WO1999059719A1 - Double metal cyanide catalysts containing cyclic, bidentate complexing agents - Google Patents
Double metal cyanide catalysts containing cyclic, bidentate complexing agents Download PDFInfo
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- WO1999059719A1 WO1999059719A1 PCT/EP1999/003147 EP9903147W WO9959719A1 WO 1999059719 A1 WO1999059719 A1 WO 1999059719A1 EP 9903147 W EP9903147 W EP 9903147W WO 9959719 A1 WO9959719 A1 WO 9959719A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
- C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
- C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
- C08G65/2645—Metals or compounds thereof, e.g. salts
- C08G65/2663—Metal cyanide catalysts, i.e. DMC's
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
- B01J27/26—Cyanides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
Definitions
- the invention relates to double metal cyanide (DMC) catalysts and methods for making them.
- DMC double metal cyanide
- the invention relates to DMC catalysts useful for making polyether polyols that contain reduced levels of a high-molecular-weight component compared with polyols made using other known DMC catalysts.
- Double metal cyanide complexes are well-known catalysts for epoxide polymerization. These active catalysts give polyether polyols that have low unsaturation compared with similar polyols made using basic (KOH) catalysis.
- the catalysts can be used to make many polymer products, including polyether, polyester, and polyetherester polyols. These polyols are useful in polyurethane coatings, elastomers, sealants, foams, and adhesives.
- DMC catalysts are usually made by reacting aqueous solutions of metal salts and metal cyanide salts to form a precipitate of the DMC compound.
- a water-soluble, low-molecular-weight organic complexing agent typically an ether or an alcohol, is included in the catalyst preparation.
- the organic complexing agent is needed for favorable catalyst activity. Preparation of typical DMC catalysts is described, for example, in U.S. Pat. Nos. 3,427,256, 3,829,505, and 5,158,922.
- the organic complexing agent preferably has "a substantially straight chain” or is "free of bulky groups.”
- U.S. Pat. Nos. 5,158,922 (column 6) and 5,470,813 (column 5) add nitriles and ureas to the list of suitable complexing agents.
- Japanese Pat. Appl. Kokai No. H3- 128930 (Morimoto et al.) teaches to use N,N-dialkylamides (e.g., N,N- dimethylacetamide) as the organic complexing agent to make catalysts with improved activity.
- DMC catalysts having a relatively high degree of crystallinity were used for making epoxide polymers.
- the most popular catalyst contained an organic complexing agent (usually glyme), water, excess metal salt (typically zinc chloride), and the DMC compound.
- Activity for epoxide polymerization which exceeded the activity available from the commerical standard (KOH), was thought to be adequate. Later, it was appreciated that more active catalysts would be valuable for successful commercialization of polyols from DMC catalysts.
- DMC catalysts with exceptional activity for epoxide polymerization.
- U.S. Pat. No. 5,470,813 describes substantially amorphous or non- crystalline catalysts that have much higher activities compared with earlier DMC catalysts.
- Other highly active DMC catalysts include, in addition to a low molecular weight organic complexing agent, a functionalized polymer such as a polyether (see U.S. Pat. Nos. 5,482,908 and 5,545,601) or other functional group-containing polymer (U.S. Pat. No. 5,714,428).
- Highly active DMC catalysts are generally substantially non-crystalline, as is evidenced by powder X-ray diffraction patterns that lack many sharp lines.
- the catalysts are active enough to allow their use at very low concentrations, often low enough to overcome any need to remove the catalyst from the polyol. Even the best DMC catalysts known could be improved.
- High catalyst activity has sometimes come at a price, namely the unexpected formation of traces of polyether having extremely high (greater than 400,000 or >400K) number average molecular weight (Mn).
- Mn number average molecular weight
- This high-molecular-weight component even at part-per-milliion levels, can negatively impact the way polyether polyols made from the catalysts perform in urethane applications such as flexible or molded polyurethane foams. For example, polyols that contain too much high-molecular-weight component can process poorly, give tight foams, or cause foam settling or collapse.
- a preferred catalyst would have high activity similar to that of the substantially non-crystalline DMC catalysts now known (e.g., from U.S. Pat. Nos. 5,470,813 or 5,482,908).
- a preferred catalyst would still give polyol products with low viscosities and low unsaturation. Ideally, however, the catalyst would not produce significant amounts of high-molecular-weight polyol components, particularly those having number average molecular weights greater than about 400,000.
- the invention provides a way to make polyether polyols that perform more consistently in urethane applications.
- the invention is a double metal cyanide (DMC) catalyst and a method for making it.
- the catalyst comprises a DMC compound, an organic complexing agent, and optionally, from about
- the key component is the organic complexing agent. It comprises a C 3 -C 5 aliphatic alcohol and from about 5 to about 95 mole percent, based on the total amount of organic complexing agent, of a cyclic, bidentate compound selected from lactams and lactones.
- the invention also includes a process for making an epoxide polymer using the catalysts.
