HK1110825A

HK1110825A - Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto

Info

Publication number: HK1110825A
Application number: HK08105634.3A
Authority: HK
Inventors: Le-Khac Bi; Wang Wei
Original assignee: Bayer Corporation; Bayer Antwerpen N.V.
Priority date: 2002-09-20
Filing date: 2004-11-01
Publication date: 2008-07-25

Description

Double metal cyanide catalysts useful for preparing polyols and related methods

The application is a divisional application of the patent application of CN 03132776.1, and the application date of China is 9/19/2003, and the name of the invention is not changed.

Technical Field

The present invention relates to Double Metal Cyanide (DMC) catalysts that can be used to prepare polyols. The invention also relates to a method for producing the DMC catalyst. The invention also relates to a process for polymerizing alkylene oxide in the presence of the DMC catalyst prepared according to the process of the invention.

Background

In the preparation of polyoxyalkylene polyols, the starting compounds having active hydrogen atoms are alkoxylated with alkylene oxides in the presence of suitable catalysts. For many years, both base catalysts and DMC catalysts have been used in alkoxylation reactions to produce polyoxyalkylene polyols. Base-catalyzed oxyalkylation involves the oxyalkylation of a low molecular weight starter compound (e.g., propylene glycol or glycerol) with an alkylene oxide (e.g., ethylene oxide or propylene oxide) in the presence of a base catalyst (e.g., potassium hydroxide (KOH)) to produce a polyoxyalkylene polyol.

In base-catalyzed alkoxylation reactions, propylene oxide and certain other alkylene oxides undergo competing internal rearrangements that produce unsaturated alcohols. For example, alkoxylation with propylene oxide catalyzed with KOH yields a product that may contain allyl alcohol-initiated monofunctional impurities. As the molecular weight of the polyol increases, the isomerization reaction becomes more prevalent. Thus, the use of KOH to produce 800 or higher equivalents of polypropylene oxide product is prone to significant amounts of monofunctional impurities. Monofunctional impurities tend to reduce the average functionality and broaden the molecular weight distribution of the polyol.

Unlike base catalysts, DMC catalysts do not significantly promote the isomerization of propylene oxide. Thus, DMC catalysts can be used to prepare polyols having low unsaturation values and relatively high molecular weights. DMC catalysts can be used to produce polyether, polyester, and polyetherester polyols, which are useful in applications such as polyurethane coatings, elastomers, sealants, foams, and adhesives.

However, DMC-catalyzed alkoxylation reactions are known to produce small amounts of high molecular weight polyol impurities (typically, molecular weights in excess of 100000 Da). These high molecular weight impurities are often referred to as "high molecular weight tails". In elastomer and like systems, high molecular weight tail may affect the hard segments outside the hard segments that are critical to strength and modulus properties, as well as affect the straightening of the hard segments that are critical to strength and modulus properties. In polyurethane foam systems, for example, polyols with high molecular weight tails produce foam cells that are layered, very dense or not very rigid, or contribute to foam collapse.

DMC catalysts are known and described, for example, in US 3278457, 3278459, 3289505, 3427256, 4477589, 5158922, 5470813, 5482908, 5545601, 5627122 and 6423662, and in WO 01/04180 and WO 02/09875. Typically, DMC catalysts are prepared by combining an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complexing ligand. When the two solutions are mixed together, a precipitate is formed. The resulting precipitate is separated and washed.

The prior art teaches that alkali metal salts are added to the DMC catalyst during its preparation. See Huang et al, "controlled ring opening polymerization of propylene oxide catalyzed by double metal cyanide complexes",journal of Polymer Science (Journal of Polymer Science)Volume 40, page 1144 (2002); US 3278457, column 5, lines 40-44; WO02/09875, page 5, lines 5 to 12. The prior art also teaches that these occluded ions should be removed during the DMC catalyst preparation. See Huang et al, page 1144; US 3278457, column 5, lines 57-58; WO02/09875, page 5, lines 5 to 12, US 6423662 (column 6, lines 47 to 50), WO 01/04180 (page 8, lines 17 to 19) and US 3278457 (column 5, lines 45 to 58), for example, teach those skilled in the art to wash the precipitate formed as thoroughly as possible during the preparation of the DMC catalyst in order to remove substantially all of these occluded ions.

Disclosure of Invention

The present invention relates to a process for preparing a DMC catalyst, the process comprising: reacting i) at least one metal salt; ii) at least one metal cyanide salt; iii) at least one organic complexing ligand; iv) at least one alkali metal salt; and optionally, v) at least one functionalized polymer.

The invention also relates to a process for preparing polyols in the presence of the DMC catalyst prepared according to the process of the invention.

