullioscopically 15 of said polyhalogenhydrin ethers with a concentrated; from dioxane) which corresponds to a content of some aqueoussolution of an. alkali metal‘ hydroxide at a temwhat-more, than 2 epoxy groups per molecule. , perature of about ~20” C. to‘ about. +30° C., the im Example 2 provement which comprises’carrying out, said dehydro-l halogenation in the presence of a monohydric alcohol? 384 parts of the chlorhydrin ether of 1.2.4-butane-triol 20 selected from the’ group consisting oi n-butanol andi which has been obtained from 1 mol of butane-triol and. alkanols having fromS to 8 carbon‘ atoms, in the, molecule: 3 mols of epichlorhydrin with boron tri?uoride as cat in an amount of about 33 to 66% by weight with refer alyst, are, dissolved in 200 parts of a mixture. of equal. ence to the amount of the halogenhydrin ether. parts of butanol and toluene and while stirring vigor ously at --5° C., 310 parts ofv a- 38.% caustic soda solu 25 References Cited in the?le of this patent tion are slowly added so that the temperature. remains UNITED‘ STATES PATENTS; between about --2° C..and,-6,° C. When all the caustic. Groll‘ _______________ __ Nov. 17; 1936; 2,061,377 soda solution has been run in, the whole is stirred for a further 3 hours at, 0° C. to —5‘’ 0., then 150 parts 2,164,007‘ Evans _______________ __ June 27,1939‘ of water are; added, the aqueous layer separated and 30 2,224,849 1 Groll __ _____________ .. Dec” 17,v 1940; the solvent distilled off in vacuo from the non-aqueous. 2,248,635 Marple. et a1. ________ __ July 8,‘ 1941' layer. There» remain behind 294 parts of a pale yellow 2,314,039’ 2,434,414 Evans ______________ _.. Mar. 16', 1943-‘ Kharasch ___________ __ Jan. 13, 1948‘ chlorine" content of 10.25%. The product obtained has 2,581,464 Zech _______________ __ Jan. 8, 1952. a mean molecular weight of 350 corresponding to a. 35 2,680,109 Stevens ______________ __,._, June 1, 19541 colored liquid. It has an epoxy value of’ 0.67 and a. contentof 2.14‘epoxy groups per molecule. Example 3 990'parts of a chlorhydrin ether which has. been. pre pared in known manner from 46 parts of glycerine, 829. 40 parts of pentaerythritol and 2,128 parts of epichlorhydrin' are dissolvedv in 600 parts of amyl alcohol and then at. . FOREIGNv PATENTS 513,388 Canada, _______.._,_..__,_ May 31', 1955,‘ OTHER REFERENCES . .Fieser: “Org. Chemistry” (1944), page 117. Cohen et aL: Jj.A.-C;S-,. 75:173.‘ (1953‘).