- DMC catalysts with a complexing agent comprising a mixture of a C 3 -C 5 aliphatic alcohol and a cyclic, bidentate compound selected from lactams and lactones
- a complexing agent comprising a mixture of a C 3 -C 5 aliphatic alcohol and a cyclic, bidentate compound selected from lactams and lactones
- polyether polyols made from the catalysts contain reduced levels of high-molecular-weight (Mn greater than 400,000) components. This reduction makes the polyols process better in urethane applications such as flexible and molded foams.
- Catalysts of the invention comprise a double metal cyanide (DMC) compound, an organic complexing agent mixture, and optionally, a functionalized polymer.
- DMC double metal cyanide
- Double metal cyanide compounds useful in the invention are the reaction products of a water-soluble metal salt and a water-soluble metal cyanide salt.
- the water-soluble metal salt preferably has the general formula M(X) n in which M is selected from the group consisting of Zn(ll), Fe(ll), Ni(ll), Mn(ll), Co(ll), Sn(ll), Pb(ll), Fe(lll), Mo(IV), Mo(VI), AI(III), V(V),
- M is selected from the group consisting of Zn(ll), Fe(ll), Co(ll), and Ni(ll).
- X is preferably an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate.
- n is from 1 to 3 and satisfies the valency state of M.
- Suitable metal salts include, for example, zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetate, zinc benzoate, zinc nitrate, iron(ll) sulfate, iron(li) bromide, cobalt(ll) chloride, cobalt(ll) thiocyanate, nickel(ll) formate, nickel(ll) nitrate, and the like, and mixtures thereof.
- Zinc halides are preferred.
- the water-soluble metal cyanide salts used to make the double metal cyanide compounds useful in the invention preferably have the general formula (Y) a M'(CN) b (A) c in which M' is selected from the group consisting of Fe(ll), Fe(lll), Co(ll), Co(lll), Cr(ll), Cr(lll), Mn(ll), Mn(lll), Ir(lll), Ni(ll), Rh(lll), Ru(ll), V(IV), and V(V). More preferably, M' is selected from the group consisting of Co(ll), Co(lll), Fe(ll), Fe(lll), Cr(lll), Ir(lll), and Ni(ll).
- the water- soluble metal cyanide salt can contain one or more of these metals.
- Y is an alkali metal ion or alkaline earth metal ion.
- A is an anion selected from the group consisting of halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. Both a and b are integers greater than or equal to 1 ; the sum of the charges of a, b, and c balances the charge of M'.
- Suitable water-soluble metal cyanide salts include, for example, potassium hexacyanocobaltate(lll), potassium hexacyanoferrate(ll), potassium hexacyanoferrate(lll), calcium hexacyanocobaltate(lll), lithium hexacyanoiridate(lll), and the like.
- suitable double metal cyanide compounds are listed in U.S. Patent No. 5,158,922, the teachings of which are incorporated herein by reference. Zinc hexacyanocobaltates are preferred.
- the catalysts of the invention include an organic complexing agent comprising an alcohol and a cyclic, bidentate compound.
- the alcohol is a C 3 -C 5 aliphatic alcohol.
- Suitable alcohols include, for example, n-propyl alcohol, isopropyl alcohol, isobutyl alcohol, tert-butyl alcohol, tert-amyl alcohol, and the like, and mixtures thereof. Branched alcohols are preferred; tert-butyl alcohol is particularly preferred.
- the complexing agent includes a cyclic, bidentate compound selected from the group consisting of lactams and lactones.
- the lactam or lactone is at least partially soluble in water.
- Especially preferred are C 3 -C 6 lactams and lactones.
- Lactams are cyclic amides. Many are conveniently produced by dehydrating common amino acids.
- the lactams can be substituted on the ring carbons or on the nitrogen atom with one or more alkyl, hydroxyalkyl, hydroxy, halogen, or alkoxy groups, or the like.
- Suitable lactams include, for example, ⁇ -propiolactam, 2-pyrrolidone, 1-methyl-2-pyrrolidone (N- methylpyrrolidone), ⁇ -valerolactam, e-caprolactam, 1-(2-hydroxyetyl)-2- pyrrolidone, 1-ethyl-2-pyrrolidone, methyl-2-oxo-1-pyrrolidineacetate, and the like, and mixtures thereof.
- Particularly preferred are ⁇ -valerolactam and pyrrolidones such as 2-pyrrolidone and 1-methyl-2-pyrrolidone.
- Lactones are cyclic esters. Like the lactams, the lactones can contain ring substituents such as alkyl, hydroxyalkyl, hydroxy, halogen, or alkoxy groups, or the like. Suitable lactones include, for example, ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, e-caprolactone, and the like, and mixtures thereof. ⁇ -Butyrolactone is particularly preferred.
- Both the C 3 -C 5 aliphatic alcohol and the cyclic, bidentate compound are needed to give a catalyst that is highly active and also gives the desirable reduction in the amount of high-molecular-weight polyether component. If the cyclic, bidentate compound is omitted, the catalyst has high activity (like the ones disclosed in U.S. Pat. No. 5,470,813), but polyols made from the catalyst can contain undesirable levels of the high-molecular- weight component. On the other hand, if only the cyclic, bidentate compound is present as the complexing agent, the catalysts tend to have relatively low activity and/or give polyols with broad molecular weight distributions and high viscosities.
