TW572781B - Metal catalysts complexed with sulfone or sulfoxide compounds - Google Patents

Description

572781 Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau, Ministry of Economic Affairs 5. Description of the Invention (y This invention is a metal catalyst for the polymerization of alkylene oxides. The alkylene oxides such as ethylene oxide, propylene oxide, and 1,2-ring Oxybutane is polymerized to form a wide variety of polyether products. For example, polyether polyols are produced in large quantities for polyurethane applications. Other polyethers are used in many applications, and many other applications. These polyethers The preparation is generally based on the polymerization of one or more alkylene oxides in the presence of a starting compound and a basic metal catalyst. The starting compound is mainly one or more hydroxyl groups, primary or secondary amines, carboxy groups or hydrogen sulfur. The material of the radical group. The function of the initiator is to set the nominal function of the product polyether (the number of hydroxyl groups / molecules), and in some cases to incorporate some required functional groups into the product. Until recently 'The choice of catalyst is to test metal gas oxides such as nitrogen oxide bells. The advantages of potassium nitrogen oxides are inexpensive, suitable for the polymerization of different alkylene oxides, and easy to recover from the product polyether. However, for different grades, Metal hydroxide catalyzes the isomerization of propylene oxide to form allyl ethanol. Allyl ethanol plays the role of a single functional initiator during the polymerization of propylene oxide. Therefore, when potassium hydroxide is used to catalyze propylene oxide During the polymerization, the product contains allyl ethanol-starting, single-functional impurities. As the molecular weight of the product polyether increases, the isomerization reaction becomes more common. Therefore, when using KOH as a catalyst, it has equivalent weight. Poly (propylene oxide) products with a molecular weight of about 800 or more are liable to produce a large amount of single functional impurities. This reduces the average functionality and broadens the molecular weight distribution of the product. Recently, it is also known as a catalyst for double metal cyanide (DMC) Commercially used as a catalyst for the polymerization of alkylene oxides. DMC catalysts are described in, for example, U.S. Patent Nos. 3,278,457, 3,278,458, 3,278,459, 3,404,109, 3 , 427, 256, 3, 427, 334, 3, 427,335 and 5, 470, 813, among many others. These DMC catalysts usually do not significantly promote the isomerization of propylene oxide when activated, Compared to hydrogen Catalytic polymerization of potassium chloride, which can prepare polytransfers with saturated parameters & and higher molecular weight. Recently, the developer-4- This paper size is applicable to China National Standard (CNS) A4 (210 X 297) Mm) ---------------- ^ ---- Order --------- line (read the phonetic on the back first? Matters and then fill out this page) 572781 A7 B7 V. Description of the invention (2) The focus has been almost completely focused on zinc hexacyanocobaltate, which is combined with the special complexing agent t-butanol. / As described in US Patent No. 5,470,813, in some cases The lack of DMC catalysts tends to require an induction period of nearly 丨 hours to many hours before increasing its activity. A small amount of polymerization occurs during this induction period, but it is accompanied by a strong exothermic reaction. For some effects, it is desirable to reduce the induction period and provide less exothermic response. Therefore, it is desirable to provide a living catalyst which exhibits a short induction period before the rapid polymerization of alkylene oxides during the polymerization of the alkylene oxides and more exothermic control during the rapid polymerization of the polymers. In one aspect, the present invention is a metal cyanide catalyst complexed with an organic fluorene (R5_s (〇) 2_R5) or a fluorene compound (R5S (0) ~ R5). -On the other hand, the present invention improves a method for polymerizing an epoxide compound in the presence of a catalyst. In this modification, the catalyst is a metal cyanide catalyst that is mixed with an organic amidine or sulfonium compound. It has been found that the metal cyanide catalytic complex of the present invention has very good activity as an epoxide polymerization catalyst. Especially during polymerization, compared with the more commonly used hexacyanosulfonate zinc / t-butanol / poly (propylene oxide) complex, this catalyst often shows a significant reduction in the intellectual property of the Ministry of Economic Affairs. Bureau employee consumer cooperative prints the guidance period. In addition to this, when rapid oxyalkylene polymerization begins, a small or easily controlled exotherm is usually seen. "Metal cyanide catalysts refer to catalysts that have no formula

