High-activity double-metal-cyanide catalyst, method for fabricating the same, and applications of the same

Abstract

A high-activity double-metal-cyanide catalyst, a method for fabricating the same, and applications of the same are disclosed. An organic complexing ligand, which is formed via mixing fatty alcohols and alicyclic carbonates, is used to generate a high-activity double-metal-cyanide catalyst. The high-activity double-metal-cyanide catalyst includes at least one double-metal-cyanide compound, at least one organic complexing ligand, and an optional functionalized polymer. The double-metal-cyanide catalyst of the present invention has a higher activity than the conventional double-metal-cyanide catalysts. The polyols generated by the present invention has an insignificant amount of high-molecular-weight compounds.

What is claimed is: 
     
         1 . A high-activity double-metal-cyanide catalyst comprising
 at least one double-metal-cyanide compound; and   at least one organic complexing ligand including a fatty alcohol containing 2-7 carbon atoms and an alicyclic carbonate, wherein a concentration of said fatty alcohol in said organic complexing ligand is 2-98 mole %, and wherein said alicyclic carbonate has a structural formula expressed by Equation (I):   
       
         
           
           
               
               
           
         
       
       wherein R and R′ are identical or different, and wherein each of R and R′ is selected from a group including hydrogen atoms, saturated alkyl groups each containing 1-20 carbon atoms, cyclic alkyl groups, hydroxyl groups, vinyl groups, and phenyl groups. 
     
     
         2 . The high-activity double-metal-cyanide catalyst according to  claim 1 , wherein said double-metal-cyanide compound is a product of an reaction of at least one metal salt and at least one metal cyanide salt, and
 wherein said metal salt has a general formula expressed by Equation (II):
   M(X) n   (II)
 
   wherein M in equation (II) is selected from a group including bivalent zinc (Zn (II)), bivalent iron (Fe (II)), bivalent nickel (Ni (II)), bivalent manganese (Mn (II)), bivalent cobalt (Co (II)), bivalent tin (Sn (II)), bivalent lead (Pb (II)), trivalent iron (Fe (III)), tetravalent molybdenum (Mo (IV)), hexavalent molybdenum (Mo (VI)), trivalent aluminum (Al (III)), pentavalent vanadium (V (V)), tetravalent vanadium (V (IV)), bivalent strontium (Sr (II)), tetravalent tungsten (W (IV)), hexavalent tungsten (W (VI)), bivalent copper (Cu (II)), and trivalent chromium (Cr (III)), and   wherein X is selected from a group including halogens, hydroxyl ion, sulfate ion, carbonate ion, cyanide ion, isocyanide ion, isothiocyanate ion, carboxylate ion, and nitrate ion, and   wherein n equals 1-3 and charges in Equation (II) are in balance, and wherein said metal cyanide salt has a general formula expressed by Equation (III):
   (M′) a M(CN) b (A) c   (III)
 
   wherein M in Equation (III) is selected from a group including bivalent iron (Fe (II)), trivalent iron (Fe (III)), bivalent cobalt (Co (II)), trivalent cobalt (Co (III)), bivalent chromium (Cr (II)), trivalent chromium (Cr (III)), bivalent manganese (Mn (II)), trivalent manganese (Mn (III)), trivalent iridium (Ir (III)), bivalent nickel (Ni (II)), trivalent rhodium (Rh (III)), bivalent ruthenium (Ru (II)), tetravalent vanadium (V (IV)), and pentavalent vanadium (V (V)), and   wherein M′ is selected from a group including alkali metal ions and alkaline earth metal ions, and   wherein A is an anion which is selected from a group including halides, hydroxyl ion, sulfate ion, carbonate ion, cyanide ion, oxalate ion, thiocyanate isocyanide ion, isothiocyanate ion, carboxylate ion, and nitrate ion, and   wherein each of a and b is an integer greater than 1, and   wherein a sum of charges of groups subscripted by a, b and c is equal to a number of charges of M.   
     
     
         3 . The high-activity double-metal-cyanide catalyst according to  claim 2 , wherein M in equation (II) is selected from a group including bivalent zinc (Zn (II)), bivalent iron (Fe (II)) and bivalent cobalt (Co (II)), and wherein M in equation (III) is selected from a group including bivalent cobalt (Co (II)), trivalent cobalt (Co (III)), bivalent iron (Fe (II)), trivalent iron (Fe (III)), trivalent chromium (Cr (III)), trivalent iridium (Ir (III)) and bivalent nickel (Ni (II)). 
     
     
         4 . The high-activity double-metal-cyanide catalyst according to  claim 2 , wherein said metal salt is selected from a group including zinc chloride, zinc sulfate, zinc bromide, zinc formate, zinc acetate, zinc propionate, zinc acetonylacetate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) formate, and nickel (II) nitrate, and wherein said metal cyanide salt is selected from a group including potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), lithium hexacyanoiridate (III), lithium hexacyanocobaltate (III), sodium hexacyanocobaltate (III), calcium hexacyanocobaltate (III), and cesium hexacyanocobaltate (III). 
     
     
         5 . The high-activity double-metal-cyanide catalyst according to  claim 2 , wherein said double-metal-cyanide compound is selected from a group including zinc hexacyanocobaltate (III), zinc hexacyanoferrate (II), zinc hexacyanoferrate (III), nickel (II) hexacyanofenate (II), and cobalt (II) hexacyanocobaltate (III). 
     