The invention also relates to a DMC catalyst which can be represented by the following general formula (I):

M¹ _x(M² _x′(CN)_y]_z·[M³ _(x)(y))·L¹·L²·M⁴ _z (I)

surprisingly, the DMC catalysts of the present invention and DMC catalysts prepared by the process of the present invention are preferably prepared using at least one alkali metal halide which has acceptable activity for catalyzing alkoxylation reactions.

In addition, the DMC catalysts prepared by the process of the present invention can be used to produce polyols having reduced high molecular weight tail content.

In a first aspect, the present invention is a method of making a DMC catalyst, the method comprising: under conditions sufficient to form a catalyst, reacting i) at least one metal salt; ii) at least one metal cyanide salt; iii) at least one organic complexing ligand; iv) at least one alkali metal salt; and optionally, v) at least one functionalized polymer.

In a second aspect, the present invention is a process for preparing a polyol, the process comprising: i) at least one starter compound having active hydrogen atoms and ii) at least one oxide are reacted in the presence of iii) at least one DMC catalyst prepared according to the process of the present invention under conditions sufficient to form a polyol.

In another aspect, the invention is a DMC catalyst, which can be represented by the following general formula (I):

M¹ _x([M² _x′(CN)_y]_z·[M³ _(x)(y))·L¹·L²·M⁴ _z (I)

in the formula:

M¹represents at least one metal salt;

M²represents at least one metal cyanide salt;

M³represents at least one transition metal salt;

M⁴represents at leastAn alkali metal salt;

L¹represents at least one organic complexing ligand;

L²is optional and may represent at least one functionalized polymer, and

x, x', y, and z are integers and are selected such that the DMC catalyst is electrically neutral.

In another aspect, the present invention is a process for preparing a polyol, the process comprising: reacting i) at least one starter compound having active hydrogen atoms with ii) at least one oxide in the presence of iii) at least one DMC catalyst, which can be represented by the following general formula;

M¹ _x([M² _x′(CN)_y]_z·[M³ _(x)(y)])·L¹·L²·M⁴ _z

in the formula:

M¹represents at least one metal salt;

M²represents at least one metal cyanide salt;

M³represents at least one transition metal salt;

M⁴represents at least one alkali metal salt;

L¹represents at least one organic complexing ligand;

L²is optional and may represent at least one functionalized polymer, and

Any metal salt may be used in the present invention. Preferably, water-soluble metal salts known in the art are all useful in the present invention. Examples of metal salts useful in the present invention include, for example, zinc chloride, zinc bromide, zinc acetate, zinc cetylacetonate, zinc benzoate, zinc nitrate, zinc propionate, zinc formate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, nickel (II) formate, nickel (II) nitrate, and mixtures thereof.

Any metal cyanide salt may be used in the present invention. Examples of metal cyanide salts that may be used in the present invention include, for example, cyanometalates and water soluble metal cyanide salts. Preferably, water soluble metal cyanide salts known in the art are all useful in the present invention. The metal cyanide salts which can be used in the present invention include, for example, potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), lithium hexacyanoiridium (III), lithium hexacyanocobaltate (III), sodium hexacyanocobaltate (III) and cesium hexacyanocobaltate (III), and these metal cyanide salts can be used in the present invention.

The metal salts of the present invention are preferably combined with the metal cyanide salts of the present invention to form DMC compounds. DMC compounds which can be used in the present invention include, for example, zinc hexacyanocobaltate (III), zinc hexacyanocoridium (III), zinc hexacyanoferrate (II), zinc hexacyanoferrate (III), zinc hexacyanocobaltate, cobalt (II) hexacyanocobaltate (III), and nickel (II) hexacyanoferrate (II). Zinc hexacyanocobaltate is particularly preferred.

Any organic complexing ligand may be used in the present invention. Organic complexing ligands which can be used in the present invention are known and described, for example, in the following references; US 3404109, 3829505, 3941849, 5158922 and 5470813, and EP 700949, EP 761708, EP 743093, WO 97/40086 and JP 4145123. Organic complexing ligands which may be used in the present invention include, for example, water-soluble organic compounds having heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which form complexes with the DMC compound.

Suitable organic complexing ligands that may be used in the present invention include, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, sulfides, and mixtures thereof. Preferred organic complexing ligands which can be used in the present invention include water-soluble aliphatic alcohols such as ethanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol. Tert-butanol is particularly preferred.

Any alkali metal salt may be used in the present invention. Preferably, alkali metal halides are useful in the present invention. More particularly, sodium chloride, sodium bromide, sodium iodide, lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, and mixtures thereof may be used in the present invention.

The relative amounts of organic complexing ligand and alkali metal salt used in the present invention may vary. One skilled in the art can control the activity of the catalyst, the polyol viscosity, etc. by varying these amounts. Preferably, the DMC catalyst produced by the process of the present invention is comprised of at least one alkali metal salt in an amount of from about 0.1 to about 10 wt.%, more preferably from about 0.4 to about 6 wt.%, most preferably from about 1 to about 3 wt.%, based on the total weight of the DMC catalyst.