- the relative amounts of C 3 -C 5 aliphatic alcohol to cyclic, bidentate compound needed in the catalyst can vary over a wide range, and a skilled person can control catalyst activity, polyol viscosity, and the like, by varying them.
- preferred catalysts will contain from about 5 to about 95 mole percent, based on the total amount of organic complexing agent, of the cyclic, bidentate compound. More preferred are catalysts that contain from about 10 to about 80 mole percent of the cyclic, bidentate compound; most preferred is the range from about 20 to about 60 mole percent.
- Catalysts of the invention optionally include a functionalized polymer or its water-soluble salt.
- “functionalized polymer” we mean a polymer that contains one or more functional groups containing oxygen, nitrogen, sulfur, phosphorus, or halogen, wherein the polymer, or a water-soluble salt derived from it, has relatively good water solubility, i.e., at least about 3 wt.% of the polymer or its salt dissolves at room temperature in water or mixtures of water with a water-miscible organic solvent.
- water-miscible organic solvents are tetrahydrofuran, acetone, acetonitrile, t-butyl alcohol, and the like. Water solubility is important for incorporating the functionalized polymer, when used, into the catalyst structure during formation and precipitation of the double metal cyanide compound.
- Polyethers are preferred functionalized polymers. Catalysts that incorporate a polyether are taught in U.S. Pat. Nos. 5,482,908 and 5,545,601 , the teachings of which are incorporated herein by reference. A particularly preferred catalyst of the invention incorporates a polyether polyol as the functionalized polymer.
- Suitable functionalized polymers include, for example, poly(acrylamide), poly(acrylic acid), poly(acrylic acid-co-maleic acid), poly(alkyl acrylate)s, poly(alkyl methacrylate)s, poly(vinyl methyl ether), poly(vinyl acetate), poly(vinyl alcohol), poly(N-vinylpyrrolidone), poly(N- vinyipyrrolidone-co-acrylic acid), poly(N,N-dimethylacrylamide), poly(4- vinylpyridine), poly(vinyl chloride), poly(acrylic acid-co-styrene), poly(vinyl sulfate), poly(vinyl sulfate) sodium salt, and the like.
- the functionalized polymer when used, comprises from about 2 to about 80 wt.% of the catalyst.
- the catalyst contains from about 5 to about 70 wt.% of the functionalized polymer; most preferred is the range from about 10 to about 60 wt.%.
- Catalysts of the invention are preferably substantially non-crystalline.
- substantially non-crystalline we mean lacking a well-defined crystal structure, or characterized by the substantial absence of sharp lines in the powder X-ray diffraction pattern of the composition.
- Conventional zinc hexacyanocobaltate-glyme catalysts show a powder X-ray diffraction pattern containing many sharp lines, which indicates that the catalyst has a high degree of crystallinity.
- Zinc hexacyanocobaltate prepared in the absence of a complexing agent is also highly crystalline (and is inactive for epoxide polymerization).
- catalysts of the invention are preferably substantially non-crystalline.
- Catalysts of the invention also feature unique infrared spectra. Many prior DMC catalysts, particularly the highly active, substantially non- crystalline varieties, exhibit absorption bands for free Zn-OH vibrations at 3650 cm “1 and 642 cm “1 . In contrast, preferred catalysts of the invention lack these bands or have reduced absobances at these wavenumbers. These observations are significant because the lack of infrared absorption bands from free Zn-OH appears to correlate well with reduced formation of high- molecular-weight polyol components (see Examples 1 , 2, 4, and C10; Tables 1 and 2).
- catalysts of the invention uniquely show a low- energy carbonyl absorption (e.g., about 1630 cm “1 for 2-pyrrolidones), which suggests the presence of a stable complex of the cyclic, bidentate compound and the DMC catalyst.
- the invention includes a method for making the catalysts.
- the method comprises reacting, preferably at a temperature within the range of about room temperature to about 80°C, aqueous solutions of a metal salt (usually used in excess) and a metal cyanide salt in the presence of the organic complexing agent and optional functionalized polymer.
- the organic complexing agent components are included with either or both of the aqueous salt solutions, or they are added to the catalyst slurry immediately following precipitation of the DMC compound. It is generally preferred to pre-mix one or both of the complexing agent components with either aqueous solution, or both, before combining the reactants.
- the resulting catalyst is isolated (by centrifugation, filtration, decanting, or the like), washed, and dried as described previously (see, e.g., U.S. Pat. Nos. 5,470,813, 5,482,908, and 5,714,428, the teachings of which are incorporated herein by reference).
- the cyclic, bidentate compound is included in one or both of the aqueous reactant solutions.
- the aqueous metal salt e.g., zinc chloride
- the aqueous metal cyanide salt e.g., potassium hexacyanocobaltate
- the reactant solutions are combined using efficient mixing (preferably by homogenization or high-shear stirring, e.g.) to produce a catalyst slurry that contains the DMC compound.