Mb [M (CN) r (X) t] c [M2 (X) 6] d · ZL · aHkO · nM3xAy where M is a metal ion that forms an insoluble precipitate with the Ml (CN) r (x) t group And at least one water-soluble salt; M1 and M2 are the same or different transition metal ions;

572781 Printed by A7 B7___, Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the Invention (3) ^ Each X represents a group different from cyanide, which is coordinated with mM2 ion; __ Anionic water salts composed of anions A, where M3 and M are the same or different; L represents the organic fluorene or sulfonium compound; b and c are positive numbers, which together with d reflect _ static electricity Neutral complex; d is zero or a positive number; X and y are numbers that reflect an electrostatic neutral salt; r is from 4 to 6; t is 0 to 2; and a and η 疋 positive numbers (which It can be a fraction), which respectively indicate the relative amount of water hindering or sub-maple compounds and M'Ay. The X groups need not be the same in any M (X) 6. The molecular ratio of c: d is advantageous from about 100: 0 to 20:80, preferably from about 100: 0 to 50:50, and even more preferably from about 100: 0 To 80:20. Similarly, a mixture of two or more different groups can be used. M and M3 are preferably metal ions composed of the following groups: Zn + 2, Fe + 2, co + 2, Ni + 2 ^ Mo + 4 ^ Mo + 6 > Al + 3 ^ V + 4 ^ V + 5 > Sr + 2 ^ W + 4 ^ W + 6 'Mn + 2 ^ Sn + 2 ^ Sn4 ^ Pb + 2 ^

Cu + 2, La + 3 and Cr + 3. M and M3 are more preferably Zn + 2, Fe + 2, Co + 2, Ni + 2, La + 3, and Cr + 3. M is optimally Zn + 2. M1 and M2 are preferably Fe + 3, Fe + 2, Co + 3, Co + 2, Cr + 2, Cr + 3, Mn + 2, Mn + 3, Ir + 3,

Ni2, Rh + 3, RU + 2, v + 4, and V + 5. Among the foregoing items, a state having a trivalent cationic oxide is preferable. Co + 3 and Fe + 3 are equally preferred and Co + 3 is optimal. μ1 and M2 can be the same or different. Preferred X groups include anions such as halides (especially gas ions), hydroxides, sulfates, carbonates, oxalates, thiocyanates, isocyanates, isothiocyanates, Cm carboxylates. -6-This paper size is in accordance with China National Standard (CNS) A4 (210 x 297 mm) (tl read the note on the back first? Matters and then fill out this page)-Install ---------- Order --------- Line 572781

Employees' cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs print acid salts and nitrites (), as well as non-charged types such as c0, h20 and No. Particularly preferred χ groups are NO, N (V, and CO. Γ is preferably 5 or 6 ′, most preferably 6 and t is preferably 0 or 1, and most preferably 0. Most cases are r + t is equal to 6. Suitable anions A include compounds such as gas and molybdenum, nitrites, sulfates, carbonate nitrides, oxalates, thiocyanates, isocyanates, isothiocyanates, persulfates Gas acid salts and Ci-4f acid gas ions are particularly preferred. \ / YL / is not an organic rhenium or rhenium compound. Suitable rhenium compounds are generally based on the chemical formulas r5a4-r5, where each R5 is unsubstituted Or inertly substituted alkynyl, cycloalkynyl, sphenyl, or together with another R5 to form a mysterious-portion of a sulfur atom containing a maple group (one_2 one). Suitable marriage compounds are generally It is represented by the chemical formula r5_s (〇) -R5, where the parent p is as just described. In the above, "inertly substituted" refers to a group without a substituent, which is related to the metal cyanide and its precursor (As described below) or poor reaction with oxygen or dilute interference with oxidative lean polymerization. These inert substituents include Hydroxy, hydroxyl, nitrile, acid, acetone, ammonium, sulfide, additional fluorene or sulfenyl groups. Each R5 is preferably unsubstituted, and preferably if it is not an alkyl group For example, 疋 and another R5- form a part of a ring structure containing a hindering or sub-radical group. Basically the preferred R5 group is a 1-4 carbon atom alkynyl group. The