The DMC catalyst of the present invention may optionally include at least one functionalized polymer. "functionalized polymer" is defined as a polymer or salt thereof containing one or more functional groups including oxygen, nitrogen, sulfur, phosphorus, or halogen. Examples of functionalized polymers that can be used in the present invention include, for example, polyethers; a polyester; a polycarbonate; a polyalkylene glycol sorbitan ester; polyalkylene glycol glycidyl ethers; polyacrylamide; acrylamide-acrylic acid copolymers, polyacrylic acid, acrylic acid-maleic acid copolymers, N-vinylpyrrolidone-acrylic acid copolymers, acrylic acid-styrene copolymers, and salts thereof; copolymers of maleic acid, styrene and maleic anhydride and salts thereof; a block copolymer comprised of a branched ethoxylated alcohol; alkoxylated alcohols such as NEODOL commercially available from Shell Chemical Company; a polyether; polyacrylonitrile; a polyalkyl acrylate; polyalkylmethacrylate; polyvinyl methyl ether; polyvinyl ethyl ether; polyvinyl acetate; polyvinyl alcohol; poly-N-vinyl pyrrolidone; polyvinyl ketones; poly (4-vinylphenol), oxazoline polymers; a polyalkyleneimine; hydroxyethyl cellulose; a polyacetal; a glycidyl ether; a glycoside; a carboxylic acid polyol ester; bile acids and salts, esters or amides thereof; a cyclodextrin; a phosphorus compound; an unsaturated carboxylic acid ester; and ionic surface-active compounds or interface-active compounds. Polyether polyols are preferably used.

When functionalized polymers are used, the amount of functionalized polymer in the DMC catalyst is from about 2 to about 80 wt.%, preferably from about 5 to about 70 wt.%, more preferably from about 10 to about 60 wt.%, based on the total weight of the DMC catalyst.

The compounding of the metal salt, metal cyanide salt, organic complexing ligand, alkali metal salt and optionally functionalized polymer may be accomplished by any method known in the art. Such methods include, for example, precipitation, dispersion and incipient wetness methods. Preferably, the process of the present invention comprises using a precipitation process wherein an aqueous solution of at least one metal salt in stoichiometric excess, i.e., at least 50 mole%, based on the molar amount of metal cyanide salt, is mixed with an aqueous solution of at least one metal cyanide salt, at least one alkali metal salt, and optionally at least one functionalized polymer in the presence of at least one organic complexing ligand.

The alkali metal salt may be added to the aqueous metal salt solution or to the aqueous metal cyanide salt solution, or to both solutions, or to a mixture of the two combined solutions. Preferably, the alkali metal salt is added to the aqueous metal salt solution. The organic complexing ligand may be added to the aqueous metal salt solution or to the aqueous metal cyanide salt solution, or to both aqueous solutions, or to a mixture of the two aqueous solutions after they are combined, or it may be added after a precipitate has formed. The functionalized polymer may be added to the aqueous metal salt solution or to the aqueous metal cyanide salt solution, or to both aqueous solutions, or to a mixture of the two aqueous solutions after they are combined, or it may be added after a precipitate has formed.

The reactants may be mixed by any mixing method known in the art, for example by simple mixing, high shear mixing or homogenization. Preferably, these reactants are combined using simple mixing at a temperature of from about room temperature to about 80 ℃. When these reactants are mixed, a precipitate is formed.

The resulting precipitate is separated from the suspension using known techniques, such as centrifugation, filtration, pressure filtration, decantation, phase separation or water separation techniques.

The separated precipitate is preferably washed at least once with water and/or a mixture preferably consisting of water and at least one organic complexing ligand. More preferably, such a mixture consists of water, at least one organic complexing ligand and at least one alkali metal salt. Most preferably, such a mixture consists of water, at least one organic complexing ligand, at least one alkali metal salt and at least one functionalized polymer.

Preferably, the separated precipitate is filtered from the washing mixture using known techniques, such as centrifugation, filtration, pressure filtration, decantation, phase separation or water separation techniques. The filtered precipitate is preferably washed at least once with a mixture preferably consisting of at least one organic complexing ligand. More preferably, such a mixture consists of water, at least one organic complexing ligand and at least one alkali metal salt. Most preferably, such a mixture consists of water, at least one organic complexing ligand, at least one alkali metal salt and at least one functionalized polymer.

The invention also relates to a process for preparing polyols in the presence of the DMC catalyst of the invention or of the DMC catalyst prepared according to the invention.

