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Jan. 23, 1962 H. s. HALBEDEL ETAL 3,018,162 ANHYDROUS METAL FLUOBORATES Filed April 15. 1960 ——————-—> METAL PLUORIDE _ *—’—* BF, POLAR SOLVENT soLu'noN REACT SEVERAL DAV-9 WITH 146/ TA 7'/0/V AND DEC/7N7’ RE SIDUE METAL FLUORIDE . so LUTION PRODUCT A METAL an, 1 soumou 1N pomp. sowam BFa BFg TREATME/VTW/Tf/ COOLING; F/LTER mpuma METAL FILTRATE f 3P4 CRYSTALS T WASH W/TH ETHER AND 3P3 SOLVENT PUMP DRV PRODUCT B METAL BF4 CRYSTALS HAROLD S. HALBEDEL & WALTER B.FIELD, INVENTORS. BY WM Att/a United States Patent O?ice E?ldddd Patented Jan. 23, 1962 1 2 3,018,162 down, agitating the resultant solution, treating the solution with additional boron tri?uoride, preferably diluted with ANHYDRGUS METAL FLUOBQRATES small amounts of inert gas and recovering resultant anhy drous metal ?uoborate crystals. The anhydrous metal ?uoborate crystals are found to be crystals of the solvated pany, Cleveland, Chic, a corporation oft‘ Uhio type, that is, their crystalline structure has a polar solvent Filed Apr. i5, 196%), Ser. No. 22,447 rather than water coupled therein. 6 Claims. (Ci. 23-59) If a solution of anhydrous meal ?uoborate is desired, This invention relates to anhydrous metal ?uoborates the above procedure may be modi?ed by elimination of and to the methods of their preparation. the BF3 crystallization addition step. The resultant metal Metal ?uoborates have found application as curing 10 ?uoborate solution may be packaged for use as a resin catalysts for various resins, such as, for instance, epoxy curing catalyst. resins, and for electroplating bath addition agents. The A better understanding of the general type of applicants’ curing of epoxy resins, however, frequently takes place in procedure may be obtained from the accompanying ?ow Harold S. Halhedel, Euclid, and Walter B. Field, Cleve iand, @hio, assignors to The Harshaw Chemical Com a volatile organic solvent wherein the presence of water sheet. The ?ow sheet shows the addition of a metal ?uo and particularly the presence of water in the curing cata 15 ride to a B133 polar solvent solution. The concentration lyst is undesirable. Fluoborates of lead, tin, cadmium, of BFB may be in the range of from 5% to 50%; the preiron, indium, nickel and silver are valuable salts in plat ferred range being from 15 % to 40%. The resultant mix ing baths and are commonly sold in solution form as 50% ture is then reacted for tWo or more days with agitation concentration. The shipping and packaging of such solu tions, however, is a major problem which could be elimi nated by the preparation of ?uoborates in anhydrous form. and then decanted. The residue which is primarily metal ?uoride or metal ?uorideaBFa complex may be recycled to the B133 polar solvent solution. The resultant solution, Most ?uoborates as commonly prepared contain a cer which is designated on the ?ow sheet as Product A, may tain amount of water of hydration. The better known be drawn ed and packaged for use as a resin curing agent.‘ ‘methods of preparation are: (a) the reaction of boron 25 This product is particularly useful where a slight excess tri?ucride with heated ?uorides of certain metals; and of BFS is not undesirable in the end use. As an alter (b) the reaction of ?uoboric acid with a halide, oxide, nate to the packaging of the product at this point, the hydroxide, carbonate, nitrate or sulfate of a metal. In solution which consists of a metal ?uoborate in a BF3 general, ?uoborates of group III-B meta-ls and the alkali polar solvent solution may be drawn oil’ and the BFa con metals, with the exception of lithium, are readily dehy centration slowly increased with cooling to about 15% to drated by warming ‘or the use of desiccants. Other ?uo~ 40% of B133 in polar solvent, the amount of 8P3 added borates and more speci?cally the ?uoborates of lithium, groups lI-B, II~B, III, IV-B, transition metals and alkaline being that which will produce maximum precipitation. the strongly coupled Water of hydration which is found solution. Crystals recovered from the ?ltration operation The solution, thus treated, is then ?ltered. The ?ltrate earth metals are strongly coupled to their waters of hy from this operation with the addition of BFg and polar dration. Various attempts have been made to remove 35 solvent may be recycled to the initial BF3 polar solvent in certain metal ?uoborate crystals. When a simple ap are impure metal ?uoborate crystals which are washed plication of heat is employed, it is found that these metal with ether and pump dried to obtain puri?ed metal ?uo ?uoborate crystals lose water at about 40° C. to 60° C. borate crystals, designated as Product B on the flow sheet. However, the metal fluoborate is also subjected to a de 40 The reaction which takes place may be written as fol composition process wherein