- the catalyst is then isolated, usually by filtration under pressure, and the residue is washed with an aqueous mixture that contains the C 3 -C 5 aliphatic alcohol.
- this washing mixture also includes a functionalized polymer.
- the catalyst is then isolated as before, and additional washings with the C 3 -C 5 aliphatic alcohol or aqueous mixtures containing the alcohol and/or functionalized polymer are used.
- the final wash uses no water.
- the method of the invention offers some valuable and unexpected benefits for catalyst manufacture that result from using a cyclic, bidentate compound.
- DMC catalysts made in the presence of the cyclic, bidentate compound are easier to filter than prior DMC catalysts, so the total amount of time needed to make them is reduced (see Example 15 and Comparative Example 16).
- the cyclic, bidentate compound acts as a defoamer in the catalyst preparation, so less catalyst is deposited on the walls of the reactor used for catalyst manufacture. This results in improved catalyst consistency and less wasted catalyst.
- the invention includes a process for making an epoxide polymer.
- This process comprises polymerizing an epoxide in the presence of a DMC catalyst of the invention.
- Preferred epoxides are ethylene oxide, propylene oxide, butene oxides, styrene oxide, and the like, and mixtures thereof.
- the process can be used to make random or block copolymers.
- the epoxide polymer can be, for example, a polyether polyol derived from the polymerization of an epoxide in the presence of a hydroxyl group-containing initiator.
- epoxides copolymerize with oxetanes (as taught in U.S. Patent Nos. 3,278,457 and 3,404,109) to give polyethers, or with anhydrides (as taught in U.S. Patent Nos. 5,145,883 and 3,538,043) to give polyester or polyetherester polyols.
- Polyether polyols (or monols) made with the catalysts of the invention preferably have average hydroxyl functionalities from about 1 to 8, more preferably from about 2 to 6, and most preferably from about 2 to 3.
- the polyols preferably have number average molecular weights (Mn) within the range of about 500 to about 50,000. A more preferred range is from about
- polyols made using DMC catalysts of the invention contain reduced levels of high-molecular-weight components compared with similar catalysts prepared without a cyclic, bidentate compound.
- the amount of high- molecular-weight component is quantified by any suitable method. A particularly convenient way to measure this component is by gel permeation chromatography (GPC). A suitable technique is described below in Example B.
- Polyols made according to the invention consistently contain less than about 10 ppm of polyether components having a number average molecular weight greater than 400,000 (i.e., Mn > 400K). Polyols made with most highly active DMC catalysts normally contain higher levels (at least 10 ppm) of material having Mn >400K. While this reduction in the amount of high- molecular-weight polyol component may appear trivial, we surprisingly found that polyols of the invention consistently pass the "supercritical foam test" (SCFT)-a sensitive foam test designed to reveal whether or not polyols will cause foam settling or collapse in the field-while polyols made with other highly active DMC catalysts did not always pass the same test.
- SCFT supercritical foam test
- Aqueous zinc chloride solution 120 g of 62.5 wt.% ZnCI 2 is diluted with deionized water (230 g) and HEP (50 mL) in a one-liter beaker (Solution 1). Potassium hexacyanocobaltate (7.5 g) is dissolved in a second beaker with deionized water (100 mL) and HEP (20 mL) (Solution 2).
- Solution 3 is prepared by dissolving a 1000 mol. wt. poiyoxypropylene diol (8.0 g) in deionized water (50 mL) and tetrahydrofuran (THF) (2 mL). Solution 2 is added to Solution 1 over 35 min. while homogenizing at 20% of maximum intensity. Following the addition, homogenization continues at 40% intensity for 10 min. The homogenizer is stopped. Solution 3 is added, followed by slow stirring for 3 min.
- the reaction mixture is filtered at 40 psig through a 20 ⁇ m nylon membrane.
- the catalyst cake is reslurried in a mixture of tert-butyl alcohol (130 mL) and deionized water (55 mL), and is homogenized at 40% intensity for 10 min.
- the homogenizer is stopped. More 1000 mol. wt. poiyoxypropylene diol (2.0 g) dissolved in THF (2 g) is added, and the mixture is stirred slowly for 3 min.
- the catalyst is isolated as described above.
- the cake is reslurried in tert-butyl alcohol (185 mL) and homogenized as described above. More 1000 mol. wt.
- Example 2 The procedure of Example 1 is followed, except that a 50/50 mixture of N-methyl-2-pyrrolidone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- Example 3 The procedure of Example 1 is followed, except that a 25/75 mixture of N-methyl-2-pyrrolidone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- EXAMPLE 4 The procedure of Example 1 is followed, except that poly(vinyl pyrrolidone) is used instead of the 1000 mol. wt. poiyoxypropylene diol.