Any starting compound having an active hydrogen atom may be used in the present invention. Starting compounds useful in the present invention include compounds having a number average molecular weight of 18 to 2000, preferably 32 to 2000, and having 1 to 8 hydroxyl groups. Examples of starting compounds that can be used in the present invention include, for example, polyoxypropylene polyols, polyoxyethylene polyols, polytetramethylene ether glycol, glycerol, propoxylated glycerols, tripropylene glycol, alkoxylated allylic alcohols, bisphenol a, pentaerythritol, sorbitol, sucrose, degraded starch, water and mixtures thereof.

Monomers or polymers which copolymerize with the oxide in the presence of the DMC catalyst may be included in the process of the present invention for the production of various types of polyols. The establishment of the polymer chains by alkoxylation can be done randomly or in blocks. Additionally, using the DMC catalysts prepared according to the methods of the present invention, any copolymer known in the art that is prepared using conventional DMC catalysts can be prepared.

Any alkylene oxide may be used in the present invention. Alkylene oxides preferably used in the present invention include, for example, ethylene oxide, propylene oxide, butylene oxide and mixtures thereof.

Alkoxylation of the starting compounds can be accomplished using any method known in the art, such as batch, semi-batch, or continuous processes. The alkoxylation is carried out at a temperature of about 20 to 200 deg.C, preferably about 40 to 180 deg.C, more preferably about 50 to 150 deg.C, and a total pressure of about 0.0001 to about 20 bar. The amount of DMC catalyst used in the alkoxylation reaction is selected such that sufficient control of the reaction is possible under the given reaction conditions. The DMC catalyst concentration for the alkoxylation reaction is typically from about 0.0005 to about 1 weight percent, preferably from about 0.001 to about 0.1 weight percent, and more preferably from about 0.001 to 0.0025 weight percent, based on the total weight of the polyol to be produced.

The number average molecular weight of the polyols prepared by the process of the present invention is from about 500 to about 100000 g/mole, preferably from about 1000 to about 12000 g/mole, more preferably from about 2000 to about 8000 g/mole. The polyols produced by the process of the present invention have an average hydroxyl functionality of from about 1 to about 8, preferably from about 2 to about 6, and more preferably from about 2 to about 3.

The DMC catalysts of the present invention can be used to prepare polyols having reduced levels of high molecular weight tail (> 400K). The amount of high molecular weight tail may be quantified using any suitable method. Gel Permeation Chromatography (GPC) is a particularly suitable method for determining the amount of high molecular weight tailings. Suitable methods for determining high molecular weight tails are described below and for example in US 6013596.

The following examples merely illustrate the invention. Those skilled in the art will recognize many variations that are within the spirit of the invention and scope of the claims.

Detailed Description

Examples

The DMC catalyst prepared according to any of the examples 1-16 set forth below was used to prepare 6000MW polyoxypropylene triol by adding propylene oxide to an activated mixture of DMC and propoxylated glycerol starter compound (hydroxyl number 240 mg KOH/g) over a period of 4 hours. The catalyst was used at a level of 30 ppm. The hydroxyl number, viscosity and unsaturation of each product were determined using standard methods. The amount of polyol component having a number average molecular weight (Mn) of 40000 to > 400000 was determined using Gel Permeation Chromatography (GPC) techniques as described in US 6013596, the teachings of which are incorporated herein by reference. The amount present (in ppm) is recorded and the percent reduction of the High Molecular Weight (HMW) heel of the catalyst in each molecular weight range is calculated using the following formula (hereinafter "formula I"):

% reduction^*HMW heel of comparative example 100%/HMW heel of comparative control using polyol HMW heel prepared with DMC catalyst of the present invention

^*If the% reduction is less than zero, there is no reduction in the HMW heel.

Example 1

Preparation of DMC catalyst with sodium chloride and polyoxypropylene diol:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) and sodium chloride (4 g) (solution 2) were dissolved with deionized water (100 g) and t-butanol (15.5 g). 1000 molecular weight polyoxypropylene glycol (8 g) was dissolved in deionized water (50 g) and t-butylSolution 3 was prepared in alcohol (2 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 1500 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 1500 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 grams), deionized water (55 grams), and sodium chloride (2 grams) and mixed at 1500 rpm for 20 minutes. The mixing was stopped, 1000 molecular weight polyoxypropylene glycol (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was filtered as described above. The filter cake was reslurried in t-butanol (144 g) and mixed as above. 1000 molecular weight polyoxypropylene diol (1 g) was added and the product was filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 9 wt%; 21.7 percent by weight of zinc; sodium 0.75 wt%; chlorine ═ 6.1 wt%.