sulfur atom of the group forms a 5- to 8-membered ring. More preferred compounds are water-soluble, including, for example, dimethylmethylene (DMSO), tetramethylene fluorene, 2, 2-fluorenyl diethanol, Dimethyl maple and cyclobutyl maple (tetramethylene maple). DMS0 is the best compound because it exhibits a particularly short induction period at the beginning of the propylene oxide polymerization. Thallium or thallium compounds are generally as well as Better individual mismatch factor. By dissolving or dispersing the water-soluble metal cyanide in an inert solvent such as water or A-7 for the first time- This paper size applies the Chinese National Standard (CNS) A4 specification. --· III-(Read the notes on the back before filling out this page) ---- II --------- line · 572781 Bureau of Intellectual Property, Ministry of Economic Affairs Printed by employee consumer cooperatives A7 _B7_ V. Description of the invention (5) Alcohols, catalytic complexes are easy to manufacture. Mixtures of two or more metal cyanides can be used. Water-soluble metal cyanides are generally of chemical formula, where β is Hydrogen or a metal which forms a water-soluble salt with [M ^ CNMXh] ions, u and ν are integers, which results in an electrically neutral compound and M1, X, r, and t are as described above. B is preferably Samarium, sodium, or potassium. It is convenient for the formation of B to be hydrogen in the compound, which is passed through a cation exchange resin in an aqueous solution consistent with alkali metal salts. In addition, the dispersion of the solution or metal rat compound may also include A compound having a Bu [M2 (x) 6] v structure, where M2 is a transition metal, and x, B, u, and V are as before. M2 can be the same or different from M1. The solution or dispersion is then combined with a solution produced with an aqueous water-soluble metal ion solution in the presence of a rhenium or rhenium compound. Metal salts are represented by the general chemical formula MxAy, where M, A, X and y are as previously defined. Particularly suitable metal salts include zinc functional compounds, zinc hydroxide, zinc sulfate, zinc carbonate, zinc cyanide, zinc cyanide, zinc oxalate, zinc thiocyanate, zinc isocyanate, and G-4 carboxylic acid. Salt zinc and zinc nitrite. Gasified zinc is optimal. The mixing temperature is not very important, and the starting material is dispersed in the solution towel or sufficiently dispersed until the mixing is complete. The temperature of the inert solvent is about 10 to boiling, especially 15 to 40. 〇 is the most suitable. Can be quickly stirred for mixing. New dense mixing techniques such as those described in U.S. Patent No. 5,47,813 may be used, or they are not required. In Shendian of the catalyst, use at least enough metal salts to provide equivalent metal ions (M) per metal cyanide ion (mXcnmxx) plus M2 (X) 6 ions per equivalent if used. Catalysts that have been found to be generally more active are those prepared using excess metal salts. These excess metals are believed to be present in the catalyst complex as a team or "salt." This excess metal salt can be added in the Shen Dian step, such as by adding to about 3 equivalents of metal salt, preferably about 1] to 3, more preferably about 15 to 2 · 5 metal paper size applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public love) ---------- 1T ---- ----- line i ^ w. (Please read the precautions on the back before filling this page) 572781 A7 V. Description of the invention (6) Salt equivalents, each metal cyanide ion combined equivalent plus any! ^ (幻6 ions. Another method of adding excess metal salts is the separation step following the precipitation step, which will be explained in detail below. The metal ions of the excess salts may be different from the metal ions used in the precipitation catalyst. Adding a metal cyanide solution Metal salts are preferred and mixing is also preferred. Stirring is best continued after mixing is complete. Metal cyanide catalysts precipitate and form dispersions in suspensions. Catalyst complexes can be obtained by mixing solutions or Disperse metal cyanide in solution or in tincture or Asian maple Disperse the metal cyanide to achieve precipitation in the presence of the compound. The method to achieve the precipitation is to add the rhenium or safranine compound to the solution or disperse the metal cyanide before the solution is mixed. In turn, both starting solutions or dispersions