- Example 1 The procedure of Example 1 is followed, except that a 50/50 mixture of 2-pyrrolidone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- Example 1 The procedure of Example 1 is followed, except that a 25/75 mixture of 2-pyrrolidone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- Example 1 The procedure of Example 1 is followed, except that a 10/90 mixture of ⁇ -butyrolactone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- EXAMPLE 8 The procedure of Example 1 is followed, except that a 25/75 mixture of ⁇ -butyrolactone and tert-butyl alcohol replaces HEP in reactant Solutions 1 and 2.
- Example 1 The procedure of Example 1 is followed, except tert-butyl alcohol replaces all of the HEP used.
- This catalyst is prepared essentially by the method of U.S. Pat. No. 5,482,908.
- Examples 1-9 and Comparative Example 10 show (see Table 2), including a cyclic, bidentate compound in the preparation of a substantially non-crystalline double metal cyanide catalyst offers unexpected benefits.
- polyols made using the catalysts contain reduced levels of high-molecular-weight (> 400,000 mol. wt.) polyol component.
- the polyols perform better than the control polyols (ones made using a catalyst not prepared in the presence of a cyclic, bidentate compound) in the supercritical foam test, i.e., they exhibit a reduced level of settling compared with prior DMC-catalyzed polyols.
- EXAMPLE 11 This example illustrates the preparation of a substantially non- crystalline zinc hexacyanocobaltate catalyst that incorporates 1-(2- hydroxyethyl)-2-pyrrolidone (HEP) as a complexing agent in addition to tert-butyl alcohol (but without a polyether diol).
- HEP 1-(2- hydroxyethyl)-2-pyrrolidone
- Aqueous zinc chloride solution 120 g of 62.5 wt.% ZnCI 2 is diluted with deionized water (230 g) and HEP (50 mL) in a one-liter beaker (Solution 1). Potassium hexacyanocobaltate (7.5 g) is dissolved in a second beaker with deionized water (100 mL) and HEP (20 mL) (Solution 2). Solution 2 is added to Solution 1 over 40 min. while homogenizing at 20% of maximum intensity. Following the addition, homogenization continues at 40% intensity for 10 min.
- the reaction mixture is filtered at 40 psig through a 20 ⁇ m nylon membrane.
- the catalyst cake is reslurried in a mixture of tert-butyl alcohol (130 mL) and deionized water (55 mL), and is homogenized at 40% intensity for 10 min.
- the catalyst is isolated as described above.
- the cake is reslurried in tert-butyl alcohol (185 mL) and homogenized as described above.
- the catalyst is isolated as described above, and is dried in a vacuum oven at 60°C, 30 in (Hg) to constant weight.
- COMPARATIVE EXAMPLE 13 The procedure of U.S. Pat. No. 5,470,813 (Example 1) is used to prepare the catalyst.
- the complexing agent is tert-butyl alcohol only, and no polyether is included.
- the benefits of the invention are not limited to catalysts made in the presence of a functionalized polymer.
- polyols made using the catalysts of the invention contain reduced levels of high-molecular- weight (> 400,000 mol. wt.) polyol component and perform better than the control polyols in the supercritical foam test.
- Each polyol is also evaluated in the "supercritical foam test” (SCFT), which is described below in Example A.
- SCFT supercritical foam test
- Each polyol's performance is compared against the performance of a KOH-based polyol (3000 mol. wt. poiyoxypropylene triol) in the same test. The % settling of both samples is measured. The ratio of the % settle in the foam made using the KOH standard to the % settle in the foam made using the polyol to be tested is calculated.
- a ratio in the SCFT test of 0.6 or greater is deemed a "pass," while a ratio less than 0.6 fails.
- SCFT Supercritical Foam Test
- the B-side is prepared from the polyol sample to be analyzed (100 parts, typically a 3000 mol. wt. polyether triol), water (6.5 parts), dichloromethane (15 parts), A-1 catalyst (product of Witco, 0.1 parts), T-9 catalyst (product of Air Products, 0.25 parts), and L-550 surfactant (product of Witco, 0.5 parts).
- Toluene diisocyanate (78.01 parts, 110 NCO/OH index) is rapidly added to the B-side components, the ingredients are mixed well and poured into a cake box. The foam rises and cures, and the % settling (or collapse) is noted.
- the molecular weight of the high molecular weight component of the polyol samples is quantified by comparing elution times in a GPC column with that of polystyrene samples of known molecular weights.
- a Jordi Gel DVB 10 3 angstrom column, 10x250mm, 5 micron particle size, is employed with a mobile phase which consists of tetrahydrofuran.
- the detector is a Varex Model IIA evaporative light scanning detector.
- Polystyrene stock solutions are made from polystyrenes of different molecular weights by dilution with tetrahydrofuran to form standards containing 2, 5, and 10 mg/L of polystyrene. Samples are prepared by weighing 0.1 g of polyether polyol into a one-ounce bottle and adding tetrahydrofuran to the sample to adjust the total weight of the sample and solvent to 10.0 g. Samples of the calibration solutions are sequentially injected into the GPC column.
- Duplicates of each polyether polyol sample are then injected, followed by a reinjection of the various polystyrene standards.
