The method of obtaining dual metallocyanide catalysts

 

(57) Abstract:

The invention relates to methods of producing double metallocyanide (D) catalysts for the polymerization of epoxy compounds. Described is a method of obtaining essentially non-crystalline double metallocyanide (DMC) catalysts with enhanced activity and improved characteristics. The method includes the interaction of the aqueous solution of metal salt with an aqueous solution of a metal cyanide in the presence of organic complexing agent, thus prepared aqueous solution of metal salt and regulate its alkalinity so that it ranged from 0.2 to 2.0 wt.% in terms of the metal oxide relative to the amount of metal salt. Technical result: the properties of the polyol, for example viscosity and unsaturation, improve when appropriate regulation alkalinity mentioned metal salt used to produce DC catalysts. The method allows manufacturers of catalyst in the full use of the advantages of essentially non-crystalline DM catalysts even in the case of use for the preparation of the catalyst is relatively inexpensive metal salts of technical purity. 2 C. and 12 C.p. f-crystals, 3 tab is pushed metallocyanide (DMC) catalysts and methods for their preparation. In particular, the present invention relates to a method for obtaining essentially non-crystalline DMC catalysts of improved quality through regulation alkali metal salt used to produce the above-mentioned catalyst.

Background of the invention

Double metallocyanide complexes are well known as catalysts for the polymerization of epoxy compounds. Mentioned active catalysts allow to obtain the polyether polyols having a low degree of unsaturation compared with similar polyols obtained by using the basic (KOH) catalysis. The above catalysts can be used to produce a variety of polymer products, including polyethers, polyesters and simple and complex polyether polyols. The above-mentioned polyols can be used to obtain a polyurethane coating materials, elastomers, sealants, foams and adhesives.

DMC catalysts usually get by reaction of aqueous solutions of salts of metals and cyanides of metals with the formation of DMC compound. In the process of obtaining the above-mentioned catalysts include organic complexing agent is a low nobrazumi agent necessary to ensure favorable activity of the catalyst. Obtaining a typical DMC catalysts is described, for example, in U.S. patents 3427256, 3829505 and 5158922.

Within a few decades to get polyepoxides used DMC catalysts having a relatively high degree of crystallinity. The most common catalyst include organic complexing agent (usually glyme), water, salt of the metal with a slight excess (usually zinc chloride) and DMC compound. The activity of polymerization of epoxy compounds, surpassing the activity, provide commercial standard (KOH) catalyst, was considered sufficient. Later began to understand that successful commercialization polyols obtained using DMC catalysts, the value could be more active catalysts.

Recent improvements of technology for DMC catalysts allowed to obtain catalysts with exceptionally high activity for polymerization of epoxy compounds. For example, in U.S. patent 5470813 describes essentially amorphous or non-crystalline catalysts with much higher activity compared with the activity of the previous DMC catalysts. In approximately the agent of low molecular weight from about 5 to about 80 wt.% polyether, for example polyoxypropyleneglycol (see U.S. patent 5482908 and 5545601). Recently was given a description of DMC catalysts, which include functionalized polymer, which is not a simple polyester (simultaneously considering the application 08/731495). In General, the DMC catalysts having high activity, are essentially non-crystalline, as evidenced by powder x-ray that do not have many sharp lines. The above catalysts have a high activity level, which allows their use in very low concentrations, which are often low enough to eliminate any need for removal of the above-mentioned catalyst from the polyol. In EP-A-0755716 disclosed dual metallocyanide (DMC) complex catalyst having a high activity, which unlike other DMC catalysts having high activity and which is essentially crystalline, includes DMC compound, an organic complexing agent and metal salt, where the said catalyst contains less than about 0.2 mol mentioned metal salt per mole of DMC compound.

Even the best of izvest activity. Along with this the necessary catalysts, providing polianovich products with lower viscosity, low unsaturation and fewer tail polianovich fractions of high molecular weight.

