(12) United States Patent (10) Patent No.: US 6,867,162 B2 Le-Khac Et Al

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USOO6867162B2 (12) United States Patent (10) Patent No.: US 6,867,162 B2 Le-Khac et al. (45) Date of Patent: *Mar. 15, 2005

(54) DOUBLE-METAL CYANIDE CATALYSTS 5,482.908 A 1/1996 Le-Khac ...... 502/156 WHICH CAN BE USED TO PREPARE 5,536,883 A 7/1996 Le-Khac ...... 568/620 POLYOLS AND THE PROCESSES RELATED 5,545,601 A 8/1996 Le-Khac ...... 502/156 THERETO 5,693,584 A 12/1997 Le-Khac ------502/159 5,712.216 A 1/1998 Le-Khac et al...... 502/175

(75) Inventors: Bi Le-Khac, Westchester, PA (US); Wie 2:2 . . . . A 2.1998A 1998 PazosLe-Khac ...... 568/679502/159 Wang, Boothwyn, PA (US) 6,013,596. A 1/2000 Le-Khac et al...... 502/175 O 1 O 6,018,017 A 1/2000 Le-Khac ...... 528/421 (73) Assignees: Bayer MaterialScience LLC, 6,063.897 A 5/2000 Le-Khac et al...... 528/410 Pittsburgh, PA (US); Bayer Antwerpen, 6,303,533 B1 10/2001 Grosch et al...... 502/175 J.V., Antwerp (BE) 6,423,662 B1 7/2002 Molzahn et al...... 502/175 6,696,383 B1 * 2/2004 Le-Khac et al...... 502/175 (*) Notice: Subject to any disclaimer, the term of this 2003/O158449 A1 8/2003 Hofmann et al...... 568/675 patent is extended or adjusted under 35 U.S.C. 154(b) by 0 days. FOREIGN PATENT DOCUMENTS JP 4-145123 5/1952 JP 5-17569 1/1993 ThR tentent IS Subjectbiect tto a tterminal 1 dISdis JP 5-25267 2/1993 WO O1/04180 1/2001 WO O2/O9875 2/2002 (21) Appl. No.: 10/717,094 OTHER PUBLICATIONS (22) Filed: Nov. 19, 2003 Journal of Polymer Scienc Part A: Polymer Chemistry vol. (65) Prior Publication Data 40, (month unavailable)(2000) pp. 1142-1150, Yi-Jun US 2004/0102314 A1 May 27, 2004 Huang, Guo-Rong Qi, Yu-Hua Wang, “Controlled Ring 2 Opening Polymeriation of Propylene Oxide Catalyzed by Related U.S. Application Data Double Metal-Cyanide Complex”. (62) Division of application No. 10/251,155, filed on Sep. 20, sk cited- by examiner 2002, now Pat. No. 6,696,383. Primary Examiner Elizabeth D. Wood (51) Int. Cl...... B01J 31/00; B01J 31/02; (74) Attorney, Agent, or Firm Joseph C. Gil; John E. B01J 31/06; B01J 27/26 Mrozinski, Jr. (52) U.S. Cl...... 502/175; 502/152; 502/153; 502/154; 502/155; 502/156; 502/157: 502/159; (57) ABSTRACT 502/169; 502/172; 502/200 The present invention is directed to double metal cyanide (58) Field of Search ...... 502/175, 200, catalysts ("DMC”) which are prepared by combining i) at 502/159, 172, 152, 153, 154, 155, 156, least one metal salt; ii) at least one metal cyanide salt; iii) at 157, 169 least one organic complexing ligand; iv) at least one alkali metal salt; and, optionally, v) at least one functionalized (56) References Cited polymer under conditions Sufficient to form a catalyst; and adding a Sufficient amount of the at least one alkali metal Salt U.S. PATENT DOCUMENTS to the catalyst So formed in an amount Such that the catalyst 3.278,459 A 10/1966 Herold ...... 260/2 includes the at least one alkali metal Salt in an amount of 3,404,109 A 10/1968 Milgrom...... 260/611 from about 0.4 to about 6 wt.% based on the total weight of 3.427,256 A 2/1969 Milgrom ...... 252/431 the catalyst. The polyols produced in the presence of the

E.. A s E. Hels ------2.O catalysts of the present invention have reduced levels of high 4472,560 A 9/1984. Kuyper et al... S.C. molecular weight tail. 4,477,589 A 10/1984 van der Hulst et al. .... 502/169 5,470,813 A 11/1995 Le-Khac ...... 502/175 7 Claims, No Drawings US 6,867,162 B2 1 2 DOUBLE-METAL CYANDE CATALYSTS DMC catalysts are known and are described in, for WHICH CAN BE USED TO PREPARE example, U.S. Pat. Nos. 3,278,457, 3,278,459, 3,289,505, POLYOLS AND THE PROCESSES RELATED 3,427,256, 4,477,589, 5,158,922, 5,470,813, 5,482,908, THERETO 5,545,601, 5,627,122 and 6,423,662 as well as in WO 01/04180 and WO 02/09875. DMC catalysts are typically This application is a divisional of U.S. Ser. No. 10/251, prepared by mixing an aqueous Solution of a metal Salt with 155, which was filed on Sep. 20, 2002, now U.S. Pat. No. an aqueous Solution of a metal cyanide Salt in the presence 6,696,383. of an organic complexing ligand. A precipitate forms when these two Solutions are mixed together. The resulting pre TECHNICAL FIELD OF THE INVENTION cipitate is isolated and then washed. The art teaches that, during the preparation of a DMC The present invention is directed to double-metal cyanide catalyst, alkaline metal Salts are incorporated into the cata ("DMC’) catalysts which can be used to prepare polyols. lyst. See Huang et al., “Controlled Ring-Opening Polymer The present invention is also directed to a process for ization of Propylene Oxide Catalyzed by Double Metal preparing DMC catalysts. The present invention is further 15 Cyanide Complex,”, Journal of Polymer Science, Vol. 40, directed to a process for polymerizing an alkylene oxide in page 1144 (2002); U.S. Pat. No. 3.278,457, column 5, lines the presence of a DMC catalyst prepared according to the 40–44; and WO 02/09875, page 5, lines 5-12. The art also process of the present invention. teaches that these occluded ions must be removed during the preparation of a DMC catalyst. See Huang et al., page 1144, BACKGROUND OF THE INVENTION U.S. Pat. No. 3,278,457, column 5, lines 57–58; and WO In the preparation of polyoxyalkylene polyols, starter 02/09875, page 5, lines 5–12. U.S. Pat. No. 6,423,662 (at compounds having active hydrogen atoms are oxyalkylated column 6, lines 47–50), WO/01/04180 (at page 8, lines with alkylene oxides in the presence of a Suitable catalyst. 17–19), and U.S. Pat. No. 3.278,457 (at column 5, lines For many years, basic as well as DMC catalysts have been 45-58), for example, teach those skilled in the art to wash used in Oxyalkylation reactions to prepare polyoxyalkylene 25 the precipitate formed during the preparation of a DMC polyols. Base-catalyzed oxyalkylation involves oxyalkylat catalyst as thoroughly as possible in order to remove essen ing a low molecular weight starter compound (Such as tially all of these occluded ions. propylene glycol or glycerine) with an alkylene oxide (Such as ethylene oxide or propylene oxide) in the presence of a SUMMARY OF THE INVENTION basic catalyst (such as potassium hydroxide (KOH)) to form The present invention is directed to proceSS for preparing a polyoxyalkylene polyol. a DMC catalyst which involves combining: i) at least one In base-catalyzed oxyalkylation reactions, propylene metal salt; ii) at least one metal cyanide salt; iii) at least one oxide and certain other alkylene oxides are Subject to a organic complexing ligand; iv) at least one alkali metal salt; competing internal rearrangement which generates unsatur 35 and, optionally, V) at least one functionalized polymer. ated alcohols. For example, when KOH is