- the peak areas for the standards are electronically integrated, and the electronically integrated peaks for the two sets of each candidate polyol are electronically integrated and averaged. For each sample, the fraction of material having Mn>400,000 is calculated and reported.
- Example 1 The procedure of Example 1 is generally followed, except that the times for each filtration step (see last paragraph of Example 1) are noted.
Abstract
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Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU41401/99A AU4140199A (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
CA002332599A CA2332599A1 (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
BR9910605-1A BR9910605A (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic bidentate complexing agents |
JP2000549376A JP2002515517A (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic bidentate complexing agents |
DE69914603T DE69914603T2 (en) | 1998-05-18 | 1999-05-07 | DOUBLE METAL CYANIDE CATALYSTS CONTAIN CYCLIC, TWO-STAGE COMPLEX IMAGES |
HU0102318A HUP0102318A3 (en) | 1998-05-18 | 1999-05-07 | Double metal cyanid catalysts containing cyclic, bidentate complexing agents |
EP99924904A EP1094895B1 (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
HK02101287.8A HK1039910B (en) | 1998-05-18 | 2002-02-21 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US09/080,780 US6013596A (en) | 1998-05-18 | 1998-05-18 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
US09/080,780 | 1998-05-18 |
Publications (1)
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WO1999059719A1 true WO1999059719A1 (en) | 1999-11-25 |
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PCT/EP1999/003147 WO1999059719A1 (en) | 1998-05-18 | 1999-05-07 | Double metal cyanide catalysts containing cyclic, bidentate complexing agents |
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US (1) | US6013596A (en) |
EP (1) | EP1094895B1 (en) |
JP (1) | JP2002515517A (en) |
KR (1) | KR100568064B1 (en) |
CN (1) | CN1121273C (en) |
AR (1) | AR018606A1 (en) |
AU (1) | AU4140199A (en) |
BR (1) | BR9910605A (en) |
CA (1) | CA2332599A1 (en) |
DE (1) | DE69914603T2 (en) |
ES (1) | ES2214855T3 (en) |
HK (1) | HK1039910B (en) |
HU (1) | HUP0102318A3 (en) |
ID (1) | ID26834A (en) |
PT (1) | PT1094895E (en) |
TW (1) | TW460324B (en) |
WO (1) | WO1999059719A1 (en) |
Cited By (12)
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EP1256596A1 (en) * | 2001-05-07 | 2002-11-13 | Bayer Aktiengesellschaft | Double metal cyanide catalysts for the production of polyetherpolyols |
EP1469024A2 (en) | 2003-04-16 | 2004-10-20 | tesa AG | Polyurethane based pressure sensitive adhesive |
US6953765B2 (en) | 2001-05-07 | 2005-10-11 | Bayer Aktiengesellschaft | Double metal cyanide catalysts for preparing polyether polyols |
US7091300B2 (en) | 2003-04-16 | 2006-08-15 | Tesa Aktiengesellschaft | Polyurethane PSA for sensitive surfaces |
US7175898B2 (en) | 2003-04-16 | 2007-02-13 | Tesa Aktiengesellschaft | Reusable elastic adhesive sheet redetachable without residue or damage |
CN1325165C (en) * | 2002-05-17 | 2007-07-11 | 中国石化集团金陵石油化工有限责任公司 | Process for continuously preparing double metal cyanide complex catalyst |
US7495059B2 (en) | 2006-04-28 | 2009-02-24 | Tesa Ag | Removable polyurethane PSA |
EP2119735A1 (en) | 2008-05-13 | 2009-11-18 | tesa SE | Hot melt method for the preparation of a chemically cross-linked polyurethane film |
WO2010094585A1 (en) | 2009-02-20 | 2010-08-26 | Tesa Se | Pressure-sensitive adhesive mass |
DE102009046657A1 (en) | 2009-11-12 | 2011-05-19 | Tesa Se | Pressure-sensitive adhesive based on polyurethane |
US8268922B2 (en) | 2006-07-19 | 2012-09-18 | Tesa Se | Pressure-sensitive adhesive from a resin-modified polyurethene |
US10357588B2 (en) | 2012-05-29 | 2019-07-23 | 3M Innovative Properties Company | Absorbent article comprising polymeric foam and intermediates |
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JP2001519468A (en) * | 1997-10-13 | 2001-10-23 | バイエル・アクチエンゲゼルシヤフト | Crystalline double metal cyanide catalyst for producing polyether polyols |
NO980552D0 (en) * | 1998-02-09 | 1998-02-09 | Borealis As | Catalyst component and catalyst for (co) polymerization of ethylene, and process for preparing such |