can be mixed with The osmium compound is added at the same time. The third method is to mix the starting solution or disperse directly after the maple or osmium compound is added. After the initial amount of the osmium or osmium compound is added, the mixture is generally stirred for several minutes to make the desired Formation of catalyst complexes and precipitation. The formation of catalyst compound precipitates can then be recovered by appropriate techniques such as filtration or centrifugation. Preferably, the catalyst complexes are subsequently multiplied with water, maple or sub-maple compounds, polyethers. Alcohol (when used) or some of the combinations herein are rinsed one or more times. It is convenient to reslurry the catalyst by stirring in the liquid for a few minutes and filtering. Basically the rinse is preferably continued until At least all unwanted ions, especially alkali metals and ions are removed from the complex. It has been found that if the catalyst is applied to a molecular weight of about 300-4000 Ether polyols are sometimes easy to prepare catalysts. When polyether polyols are used in the catalyst complex, they can be added with rhenium or sulfonium compounds, or subsequently -9- This paper is applicable to Chinese National Standards (CNS) A4 specification (210 X 297 mm) (green first read the precautions on the back before filling out this page) ^ ---- l · —.— I ^ --------- Consumption by Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the cooperative 8 27 7 5 Five employees of the Intellectual Property Bureau of the Ministry of Economic Affairs printed A7 by the consumer cooperative --- ~ -----, invention description (7) Rinse the compound one or more times. Finally, the drying of the catalyst complex is convenient The preferred method is to remove excess water and volatile organic compounds under vacuum and appropriate heating (such as about 50-60γ). Drying is preferably continued until the catalyst complex reaches a constant weight. One way to form a side complex is to use a stoichiometrically calculated amount of a metal_aqueous solution in the initial mixing and Shen Dian steps, which contains only the stoichiometrically calculated amount of the metal cyanide bound amount (and any M2⑴6 compound used). After the initial silence, the precipitate was washed with water to remove unwanted particles. Then Shen Jiya a small amount of water-containing impurities, additional gold and other difficult and sub-maple compounds. The metal salts used may be the same or different metal salts used to form the precipitate. The amount of solution added is preferably the amount absorbed by the precipitate. The amount of the mainly used solution is from about 0.5 to 2, preferably from 0.8 to 1.5, and more preferably from 1 to 15 l / g of separated sediment. Advantageous amounts of metal salts added to this solution are about 9 to 30, preferably 11 to 25 parts per 100 parts of the separated sediment, by weight. It is advantageous that the weight ratio of the rhenium or osmium compound to water is about 90:10 to 10:90, and preferably about 70:30 to 30:70. If desired, ' polyether polyols may be included in the solution. The formed catalyst complex is dried and used without further treatment, or may be rinsed with water first, although it is preferred not to rinse with an amidine compound, a rhenium compound or a polyether polyol. The catalyst complex of the present invention is used to polymerize oxidized women to make polyethers. Generally, the method includes mixing a catalytic amount of a catalyst with an alkylene oxide in the case of polymerization, and allowing the polymerization to continue until the substantially provided alkylene oxide is depleted. The catalyst concentration is selected to depolymerize and dilute at the required rate or within the required time. Generally, the appropriate amount of catalyst is from about 5 to 10,000 parts by weight of metal cyanide catalyst per million parts by weight (PPm) of combined alkylene oxide, and if starting materials are present Paper size applies to China National Standard (CNS) A4 (210 X 297 g) (Please read the precautions on the back before filling this page) --------- II · -------- Line · 572781 A7 B7 Five printed by the Consumers' Cooperative of the Ministry of Economics and Intellectual Property of the Ministry of Economic Affairs (8) and comonomer. On the same basis, more preferably from about 25 to 1,000, and even more preferably from