     
         6 . The high-activity double-metal-cyanide catalyst according to  claim 1 , wherein said fatty alcohol is one or more compounds selected from a group including ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, isobutyl alcohol, sec-butyl alcohol, tert-butyl alcohol, 2-methyl-3-buten-2-ol, and tert-amyl alcohol, and wherein said alicyclic carbonate is selected from a group including ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, pentylene carbonate, hexylene carbonate, octylene carbonate, dodecylene carbonate, glycerol carbonate, styrene carbonate, 3-phenyl propylene carbonate, cyclohexene carbonate, vinyl ethylene carbonate, 4, 4-dimethyl-5-methylene-(1, 3) dioxolan-2-one, and 4-allyl-4, 5-dimethyl-5-(10-undecenyl)-1, 3-dioxolan-2-one. 
     
     
         7 . The high-activity double-metal-cyanide catalyst according to  claim 1 , wherein a concentration of said alicyclic carbonate in said organic complexing ligand ranges from 2 to 98 mole %. 
     
     
         8 . The high-activity double-metal-cyanide catalyst according to  claim 1  further comprising at least one functionalized polymer or a water-soluble salt of said functionalized polymer, wherein a concentration of said functionalized polymer or said water-soluble salt of said functionalized polymer in said high-activity double-metal-cyanide catalyst is 2-80 wt %, and wherein said functionalized polymer is a polymer containing at least one functional group, and wherein said functional group is selected from a group including oxygen, nitrogen, sulfur, phosphorus, and halogens. 
     
     
         9 . The high-activity double-metal-cyanide catalyst according to  claim 8 , wherein said functionalized polymer is selected from a group including polyethers, polyesters, polycarbonates, polyalkylene glycol sorbitan esters, polyalkylene glycol glycidyl ethers, polyacrylamides, poly(acrylamide-co-acrylic acids), polyacrylic acids, poly(acrylic acid-co-maleic acid), poly(N-vinylpyrrolidone-co-acrylic acids), poly(acrylic acid-co-styrenes), salts of poly(acrylic acid-co-styrenes), maleic acids, styrenes and maleic anhydride copolymers, salts of styrenes and maleic anhydride copolymers, polyacrylonitriles, polyalkyl acrylates, polyalkyl methacrylates, polyvinyl methyl ethers, polyvinyl ethyl ethers, polyvinyl acetates, polyvinyl alcohols, poly-N-vinylpyrrolidones, polyvinyl methyl ketones, poly(4-vinylphenols), oxazoline polymers, polyalkyleneimines, hydroxyethylcelluloses, polyacetals, glycidyl ethers, glycosides, carboxylic acid esters of polyhydric alcohols, bile acids, salts, esters and amides of bile acids, cyclodextrins, phosphorus compounds, unsaturated carboxylic acid esters, and ionic surface- or interface-active compounds. 
     
     
         10 . A method for fabricating a high-activity double-metal-cyanide catalyst stated in  claim 1 , which comprises steps:
 mixing two metal precursor solutions to react in the presence of said organic complexing ligand to generate a resultant solution, wherein at least one of said two metal precursor solutions contains a cyanide ligand;   flushing and filtering said resultant solution; and   separating said high-activity double-metal-cyanide catalyst from said resultant solution.   
     
     
         11 . The method for fabricating a high-activity double-metal-cyanide catalyst according to  claim 10 , wherein said organic complexing ligand exists in at least one of said two metal precursor solutions and mixes with a metal precursor; alternatively, said organic complexing ligand is added to said resultant solution immediately after said two metal precursor solutions are mixed. 
     
     
         12 . The method for fabricating a high-activity double-metal-cyanide catalyst according to  claim 11 , wherein at least one functionalized polymer or a water-soluble salt of said functionalized polymer is mixed with said two metal precursor solutions to react in the presence of said organic complexing ligand to generate a resultant solution. 
     
     
         13 . The method for fabricating a high-activity double-metal-cyanide catalyst according to  claim 11 , wherein said two metal precursor solutions are mixed to react in an aqueous solution system, and wherein said aqueous system is at a temperature of 10-80° C. 
     
     
         14 . A method for fabricating polyols, comprising a step:
 providing said high-activity double-metal-cyanide catalyst stated in  claim 1  to enable a polyaddition reaction of at least one alkylene oxide and at least one starter compound having active hydrogen to generate polyols.   
     
     
         15 . The method for fabricating polyols according to  claim 14 , wherein in said polyaddition reaction, monomers of a single kind of alkylene oxide, monomers of 2-3 kinds of alkylene oxides arranged arbitrarily, or monomers of 2-3 kinds of alkylene oxides arranged blockwise are alkoxylated to form polyether chains of said polyols. 
     
     
         16 . The method for fabricating polyols according to  claim 14 , wherein said alkylene oxide is selected from a group including ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof, and wherein said starter compound having active hydrogen is a compound containing 1-8 hydroxyl groups and having an average molecular weight of 18-2000. 
     
     
         17 . The method for fabricating polyols according to  claim 16 , wherein said starter compound having active hydrogen is selected from a group including polyoxypropylene polyols, polyoxyethylene polyols, poly(tetramethylene ether) glycols, glycerol, propoxylated glycerols, propylene glycol, tripropylene glycol, alkoxylated allylic alcohols, bisphenol A, pentaerythritol, sorbitol, sucrose, degraded starch, Mannich polyols, water, and combinations thereof. 
     
     
         18 . The method for fabricating polyols according to  claim 14 , wherein said polyaddition reaction is undertaken at a temperature of 25-200° C. and a pressure of 0.0001-20 bar. 
     
     
         19 . The method for fabricating polyols according to  claim 14 , wherein a concentration of said high-activity double-metal-cyanide catalyst in said polyaddition reaction is 0.0005-1 wt %. 
     
     
         20 . The method for fabricating polyols according to  claim 14 , wherein said polyol contains 1-8 hydroxyl groups, and wherein a range of molecular weights of said polyols is 500-100000 g/mole.