US6211048B1 (en) * | 1998-12-21 | 2001-04-03 | United Microelectronics Corp. | Method of reducing salicide lateral growth |
AU2001255735A1 (en) | 2000-04-28 | 2001-11-12 | Synuthane International, Inc. | Double metal cyanide catalysts containing polyglycol ether complexing agents |
ATE279463T1 (en) * | 2000-11-22 | 2004-10-15 | Basf Ag | METHOD FOR PROCESSING POLYETHERAL CARBONS |
KR100418058B1 (en) * | 2001-04-18 | 2004-02-14 | 에스케이씨 주식회사 | Catalyst of double metal cyanide complex for polyol manufacturing |
DE10142747A1 (en) | 2001-08-31 | 2003-03-20 | Bayer Ag | Double metal cyanide catalysts for the production of polyether polyols |
US6797665B2 (en) | 2002-05-10 | 2004-09-28 | Bayer Antwerpen | Double-metal cyanide catalysts for preparing polyether polyols |
US6696383B1 (en) * | 2002-09-20 | 2004-02-24 | Bayer Polymers Llc | Double-metal cyanide catalysts which can be used to prepare polyols and the processes related thereto |
CN103429638B (en) | 2010-12-20 | 2016-06-22 | 拜耳知识产权有限责任公司 | The preparation method of polyether polyol |
US9562134B2 (en) | 2013-03-12 | 2017-02-07 | Covestro Llc | Catalyst for the production of polyols having lower amounts of high molecular weight tail |
EP4093539B1 (en) | 2020-01-21 | 2023-10-04 | Covestro Deutschland AG | Method for the production of double metal cyanide catalysts |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5032671A (en) * | 1990-09-04 | 1991-07-16 | Arco Chemical Technology, Inc. | Preparation of lactone polymers using double metal cyanide catalysts |
US5470813A (en) * | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5714428A (en) * | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
Family Cites Families (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3278457A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3427256A (en) * | 1963-02-14 | 1969-02-11 | Gen Tire & Rubber Co | Double metal cyanide complex compounds |
GB1063525A (en) * | 1963-02-14 | 1967-03-30 | Gen Tire & Rubber Co | Organic cyclic oxide polymers, their preparation and tires prepared therefrom |
US3278458A (en) * | 1963-02-14 | 1966-10-11 | Gen Tire & Rubber Co | Method of making a polyether using a double metal cyanide complex compound |
US3442876A (en) * | 1966-02-16 | 1969-05-06 | Gen Tire & Rubber Co | Novel rubbery polyoxyalkylene copolymers |
GB1225803A (en) * | 1967-06-02 | 1971-03-24 | ||
US3900518A (en) * | 1967-10-20 | 1975-08-19 | Gen Tire & Rubber Co | Hydroxyl or thiol terminated telomeric ethers |
US3829505A (en) * | 1970-02-24 | 1974-08-13 | Gen Tire & Rubber Co | Polyethers and method for making the same |
US3941849A (en) * | 1972-07-07 | 1976-03-02 | The General Tire & Rubber Company | Polyethers and method for making the same |
AU551979B2 (en) * | 1982-03-31 | 1986-05-15 | Shell Internationale Research Maatschappij B.V. | Epoxy polymerisation catalysts |
AU552988B2 (en) * | 1982-03-31 | 1986-06-26 | Shell Internationale Research Maatschappij B.V. | Polymerizing epoxides and catalyst suspensions for this |
JP2995568B2 (en) * | 1989-05-09 | 1999-12-27 | 旭硝子株式会社 | Manufacture of polyalkylene oxide derivative |
JP3097854B2 (en) * | 1989-05-12 | 2000-10-10 | 旭硝子株式会社 | Method for producing polyurethanes |
JPH03128930A (en) * | 1989-10-16 | 1991-05-31 | Asahi Glass Co Ltd | Production of polyether compound |
US5158922A (en) * | 1992-02-04 | 1992-10-27 | Arco Chemical Technology, L.P. | Process for preparing metal cyanide complex catalyst |
US5482908A (en) * | 1994-09-08 | 1996-01-09 | Arco Chemical Technology, L.P. | Highly active double metal cyanide catalysts |
US5545601A (en) * | 1995-08-22 | 1996-08-13 | Arco Chemical Technology, L.P. | Polyether-containing double metal cyanide catalysts |
-
1998
- 1998-05-18 US US09/080,780 patent/US6013596A/en not_active Expired - Fee Related
-
1999
- 1999-05-07 HU HU0102318A patent/HUP0102318A3/en unknown
- 1999-05-07 CA CA002332599A patent/CA2332599A1/en not_active Abandoned
- 1999-05-07 ES ES99924904T patent/ES2214855T3/en not_active Expired - Lifetime
- 1999-05-07 PT PT99924904T patent/PT1094895E/en unknown
- 1999-05-07 BR BR9910605-1A patent/BR9910605A/en not_active Application Discontinuation
- 1999-05-07 DE DE69914603T patent/DE69914603T2/en not_active Expired - Fee Related