about 25 to 卯 = degree 疋 from about 10 '. Mesh: = sub-quantity to inform the desired functional group (oxygen group / The number of molecules or the required terminal functional group, the starting compound previously described is preferably mixed with the catalyst complex at the beginning of the reaction. Suitable starting compounds include-ethanol such as methanol, ethanol, n-propanol, Isopropanol, butanol, isobutanol, butanol, octanol, stearyl alcohol, 3-butane small hydrocarbyl, 3-butane + hydrocarbyl, proparyl alcohol, 2-methyl-2-propanol, 2 monomethyl I butane_2 —nicotyl, 2-methyl-3-butane-2 —hydrocarbyl, 3-butane_hydrocarbyl, butene + hydrocarbyl. Suitable monoethanol starting compounds include tooth alcohol Such as 2-chloroethanol, 2-bromoethanol, 2-gas + propanol, 3-gas-propanol, 3-mo + propanol " _ digas-2-propanol, and propane_2-methyl_ 2_propanol is as good as Shisha ethanol, ah_ethanol, vinegar-ethanol, cyanoethanol, and other inert substituted ethanol. Suitable polyethanol starting materials include ethylene glycol, propylene glycol, glycerol, I, 〖—Trimethylhydrocarbyl propane,- Trimethylhydrocarbylethane, 1 > 2,3-trichlorooxybutane isopentaerythritol, xylitol, arabinitol, mannitol, U-dimethyl-3-hexyne-2, 5-di Hydrocarbyl, 2, 4, 7,9-tetramethyl-5, 5-decyne, 4,7-diyl: vegetable sugar, glucose alcohol, glucosinolates such as methylglucosyl and glucosinolate. Low molecular weight polyether Polyols, especially those having a surface weight of about 35G or less, and more preferably about 125-250, are also useful starting compounds. Epoxides that can be polymerized by the catalyst complex of the present invention between alkylene oxides Ethylene fired, propylene oxide fired, 1 > 2-butene oxide fired, styrene oxide, and its mixture. Different alkylene oxides can be polymerized to produce the alkyl hydrocarbons.丨 · Install l · --- Order '---------_ (Please read the precautions on the back before filling this page) -11-This paper size applies to China National Standard (CNS) A4 (210 X 297 Public Love) 572781 A7 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (9) Block copolymer. More preferably, the alkylene oxide is propylene oxide or propylene oxide and cyclic A mixture of ethylene oxide and / or butylene oxide. Particularly preferred is propylene oxide alone or at least mixed with 50% by weight of propylene oxide and greater than about 50% by weight of oxyethylene. V Xu ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ Copolymerizes with alkylene oxide in the presence of a catalyst complex of an alcohol. This comonomer includes oxetane, such as US Patent Nos. 3,278,457 and 3,404. No. 109, and anhydrides such as those described in U.S. Patent Nos. 5,145,883 and 3,538,043, which respectively produce polyethers and polyols or polyether polyols. Hydroxyl alkanoates such as lactic acid, 3-hydrobutyrate, 3-hydrovalerate (and its dimers), lactones, and carbon dioxide are other examples of suitable monomers. Catalyst polymerization. The reaction is mainly carried out at a temperature of about 25 to 150 ° C, preferably 80 to 130 ° C. A convenient polymerization technique involves mixing the catalyst complex with the starting material and pressurizing the reactor with an alkylene oxide. After a short induction period, the polymerization proceeded with the reduction in reactor pressure as an indicator. Once the polymerization begins, the added alkylene oxide is conveniently added to the reaction furnace as needed until the added alkylene oxide is sufficient to produce the required equivalent weight of polymer. Another convenient polymerization technique is a continuous process. In this continuous process, the activated starter / catalyst mixture is continuously fed into a continuous reaction furnace such as a continuous stirred tank reactor (CSTR) or a reaction tube. The added oxidant (\ dilute is introduced into the reaction furnace and the product is to be continuously removed. The catalyst of the present invention is particularly useful for the production of propylene oxide homopolymer with propylene oxide and ethylene oxide greater than 15 weight percent ( According to all -12- this paper applies Chinese National Standard (CNS) A4 specifications (21G X 297 public love) ----- ---: --------- install ----- ^- --Order --------- line. (Please read the precautions on the back before filling out this page) 572781 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Invention Description (10) Single Unit) Random