United States Patent (19) 11 Patent Number: 4,667,045 Briggs et al. (45) Date of Patent: May 19, 1987 ORGANOSALTS OF METALATE ANONS 4,283,580 8/1981 Odanaka et al. 54) 4,406,837 9/1983 Kroenke . AND PROCESS FOR THE PRODUCTION OF 4,406,838 9/1983 Kroenke . ALKYLENE GLYCOLS THEREWITH 4,406,839 9/1983 Kroenke et al. (75) Inventors: John R. Briggs; John H. Robson, both 4,406,840 9/1983 Kroenke . of Charleston, W. Va. 4,412,956 1 1/1983 Abramson et al. ............. 260/429 R (73) Assignee: Union Carbide Corporation, FOREIGN PATENT DOCUMENTS Danbury, Conn. 1577293 8/1969 France ............................ 260/429 R 54-128507 10/1979 Japan. 21 Appl. No.: 594,264 56073035 11/1979 Japan. Filed: Mar. 28, 1984 56073036 11/1979 Japan. 22 56-92228 7/1981 Japan. (51) Int. Cl'.......................... C07F 9/00; CO7F 11/00 (52) U.S. C. ........................................ 556/20; 556/21; OTHER PUBLICATIONS 556/42; 556/51 Brown, J. Inorg. Nucl. Chem. V 17, pp. 146-151 (1961). (58) Field of Search ........................ 260/429R, 429 J; Chemical Abstracts, 99:121790k (1983). 556/20, 21, 42, 57 R. A. Sheldon, "Molybdenum-Catalyzed Epoxidation 56) References Cited of Olefins with Alkyl Hydroperoxides, Recl. Trav. Chem., Pays-Bas, 92, p. 253, et seq. (1973). U.S. PATENT DOCUMENTS R. A. Sheldon, "Molybdenum-Catalyzed Epoxidation 2,795,549 6/1957 Abbott et al. .............. 260/429 RX of Olefins with Alkyl Hydroperoxide II, Isolation and 2,795,552 6/1957 Abbott et al. .............. 260/429 RX 2,805,997 9/1957 Benoit et al. ............... 260/429 RX Structure of Catalyst', Recl. Trav. Chim, Pays-Bas 92, 3,285,942 11/1966 Price et al. ...................... 260/429 R p. 367, et seq. (1973). 3,290,245 12/1966 Elliott et al. ............... 260/429 RX Primary Examiner-Helen M. S. Sneed 3,475,499 10/1969 Winnick. Attorney, Agent, or Firm-Steven T. Trinker 3,480,563 11/1969 Bonetti et al. 3,632,617 1/1972 Suzuki et al. ................... 260/429 R 57 ABSTRACT 3,668,227 6/1972 Mattucci et al. 3,778,451 12/1973 Poite. Novel vicinal dioxyalkylene organometalates compris 3,836,557 9/1974 Knowles ..................... 260/429 RX ing a cation having a hydrocarbyl-containing substitu 3,991,090 1 1/1976 Hagstrom et al. ent are disclosed. The vicinal dioxyalkylene or 4,009,122 2/1977 Lines et al. ................. 260/429 RX ganometalates can be reacted with water to yield alkyl 4,014,911 3/1977 Muntz et al. .................... 260/429 R 4,014,912 3/1977 Muntz et al. .................... 260/429 R ene glycols. 4,217,292 8/1980 Kroenke . 4,277,632 7/1981 Kumazawa et al. 17 Claims, No Drawings 4,667,045 1. 2 lybdates disclosed by Kroenke are described as smoke ORGANOSALTS OF METALATE ANIONS AND retardant additives for vinyl chloride polymer composi PROCESS FOR THE PRODUCTION OF tions. ALKYLENE GLYCOLS THEREWTH Organomolybdenum compounds have been pro 5 posed, for instance, as catalysts for the oxidation of This invention relates to organometalate-containing certain ethylenically unsaturated compounds, e.g., for compounds and to processes for the production of al the epoxidation of certain olefinic compounds. For kylene glycols from alkylene oxides and water involv example, in U.S. Pat. No. 3,668,227, issued June 6, 1972, ing the use of such compounds. The compounds of this a molybdenum alkylene-dioxy-derivative is prepared by invention are organosalts of metalate anion having at 10 reacting an organomolybdenum compound, e.g., mo least one cyclic alkylene dioxy moiety thereon. A meta lybdenum acetylacetonate, with an organic material late anion is characterized as being an anion of a polyva having vicinal hydroxyl groups. The organo-molyb lent metallic element with oxygen bonded thereto. The denum compounds are represented by the patentees as compounds are useful for the preparation of alkylene having the general formulae: glycols by contact with water, either as a liquid or 15 vapor. Introduction to Compounds Having Metal and R2-C-O O O-C-R VI W Organic-Containing Moieties Mo Various organometalates have been disclosed. For 20 / V instance, Kroenke, in U.S. Pat. No. 4,217,292, issued R.