used to catalyze The present invention is also directed to a process for an oxyalkylation reaction using propylene oxide, the result preparing a polyol in the presence of a DMC catalyst ing product will contain allyl alcohol-initiated, monofunc prepared according to the process of the present invention. tional impurities. AS the molecular weight of the polyol The present invention is also directed to a DMC catalyst increases, the isomerization reaction becomes more preva 40 which is represented by the following general formula (I) lent. As a result, 800 or higher equivalent weight poly (propylene oxide) products prepared using KOH tend to M", CIM (CN), LIMD.L.L.M. (I) have significant quantities of monofunctional impurities. Surprisingly, DMC catalysts of and produced by the Monofunctional impurities tend to reduce the average func process of the present invention, which are preferably pre tionality and broaden the molecular weight distribution of 45 pared with at least one alkaline metal halide, have acceptable the polyol. activity and can be used to catalyze Oxyalkylation reactions. Unlike basic catalysts, DMC catalysts do not significantly Additionally, DMC catalysts produced by the process of promote the isomerization of propylene oxide. As a result, the present invention can be used to produce polyols which DMC catalysts can be used to prepare polyols which have have reduced levels of high molecular weight tail. low unsaturation values and relatively high molecular 50 weights. DMC catalysts can be used to produce polyether, DESCRIPTION OF THE INVENTION polyester and polyetherester polyols which are useful in In a first aspect, the present invention is a process for applications Such as polyurethane coatings, elastomers, preparing a DMC catalyst comprising combining: i) at least Sealants, foams and adhesives. 55 one metal salt; ii) at least one metal cyanide Salt; iii) at least DMC-catalyzed oxyalkylation reactions, however, are one organic complexing ligand; iv) at least one alkali metal known to produce Small amounts of high molecular weight salt; and, optionally, V) at least one functionalized polymer, polyol impurities (typically, molecular weights in excess of under conditions Sufficient to form a catalyst. 100,000 Da). These high molecular weight impurities are In a Second aspect, the present invention is a process for often referred to as the “high molecular weight tail”. In 60 preparing a polyol comprising reacting i) at least one starter elastomers and other Systems, the high molecular weight tail compound having active hydrogen atoms withii) at least one may interfere with hard Segment phase out as well as with oxide in the presence of iii) at least one DMC catalyst which the alignment of hard Segments responsible for Strength and is prepared according to the process of the present invention, modulus properties. In polyurethane foam Systems, for under conditions Sufficient to form a polyol. example, polyols which have a high molecular weight tail 65 In another aspect, the present invention is a DMC catalyst produce course foam cells, very tight foams or weak foams which is represented by the formula M.,(IM (CN), MI) or contribute to foam collapse. L.L.M US 6,867,162 B2 3 4 wherein Any organic complexing ligand can be used in the present M' represents at least one metal; invention. Organic complexing ligands useful in the present IM (CN), represents at least one metal cyanide; invention are known and are described in, for example, U.S. Pat. Nos. 3,404,109, 3,829,505, 3,941,849, 5,158,922 and M represents at least one transition metal salt; 5,470,813, as well as in EP 700 949, EP 761 708, EP 743 M" represents at least one alkali metal Salt present in an 093, WO 97/40086 and JP 4145123. Organic complexing amount within the range of from about 0.4 to about 6 ligands useful in the present invention include, for example, wt.%, based on the total weight of the double metal water-Soluble organic compounds with heteroatoms, Such as cyanide catalyst; oxygen, nitrogen, phosphorus or Sulfur, which can form L' represents at least one organic complexing ligand; 1O complexes with the DMC compound. L is optional and can represent at least one functionalized Suitable organic complexing ligands useful in the present polymer; invention include, for example, alcohols, aldehydes, and ketones, ethers, esters, amides, ureas, nitriles, Sulfides and X, X', y and Z are integers chosen Such that electroneu mixtures thereof. Preferred organic complexing ligands use trality of the DMC catalyst is maintained. 15 ful in the present invention include water-Soluble aliphatic In yet another aspect, the present invention is a process for alcohols, Such as, for example, ethanol, isopropanol, preparing a polyol comprising reacting i) at least one starter n-butanol, iso-butanol, Sec-butanol and tert-butanol. Tert compound having active hydrogen atoms withii) at least one butanol is particularly preferred. oxide in the presence of iii) at least one DMC catalyst which Any alkaline metal Salt can be used in the present inven is represented by the formula tion. Preferably, alkali metal halides are used in the present invention. More preferably, sodium chloride, sodium bromide, Sodium iodide, lithium chloride, lithium bromide, wherein lithium iodide, potassium chloride, potassium bromide, M' represents at least one metal; potassium iodide and mixtures thereof are used in the IM (CN), represents at least one metal cyanide; 25 present invention. The relative amounts of organic complexing ligand and Mrepresents at least one transition metal salt; alkali metal Salt used in the present invention can vary. A M"represents at least one alkal metal salt present in an skilled person can control catalyst activity, polyol Viscosity amount within the range of from about 0.4 to about 6 and the like by varying these amounts. Preferably, DMC wt.%, based on the total weight of the double metal catalysts produced by the process of the present invention cyanide catalyst; are composed of at least one alkali metal Salt which is L' represents at least one organic complexing ligand; present in an amount within the range of from about 0.1 to L is optional and can represent at least one functionalized about 10 wt.%, more preferably, from about 0.4 to about 6 polymer; wt.%, most preferably, from about 1 to about 3 wt.