co-polymers. Polymers of particular interest have a hydroxyl equivalent weight from about 800, preferably from 10,000 to 5,000, preferably from 4000 to 2500, and even more preferably to 2500. And the unsaturation does not exceed 0.02 milliequivalents / gram, preferably not more than 0.001 milliequivalents / gram. Depending on the molecular weight, equivalent weight, functionality, and the presence of any functional group, the polymerization product can have a variety of Uses. The polyether mannitol produced in this way can be used as a material for the production of polyurethane Us. Each ether can be used as ^ ® ^ ^ Λ ^ Λ H ^ ii : # Fij ΐχ Aminated Poly St starting material All parts and percentages are by weight unless otherwise indicated. Example 1k Catalyst Preparation A solution of potassium hexacyanocobaltate (8.0 g, 0 024 mol) was prepared in 140 ml of distilled water. Add it to 25 Gram (0.18 mol) of zinc oxide dissolved in 40 ml of water. Immediately add a solution of 100 ml of dimethyl sulfoxide (DMSO) in 100 ml of water and mix the resulting mixture. The liquid was formed for 10 minutes. A slurry was formed, which was filtered with a Buchner filter. The collected solid was reslurried in a solution containing 60 ml of water and 140 liters of DMSO, stirred for 10 minutes, and filtered as before. The solid It was slurried in 200 ml of DMSO, allowed to stir for 10 minutes, and then filtered. The solid was dried under vacuum at 50. (: dried for 18 hours. The temperature was raised to 30 grams of 700 molecular weight polyether triol. With 0.2 grams of catalysis from Part A-13- This paper size applies to China Standard (CNS) A4 (210 x 297 mm) (please read the precautions on the back before filling in this page), install ----- ^ ---- tT --------- line · 572781

Agent complexes are older than reaction shots. After the Wei rinse, the mixture and propylene oxide were added to 2 to 10 G C and pressurized to 5 Qpsig. Polymerization began immediately, but no measurable exotherm was seen. While the polymerization is proceeding, propylene oxide is continuously added to the reaction furnace to maintain the pressure from 50 ° to 140 grams of all the oxygen and oxygen. $ 全 投 人 polymerization reaction takes about 3 hours. The degree of unsaturation of the formed polyhydric polyol is 3 meq / g, and the polydispersity is about 1.29. Example 2 A. Preparation of a catalyst A solution of 4.1 g of sodium nitroferricyanide in 50 ml of deionized water was passed through a 25 g macroporous 0-p-vinylbenzene strong acid cation exchange resin (Dowex MSC-1 (Available from The Dow Chemical Company) in hydrogen form. The rinsing solution (containing 0.014 mol H2 [Fe (CN) 5 (N〇) D) was added to another 4.5 g of potassium hexacyanophosphate (0014 mol) and dissolved in 50 ml of deionized Water solution. The mixture was then added to a stirred solution of 25 g of zinc chloride in 40 ml of deionized water. Then immediately added 200 ml of a 50/50 solution of water and DMS0 in a volume ratio. The resulting slurry was The body was homogenized for 10 minutes and then poured into a stirred large beaker. 2,000 liters of water, 2 ml of DMS0, 2 g of a 4000-molecular weight trifunctional poly (propylene oxide) solution were added, followed by stirring for 3 minutes. The body was filtered through a Buchner filter tube to separate the solid. The solid was reslurried in a solution containing 60 ml of water, 140 liters of DMS0, and 2 g of the same poly (propylene oxide). Stir for 10 minutes and filter as previously described. The solid formed was then polymerized in a solution of 200 ml of DMS0 and 1 g of poly (propylene oxide) and stirred for another 10 minutes and filtered. The final product was dried under vacuum at 50 ° C. Paper size applies to China National Standard (CNS) A4 (210 X 297 public love) (Please read first Note on the back, please fill out this page again) One Pack ----- ^ ---- Order --------- Line _ Printed by the Intellectual Property Bureau of the Ministry of Economy Staff Consumer Cooperative 572781 A7 B7 V. Description of the Invention (12) Overnight. B ^ .