In the field of technology relating to the receipt of DMC catalysts, no mention of the influence of the alkaline metal salt. The information presented in the open literature, suggest the possibility of using metal salt or solution of a metal salt of any of purity, regardless of whether the ultimate purpose of obtaining traditional DMC catalyst (for example, as in U.S. patent 5158922) or newer non-crystalline varieties, which are more active. In fact, however, the alkalinity of the metal salt makes the difference, in particular, in the case where the purpose is to obtain essentially non-crystalline DMC catalyst. In that case, when to get, essentially non-crystalline DMC catalysts are relatively inexpensive metal salts of technical purity (for example, zinc chloride technical grade), the activity often decreases and polyols obtained by the above-mentioned catalysts, the ima is high molecular weight. As a consequence, eroded some of the benefits of using non-crystalline DMC catalyst.

Therefore, the improved method of obtaining DMC catalysts. The above-mentioned method in the preferred embodiment, should provide essentially non-crystalline DMC catalysts having high activity. The catalysts obtained by the above method, have, in the preferred embodiment, to provide polyether polyols with a low degree of unsaturation and low viscosity. In the ideal case, the above method would obtain catalysts having a sufficiently high activity for use in very low concentrations, in the preferred case in concentrations low enough to eliminate the need to remove them from the above-mentioned polyol. The above-mentioned method in the preferred embodiment, would be the catalyst manufacturers the ability to use the full advantages of essentially non-crystalline DMC catalysts even in the case of use in the manufacture of the above-mentioned catalyst inexpensive metal salts of technical purity.

A summary of the dual metallocyanide catalyst. The above method involves the reaction of aqueous solutions of metal salt and metal cyanide in the presence of organic complexing agent method is effective for obtaining the above-mentioned catalyst. The said solution of metal salt used in the above-mentioned method, has an alkalinity in the range from about 0.2 to about 2.0 wt.% the metal oxide based on the amount of metal salt.

The authors of the present invention surprisingly found that the alkalinity of solution used metal salt plays a significant role, in particular, in the case of obtaining essentially non-crystalline DMC catalyst. While in the field of technology relating to the receipt of DMC catalysts, no mention of the influence of the alkaline metal salt, we found that the activity of the catalyst and important properties of polyols, such as viscosity and unsaturation, are improved in the case when the alkalinity of the solution of metal salt is properly regulated. The above method corresponding to the present invention allows all interested in getting essentially non-crystalline DMC catalysts having a high activity, the full extent of the catalyst is obtained using relatively inexpensive metal salts of technical purity.

Detailed description of the invention

In the process corresponding to the present invention, aqueous solutions of metal salt and metal cyanide react in the presence of organic complexing agent with the formation of essentially non-crystalline double metallocyanide (DMC) catalyst.

Mentioned salt of the metal in the preferred embodiment, is water-soluble and has the General formula M(X)nwhere M is chosen from the group composed of Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III). In a more preferred embodiment, M is chosen from the group composed of Zn(II), Fe(II), Co(II) and Ni(II). In the above formula X in the preferred embodiment represents an anion selected from the group which includes a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate, n has a value from 1 to 3, which satisfies the valence state of M. examples of suitable metal salts include, but not limited to, zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetone, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt is zinc chloride.

An important aspect of the present invention is an alkaline metal salt used in the above-mentioned method. Regulation alkali metal salt is key to increasing the activity of the catalyst and improve the physical properties of the polyol. In the above method corresponding to the present invention, the alkalinity of aqueous solutions of metal salt is in the range from about 0.2 to about 2.0 wt.% the metal oxide based on the amount of metal salt. For example, if the metal salt is zinc chloride (which is traditionally used in obtaining hexacyanocobaltate zinc), the alkalinity of an aqueous solution of zinc chloride used in the above-mentioned way, is from about 0.2 to about 2.0 wt.% the zinc oxide based on the amount of zinc chloride in the above-mentioned solution. A more preferred range for the above-mentioned metal salt is from about 0.3 to about 1.0 wt.% the metal oxide; the most preferred is the range from about 0.4 to about 0.9 wt.% the metal oxide.