%, based and 35 on the total weight of the DMC catalyst. X, X, y and Z are integers chosen Such electroneutrality DMC catalysts of the present invention can optionally that of the DMC catalyst maintained. include at least one functionalized polymer. "Functionalized Any metal Salt can be used in the present invention. polymer' is defined as a polymer or its Salt which contains Preferably, water soluble metal salts which are known in the one or more functional groups including oxygen, nitrogen, art are used in the present invention. Examples of metal Salts 40 Sulfur, phosphorus or halogen. Examples of functionalized which are useful in the present invention include, for polymers useful in the present invention include, for example, Zinc chloride, Zinc bromide, Zinc acetate, Zinc example: polyethers, polyesters, polycarbonates, polyalky cetylacetonate, Zinc benzoate, Zinc nitrate, Zinc propionate, lene glycol Sorbitan esters, polyalkylene glycol glycidyl Zinc formate, iron(II) sulfate, iron(II) bromide, cobalt(II) ethers; polyacrylamides; poly(acrylamide-co-acrylic acids), chloride, cobalt(II) thiocyanate, nickel(II) formate, nickel 45 polyacrylic acids, poly(acrylic acid-co-maleic acids), poly (II) nitrate and mixtures thereof. (N-vinylpyrrolidone-co-acrylic acids), poly(acrylic acid-co Any metal cyanide Salt can be used in the present inven styrenes) and their salts; maleic acids, Styrenes and maleic tion. Examples of metal cyanide Salts which can be used in anhydride copolymers and their Salts, block copolymers the present invention include, for example, cyanometalic which are composed of branched chain ethoxylated alco acids and water-Soluble metal cyanide Salts. Preferably, 50 hols; alkoxylated alcohols such as NEODOL which is sold water Soluble metal cyanide Salts which are known in the art commercially by Shell Chemical Company, polyether, poly are used in the present invention. Metal cyanide Salts which acrylonitriles, polyalkyl acrylates, polyalkyl methacrylates, are useful in the invention include, for example, potassium polyvinyl methyl ethers; polyvinyl ethyl ethers; polyvinyl hexacyanocobaltate(III), potassium hexacyanoferrate(II), acetates, polyvinyl alcohols, poly-N-Vinylpyrrollidones, potassium hexacyanoferrate(III), lithium hexacyanoiridate 55 polyvinyl methyl ketones; poly(4-vinylphenols); oxazoline (III), lithium hexacyanocobaltate(III), sodium polymers, polyalkyleneimines, hydroxyethylcelluloses, hexacyanocobaltate(III) and cesium hexacyanocobaltate(III) polyacetals, glycidyl ethers, glycosides, carboxylic acid are used in the present invention. esters of polyhydric alcohols; bile acids and their Salts, esters Metal salts of the present invention are preferably com or amides, cyclodextrins; phosphorus compounds, unsatur bined with metal cyanide Salts of the present invention to 60 ated carboxylic acid esters, and ionic Surface- or interface form DMC compounds. DMC compounds which are useful active compounds. Polyether polyols are preferably used. in the present invention include, for example, Zinc When used, functionalized polymers are present in the hexacyanocobaltate(III), Zinc hexacyanoiridate(II), Zinc DMC catalyst in an amount within the range of from about hexacyanoferrate(II), Zinc hexacyanoferrate(III), Zinc 2 to about 80 wt.%, preferably, within the range of from hexacyanocolbaltic acid, cobalt(II) hexacyanocobaltate(III) 65 about 5 to about 70 wt.%, more preferably, within the range and nickel(II) hexacyanoferrate(II). Zinc hexacyanocobal of from about 10 to about 60 wt.%, based on the total weight tate is particularly preferred. of DMC catalyst. US 6,867,162 B2 S 6 The combination of metal Salt, metal cyanide Salt, organic polyols, polytetatramethylene ether glycols, glycerol, pro complexing ligand, alkali metal Salt and, optionally, func poxylated glycerols, tripropylene glycol, alkoxylated allylic tionalized polymer, can be accomplished by any of the alcohols, bisphenol A, pentaerythritol, Sorbitol, Sucrose, methods known in the art. Such methods include, for degraded Starch, water and mixtures thereof. example, precipitation, dispersion and incipient wetness. Monomers or polymers which will copolymerize with an Preferably, the process of the present invention involves oxide in the presence of a DMC catalyst can be included in using a precipitation method in which an aqueous Solution of the process of the present invention to produce various types at least one metal Salt employed in a Stoichiometgic excess, of polyols. The build-up of the polymer chains by alkoxy i.e., at least 50 mol.%, based on the molar amount of metal lation can be accomplished randomly or blockwise. cyanide Salt, is mixed with an aqueous Solution of at least Additionally, any copolymer known in the art made using a one metal cyanide Salt, at least one alkali metal Salt and, conventional DMC catalyst can be made with the DMC optionally, at least one functionalized polymer, in the pres catalyst prepared according to the process of the present ence of at least one organic complexing ligand. invention. The alkali metal Salt can be added to either the aqueous Any alkylene oxide can be used in the present invention. Solution of metal Salt or to the aqueous Solution of metal 15 Alkylene oxides preferably used in the present invention cyanide salt or to both solutions or to the mixture after the include, for example, ethylene oxide, propylene oxide, buty two solutions are combined. Preferably, the alkali metal salt lene oxide and mixtures thereof. is added to the aqueous Solution of metal Salt. The organic Oxyalkylation of the Starter compound can be accom complexing ligand can be added to either the aqueous plished by any of the methods known in the art, Such as, for Solution of metal Salt or to the aqueous Solution of metal example, in a batch, Semi-batch or continuous process. cyanide salt or to both solutions or to the mixture after the Oxyalkylation is carried out at a temperature in the range of two Solutions are combined or it can be added after forma from about 20 and 200 C., preferably, from about 40 and tion of the precipitate. The functionalized polymer can be 180° C., more preferably, from about 50 and 150° C. and added to either the aqueous Solution of metal Salt or to the under an overall pressure of from about 0.0001 to about 20 aqueous Solution of metal cyanide Salt or to both Solutions 25 bar. The amount of DMC catalyst used in the oxyalkylation or to the mixture after the two solutions are combined or it reaction is chosen Such that Sufficient control of the reaction can be added after formation of the precipitate. is possible under the given reaction conditions. The DMC The reactants are mixed using any of the mixing methods catalyst concentration of an oxyalkylation reaction is typi known in the art, Such as, for example, by Simple mixing, cally in the range of from about 0.0005 wt.% to about 1 wt. high-Shear mixing or homogenization. Preferably, the reac %, preferably, from about 00.001 wt.% to about 0.1 wt.%, tants are combined with Simple mixing at a temperature more preferably, from about 0.001 to about 0.0025 wt.