____ Initial increase in temperature polymerization The treatment of increase in temperature polymerization is as described in Example 1B. After the induction period of 10-15 minutes, the polymerization begins, accompanied by an exotherm at 20 ° C. It is formed The degree of unsaturation of the polyhydric alcohol is 0.09 milliequivalents / gram, and the polydispersity is 1.26. Example 3 A Catalyst Preparation A solution of 25 g of zinc gasified in 40 l of deionized water was added. Mix in a solution of 8.0 g of hexametanoic acid dissolved in 140 ml of water. Stir the mixture for a few seconds. Then add a solution of 20 g of methyl hydrazone in 200 ml of water. Stir the mixture for 10 minutes , Vacuum filtration. The filtered mud was repulped into a solution of 25 g of methyl maple dissolved in 180 ml of water, and 1 g of 450 molecular weight trifunctional poly (propylene oxide) was added. The mixture was stirred for 10 minutes, and then Filter it. The filtered sludge is reslurried and filtered again under the same conditions. The product was dried under vacuum for 85 hours. (: Dried under vacuum for 24 hours. It was then slurried in acetone, centrifuged to recover the solids, and dried at a vacuum of 100 ° C for 18 hours. Polymerization was started in the Parr reaction furnace, mixed with 30 grams A polyether triol with a molecular weight of 700 and a sufficient catalyst based on the weight of the desired product, which is from part A, provides about 1000 ppm. After flushing with nitrogen, the mixture and propylene oxide are heated to 100. (: and pressurized Up to 50 psig. -15- ^ paper size applies home standard 1CNS) A4 size ⑽ x 297 mm) (Please read the precautions on the back before filling this page) Loading ---------- Order- ------- Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 572781 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (13) After about 16 minutes of induction, the aggregation started and was slightly visible Exothermic 5. (:. Continue to add to the reactor while the polymerization is in progress to maintain the pressure at 35 psig to the propylene oxide until all 12] Gu avoids seeing that the propylene oxide has been completely added. The polymerization reaction of fully charged propylene oxide takes about 25 hours The unsaturation of the polymer obtained in one step is 0.002 亳 equivalents / gram. Example 4 A. Preparation of the catalyst A solution of 6.25 g of zinc gaseous dissolved in 10 ml of deionized water was added and mixed with 2 · 0 g of potassium hexacyanocobaltate was dissolved in a solution of 35 ml of water. The mixture was stirred for a few seconds. Then 20 ml of a mixed solution of 50/50 tetramethylene methane and distilled water was added. The mixture was stirred for 10 minutes and filtered. The filtered sludge was reslurried in a solution of 12 ml of methyl hydrazone and 1 g of trifunctional poly (propylene oxide) with a molecular weight of 450 and filtered again. The filtered sludge was then dissolved in acetone and filtered to recover the solid , Dry under vacuum at 85 ° C for 7 hours. B .__ Initial two-temperature polymerization The catalyst from Part A was evaluated for activity as described in Example 3B. After 25 minutes of induction, the polymerization started with slight exotherm. (24.0. Fully put propylene oxide The polymerization reaction of alkane takes about 26 minutes. The unsaturated of the formed polymer is 0.007 meq / g. Example 5 A. Preparation of catalyst A 6.25 g zincate is dissolved in 10 ml deionization Water solution was added and mixed in a solution of 2.0 g of potassium hexacyanocobaltate dissolved in 35 ml of water. Mixing-16- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) jpt ---- (Please read the precautions on the back before filling out this page) ---- tr --------- line · ----- 572781 A7 ''-~ 7 -________ 5 2. Description of the invention (14) Stir for a few seconds. Then add 20 liters of a mixed solution of 50-50 / 22-sulfobiethanol and distilled water in a volume ratio. Stir the mixture for 10 minutes and filter it. A solution of 15 liters of 2,2-sulfofluorenyldiethanol, 10 liters of deionized water, and 2 grams of 450-molecular weight trifunctional poly (propylene oxide) was added, stirred for 10 minutes, and filtered again. Then The filtered sludge was slurried again in 2, 2-sulfofluorenyldiethanol (37.5 liters) and 0.93 g of poly (propylene oxide). The filtered sludge was dissolved in propylene. , Filtered to recover the solid, dried under vacuum at 85 ° C for 18 hours. B. Initially elevated temperature polymerization was evaluated using 0.19 g of catalyst from Part A as described in Example 3 b. Polymerization began immediately. When propylene oxide is polymerized, no measurable exotherm is seen. It takes about 1.03 minutes to fully charge the polymerization reaction of propylene oxide. (Please read the note on the back? 