MAIMOTOMONTANT US009828318B2 DE LLUT TUTO MINI ( 12 ) United States Patent ( 10 ) Patent No. : US 9 ,828 ,318 B2 Ishihara et al. (45 ) Date of Patent: Nov . 28, 2017 (54 ) METHOD FOR PRODUCING GLYCOLS FOREIGN PATENT DOCUMENTS FROM OXIRANE COMPOUNDS S56 - 73035 A 6 / 1981 (71 ) Applicant: Sumitomo Chemical Company, WO WO 9511213 * 4 / 1995 Limited , Tokyo (JP ) OTHER PUBLICATIONS ( 72 ) Inventors : Shinjiro Ishihara , Ehime ( JP ) ; Shoko National Center for Biotechnology Information . PubChem Com Ikeda , Chiba ( JP ) ; Masayuki Yoshii , pound Database, CID = 8087 , https: // pubchem .ncbi . nlm .nih . gov / Chiba ( JP ) ; Makoto Murata , Ibaraki compound / 8087 (accessed Aug. 23 , 2015 ) , 31 pages creation date ( JP ) Mar . 26 , 2005 . * National Center for Biotechnology Information . PubChem Com pound Database , CID = 32611, https: / / pubchem .ncbi . nlm .nih . gov / ( 73) Assignee : Sumitomo Chemical Company, compound / 32611 (accessed Aug . 23 , 2015 ) , 29 pages creation date Limited , Tokyo (JP ) Aug . 8 , 2005 . * Tanabe (“ Niobic acid as an unusual acidic solid material ” , Materials ( * ) Notice : Subject to any disclaimer , the term of this Chemistry and Physics , vol. 17 , Issues 1 - 2 , Apr. -May 1987 , pp . patent is extended or adjusted under 35 217 - 225 ). * U . S . C . 154 (b ) by 0 days . Kozo Tanabe , “ Niobic acid as an unusual acidic solid material ” , Materials and Physics, vol . 17 , Issues 1 - 2 , Apr. - May 1987 , pp . 217 - 225 . * (21 ) Appl . No. : 14 /362 , 940 Iizuka et al . , “ Acidic and Catalytic Properties of Niobium Pentoxide” , Bull . Chem . Soc. Jpn . , 56 , Oct. 1983 , pp . 2927 -2931 . * (22 ) PCT Filed : Dec . 12 , 2012 Tanabe et al. , “ New Solid Acids and Bases: Their Catalytic Prop erties ” , Technology and Engineering , 1990 , pp . 60 and 61. * (86 ) PCT No. : PCT/ JP2012 / 082853 Kirk - Othmer Encyclopedia of Chemical Technology , John Wiley & Sons, Inc. , pp . 1 - 10 (2000 ) . $ 371 ( c ) ( 1 ) , “ Shokubai Kagaku ( Catalyst Chemistry ) ,” pp . 518 -519 , 525 ( 1981 ) . ( 2 ) Date : Jun . 5 , 2014 Dow Dipropylene Glycol LO + Technical Data Sheet . Dow Tripropylene Glycol, Acrylate Grade Technical Data Sheet . ( 87 ) PCT Pub . No. : WO2013 / 089271 Int' l Search Report dated Feb . 5 , 2013 in Int' l Application No . PCT Pub . Date : Jun . 20 , 2013 PCT/ JP2012 /082853 . (65 ) Prior Publication Data * cited by examiner US 2014 / 0378714 A1 Dec . 25 , 2014 Primary Examiner — Rosalynd A Keys (74 ) Attorney, Agent, or Firm — Panitch Schwarze ( 30 ) Foreign Application Priority Data Belisario & Nadel LLP Dec . 13 , 2011 ( JP ) .. .. .. .. .. 2011- 271976 (57 ) ABSTRACT May 10 , 2012 ( JP ) .. .. .. .. .. .. 2012 - 108285 The objective of the present invention is to provide a method for the highly selective production of dipropylene glycol (51 ) Int. CI. containing 1 , 1 ' -oxybis - 2 -propanol in a proportion of 0 . 10 to C07C 41/ 03 ( 2006 .01 ) 0 .70 and / or tripropylene glycol containing 1 , 1 ' - [ ( 1 -methyl (52 ) U . S . CI. 1 , 2 - ethanediyl) bis ( oxy ) ]bis - 2 -propanol in a proportion of CPC .. .. .. .. C07C 41/ 03 ( 2013 .01 ) ; YO2P 20 /582 0 . 10 to 0 .70 . The present invention is a method for produc ( 2015 . 11 ) ing dipropylene glycol containing 1 , 1 '- oxybis - 2 -propanol in (58 ) Field of Classification Search a proportion of 0 . 10 to 0 . 