Alkalinity mentioned metal salt often depends on the source mentioned salt. Preferred d is particularly when large-scale receipt of the catalyst, because they are relatively cheap. In the composition of salts of metals of technical purity, however, often consists of acidic impurities and aqueous solutions of these salts can have very low alkalinity (less than 0.2 wt.% the metal oxide). For example, the alkalinity of the solutions of zinc chloride technical grade, typically ranges from about 0 to about 0.3 wt.% the zinc oxide. We found that in the case of salts of metals having a relatively low alkalinity, to obtain essentially non-crystalline DMC catalysts, the catalysts have reduced activity, and polyols obtained by the above-mentioned catalysts are less desirable physical properties.

In the case of salts of metals of technical purity in the above method corresponding to the present invention, surprisingly, we found that, generally, there is a need to add grounds to the aforementioned aqueous solution in order to bring the alkalinity to a level within the range of from about 0.2 to about 2.0 wt.% the metal oxide. The number of suitable bases include compounds that are being dome base, for example, a metal oxide, alkali metal hydroxide or carbonate of an alkali metal or organic base, such as amine. The following example shows one way to determine alkalinity.

The above-mentioned metal cyanide in a preferred embodiment, is water-soluble and has the General formula (Y)aM'(CN)b(A)cwhere M' is chosen from the group which consists of Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V). In a more preferred embodiment, M' is chosen from the group composed of Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). In the composition of the above-mentioned metal cyanide may include one or more of these metals. In the above formula Y - ion of an alkali metal or alkali earth metal ion. And anion chosen from the group composed of a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate, carboxylate, and nitrate. As a and b are integers greater than or equal to 1; the sum of charges a, b and C balances the charge of M'. Among the suitable cyanide metals include, but not limited to, potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium, hexas are hexacyanocobaltate alkali metals.

Examples of dual metallocyanide compounds which can be obtained in a way consistent with the present invention, include, for example, zinc hexacyanocobaltate (III), zinc hexacyanoferrate (III), zinc hexacyanoferrate (II), Nickel (II) hexacyanoferrate (II), cobalt (II) hexacyanocobaltate (III), etc. Additional examples of suitable double metallocyanide compounds listed in U.S. patent 5158922, the description of which is included in the present description by reference. Most preferred is zinc hexacyanocobaltate.

Part of DMC catalysts obtained by the method corresponding to the present invention includes an organic complexing agent. Mentioned complexing agent generally should be relatively soluble in water. The number of suitable complexing agents are well known in the art, for example, described in U.S. patent 5158922. Mentioned complexing agent is added either in the process of receiving, either directly after deposition of the above-mentioned catalyst. Usually, excess complexing agent. Preferred complexing eventplex double metallocyanide connection. The number of suitable complexing agents include, but not limited to, alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Among the preferred complexing agents are water-soluble aliphatic alcohols, which are selected from the group which includes ethanol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol and tert-butyl alcohol. Most preferred is tert-butyl alcohol.

The catalysts obtained by using a method corresponding to the present invention are essentially non-crystalline. The phrase "essentially non-crystalline" refers to catalysts with no clearly defined crystalline structure or characterized essentially by the absence of sharp lines in the x-ray powder diffraction pattern of the above-mentioned composition. X-ray powder diffraction pattern of traditional catalysts, including hexacyanocobaltate zinc and glyme (for example, catalysts described in U.S. patent 5158922), contains many sharp lines, indicating the high crystallinity of the above-mentioned catalysis of the high degree of crystallinity (and devoid of activity for polymerization of epoxy compounds). In contrast, the catalysts obtained by the method corresponding to the present invention are essentially non-crystalline.