- 1999-05-07 WO PCT/EP1999/003147 patent/WO1999059719A1/en active IP Right Grant
- 1999-05-07 AU AU41401/99A patent/AU4140199A/en not_active Abandoned
- 1999-05-07 JP JP2000549376A patent/JP2002515517A/en active Pending
- 1999-05-07 ID IDW20002379A patent/ID26834A/en unknown
- 1999-05-07 EP EP99924904A patent/EP1094895B1/en not_active Expired - Lifetime
- 1999-05-07 CN CN99808800A patent/CN1121273C/en not_active Expired - Fee Related
- 1999-05-07 KR KR1020007012912A patent/KR100568064B1/en not_active IP Right Cessation
- 1999-05-13 AR ARP990102277A patent/AR018606A1/en unknown
- 1999-05-17 TW TW088107966A patent/TW460324B/en not_active IP Right Cessation
-
2002
- 2002-02-21 HK HK02101287.8A patent/HK1039910B/en not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5032671A (en) * | 1990-09-04 | 1991-07-16 | Arco Chemical Technology, Inc. | Preparation of lactone polymers using double metal cyanide catalysts |
US5470813A (en) * | 1993-11-23 | 1995-11-28 | Arco Chemical Technology, L.P. | Double metal cyanide complex catalysts |
US5714428A (en) * | 1996-10-16 | 1998-02-03 | Arco Chemical Technology, L.P. | Double metal cyanide catalysts containing functionalized polymers |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
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US6953765B2 (en) | 2001-05-07 | 2005-10-11 | Bayer Aktiengesellschaft | Double metal cyanide catalysts for preparing polyether polyols |
EP1256596A1 (en) * | 2001-05-07 | 2002-11-13 | Bayer Aktiengesellschaft | Double metal cyanide catalysts for the production of polyetherpolyols |
CN1325165C (en) * | 2002-05-17 | 2007-07-11 | 中国石化集团金陵石油化工有限责任公司 | Process for continuously preparing double metal cyanide complex catalyst |
EP1469024A2 (en) | 2003-04-16 | 2004-10-20 | tesa AG | Polyurethane based pressure sensitive adhesive |
US7091300B2 (en) | 2003-04-16 | 2006-08-15 | Tesa Aktiengesellschaft | Polyurethane PSA for sensitive surfaces |
US7160976B2 (en) | 2003-04-16 | 2007-01-09 | Tesa Aktiengesellschaft | Polyurethane PSA |
US7175898B2 (en) | 2003-04-16 | 2007-02-13 | Tesa Aktiengesellschaft | Reusable elastic adhesive sheet redetachable without residue or damage |
US7495059B2 (en) | 2006-04-28 | 2009-02-24 | Tesa Ag | Removable polyurethane PSA |
US8268922B2 (en) | 2006-07-19 | 2012-09-18 | Tesa Se | Pressure-sensitive adhesive from a resin-modified polyurethene |
EP2119735A1 (en) | 2008-05-13 | 2009-11-18 | tesa SE | Hot melt method for the preparation of a chemically cross-linked polyurethane film |
DE102008023252A1 (en) | 2008-05-13 | 2009-11-19 | Tesa Se | Hotmelt process for producing a chemically crosslinked polyurethane film |
US8580909B2 (en) | 2008-05-13 | 2013-11-12 | Tesa Se | Hotmelt process for producing a chemically crosslinked polyurethane film |
WO2010094585A1 (en) | 2009-02-20 | 2010-08-26 | Tesa Se | Pressure-sensitive adhesive mass |
DE102009009757A1 (en) | 2009-02-20 | 2010-08-26 | Tesa Se | PSA |
DE102009046657A1 (en) | 2009-11-12 | 2011-05-19 | Tesa Se | Pressure-sensitive adhesive based on polyurethane |
EP2325220A1 (en) | 2009-11-12 | 2011-05-25 | tesa SE | Pressure sensitive adhesive agent on polyurethane basis |
US10357588B2 (en) | 2012-05-29 | 2019-07-23 | 3M Innovative Properties Company | Absorbent article comprising polymeric foam and intermediates |
US11351286B2 (en) | 2012-05-29 | 2022-06-07 | 3M Innovative Properties Company | Absorbent article comprising polymeric foam and intermediates |
Also Published As
Publication number | Publication date |
---|---|
TW460324B (en) | 2001-10-21 |
EP1094895B1 (en) | 2004-02-04 |
CN1309587A (en) | 2001-08-22 |
DE69914603D1 (en) | 2004-03-11 |
CN1121273C (en) | 2003-09-17 |
HUP0102318A3 (en) | 2002-06-28 |
US6013596A (en) | 2000-01-11 |
HK1039910B (en) | 2004-07-16 |
EP1094895A1 (en) | 2001-05-02 |
BR9910605A (en) | 2001-01-16 |
PT1094895E (en) | 2004-05-31 |
CA2332599A1 (en) | 1999-11-25 |
KR20010052360A (en) | 2001-06-25 |
AU4140199A (en) | 1999-12-06 |
DE69914603T2 (en) | 2005-02-03 |
HK1039910A1 (en) | 2002-05-17 |
JP2002515517A (en) | 2002-05-28 |
KR100568064B1 (en) | 2006-04-07 |
AR018606A1 (en) | 2001-11-28 |
ID26834A (en) | 2001-02-15 |
HUP0102318A2 (en) | 2001-10-28 |
ES2214855T3 (en) | 2004-09-16 |
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