Example 2

Preparation of DMC catalyst with lithium chloride and polyoxypropylene diol:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂). To this solution was added lithium chloride (0.3 g) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) (solution 2) was dissolved with deionized water (100 g) and t-butanol (15.5 g). A solution 3 was prepared by dissolving 1000 molecular weight polyoxypropylene glycol (8 g) in deionized water (50 g) and t-butanol (2 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 1500 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 1500 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 g), deionized water (55 g), and lithium chloride (2 g) and mixed at 1500 rpm for 20 minutes. The mixing was stopped, 1000 molecular weight polyoxypropylene glycol (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was filtered as described above. The filter cake was reslurried in t-butanol (144 g) and lithium chloride (0.5 g) and mixed as above. 1000 molecular weight polyoxypropylene diol (1 g) was added and the product was filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 9.1 wt%; 21.9 percent by weight of zinc; lithium is 0.15 wt%; chlorine was 4.8 wt%.

Example 3

Preparation of DMC catalyst with sodium bromide and polyoxypropylene glycol:

the procedure of example 2 was followed except that LiCl was replaced with NaBr.

Elemental analysis; cobalt 8.1 wt%; 21.9 percent by weight of zinc; sodium is 0.48 wt%; chlorine ═ 3.8 wt%; br — 3.8 wt%.

Example 4

Preparation of DMC catalyst with lithium bromide and polyoxypropylene diol:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂). To this solution was added lithium bromide (4 g) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) solution 2 was dissolved with deionized water (100 g) and t-butanol (15.5 g). A solution 3 was prepared by dissolving 1000 molecular weight polyoxypropylene glycol (8 g) in deionized water (50 g) and t-butanol (2 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 1500 rpm. In the reaction process, an internal heating or cooling disc is adoptedThe tube maintained the reaction temperature at 50 ℃. After the addition, mixing was continued at 1500 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 g) and deionized water (55 g) and mixed at 1500 rpm for 20 minutes. The mixing was stopped, 1000 molecular weight polyoxypropylene glycol (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was filtered as described above. The filter cake was reslurried in t-butanol (144 g) and mixed as above. 1000 molecular weight polyoxypropylene diol (1 g) was added and the product was filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis; 23.4% by weight of zinc; cobalt 10.8 wt%; lithium is less than 0.02 wt%; br0.4 wt%; chlorine 3.6 wt%.

Example 5

Preparation of DMC catalysts Using sodium chloride and propylene oxide and ethylene oxide copolymer diols

An aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂). To this solution was added sodium chloride (0.3 g) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) (solution 2) was dissolved with deionized water (100 g) and t-butanol (15.5 g). 8 g of a 4000 molecular weight copolymer of propylene oxide and ethylene oxide (80: 20 by weight) glycol was dissolved in deionized water (50 g) and t-butanol (2 g) to prepare solution 3. Solution 2 was added to solution 1 over 45 minutes while mixing at 900 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 900 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 grams), deionized water (55 grams), and sodium chloride (2 grams) and mixed at 900 rpm for 20 minutes. The mixing was stopped, 4000 molecular weight diol (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was filtered as described above. The filter cake was reslurried in t-butanol (144 g) and sodium chloride (1 g) and mixed as above. 4000 molecular weight diol (1 g) was added and the product was filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 8.8 wt%; 20.3 percent by weight of zinc; sodium was 2.4 wt%.

Example 6

Preparation of DMC catalyst with potassium chloride and polyoxypropylene diol:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) and potassium chloride (4.0 g) (solution 2) were dissolved with deionized water (100 g) and t-butanol (15.5 g). A solution 3 was prepared by dissolving 1000 molecular weight polyoxypropylene glycol (8 g) in deionized water (50 g) and t-butanol (2 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 500 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 500 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 grams), deionized water (55 grams) and mixed at 500 rpm for 20 minutes. The mixing was stopped, 1000 molecular weight diol (2 g) potassium chloride (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was isolated as described above. The filter cake was reslurried in t-butanol (125 g) and deionized water (30 g) and mixed at 500 rpm for 20 minutes. The mixing was stopped. 1000 molecular weight diol (2 g) and potassium chloride (2 g) were added, the mixture was stirred slowly for 3 minutes, and the catalyst was filtered as above. The filter cake was reslurried in t-butanol (144 g) and mixed as above. 1000 molecular weight diol (1 g) was added and the product filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 9.4 wt%; 20% by weight of zinc; potassium was 6.1 wt%.

Example 7

DMC catalyst was prepared with potassium chloride, polyoxypropylene glycol and sodium salt of styrene-maleic acid alternating copolymer (30 wt.% in water):

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) and potassium chloride (4.0 g) (solution 2) were dissolved with deionized water (100 g) and t-butanol (15.5 g). 8 grams of 1000 molecular weight polyoxypropylene glycol was dissolved in deionized water (50 grams) and t-butanol (2 grams) to make solution 3. Solution 2 was added to solution 1 over 45 minutes while mixing at 500 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 500 rpm for 20 minutes. Mixing was stopped and then solution 3 was added followed by slow stirring for 3 minutes.