%, within the range of from about room temperature to about based on the total weight of polyol to be prepared. 80 C. A precipitate forms when the reactants are mixed. The number average molecular weight of the polyol The resulting precipitate is isolated from Suspension by prepared by the process of the present invention is in the known techniqueS Such as, for example, by centrifugation, 35 range of from about 500 to about 100,000 g/mol, preferably, filtration, filtration under preSSure, decanting, phase Separa from about 1,000 to about 12,000 g/mol, more preferably, tion or aqueous Separation. from about 2,000 to about 8,000 g/mol. Polyols prepared by The isolated precipitate is preferably washed at least once the process of the present invention have average hydroxyl with water and/or with a mixture which is preferably com functionalities of from about 1 to 8, preferably, from about posed of water and at least one organic complexing ligand. 40 2 to 6, and more preferably, from about 2 to 3. More preferably, this mixture is composed of water, a least DMC catalysts of the present invention can be used to one organic complexing ligand and at least one alkali metal produce polyols which have reduced levels of high molecu Salt. Most preferably, this mixture is composed of water, at lar weight tail (greater than 400 K). The amount of high least one organic complexing ligand, at least one alkali metal molecular weight tail is quantified by any Suitable method. Salt and at least one functionalized polymer. 45 A particularly convenient way to measure the amount of Preferably, the isolated precipitate is filtered from the high molecular weight tail is by gel permeation chromatog wash mixture by known techniques Such as, for example, raphy (GPC). A Suitable technique for measuring high centrifugation, filtration, filtration under pressure, decanting, molecular weight tail is described below as well as in, for phase Separation or aqueous Separation. The filtered precipi example, U.S. Pat. No. 6,013,596. tate is preferably washed at least once with a mixture which 50 The following examples merely illustrate the invention. is preferably composed of at least one organic complexing Those skilled in the art will recognize many variations that ligand. More preferably, this mixture is composed of water, are within the Spirit of the invention and Scope of the claims. at least one organic complexing ligand and at least one alkali metal Salt. Most preferably, this mixture is composed of EXAMPLES water, at least one organic complexing ligand, at least one 55 ADMC catalyst which was prepared according to any one alkali metal Salt and at least one functionalized polymer. of Examples 1-16 set forth below was used to prepare a The present invention is also directed to a process for 6000 MW polyoxypropylene triol by adding propylene preparing a polyol in the presence of a DMC catalyst of or oxide over 4 hours to an activated mixture composed of the prepared according to the present invention. DMC and a propoxylated glycerin starter (hydroxyl Any Starter compound which has active hydrogen atoms 60 number=240 mg KOH/g). Catalyst levels of 30 ppm were can be used in the present invention. Starter compounds used. The hydroxyl number, Viscosity and unsaturation of which are useful in the present invention include compounds each product were measured by Standard methods. A gel having number average molecular weights between 18 to permeation chromatography (GPC) technique as described 2,000, preferably, between 32 to 2,000, and which have from in U.S. Pat. No. 6,013,596, the teachings of which are 1 to 8 hydroxyl groups. Examples of Starter compounds 65 incorporated herein by reference, was used to measure the which can be used in the present invention include, for amount of polyol component having a number average example, polyoxypropylene polyols, polyoxyethylene molecular weight (Mn) from 40,000 to >400,000. The US 6,867,162 B2 7 8 amount present (in ppm) is recorded and the percent of high above. The cake was re-slurried in tert-butyl alcohol (144g.) molecular weight (HMW) tail reduction of the catalyst for and lithium chloride (0.5g.) and mixed as described above. each range of molecular weight is calculated using the 1000 mol. wt. polyoxypropylene diol (1 g ) was added and following formula (hereinafter referred to as “Formula I”): the product was filtered as described above. The resulting catalyst residue was dried in a vacuum oven at 60° C., 30 in. % Reduction*=(HMW tail of comparative example-HMW tail of (Hg) to constant weight. polyol prepared with a DMC catalyst of the present inven Elemental analysis: Cobalt=9.1 wt.%; Zinc=21.9 wt.%; tion)x100%/HMW tail of comparative control Lithium=0.15 wt.%; Cl=4.8 wt.%. * no reduction of HMW tail is obtained if the 76 reduction is less than Zero. Example 3 Example 1 Preparation of a DMC Catalyst Using Sodium Bromide and Preparation of a DMC Catalyst Using Sodium Chloride and a Polyoxypropylene Diol: a Polyoxypropylene Diol: The procedure of Example 2 was followed, except that An aqueous zinc chloride solution (120 g. of 62.5 wt.% NaBr was used in lieu of LiCl. ZnCl2) was diluted with deionized water (230 g.) and Elemental analysis: Cobalt=8.1 wt.%; Zinc=21.9 wt.%; tert-butyl alcohol (38 g) in a one-liter stirred reactor 15 Sodium=0.48 wt.%; Cl=3.8 wt.%; Br=3.8 wt.%. (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and Example 4 sodium chloride (4 g) were dissolved in a 500-ml beaker Preparation of a DMC Catalyst Using Lithium Bromide and with deionized water (100 g) and tert-butyl alcohol (15.5 g) a Polyoxypropylene Diol: (Solution 2). Solution 3 was prepared by dissolving a 1000 An aqueous zinc chloride solution (120 g. of 62.5 wt.% mol. wt. polyoxypropylene diol (8g.) in deionized water (50 ZnCl2) was diluted with deionized water (230 g.) and g.) and tert-butyl alcohol (2 g.). Solution 2 was added to tert-butyl alcohol (38 g.) in one-liter stirred reactor. Lithium Solution 1 over 45 min. while mixing at 1,500 rpm. The bromide (4 g) was added to this solution (Solution 1). reaction temperature was kept at 50 C. during the course of Potassium hexacyanocobaltate (7.5 g) was dissolved in a the reaction by using an internal coil for heating or cooling. 500-ml beaker with deionized water (100 g) and tert-butyl Following the addition, mixing continued at 1,500 rpm for 25 alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by 20 min. The mixing was stopped. Solution 3 was then added, dissolving a 1000 mol. wt. polyoxypropylene diol (8 g) in followed by slow stirring for 3 min. deionized water (50 g.) and tert-butyl alcohol (2g.). Solution The reaction mixture was filtered at 40 psig through a 2 was added to Solution 1 over 45 min. while mixing at 0.45ul nylon membrane. The catalyst cake was re-slurried in 1,500 rpm. The reaction temperature was kept at 50 C. a mixture of tert-butyl alcohol (100g), deionized water (55 during the course of the reaction by using an internal coil for g) and sodium chloride (2 g) and mixed at 1,500 rpm for 20 heating or cooling. Following the addition, mixing contin min. The mixing was Stopped. 