there is a reversion to boron lows: ?uoride and metal ?uoride. Attempts have also been made to remove the water of hydration by an azeotropic where M is a metal selected from the group consisting of distillation process. The azeotropic distillation process employed benzene as the immiscible liquid. The proce 45 lithium, li-B, 11-13, Ill, IV-B, alkaline earth metals and transition metals, R is an oxygen containing polar sol dure did remove the bulk of water, but complete dehy vent preferably selected from the group consisting of dration could not be effected. Continued distillation methanol and ethanol, and n is an integer equal to the merely resulted in decomposition of the meal ?uoborate. valence of the metal M. Metal ?uoborates which contain the ET, radical and The method of preparation of this invention is depend liberate the BF; ion in solution should not be confused 50 out upon the discovery that ?uobcrates result from the with metal ?uoride-B193 complexes. Anhydrous metal dissolution of metallic ?uorides in coordination complexes ?uoride-BT43 complexes may be formed by the addition of of BF3, provided the bond strength of the solvent BF3 a metal ?uoride to an ether-boron tri?uoride complex, fol complex is less than the bond strength of the desired ?uo lowed by liberation of ether. Fluoborates in comparison with corresponding anhydrous metal ?uoride-B113 com 55 borate. To a degree this principle was recognized by the teachings of the prior art. However, the only apparent plexes are generally superior for use as curing catalysts or as salts in plating baths. The metal ?uoride-BB com plexes are unsuitable in that many of them break down at room temperature, liberating BF3 and also in that metal use which was made of this principle was to separate water or others from their respective complexes with B133 in or der to form metal ?uoride-B133 complexes. In contradis tinction to this procedure, applicants’ invention is carried out by employing an organic complexing medium which is in water, the metal ?uorides being of no use in plating. also a solvent for the desired ?uoborate. Applicants are it is, therefore, an object of this invention to produce therefore able to form, by means of the controlled addi~ a method for the preparation of anhydrous metal ?uo tion of BF3, a crystallized meallic compound containing borates. it is a ?urther object of this invention to produce non 65 BF, radical. The procedure of this invention necessitates a polar sol aqueous solvated metal ?uoborates. vent which will not break down to form dehydration prod it is another object of this invention to produce a solu ucts and which has some degree of solubility for the metal tion of anhydrous metal fluoborate in an organic solvent. We have now discovered that it is possible to produce fluoborate formed. The term solvent as used herein is anhydrous metal ?uoborates by the ‘addition of a metal 70 synonymous with the term coordinating agent, that is, the fluoride to a solution of boron tri?uoride in an oxygen solvent for the metal ?uoborate is also that compound containing polar solvent which is not subject to a break which forms a coordination compound with BF3. Some ?uoride-BPS complexes form metal ?uorides when placed 4 3’: solvents which are suitable for the purposes of this in vention are methanol and ethanol, methanol being pre~ ferred because it is a better solvent for metal fluoborates. Speci?c examples of the preparation of anhydrous metal amount of nitrogen was slowly added to 390 grams and 324 grams of crystals were ?ltered o?. B133 addition was continued to 540 grams (total BR) and 611 grams of crystals separated. The total yield ‘from above being 1001 grams of zinc ?uoborate crystals. ?uoborates according to this invention are as follows: The crystals were washed well with ether on a Bli‘chner funnel and dried rapidly in a vacuum oven at 40° C. The crystals were Example I removed and packaged rapidly in glass jars with poly 393 grams of BF3 were added to 690 grams of methanol ethylene liners. Total Zn analysis 14.9% ?gured to in a 2-liter three-neck ?ask over a 11/2 hour period. An Zn(BF4)2 is 54.4% by weight of product. This agrees 10 ice water bath was used to take ‘off the heat of reaction. well with Zn(BF4)2.6CH3OH, theoretical Zn(BE4)2 ‘One-half of the resulting solution was placed in each of 55.4%. two l-liter Erlenmeyer ?asks containing 15 0 grams of What we claim is: Z11F2- The ?asks were stoppered and placed on an Eber 1. A process for the preparation of anhydrous zinc bach shaker. Alcohol was added after shaking one day ?uoborate comprising mixing Zinc ?uoride with an anhy 15 to a total of 1090 grams of alcohol (including original alcohol) ‘for dissolution of zinc ?uoborate crystals and to enable good mixing. This was equivalent to a 36% solu tion of BFa (plus Ell-7.; as SP3) in alcohol. The solutions were allowed to settle 3 hours and the milky liquors decanted into a dry 2-liter three~neck ?ask in an ice water bath. 60 grams of alcohol insoluble Znliz were recovered from the ?asks. A small ?ow of nitrogen was fed into the ?ask and BF3 impinged slowly on the surface of the liquor while stirring slowly. _ 150 grams of BB, were added over 11/2 hours. This produced an equivalent of 17% BE, in the BF3-alcohol (alcohol tied up in the solvated crystals included). The crystals were ?ltered on a Biichner fun nel, washed with two 100 ml. portions of ether and pump dried 4 hours to very slight loss in weight. 