The reaction mixture was filtered through a 0.45 micron nylon membrane at 40 psig. The catalyst filter cake was reslurried in a mixture of potassium chloride (2 grams), t-butanol (100 grams), styrene-maleic acid alternating copolymer sodium salt solution (7 grams), and deionized water (55 grams) and mixed at 800 rpm for 20 minutes. Mixing was stopped, 1000 molecular weight diol (2 g) was added and the mixture was stirred slowly for 3 minutes. The catalyst was isolated as described above. The filter cake was reslurried in t-butanol (144 g) and mixed as above. A diol (1 g) of molecular weight above 1000 was added and the product was filtered as above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 10.1 wt%; 22.4% by weight of zinc; potassium was 1.86 wt%.

Example 8

DMC catalyst was prepared with potassium chloride, polyoxypropylene glycol and sodium salt of polymethacrylic acid (30% by weight in water);

the procedure of example 7 was followed except that sodium polymethacrylate (30 wt% in water) was used in place of sodium styrene-maleic acid alternating copolymer (30 wt% in water).

Elemental analysis: cobalt 8 wt%; 21.6 percent by weight of zinc; potassium was 4.3 wt%.

Example 9

DMC catalysts were prepared using sodium chloride without any functionalized polymer:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (8 g) in a one liter stirred reactor₂). To this solution was added sodium chloride (0.3 g) (solution 1). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) (solution 2) was dissolved with deionized water (100 g) and t-butanol (15.5 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 800 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 800 rpm for 20 minutes. The mixing was stopped.

The reaction mixture was filtered through a 0.65 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 grams), deionized water (55 grams), and sodium chloride (2 grams) and mixed at 800 rpm for 20 minutes. The mixing was stopped. The catalyst was isolated as described above. The filter cake was reslurried in t-butanol (144 g) and sodium chloride and mixed as above. The product was isolated as described above. The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: 25.9% by weight of zinc; cobalt 12 wt%; sodium was 1.29 wt%.

Example 10 (comparative)

Preparation of DMC catalysts using functionalized polymers without any salts:

the procedure of example 1 was followed except that no sodium chloride was added.

Elemental analysis: cobalt 9 wt%; 21.6 percent by weight of zinc; chlorine was 4.1 wt%.

Examples 11, 12 and 13 (all comparative)

Preparation of DMC catalysts using functionalized polymers without any salts:

for examples 11, 12 and 13, DMC catalysts were prepared according to the procedure of example 1, except that no sodium chloride was added.

Elemental analysis: cobalt 10.3 wt%; 23.2% by weight of zinc; chlorine is 4.0 wt%; potassium is 0.21 wt%.

Example 14 (comparative)

The DMC catalyst was prepared without any functionalized polymer and any salt:

an aqueous solution of zinc chloride (120 g, 62.5 wt% ZnCl) was diluted with deionized water (230 g) and t-butanol (38 g) in a one liter stirred reactor₂). In a 500 ml beaker, potassium hexacyanocobaltate (7.5 g) (solution 2) was dissolved with deionized water (100 g) and t-butanol (15.5 g). Solution 2 was added to solution 1 over 45 minutes while mixing at 800 rpm. During the reaction, the reaction temperature was maintained at 50 ℃ using internal heating or cooling coils. After the addition, mixing was continued at 800 rpm for 20 minutes. The mixing was stopped.

The reaction mixture was filtered through a 0.65 micron nylon membrane at 40 psig. The catalyst cake was reslurried in a mixture of t-butanol (100 g) and deionized water (55 g) and mixed at 800 rpm for 20 minutes. The mixing was stopped. The catalyst was isolated as described above. The filter cake was reslurried in t-butanol (144 g) and mixed as above. The product was isolated as described above.

The resulting catalyst residue was dried in a vacuum oven at 60 deg.C and 30 inches (Hg) to constant weight.

Elemental analysis: cobalt 12.4 wt%; 26.8 percent by weight of zinc.

Example 15

Using sodium chloride and NEODOL- (EO)_m-preparation of DMC catalyst by lbo block copolymer:

DMC catalyst was prepared according to the procedure of example 5, except that NEODOL- (EO)_mIBO block copolymers instead of 1000 molecular weight diols. The block copolymer is prepared using NEODOL (commercially available from Shell chemical Company) as the starting material and the DMC catalyst is prepared essentially by the method of US 5482908 (the teachings of which are incorporated herein by reference) to produce a polyoxyethylene having a molecular weight of about 1000. The diblock copolymer is capped with 1-2 units of 1, 1-dimethyloxirane.