1000 mol. wt. polyoxypro ued at 1,500 rpm for 20 min. The mixing was stopped. pylene diol (2 g) was added and the mixture was stirred Solution 3 was added, followed by slow stirring for 3 min. slowly for 3 min. The catalyst was filtered as described The reaction mixture was filtered at 40 psig through a above. The cake was re-slurried in tert-butyl alcohol (144g.) 35 0.45ul nylon membrane. The catalyst cake was re-slurried in and mixed as described above. 1000 mol. wt. polyoxypro a mixture of tert-butyl alcohol (100 g.) and deionized water pylene diol (1 g.) was added and the product was filtered as (55g) and mixed at 1,500 rpm for 20 min. The mixing was described above. The resulting catalyst residue was dried in Stopped. 1000 mol. wt. polyoxypropylene diol (2 g.) was a vacuum oven at 60° C., 30 in. (Hg) to constant weight. added and the mixture was stirred slowly for 3 min. The Elemental analysis: Cobalt=9 wt.%; Zinc=21.7 wt.%; 40 catalyst was filtered as described above. The cake was Sodium=0.75 wt.%; Cl=6.1 wt.%. re-Slurried in tert-butyl alcohol (144 g.) and mixed as Example 2 described above. 1000 mol. wt. polyoxypropylene diol (1g) Preparation of a DMC Catalyst Using Lithium Chloride and was added and the product was filtered as described above. a Polyoxypropylene Diol: 45 The resulting catalyst residue was dried in a vacuum oven at An aqueous zinc chloride solution (120 g. of 62.5 wt.% 60° C., 30 in. (Hg) to constant weight. ZnCl2) was diluted with deionized water (230 g.) and Elemental Analysis Zn=23.4 wt. %; Co-10.8 wt. %; tert-butyl alcohol (38 g.) in a one-liter Stirred reactor. Li=<0.02 wt.%; Br: 0.4 wt.%; Cl=3.6 wt.%. Lithium chloride (0.3 g) was added to this solution Example 5 (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was 50 Preparation of a DMC Catalyst Using Sodium Chloride and dissolved in a 500-ml beaker with deionized water (100 g.) a Diol of Propylene Oxide and Ethylene Oxide Copolymer: and tert-butyl alcohol (15.5 g) (Solution 2). Solution 3 was An aqueous zinc chloride solution (120 g. of 62.5 wt.% prepared by dissolving a 1000 mol. wt. polyoxypropylene ZnCl2) was diluted with deionized water (230 g.) and diol (8 g) in deionized water (50 g.) and tert-butyl alcohol tert-butyl alcohol (38 g) in a one-liter Stirred reactor. (2g.). Solution 2 was added to Solution 1 over 45 min. while 55 Sodium chloride (0.3 g) was added to this solution (Solution mixing at 1,500 rpm. The reaction temperature was kept at 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in 50 C. during the course of the reaction by using an internal a 500-mi beaker with deionized water (100 g.) and tert-butyl coil for heating or cooling. Following the addition, mixing alcohol (15.5 g.) (Solution 2). Solution 3 was prepared by continued at 1,500 rpm for 20 min. The mixing was stopped. dissolving 8 g. of a 4000 mol. wt. diol of propylene oxide Solution 3 was added, followed by slow stirring for 3 min. 60 and ethylene oxide copolymer (80:20 wt. ratio) in deionized The reaction mixture was filtered at 40 psig through a water (50 g.) and tert-butyl alcohol (2 g). Solution 2 was 0.45ul nylon membrane. The catalyst cake was re-slurried in added to Solution 1 over 45 min. while mixing at 900 rpm. a mixture of tert-butyl alcohol (100g), deionized water (55 The reaction temperature was kept at 50 C. during the g.) and lithium chloride (2 g) and mixed at 1,500 rpm for 20 course of the reaction by using an internal coil for heating or min. The mixing was Stopped. 1000 mol. wt. polyoxypro 65 cooling. Following the addition, mixing continued at 900 pylene diol (2 g) was added and the mixture was stirred rpm for 20 min. The mixing was stopped. Solution 3 was slowly for 3 min. The catalyst was filtered as described added, followed by slow stirring for 3 min. US 6,867,162 B2 10 The reaction mixture was filtered at 40 psig through a course of the reaction by using an internal coil for heating or 0.45ul nylon membrane. The catalyst cake was re-slurried in cooling. Following the addition, mixing continued at 500 a mixture of tert-butyl alcohol (100g), deionized water (55 rpm for 20 min. The mixing was stopped. Solution 3 was g.) and sodium chloride (2 g) and mixed at 900 rpm for 20 added, followed by slow stirring for 3 min. min. The mixing was stopped. 4000 mol. wt. diol (2 g.) was 5 The reaction mixture was filtered at 40 psig through a added and the mixture was stirred slowly for 3 min. The 0.45ul nylon membrane. The catalyst cake was re-slurried in catalyst was filtered as described above. The cake was a mixture of potassium chloride (2 g.), tert-butyl alcohol re-slurried in tert-butyl alcohol (144 g) and sodium chloride (100 g.), poly(styrene-alt-maleic acid, Sodium salt) Solution (1 g.) and mixed as described above. 4000 mol. wt. diol (1 (7g) and deionized water (55g.) and mixed at 800 rpm for g.) was added and the product was filtered as described 20 min. The mixing was stopped. 1000 mol. wt. diol (2 g.) above. The resulting catalyst residue was dried in a vacuum was added and the mixture was stirred slowly for 3 min. The oven at 60° C., 30 in. (Hg) to constant weight. catalyst was isolated as described above. The cake was Elemental analysis: Cobalt=8.8 wt.%; Zinc=20.3 wt.%; re-Slurried in tert-butyl alcohol (144 g.) and mixed as Sodium=2.4 wt.%. described above. More 1000 mol. wt. diol (1 g.) was added Example 6 15 and the product was filtered as described above. The result Preparation of a DMC Catalyst Using Potassium Chloride ing catalyst residue was dried in a vacuum oven at 60° C., and a Polyoxypropylene Diol: 30 in. (Hg) to constant weight. An aqueous zinc chloride solution (120 g. of 62.5 wt.% Elemental analysis: Co-10.1 wt. %; Zn=22.4 wt. %; ZnCl2) was diluted with deionized water (230 g.) and K=1.86 wt.%. tert-butyl alcohol (38 g) in a one-liter stirred reactor (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and Example 8 potassium chloride (4.0 g) were dissolved in a 500-ml Preparation of a DMC Catalyst Using Potassium Chloride, beaker with deionized water (100 g) and tert-butyl alcohol a Polyoxypropylene Diol and a Poly(Methacrylic Acid, (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving Sodium Salt) (30 wt % Solution in Water): 8 g. of a 1000 mol. wt. polyoxypropylene diol (8 g.) in 25 The procedure of Example 7 was followed, except that deionized water (50 g.) and tert-butyl alcohol (2g.). Solution poly(methacrylic acid, sodium salt) (30 wt % solution in 2 was added to Solution 1 over 45 min. while mixing at 500 water) was used in lieu of poly(styrene-alt-maleic acid, rpm. The reaction temperature was kept at 50 C. during the sodium salt) (30 wt % solution in water). course of the reaction by using an internal coil for heating or Elemental analysis: Co-8 wt.