57.3 grams of 30 very hygroscopic solvated zinc ?uoborate crystals were obtained. A higher yield could have been obtained upon further addition of BF3 to about 25% BF3 in BF3-alocohl. A large excess of BF3, however, was added to the liquor, thus dissolving the crystals. 35 Example II 100 grams of BaF2 and 232 grams of CH3OH-BF3 solu tion (33.3% BF3) were placed in a one-liter Erlenmeyer drous 25% solution of ER in methanol, agitating the mixture, removing unreacted metal ?uoride, adding addi tional BFQ diluted by a small ?ow of nitrogen and ?lter~ ing off crystals of anhydrous Zinc ?uoborate. ' 2. A process for the preparation of an organic solution of anhydrous zine ?uoborate comprising mixing zinc ?uo ride with an anhydrous 25% solution or’ 13133 and methanol, agitating the mixture and removing unreacted metal ?uo ride.v 3. A process for the preparation of anhydrous barium ?uoborate comprising mixing barium ?uoride with an an hydrous 33.3 % solution of BB, in methanol, agitating with additional methanol, removing unreacted metal ?uoride, adding additional B133, and ?ltering oil crystals of anhy drous barium ?uoborate. 4. A process for the preparation of a solution of an hydrous barium ?uoborate in an anhydrous organic solvent comprising mixing barium ?uoride with a 33.3% solu tion of BFB in methanol, agitating with additional meth anol, and removing unreacted metal ?uoride. 5. A process for the preparation of an anhydrous metal ?uoborate comprising mixing a metal ?uoride selected from the group consisting of Zinc ?uoride and barium ?uo ride with a 5% to 50% solution of BF3 in an anhydrous ?ask. 249 grams of CH3O were added. The flask as stop 40 oxygen containing polar solvent, agitating the mixture, pered and shaken for 3 days. The flask was allowed to stand, the solution decanted into a one-liter three-neck ?ask in a cold water bath. BaF2 in the residue was 8.0 grams. 215 grams of B133 diluted by a small ?ow of nitro— gen were run in with mild agitation. A large crystalline 45 precipitate was then ?ltered on a Biichner funnel. The BF3 addition was equivalent to 36% BF3 in BFg-alcoho-l (alcohol tied up in solvated crystals included). 8P3 addi removing unreacted meal ?uoride, adding additional BF3 and filtering o? crystals of anhydrous metal ?uoborate. 6. A process for the preparation of a solution of anhy drous metal ?uoborate comprising mixing a metal ?uoride selected from the group of zinc ?uoride and barium ?uo ride with a 5% to 50% solution of BFs in an anhydrous oxygen containing polar solvent, agitating the mixture and removing unreacted metal ?uoride. tion was continued to a total of 310 grams (44% BE solu~ ‘tion in alcohol on original basis) for maximum precipita tion. The salt was washed twice with 100 ml. portion of anhydrous ether and pump-dried. Example III 300 grams of zinc ?uoride were reacted for two days 55 with a solution of 393 grams of BF3 in 1179 grams of methanol (25% EEK-methanol solution) in two one-liter References Cited in the ?le of this patent UNITED STATES PATENTS 2,465,989 2,796,323 Sowa _______________ __ Apr. 5, 1949 Eberle _______________ __ June 18, 1957 814,638 Great Britain __________ _._ June 10, 1959 FOREIGN PATENTS OTHER REFERENCES Erlenmeyer ?asks. Constant agitation was maintained on I. W. Mellor’s “A Comprehensive Treatise on Inorg. ‘an Eberbach shaker. The liquor Was decanted into a two-liter three-neck ?ask in an ice water bath. 23 grams 60 and Theoretical Chemistry,” vol. 5, 1924 Ed., page 123, pf zinc fluoride residue remained. 3P3 diluted by a small Longmans, Green and Co., NY. s. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION ‘ Patent No‘, 3,018,,162 January 23‘, 1962“ Harold S, Halbedel et al., It is" nerebyoer’oifmd that error appears in ,the above numbered pat entrequiring correction and‘bhat the, said Lettersv Patent should read as "corrected below. Column 2, line 63a for "meallic‘" read -- metallic: "—¥~';' column 3‘I line 32", "-alocohl" read -—— —alcohol “a; line 40‘z for "CH3O" read --.CH3OH -=-—; column 40 line ill‘z for "meal" read —— metal —-—. ' Signed and Sealed this 8th day of May 1962;. (SEAL) Attest: ERNEST W. SWIDEE Attesting Officer DAVID L. LADD Commissioner of Patents