-- O o--Rs Aug. 12, 1980, describes amine molybdates prepared by R4 H R4 reacting molybdenum trioxide with an amine in an aqueous medium that is essentially free of acid and con tains a water-soluble ammonium and/or metal salt of an 25 acid. More recently Kroenke, in U.S. Pat. Nos. R2 R3 R1-C C-R4 4,406,837; 4,406,838; 4,406,839; and 4,406,840, all issued R on Sept. 27, 1983, disclosed organo-containing ammo R nium and amine molybdates. In U.S. Pat. No. 4,406,837, R2-C-O OH O O 30 V NZO-c-R, methyltricaprylammonium molybdates are prepared by Mo-O MoS reacting ammonium dimolybdate with methyltrica W N O-C-Rs prylammonium chloride in an acidic aqueous medium. R3-C-O O OH In U.S. Pat. No. 4,406,838, trioctylammonium molyb O R4 dates are prepared by reacting ammonium dimolybdate R. with trioctyl amine in an acidic aqueous medium. In 35 U.S. Pat. No. 4,406,840, tri(tridecyl)ammonium molyb R- 1-R, dates are prepared by reacting ammonium dimolybdate R2 R3. with tri(tridecyl)amine in an acidic aqueous medium. A wherein each of R1, R2, R3 and R4 is hydrogen, hydro process for preparing amine molybdates is disclosed in carbyl of 1 to 10 carbons, -CO)R, -NO2 or R1 and U.S. Pat No. 4,406,839 in which a two liquid phase 40 R4 or R2 and R3 may form a bivalent hydrocarbon radi reaction mixture is employed. A molybdenum reactant cal. See also U.S. Pat. No. 3,991,090, issued Nov. 9, (such as molybdenum trioxide, molybdic acid or salt) is 1976. provided in solution in an aqueous phase, and an amine Organic soluble molybdenum-containing catalysts or amine salt reactant (such as primary, secondary or are disclosed in U.S. Pat. No. 3,480,563, and are pre tertiary amines or quaternary ammonium salts) is or 45 pared by reacting molybdenum trioxide with a monohy becomes dissolved in an immiscible organic phase. The dric primary saturated alcohol such as octanol-1 or with amine molybdate is dissolved in the organic phase. An a polyalkylene glycol monoalkyl ether such as diethyl inorganic acid is preferably added to the reaction mix ene glycol monomethyl ether. These catalysts are also ture. Abramson, et al., in U.S. Pat. No. 4,412,956, issued 50 disclosed as being useful for the epoxidation of olefins. Nov. 1, 1983, disclose a process for making alkyl vana R. A. Sheldon in "Molybdenum-Catalyzed Epoxida dates by reacting vanadium pentoxide with an alkyl tion of Olefins with Alkyl Hydroperoxides', Recl. Tray, alcohol in the presence of a basic nitrogenous com Chim. Pays-Bas, 92, p. 253, et seq., (1973) proposed pound which is described as a catalyst. The basic nitrog mechanisms for the epoxidation of olefins in which a enous compounds disclosed include ammonia and am 55 transfer of an oxygen atom from a Mo(VI)-hydroperox monium compounds, amines, formamide compounds, ide complex to an olefin would occur via a cyclic transi urea, pyridine, guanidine carbonate and the like. tion state analogous to that for the epoxidation of olefins A. Martinsen, et al., in "Preparation and Properties of with organic per-acids. He states that the coordination Some Bis(triphenylphosphine)iminium Salts, of the hydroperoxide to Mo(VI) renders the peroxidic (Ph3P)2NX", Acta Chemica Scandinavica, A31 (1977) 60 oxygen atoms more electrophilic, thereby facilitating No. 8, pages 645 to 650, describe the preparation of nucleophilic attack by the olefin molecule. Thus the bis(triphenylphosphine)iminium salts by precipitation polymolybdenum complex acts as a Lewis acid. He from a warm, aqueous reaction medium employing the further states that the nature of the ligands surrounding corresponding chloride salt and an alkali metal salt of the molybdenum should affect the Lewis acidity of the the desired anion. Various anions disclosed by the au 65 catalyst, and hence the rate of reaction. thors include chromate, sulfate, nitrate and nitrite. In a subsequent article, "Molybdenum-Catalyzed The compounds previously disclosed have been at Epoxidation of Olefins with Alkyl Hydroperoxides, II. tributed to have various utilities. For example, the mo Isolation and Structure of the Catalyst", Recl. Tray, 4,667,045 3 4 Chim, Pays-Bas, 92, p. 367, et seq. (1973), R. A. Sheldon toward the monoglycol product could be beneficial states that the molybdenum species which forms during from the standpoint of energy efficiency. the epoxidation reaction is a Mo(VI)-diol complex, The hydrolysis reaction proceeds uncatalyzed: how regardless of whether molybdenum hexacarbonyl or ever, the presence of acids or bases enhances the rate of molybdenum acetylacetonate had been initially em 5 reaction. Acid and base catalysts, however, do have ployed, that is, the diol complexes are formed in situ via shortcomings. For instance, base catalysts are generally reaction with the epoxide in the presence of the hydro not selective to the formation of the monoglycol prod peroxide. The diol complexes are depicted as having the uct and acid catalysts are typically associated with cor Structure: rosion problems. Hence, commercial processes typi 10 cally utilize relatively neutral hydrolysis conditions (for instance, pH 6-10). H H H Representative of the numerous acid catalysts that have been suggested for use in the hydration of alkylene oxides include fluorinated alkyl sulfonic acid ion ex 15 change resins (U.S.