Describes how to obtain several kinds, essentially non-crystalline DMC catalysts having high activity. The method corresponding to the present invention includes the use of a solution of a metal salt having an alkalinity in the range of from about 0.2 to about 2.0 wt.% the metal oxide based on the amount of metal salt in one of these procedures for obtaining essentially non-crystalline DMC catalyst. For example, in U.S. patent 5470813, the description of which is included in the present description by reference, illustrates a method of obtaining essentially non-crystalline DMC compounds using t-butyl alcohol as the preferred complexing agent. In addition, in the U.S. patents 5482908 and 5545601 describes, essentially non-crystalline DMC catalysts having a high activity, which, along with the organic complexing agent is a low molecular weight, is from about 5 to about 80 wt.% polyether, for example polyoxypropyleneglycol.

Preferred functionalityand polymers have the General structure

< / BR>
where R' is hydrogen, -COOH or C1-C5alkyl group, And one or more functional groups selected from the group comprising-OH, -NH2, -OTHER, -NR2, -SH, -SR, -COR, -CN, -C1, -Br, -C6H4-IT, -WITH THE6H4- (CH3)2HE, -CONH2, -CONHR, -CO-NR2, -OR, -NO2

Optional referred functionalized polymer includes a repeating structural unit derived from defunctionalizing vinyl monomer, such as olefin or diene, such as ethylene, propylene, butylene, butadiene, isoprene, styrene, etc., provided that the said polymer or its salt have relatively good solubility in water or mixtures of water and organic solvent miscible with water.

The number of suitable functionalized polymers include, for example, poly(acrylamide), a copolymer of polyacrylamide and acrylic acid, poly(acrylic acid), poly(2-acrylamide-2-methyl-1-propanesulfonic acid), copolymer of acrylic and maleic acid, poly(Acrylonitrile), poly(alkylacrylate)s, poly(alkylmethacrylamide)s, poly(vinylethylene ether), poly(vinylethylene ether), poly(vinyl acetate), poly(vinyl alcohol), poly(N-vinyl pyrrolidone), the copolymer poly(N-vinylpyrrolidone and acrylic acid, poly(N, N-dimethylacrylamide), poly(vinylethylene), poly(4-vinylphenol), the Wai salt poly(vinylsulfonate), etc.

Suitable functionalityand polymers include polyethers. Catalysts, including simple polyester are disclosed in U.S. patents 5482908 and 5545601, the description of which is incorporated into this description by reference. In one preferred method, the corresponding present invention, the aforementioned functionalized polymer is polyetherpolyols.

In other preferred catalysts obtained by the method corresponding to the present invention, the aforementioned functionalized polymer selected from the group comprising polyesters, polycarbonates, polymers oxazoline, polyalkylimide, copolymers of maleic acid and maleic anhydride, hydroxyethyl cellulose, starches and Polyacetals. Consequently, the said functionalized polymer can be, for example, poly(etilenglikolevye), poly(dipropyleneglycol), poly(1,6-hexaniacinate), poly(2-ethyl-2-oxazoline), copolymer has polyvinylbutyral, vinyl alcohol and vinyl acetate, etc, as well as their salts.

In the catalyst composition obtained in the mentioned manner consistent with the present invention, the optional include from about 2 to about 80 wt.% in lane is the version in the composition of the above-mentioned catalysts is from about 5 to about 70 wt.% the above-mentioned polymer; most preferred is the range from about 10 to about 60 wt.%. You can significantly improve the activity of the catalyst is necessary, at least about 2 wt.% the above-mentioned polymer as compared with the catalyst, obtained in the absence of the above-mentioned polymer. The catalysts, which include more than about 80 wt.% the above-mentioned polymer, are generally more active, and their selection is often difficult.

The molecular weight referred functionalized polymer may vary within a very wide range. In a preferred embodiment, srednekislye molecular weight is in the range from approximately 300 to approximately 500000; a more preferred range is from about 500 to about 50000.