70 and / or tripropylene glycol CPC . .. .. .. C07C 41/ 03 containing 1 , 1 ' - [ ( 1 -methyl - 1 , 2 - ethanediyl) bis (oxy ) ] bis - 2 See application file for complete search history. propanol in a proportion of 0 . 10 to 0 . 70 , the method com prising a reaction step of making a reactant comprising ( 56 ) References Cited propylene oxide and water react in the presence of a catalyst , wherein the catalyst comprises at least one element selected U . S . PATENT DOCUMENTS from the group consisting of vanadium , niobium , and tan 4 ,551 ,566 A 11/ 1985 Robson et al . talum , and the Hammett acidity function ( H ) of the catalyst 4 ,578 ,524 A 3 / 1986 Keen satisfies Hs9 . 3 . 4 ,760 , 200 A * 7 / 1988 Keen et al . 568 / 867 6 , 147 , 265 A 11 /2000 Iwakura et al . 5 Claims, No Drawings US 9 ,828 ,318 B2 METHOD FOR PRODUCING GLYCOLS PRIOR ART DOCUMENT FROM OXIRANE COMPOUNDS Patent Document CROSS -REFERENCE TO RELATED APPLICATION 5 [Patent Document 1 ] JP - A - 56 -073035 This application is a Section 371 of International Appli Non -Patent Document cation No . PCT / JP2012/ 082853 , filed Dec . 12 , 2012 , which was published in the Japanese language on Jun . 20 , 2013 , [Non -Patent Document 1 ] Alton E . Martin , “ Glycols , Pro under International Publication No . WO 2013 /089271 A1, 10 pylene Glycols ” , Kirk - Othmer Encyclopedia of Chemical and the disclosure of which is incorporated herein by Technology, 2000 reference . SUMMARY OF THE INVENTION TECHNICAL FIELD 15 Problems to be Solved by the Invention The present invention relates to a method for the highly Patent document 1 , however, contains no disclosure about selective production of dipropylene glycol containing 1 , 1' the proportion of 1 , 1 '- oxybis - 2 -propanol contained in dipro oxybis - 2 - propanol in a proportion of 0 . 10 to 0 .70 and / or pylene glycol and the proportion of 1 , 1 '- [ ( 1 -methyl - 1 , 2 tripropylene glycol containing 1 , 1 '- [ ( 1 -methyl - 1 , 2 - eth - 20 ethanediyl) bis (oxy ) ]bis - 2 -propanol contained in tripropyl anediyl ) bis ( oxy ) ]bis - 2 - propanol in a proportion of 0 . 10 to ene glycol. 0 . 70 . The objective of the present invention is to provide a method for the highly selective production of dipropylene BACKGROUND ART glycol containing 1 , 1 ' - oxybis - 2 - propanol in a proportion of Dipropylene glycol is a compound that is used as a raw 25 0 . 10 to 0 .70 and /or tripropylene glycol containing 1 , 1 '- [ ( 1 material for polyester resin or polyurethane resin , a raw methyl- 1 , 2 - ethanediyl) bis (oxy ) ]bis - 2 -propanol in a propor material for acrylates , an operating oil , an antifreezing tion of 0 . 10 to 0 .70 . solution , a wetting agent for cellophane, a compatibilizing Means for Solving the Problems agent, a solvent for printing ink , a raw material for cosmet- 30 ics , solvent for perfume, solvent for toiletries , and so on , The present invention relates to a method for producing whereas tripropylene glycol is a compound that is used as a dipropylene glycol containing 1 , 1 ' - oxybis - 2 -propanol in a raw material for polyester resin or polyurethane resin , a raw proportion of 0 . 10 to 0 . 70 and / or tripropylene glycol con material for acrylates , a solvent for a water- soluble oil, a taining 1 , 1 ' - [ ( 1 -methyl - 1 , 2 - ethanediyl) bis ( oxy ) ]bis - 2 - pro solvent for ink , and so on . Dipropylene glycol and tripro - 35 panol in a proportion of 0 . 