%; Zn=21.6 wt.%; K=4.3 cooling. Following the addition, mixing continued at 500 wt.%. rpm for 20 min. The mixing was stopped. Solution 3 was added, followed by slow stirring for 3 min. Example 9 The reaction mixture was filtered at 40 psig through a Preparation of a DMC Catalyst Using Sodium Chloride But 0.45ul nylon membrane. The catalyst cake was re-slurried in No Functionalized Polymer: a mixture of tert-butyl alcohol (100g), deionized water (55 35 An aqueous zinc chloride solution (120 g. of 62.5 wt.% g.) and mixed at 500 rpm for 20 min. The mixing was ZnCl2) was diluted with deionized water (230 g.) and stopped. 1000 mol. wt. diol (2 g) and potassium chloride (2 tert-butyl alcohol (38 g) in a one-liter Stirred reactor. g) were added and the mixture was stirred slowly for 3 min. Sodium chloride (0.3 g) was added to this solution (Solution The catalyst was isolated as described above. The cake was 1). Potassium hexacyanocobaltate (7.5 g.) was dissolved in re-slurried in tert-butyl alcohol (125 g) and deionized water 40 a 500-ml beaker with deionized water (100 g.) and tert-butyl (30 g) and was mixed at 500 rpm for 20 min. The mixing was alcohol (15.5 g.) (Solution 2). Solution 2 was added to stopped. 1000 mol. wt. diol (2 g) and potassium chloride (2 Solution 1 over 45 min. while mixing at 800 rpm. The g) were added and the mixture was stirred slowly for 3 min. reaction temperature was kept at 50 C. during the course of The catalyst was filtered as described above. The cake was the reaction by using an internal coil for heating or cooling. re-slurried in tert-butyl alcohol (144 g.) and mixed as 45 Following the addition, mixing continued at 800 rpm for 20 described above. 1000 mol. wt. diol (1g.) was added and the min. The mixing was stopped. product was filtered as described above. The resulting cata The reaction mixture was filtered at 40 psig through a lyst residue was dried in a vacuum oven at 60° C., 30 in. 0.65ul nylon membrane. The catalyst cake was re-slurried in (Hg) to constant weight. a mixture of tert-butyl alcohol (100g), deionized water (55 Elemental analysis: Co-9.4 wt.%; Zn=20 wt.%; K=6.1 50 g.) and sodium chloride (2 g.) and mixed at 800 rpm for 20 wt.%. min. The mixing was stopped. The catalyst was isolated as Example 7 described above. The cake was re-slurried in tert-butyl Preparation of a DMC Catalyst Using Potassium Chloride, alcohol (144 g.) and Sodium chloride and mixed as described a Polyoxypropylene Diol and a Poly(Styrene-Alt-Maleic 55 above. The product was isolated as described above. The Acid, Sodium Salt) (30 wt % in Water): resulting catalyst residue was dried in a vacuum oven at 60 An aqueous zinc chloride solution (120 g. of 62.5 wt.% C., 30 in. (Hg) to constant weight. ZnCl2) was diluted with deionized water (230 g.) and Elemental Analysis: Zn=25.9 wt. %; Co-12 wt. %; tert-butyl alcohol (38 g) in a one-liter stirred reactor Na=1.29 wt.%. (Solution 1). Potassium hexacyanocobaltate (7.5 g.) and 60 potassium chloride (4.0 g) were dissolved in a 500-ml Example 10 (Comparative) beaker with deionized water (100 g) and tert-butyl alcohol Preparation of a DMC Catalyst Using a Functionalized (15.5 g.) (Solution 2). Solution 3 was prepared by dissolving Polymer But No Salt: 8 g. of a 1000 mol. wt. polyoxypropylene diol in deionized The procedure of Example 1 was followed, except that no water (50 g.) and tert-butyl alcohol (2 g). Solution 2 was 65 NaCl was added. added to Solution 1 over 45 min. while mixing at 500 rpm. Elemental analysis: Cobalt=9 wt.%; Zinc=21.6 wt.%; The reaction temperature was kept at 50 C. during the Cl=4.1 wt.%. US 6,867,162 B2 11 12 Examples 11, 12 and 13 (All Comparative) The resulting catalyst residue was dried in a vacuum oven Preparation of a DMC Catalyst Using a Functionalized at 60° C., 30 in. (Hg) to constant weight. Polymer But No Salt: Elemental Analysis: Co- 12.4 wt.%; Zn=26.8 wt.%. For Comparative Examples 11, 12 and 13, DMC catalysts were prepared according to the procedure of Example 1, Example 15 except that no NaCl was added. Preparation of a DMC Catalyst Using Sodium Chloride and Elemental analysis: Cobalt=10.3 wt.%; Zinc=23.2 wt.%; a Block Copolymer of NEODOL-(EO)-IBO: The procedure of Example 5 was followed except that a block copolymer of NEODOL-(EO), IBO was used in Example 14 (Comparative) lieu of the 1000 mol. wt. diol. The block copolymer was Preparation of a DMC Catalyst Using No Functionalized prepared using NEODOL (which is available commercially Polymer and No Salt: An aqueous zinc chloride solution (120 g. of 62.5 wt.% from Shell Chemical Company) as a starter and a DMC ZnCl2) was diluted with deionized water (230 g.) and catalyst prepared essentially by the method of U.S. Pat. No. tert-butyl alcohol (38 g) in a one-liter stirred reactor 15 5,482,908 (the teachings of which are incorporated herein by (Solution 1). Potassium hexacyanocobaltate (7.5 g.) was reference) to produce a polyoxyethylene having a molecular dissolved in a 500-ml beaker with deionized water (100 g.) weight of about 1000. This di-blockcopolymer was end and tert-butyl alcohol (15.5 g) (Solution 2). Solution 2 was capped by 1-2 units of isobutylene oxide. added to Solution 1 over 45 min. while mixing at 800 rpm. Example 16 (Comparative) The reaction temperature was kept at 50 C. during the Preparation of a DMC Catalyst Using Zinc course of the reaction by using an internal coil for heating or Hexacyanocobaltate/T-Butyl Alcohol and a Polyoxypropy cooling. Following the addition, mixing continued at 800 lene Diol: rpm for 20 min. The mixing was stopped. 25 The procedure of Example 1 was followed, except that no The reaction mixture was filtered at 40 psig through a NaCl was added. 0.65ul nylon membrane. The catalyst cake was re-slurried in Elemental analysis: Cobalt=9 wt.%; Zinc=21.6 wt.%. a mixture of tert-butyl alcohol (100g), deionized water (55 As illustrated in Table 1, DMC catalysts prepared accord g.) and mixed at 800 rpm for 20 min. The mixing was ing to the process of the present invention, Such as those Stopped. The catalyst was isolated as described above. The prepared in Examples 1-5, (prepared with an alkaline metal cake was re-slurried in tert-butyl alcohol (144 g.) and mixed Salt and a functionalized polymer), can be used to produce as described above. The product was isolated as described polyols which have an acceptable amount of high molecular above. weight tail.