Example 16 (comparative)

DMC catalyst preparation using zinc hexacyanocobaltate/tert-butanol and polyoxypropylene glycol:

the procedure of example 1 was followed except that no NaCl was added.

Elemental analysis; cobalt 9 wt%; 21.6 percent by weight of zinc.

As illustrated in Table 1, DMC catalysts prepared according to the present process, such as the catalysts prepared in examples 1-5 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having acceptable amounts of high molecular weight tail.

TABLE 1

Catalyst of example #	10^*	1	2	3	4	5
Catalyst of example #	10^*	1	2	3	4	5	Additive Na or Li [ wt.% ]]Polymerization Rate [ KgPO/g.Co/min]6000MW triol: OH # [ mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings; (MW)40-60K60-80K80-100K100-200K200-400K > 400K	No 21.729.711050.005(ppm)85546528733712040	NaCl0.75(Na)16.428.411200.0055(ppm)6163161902359430	LiCl0.15(Li)19.130.610870.0048(ppm)6093302062499937	NaBr0.48(Na)23.729.811560.0056(ppm)5582501182299940	LiBr＜0.02(Li)20.730.310540.0046(ppm)72440924831811948	NaCl2.4(Na)16.129.711300.0064(ppm)6723442032619121

4 hours at 130 ℃ PO was added, using 30ppm of catalyst prepared 6000MW triol based on the amount of polyol prepared.

The HMW tails are based on GPC cut into six parts.

^*Comparison of

As illustrated in Table 2, DMC catalysts prepared according to the present process, such as the catalysts prepared in examples 1-5 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of a DMC catalyst prepared with a functionalized polymer without any alkali metal salt, such as the DMC catalyst prepared in comparative example 10. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 2

Catalyst of example #	1	2	3	4	5
Catalyst of example #	1	2	3	4	5	Additive Na or Li [ wt.% ]]6000MW triol; OH # [ mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tail (MW)40-60K60-80K80-100K100-200K200-400K > 400K	Reduction 283234302225 in NaCl0.75(Na) 28.411200.0055%	29292826188% reduction in LiCl0.15(Li) 30.610870.0048%	35465932180% reduction in NaBr0.48(Na) 29.811560.0056%	The reduction of 15121461-20% of LiBr is less than 0.02(Li) 30.310540.0046%	212629232448% reduction in NaC12.4(Na) 29.711300.0064%

The HMW tails are based on GPC cut into six parts.

As illustrated in Table 3, DMC catalysts prepared according to the present process, such as the catalyst prepared in example 6 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of a DMC catalyst prepared with a functionalized polymer without any alkali metal salt, such as the DMC catalyst prepared in comparative example 11. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 3

Catalyst of example #	11^*	6		6
Catalyst of example #	11^*	6		6	K in the additive catalyst [ wt.%]6000MW triol; OH # [ mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings; (MW)40-50.4K50.4-63.4K63.4-79.8K79.8-100.5K100.5-126.5K126.5-159.2K159.2-200.5K200.5-252.4K252.4-317.7K317.7-400K > 400K	No 0.2129.511090.006(ppm)1169920719564430245164108694833	KCl6.129.911310.0076(ppm)608448366332247126825029160		KCl6.129.911310.0076 (% reduction) 48514941434950545867100

The HMW tails are based on GPC cut into six parts.

^*Comparison of

As illustrated in Table 4, DMC catalysts prepared according to the present process, such as the catalyst prepared in example 7 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of a DMC catalyst prepared with a functionalized polymer without any alkali metal salt, such as the DMC catalyst prepared in comparative example 12. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 4

Catalyst of example #	12^*	7	7
Catalyst of example #	12^*	7	7	K in the additive catalyst [ wt.%]6000MW triol; OH # [ mgKOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings; (MW)40-50.4K50.4-63.4K63.4-79.8K79.8-100.5K100.5-126.5K126.5-159.2K159.2-200.5K200.5-252.4K252.4-317.7K317.7-400K > 400K	No 0.2129.211130.0055(ppm)1115869760603457286203131935841	KCl1.8629.510930.0061(ppm)64947942135626715611274523323	KCl1.8629.510930.0061 (% reduction) 4245454142464544444344

The HMW tails are based on GPC cut into six parts.

^*Comparison of

As illustrated in Table 5, DMC catalysts prepared according to the present process, such as the catalyst prepared in example 8 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of a DMC catalyst prepared with a functionalized polymer without any alkali metal salt, such as the DMC catalyst prepared in comparative example 13. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 5

Catalyst of example #	13^*	8	8
Catalyst of example #	13^*	8	8	K in the additive catalyst [ wt.%]6000MW triol; OH # [ mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings; (MW)40-50.4K50.4-63.4K63.4-79.8K79.8-100.5K100.5-126.5K126.5-159.2K159.2-200.5K200.5-252.4K252.4-317.7K317.7-400K > 400K	None 0.2129.811120.005512901031815641473266177109754722	KCl4.329.611080.006168547640335027715994551900	KCl4.329.611080.0061 (% reduction) 475451454140475075100100

The HMW tails are based on GPC cut into six parts.