Essentially non-crystalline catalysts disclosed in this invention, in the preferred embodiment, are powders or pastes. Preferred pasty catalysts corresponding to the present invention include from about 10 to about 60 wt.% double metallocyanide compounds, from about 40 to about 90 wt. % organizescooperation catalysts, relevant to the present invention, at least about 90% of the particles included in the composition of the catalyst have a size approximately less than 10 microns, according to the light scattering in dispersion, of the above-mentioned catalyst particles in polyetherpolyols. Full description pasty catalysts and methods for their preparation are presented in the application 08/588751, which is currently "vydatnou"; the description of the aforementioned application is incorporated into this description by reference.

The catalysts obtained by the method corresponding to the present invention have unique infrared spectra, resulting from the use of metal salts with relatively high alkalinity. The above-mentioned catalysts in the preferred embodiment, have a specific peak in the range of from about 640 cm-1to approximately 645 cm-1("642 cm-1peak"), with normalized spectral absorption capacity in the range of from about 0.2 to about 2; a more preferred range mentioned normalized absorbance ranges from approximately 0.3 to approximately 0.8. Under the "normalized spectral absorption capacity" us units the content of cyanide metal in the catalyst samples. In the case of a catalyst comprising hexacyanocobaltate zinc, this means a correction for different levels of cobalt in the catalyst samples. In General, the intensity of the mentioned 642 cm-1peak increases with increasing the alkalinity of the above-mentioned metal salt solution used to obtain the above-mentioned catalyst. The following example explains how the measured absorption capacity mentioned 642 cm-1maximum.

In a typical method of obtaining the above-mentioned catalyst initially receive an aqueous solution of metal salt (e.g. zinc chloride). The alkalinity of the above-mentioned metal salt solution is brought to a value in the range of from about 0.2 to about 2.0 wt.% the metal oxide based on the amount of metal salt, using the base if necessary. Next, a solution of metal salt with corrected alkalinity unite and include reaction with an aqueous solution of cyanide of metal (for example, hexacyanocobaltate potassium) in the presence of organic complexing agent (for example, tert-butyl alcohol) with efficient stirring to obtain a suspension of the catalyst. Uogcc reaction of the metal salt and metal cyanide, which is a double metallocyanide connection. There is also an excessive amount of metal salt, water, an organic complexing agent and any functionalized polymer; some part of each of them are included in the structure of the catalyst.

Mentioned reactive substances together with any required temperature. The above-mentioned catalyst in the preferred embodiment, receive at a temperature ranging from about room temperature up to approximately 80o; a more preferred range is from about 35 to about 60oC.

Mentioned organic complexing agent and the optional functionalized polymer can be included in any or both of an aqueous solution of salt or added to the above suspension of the catalyst immediately after the deposition of the DMC compound. Preference is usually given prior to mixing the aforementioned complexing agent with either or both of the aqueous solutions before combining the reacting substances. If, instead, mentioned complexing agent is added to the mentioned draft of the catalyst, in this case the reactions the mi to obtain the most active forms of the above-mentioned catalyst. Preference is usually given to adding the aforementioned functionalized polymer after deposition of the DMC compound. After that, the above-mentioned catalyst, as a rule, isolated from the suspension of catalyst in any appropriate way, for example by filtration, centrifugation, decantation, etc.,

Selected solid catalyst in a preferred embodiment, washed with an aqueous solution containing an additional amount of organic complexing agent and/or an additional amount of functionalized polymer. After washing the above-mentioned catalyst him in a preferred embodiment, generally dried under vacuum until such time as the said catalyst reaches a constant weight. Suitable methods of washing and selection of the above-mentioned catalyst is described in U.S. patent 5482908.

The above method corresponding to the present invention represents a significant advantage. First, due to the regulation of the alkali metal salt mentioned method provides the possibility of obtaining essentially non-crystalline DMC catalysts having high activity, even with an inexpensive metal salts technical Chi the DMC catalyst may deteriorate in the case if the alkalinity of the used solution of metal salt is not regulated. By adjusting the alkalinity in the range from about 0.2 to about 2.0 wt. % metal oxide, a high catalyst activity can be maintained even in case of using cheap sources of metal salt. By maintaining high activity of the catalysts obtained in a way consistent with the present invention, suitable even in very low concentrations, often low enough to eliminate the need to remove them from the obtained polyol.