10 to 0 .70 , the method comprising pylene glycol are known to be produced as byproducts when a reaction step of making a reactant comprising propylene producing propylene glycol. oxide and water react in the presence of a catalyst , wherein It is known that dipropylene glycol produced industrially the catalyst comprises at least one element selected from the is commonly a mixture of 1 , 1' -oxybis - 2 - propanol, 2 , 2 ' group consisting of vanadium , niobium , and tantalum , and oxybis - 1 -propanol , and 2 - ( 2 -hydroxypropoxy ) - 1 -propanol 40 the Hammett acidity function ( H ) of the catalyst satisfies (see , for example , non -patent document 1 ) . Hs9 . 3 . Moreover, it is known that tripropylene glycol produced industrially is commonly a mixture of 1 , 1' - [ ( 1 -methyl - 1 , 2 Effect of the Invention ethanediyl) bis ( oxy ) ]bis - 2 - propanol, 2 , 2 '- [ ( 1 -methyl - 1 , 2 - 45 According to the present invention , it is possible to highly ethanediyl ) bis ( oxy ) ]bis - 1 -propanol , 2 - [ 1 - ( 2 -hydroxy - selectively produce dipropylene glycol containing 1 . 1 -OXV propoxy ) - 1 , 2 -propoxy ] - 1 - propanol, and 2 - [ 2 - ( 2 - bis - 2 - propanol in a proportion of 0 . 10 to 0 . 70 and /or tripro hydroxypropoxy ) -propoxy ] - 1 -propanol ( see , for example , pylene glycol containing 1 , 1 '- [ ( 1 -methyl - 1 , 2 -ethanediyl )bis non -patent document 1 ) . ( oxy) ] bis - 2 - propanol in a proportion of 0 . 10 to 0 . 70 . The proportion of 1 , 1 ' - oxybis - 2 - propanol contained in 50 commercially available dipropylene glycol is 0 . 10 to 0 . 70 , MODE FOR CARRYING OUT THE INVENTION and the proportion of 1, 1 '- [ ( 1 -methyl - 1 , 2 - ethanediyl ) bis ( oxy ) ] bis - 2 - propanol contained in commercially available in the method of the present invention , while a reactant tripropylene glycol is 0 . 10 to 0 . 70 . Such commercially containing propylene oxide and water is made to react in the available dipropylene glycol and tripropylene glycol are 55 presence of a catalyst comprising at least one element known to be produced as byproducts when producing pro selected from the group consisting of vanadium , niobium pylene glycol by making propylene oxide react with exces - and tantalum in order to produce dipropylene glycol con sive water in the absence of a catalyst (see , for example , taining 1 , 1 ' -oxybis - 2 -propanol in a proportion of 0 . 10 to non - patent document 1 ) . 0 .70 and /or tripropylene glycol containing 1 , 1' - [ ( 1 -methyl On the other hand , patent document 1 , for example , 60 1 , 2 - ethanediyl) bis (oxy ) ]bis - 2 - propanol in a proportion of discloses a production method to obtain an alkylene glycol 0 . 10 to 0 .70 , the Hammett acidity function ( H ) of the with high selectivity while generating almost no dialkylene catalyst is required to satisfy Hs9 . 3 . glycol or trialkylene glycol by making an alkylene oxide In the present invention , dipropylene glycol and /or tripro react with water in the presence of carbon dioxide using a pylene glycol can be produced with higher selectivity by compound one or more element selected from the group 65 using a catalyst which contains at least one element selected consisting of titanium , zirconium , vanadium , niobium , tan - from the group consisting of vanadium , niobium and tanta talum , and chromium as a catalyst.