^*Comparison of

As illustrated in Table 6, DMC catalysts prepared according to the present process, such as the catalyst prepared in example 9 (prepared using an alkali metal salt but not with a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of DMC catalysts prepared without a functionalized polymer and an alkali metal salt, such as the DMC catalyst prepared in comparative example 14. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 6

Catalyst of example #	14^*	9	9
Catalyst of example #	14^*	9	9	Sodium in additive catalyst [ wt.%]Polymerization rate [ Kg.PO/g.Co/min]6000MW triol: OH # [ mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings: (MW)40-60K60-80K80-100K100-200K200-400K > 400K	No 14.329.411690.0043(ppm)168090653759119663	NaCl1.2912.929.211980.0049(ppm)141274543647617564	NaCl1.2912.929.2119800049 (% reduction) 1618191911-2

The HMW tails are based on GPC cut into six parts.

^*Comparison of

As illustrated in Table 7, DMC catalysts prepared according to the present process, such as the catalyst prepared in example 15 (prepared using an alkali metal salt and a functionalized polymer), can be used to prepare polyols having reduced amounts of high molecular weight tail as compared to polyols prepared in the presence of a DMC catalyst prepared with a functionalized polymer without any alkali metal salt, such as the DMC catalyst prepared in comparative example 16. The percent reduction of high molecular weight tail was determined using formula I.

TABLE 7

Catalyst of example #	16 (comparison)	15	15
Catalyst of example #	16 (comparison)	15	15	Sodium in additive catalyst [ wt.%]6000MWOH#[mg KOH/g]Viscosity [ cps ]]Unsaturation [ meq/g ]]HMW tailings: (MW)40-60K60-80K80-100K100-200K200-400K > 400K	No 29.810950.0052(ppm)106458135238212341	NaCl0.883011370.0051(ppm)5742811541998023	NaCl0.883011370.0051 (% reduction) 465256483544

The HMW tails are based on GPC cut into six parts.

Claims

1. A double metal cyanide catalyst having the general formula:

M¹ _x([M² _x′(CN)_y]_z·[M³])·L¹·L²·M⁴ _z

in the formula:

M¹represents at least one metal;

[M² _x′(CN)_y]represents at least one metal cyanide;

M³represents at least one transitionA metal;

M⁴represents at least one alkali metal salt in an amount of from about 0.4 to about 6 wt.%, based on the total weight of the double metal cyanide catalyst;

L¹represents at least one organic complexing ligand;

L²is optional and may represent at least one functionalized polymer, and

x, x', y and z are integers and are selected such that the double metal cyanide catalyst is electrically neutral.

2. The double metal cyanide catalyst of claim 1, wherein at least one metal is zinc.

3. The double metal cyanide catalyst of claim 1, wherein at least one metal cyanide is hexacyanocobaltate (-copaltate).

4. The double metal cyanide catalyst of claim 1, wherein at least one organic complexing ligand is t-butanol.

5. The double metal cyanide catalyst of claim 1, wherein at least one alkali metal salt is potassium chloride, sodium bromide, lithium chloride, or lithium bromide.

6. The double metal cyanide catalyst of claim 1, wherein the amount of the at least one functionalized polymer is from about 2 to about 98 weight percent based on the total weight of the double metal cyanide catalyst.

7. The double metal cyanide catalyst of claim 1, wherein at least one functionalized polymer is a polyether; a polyester; a polycarbonate; a polyalkylene glycol sorbitan ester; polyalkylene glycol glycidyl ethers; polyacrylamide; acrylamide acrylic acid copolymer, polyacrylic acid, acrylic acid maleic acid copolymer, N-vinyl pyrrolidone acrylic acid copolymer, acrylic acid styrene copolymer, or salts thereof; maleic acid, styrene or maleic anhydride copolymers or salts thereof; polyacrylonitrile; a polyalkyl acrylate; polyalkylmethacrylate; polyvinyl methyl ether; polyvinyl ethyl ether; polyvinyl acetate; polyvinyl alcohol; poly-N-vinyl pyrrolidone; polyvinyl ketones; poly (4-vinylphenol); an oxazoline polymer; a polyalkyleneimine; hydroxyethyl cellulose; a polyacetal; a glycidyl ether; a glycoside; a carboxylic acid polyol ester; a bile acid or a salt, ester or amide thereof; a cyclodextrin; a phosphorus compound; an unsaturated carboxylic acid ester; or an ionic surface-active compound or a surface-active compound.