TABLE 1. Catalyst of Ex #

10* 1. 2 3 4 5 Additive None NaCl LiCl NaBr LiBir NaCl Na or Li in Catalyst wt.% None 0.75 (Na) 0.15 (Li) 0.48 (Na) <0.02 (Li) 2.4 (Na) Polym rization Rate 21.7 16.4 19.1 23.7 20.7 16.1 Kg. POfg. Co?min. 6OOO MW Trio:

29.7 28.4 30.6 29.8 30.3 29.7 Viscosity cps 1105 112O 1087 1156 1054 1130 Unsaturation med/g O.OO5 O.OOSS O.OO48 O.OO56 O.OO46 O.OO64 HMW Tail: (MW) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) 40-60 K. 855 616 609 558 724 672 60-80 K. 465 316 330 250 409 344 80-100 K. 287 190 2O6 118 248 2O3 100-2OOK 337 235 249 229 31.8 261 200-400K 12O 94 99 99 119 91 >4OOK 40 3O 37 40 48 21 6000 MW Triol prepared at 130° C., 4 hour-PO addition with 30 ppm of catalyst based on the amount of polyol made. HMW tail bas d on six portion-cut GPC. *Comparative

60 As illustrated in Table 2, DMC catalysts prepared accord ing to the process of the present invention, Such as those prepared in Examples 1-5 (prepared with an alkaline metal Salt and a functionalized polymer), can be used to produce 65 polyols having a reduced amount of high molecular weight tail compared to a polyol produced in the presence of a DMC catalyst which is prepared with a functionalized polymer but US 6,867,162 B2 13 14 no alkaline metal Salt, Such as the one prepared in Com and a functionalized polymer), can be used to produce a parative Example 10. The percent reduction of high molecu polyol having a reduced amount of high molecular weight lar weight tail was determined by Formula I. tail compared to a polyol produced in the presence of a DMC

TABLE 2 Catalyst of Ex #

1. 2 3 4 5 Additive NaCl LiCl NaBr LiBir NaCl Na or Li in Catalyst wt.% 0.75 (Na) 0.15 (Li) 0.48 (Na) <0.02 (Li) 2.4 (Na) 6OOO MW Trio: OH+ mg KOH.g 28.4 30.6 29.8 3O3 29.7 Viscosity cps 112O 1087 1156 1054 1130 Unsaturation med/g O.OO55 OOO48 O.OO56 O.OO46 OOO64 HMW Tail:

(MW) % Reduction 26 Reduction 26 Reduction 26 Reduction 26 Reduction 40-60 K. 28 29 35 15 21 60-80 K. 32 29 46 12 26 80-1OOK 34 28 59 14 29 100-2OOK 3O 26 32 6 23 200-400 K. 22 18 18 1. 24 >400K 25 8 O -20 48 6000 MW Triol prepared at 130 C., 4 hour-PO addition with 30 ppm of catalyst based on the amount of polyol made HMW tail based on six portion-cut GPC.

As illustrated in Table 3, DMC catalysts prepared accord catalyst which is prepared with a functionalized polymer but ing to the process of the present invention, Such as the one no alkaline metal Salt, Such as the one prepared in Com prepared in Example 6 (prepared with an alkaline metal Salt parative Example 12. The percent reduction of high molecu and a functionalized polymer), can be used to produce a polyol having a reduced amount of high molecular weight lar weight tail was determined by Formula I. tail compared to a polyol produced in the presence of a DMC catalyst which is prepared with a functionalized polymer but TABLE 4 no alkaline metal Salt, Such as the one prepared in Com 35 Catalyst of Ex # parative Example 11. The percent reduction of high molecu lar weight tail was determined by Formula I. 12: 7 7 Additive None KC KC TABLE 3 Potassium in catalyst wt.% O.21 186 186 6OOO MW Trio: Catalyst of Ex # 40 OH+ mg KOH.g 29.2 29.5 29.5 11 * 6 6 Viscosity cps 1113 1093 1093 Unsaturation med/g O.OO55 O.OO61 OOO61 Additive None KC KCI HMW Tail: Potassium in catalyst wt.% O.21 6.1 6.1 6OOO MW Trio: 45 (MW) (ppm) (ppm) (% Reduction) 40-50.4 K 1115 649 42 OH+ mg KOH.g 29.5 29.9 29.9 50.4-63.4 K 869 479 45 Viscosity cps 1109 1131 1131 63.4-79.8 K. 760 421 45 Unsaturation med/g O.OO6 O.OO76 O.OO76 798-100.5 K. 603 356 41 HMW Tail: 100.5-126.5 K. 457 267 42 50 126.5-159.2 K. 286 156 46 (MW) (ppm) (ppm) (% Reduction) 159.2-200.5 K. 2O3 112 45 40-50.4K 1169 608 48 200.5-252.4 K 131 74 44 50.4-63.4 K 92O 448 51 252.4-317.7 K. 93 52 44 634-79.8 K. 719 366 49 317.7-4.OOK 58 33 43 798-100.5 K. 564 332 41 >4OOK 41 23 44 100.5-126.5 K. 430 247 43 55 126.5-159.2 K. 245 126 49 6000 MW Triol prepared at 130 C., 4 hour-PO addition with 30 ppm of 159.2-200.5 K. 164 82 50 catalyst base on the amount of polyol made. 200.5-252.4 K 108 50 54 HMW tail based on ten portion-cut GPC. 252.4-317.7 K. 69 29 58 *Comparative 317.7-4.OOK 48 16 67 >400K 33 O 1OO 60 As illustrated in Table 5, DMC catalysts prepared accord 6000 MW Triol prepared at 130 C., 4 hour-PO addition with 30 ppm of ing to the process of the present invention, Such as the one catalyst based on the amount of polyol prepared in Example 8 (prepared with an alkaline metal Salt HMW tail based on ten portion-cut GPC. and a functionalized polymer), can be used to produce a * Comparative polyol having a reduced amount of high molecular weight As illustrated in Table 4, DMC catalysts prepared accord- 65 tail compared to a polyol produced in the presence of a DMC ing to the process of the present invention, Such as the one catalyst which is prepared with a functionalized polymer but prepared in Example 7 (prepared with an alkaline metal Salt no alkaline metal Salt, Such as the one prepared in Com US 6,867,162 B2 15 16 parative Example 13. The percent reduction of high molecu and a functionalized polymer), can be used to produce a lar weight tail was determined by Formula I. polyol having a reduced amount of high molecular weight tail compared to a polyol produced in the presence of a DMC TABLE 5 catalyst which is prepared with a functionalized polymer but 5 no alkaline metal Salt, Such as the one prepared in Com Catalyst of Ex # parative Example 16. The percent reduction of high molecu 13 * 8 8 lar weight tail was determined by Formula I. Additive None KC KCI TABLE 7 Potassium in catalyst wt.