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572781 1¾ Scope No. 89 1 1 3570 Patent Application Application Amendment to Patent Scope Amendment Date: August 1992 1. A metal cyanide catalyst, which is incompatible with organic rhenium compounds, where the metal cyanide catalyst is the following Column general structure to represent ... MbtM ^ CNUX ^^ M ^ d zL · aH20 · nM3xAy where M is a metal ion that forms an insoluble precipitate with the Mi (CN) r (x) t group, and its at least Has a water-soluble salt; M1 and M2 are the same or different transition metal ions; X each represents a group different from cyanide, which is coordinated with a Mi or M2 ion; M3xAy represents a metal ion M3 And an anion A, water-soluble salts, where M3 and M are the same or different; L represents the organic hydrazone compound; b and c are positive numbers, and the same as d reflects an electrostatic neutral complex D is zero or a positive number; X and y are to reflect the number of an electrostatic neutral salt; r is from 4 to 6; t is from 0 to 2; and z, a and η are positive numbers, etc. Indicate the differences between organic hydrazone compounds, water and M3xAy And the organic fluorene is represented by the general chemical structure R5-S (0) rR5, where R5 is an unsubstituted or inertly substituted alkyl group, cycloalkyl group, aromatic group, or The other R5 together forms part of a ring structure containing a sulfur atom containing a fluorene group. -18- VI. ί Please special wu ------ ο 2 · A metal cyanide catalyst, which is in combination with an organic sulfonium compound, wherein the metal cyanide catalyst is represented by the following general structure: MbtM'CCNUX ^ ctM ^ dd · ZL · aH20 · nM3xAy where M is a metal ion, which forms an insoluble precipitate with the m ^ CNMXX group, and it has at least one water-soluble salt; M1 and M2 are the same or different transition metal ions; X Each represents a group different from cyanide, which is coordinated with an M1 or μ2 ion; M3xAy represents a water-soluble salt composed of a metal ion M3 and an anion A, where M3 and M are the same or different L represents the organic interfering compound; b and c are positive numbers, which together with d reflect an electrostatic neutral complex; d is zero or a positive number; X and y are to reflect an electrostatic neutral salt Number; r is from 4 to 6; t is from 0 to 2; and z, a, and n are positive numbers, which respectively indicate the respective related amounts of the organic amidine compound, water, and M3xAy, and the organic sub actinide system Represented by the general chemical formula structure R_S (c >) _ r5 Respective wherein R5 is an unsubstituted or inertly substituted alkyl with a group, the wire ring, an aromatic group, or with another - R5- is formed from a - a part of a ring structure containing a sulfur atom of the alkylene group obstacle. 3. The catalyst according to item i or 2 of the scope of the patent application, wherein each r5 is an alkyl group having 1 carbon atom. 4 · If you apply for a patent butterfly! Or 2 catalyst, in which the rS group and the sulfur of the maple group form -19 · 572781 ---- original ^? To form a 5-8 member ring. 5. The catalyst according to item 1 or 2 of the patent application scope, wherein M and] VI3 are zinc ions, M1 is the starting ion, t is 0, d is 0, A is chloride ion, X is 1 and y is 2. 6. The catalyst according to item 1 or 2 of the scope of patent application, in which] V [and M3 are zinc ions, and M (CN) r (X) t is a hexacyanodianate and nitroferricyanide ion. In the resulting mixture, d is zero, A is chloride ion, X is 1 and y is 2. 7 · —A method of polymerizing an epoxide compound in the presence of a catalyst and a starting compound ', wherein the improvement is that the catalytic system is one as defined in item 1 or 2 of the scope of patent application A metal cyanide catalyst in which the polymerization is performed at a catalyst concentration of from 5 to 10,000 parts by weight (based on the weight per million parts of epoxide) at from 25 to 250 ° C. 8. The method according to item 7 of the patent application, wherein the epoxide compound is propylene oxide or a mixture of propylene oxide and ethylene oxide. 9. The method according to item 8 of the patent application, wherein the product is a polyether polyol having an oxynitride equivalent weight of at least 1,000 and an unsaturated content of less than 0.02 亳 equivalent / gram. -20-