% O.21 4.3 4.3 6OOO MW Trio: 1O Catalyst of Ex OH+ mg KOH.g 29.8 29.6 29.6 16 (Comparative) 15 15 Viscosity cps 1112 1108 1108 Unsaturation med/g O.OO55 O.OO61 O.OO61 Additive None NaCl NaCl HMW Tail: o 15 Na in Catalyst wt.% None O.88 O.88 6OOO MW (MW) % Reduction 40-50.4K 1290 685 47 OH+ mg OH/g 29.8 3O 3O 50.4-63.4 K 1031 476 54 Viscosity cps 1095 1137 1137 634-79.8 K. 815 403 51 Unsaturationmeq/g O.OO52 O.OO51 O.OO51 798-100.5 K. 641 350 45 HMW Tail: 100.5-126.5 K. 473 277 41 2O 126.5-159.2 K. 266 159 40 (MW) (ppm) (ppm) % Reduction 159.2-200.5 K. 177 94 47 40-60 K. 1064 574. 46 200.5-252.4 K 109 55 50 60-80 K. 581 281 52 252.4-317.7 K. 75 19 75 80-100 K. 352 154 56 317.7-4.OOK 47 O 1OO 100-2OOK 382 199 48 >400K 22 O 1OO 25 200-400K 123 8O 35 >4OOK 41 23 44 6000 MW Triol prepared at 130 C., 4 hour-PO addition with 30 ppm of catalyst based on the amount of polyol made. 6000 MW Triol prepared at 130 C., 4-hour PO addition with 30 ppm cata HMW tail based on ten portion-cut GPC. lyst based on the amount of polyol made. * Comparative HMW tail based on six portion cut GPC As illustrated in Table 6, DMC catalysts prepared accord- 30 What is claimed is: ing to the process of the present invention, Such as the one 1. A double-metal cyanide catalyst having the formula prepared in Example 9 (prepared with an alkaline metal Salt M',(IM.(CN)]...IM).L.L.M., wherein but no functionalized polymer), can be used to produce a M' represents at least one metal; polyol having a reduced amount of high molecular weight tail compared to a polyol produced in the presence of a DMC 35 IM (CN), represents at least one metal cyanide; catalyst which is prepared without a functionalized polyol M represents at least one transition metal; and alkaline metal Salt, Such as the one prepared in Com M' represents at least one alkali metal salt, present in an parative Example 14. The percent reduction of high molecu amount within the range of from about 0.4 to about 6 wt.%, based on the total weight of the double metal lar weight tail was determined by Formula I. cyanide catalyst; 40 L' represents at least one organic complexing ligand; TABLE 6 L is optional and can represent at least one functionalized Catalyst of EX # polymer; and 14* 9 9 45 X, X', y and Z are integers chosen Such that electroneu Additive None NaCl NaCl trality of the double-metal cyanide catalyst is main Sodium in catalyst wt.% None 1.29 1.29 tained. Polymerization Rate Kg.POf 14.3 12.9 12.9 g.Co?min. 2. The double metal cyanide catalyst according to claim 1, 6OOO MW Trio: wherein at least one metal is zinc. 50 3. The double metal cyanide catalyst according to claim 1, OH+ mg KOH.g 29.4 29.2 29.2 Viscosity cps 1169 1198 1198 wherein at least one metal cyanide is hexacyanocobalt(III). Unsaturation med/g O.0043 O.OO49 O.0049 4. The double metal cyanide catalyst according to claim 1, HMW Tail: wherein at least one organic complexing ligand is tert-butyl alcohol. (MW) (ppm) (ppm) (% Reduction) ss 40-60 K. 168O 1412 16 5. The double metal cyanide catalyst according to claim 1, 60-80 K. 906 745 18 wherein at least one alkali metal Salt is potassium chloride, 80-1OOK 537 436 19 Sodium chloride, Sodium bromide, lithium chloride or 100-2OOK 591 476 19 lithium bromide. 200-400 K. 196 175 11 6. The double metal cyanide catalyst according to claim 1, >400K 63 64 -2 60 wherein at least one functionalized polymer is present in an 6000 MW Triol prepared at 130 C., 4 hour-PO addition with 30 ppm of amount in the range of from about 2 to about 98 wt.%, based catalyst based on the amount of polyol made. on the total weight of the double-metal cyanide catalyst. HMW tail based on six portion-cut GPC. * Comparative 7. The double metal cyanide catalyst according to claim 1, wherein at least one functionalized polymer is a polyether; As illustrated in Table 7, DMC catalysts prepared accord- 65 polyester, polycarbonate, polyalkylene glycol Sorbitan ester; ing to the process of the present invention, Such as the one polyalkylene glycol glycidyl ether, polyacrylamide, poly prepared in Example 15 (prepared with an alkaline metal Salt (acrylamide-co-acrylic acid), polyacrylic acid, poly(acrylic US 6,867,162 B2 17 18 acid-co-maleic acid), poly(N-vinylpyrrolidone-co-acrylic mer polyalkyleneimine, hydroxyethylcellulose; polyacetal; acid), poly(acrylic acid-co-styrene) or their salts; maleic glycidyl ether, glycoside; carboxylic acid ester of polyhydric acid, Styrene or maleic anhydride copolymers or their Salts; alcohol; bile acid or its Salt, ester or amide, cyclodextrin; polyacrylonitriles, polyalkyl acrylate; polyalkyl methacry- phosphorus compound; unsaturated carboxylic acid ester; or late; polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl 5 an ionic Surface- or interface-active compound. acetate; polyvinyl alcohol; poly-N-Vinylpyrrolidone; poly vinyl methyl ketone; poly(4-vinylphenol); Oxazoline poly- k . . . .