Secondly, the quality of the polyols obtained by using the above catalyst, a higher use to obtain the above-mentioned catalyst method corresponding to the present invention. Compared with polyols derived from salts of metals having alkalinity outside the above range, the polyols corresponding to the present invention have a lower viscosity, a narrower distribution of molecular masses, a lower degree of unsaturation and reduced levels of paleologou tail fractions of high molecular weight. Low viscosity and a narrow distribution of molecular weight of pic is enable to improve the content of filler. In addition, the polyols with a narrow distribution of molecular weight and low degree of unsaturation provide polyurethanes with improved physical properties. And finally, lower levels of polianovich tail fractions of high molecular weight can reduce or eliminate problems associated with the destruction of the foam cells.

The following examples are only illustrative of the present invention. Those skilled in the art is evident in numerous ways, corresponding to the spirit of the present invention and within the volume defined by the points of the attached claims.

AN EXAMPLE OF A

Determination of alkalinity of aqueous solutions of zinc chloride

The alkalinity of aqueous solutions of zinc chloride is determined by potentiometric titration with a 0.1 N aqueous solution of hydrochloric acid set titer as follows.

The titer aqueous solution of Hcl (approximately 0,1 N) is determined by potentiometric titration accurately weighed sample (about 0.15 g) dry Tris(hydroxymethyl)aminomethane (TAM) in distilled water (80 ml). Konecne(0,12114 volume of Hcl (ml).

Samples of zinc chloride are analyzed as follows. The sample dissolved in distilled water to obtain approximately 8.5 wt.% solution of chloride of zinc. The above sample is titrated with a 0.1 N aqueous solution of Hcl prescribed title. The volume of the titrated solution required to reach the equivalence point is determined graphical way.

Alkalinity (expressed in wt.% ZnO) is calculated as follows:

ZnO=(VN4,0685100)/(W% ZnCl2)

where V is the volume of Hcl (ml) required to reach the equivalence point, N is the normality of the above-mentioned solution of Hcl, W - weight of the above-mentioned sample of zinc chloride (in grams) and percent ZnCl2- the percentage by weight of zinc chloride in the original sample.

THE EXAMPLE IN

Determination of the absorbance of infrared 642 cm1the peak of the catalyst, which is used hexacyanocobaltate zinc 8 wt.% the solution of catalyst, which is used hexacyanocobaltate zinc, powder potassium bromide contribute scattering in the time domain, where spektroskopiya Raman scattering Fourier transform using a detector having a working range, as the Oia number of samples= 2; Apodization: triangular; zero fill factor: 2.

After this, use a clean powder CVG as a source of background spectrum, calculates the spectrum of a solution of Kubelka-Munch. The height of the 642 cm-1peak detect or graphics, or computer macro as follows: to conduct a tangent line connecting the base points of the spectrum at 663 cm-1and 559 cm-1. To spend the second line from the maximum peak at 642 cm-1(plus or minus 4 cm-1the resolution of the registration) of the said tangent line. The length of the mentioned second line measured in units of the measured absorbance (A) or converted into units of the measured absorbance (A).

Normalized spectral absorption capacity (A*), i.e., the spectral absorption capacity adjusted for the content of cobalt in the catalyst, which is used hexacyanocobaltate zinc, is expressed as follows:

A*=100A/8%

For example, the catalyst, which consists of 9.0 wt.% cobalt and measured spectral absorption capacity (A) which is equal 0,26, has normaltown is Getting hexacyanocobaltate zinc using zinc chloride different alkalinity and receiving polyetherdiols, having a molecular weight of 8000, with the help of the mentioned catalysts

To obtain a catalyst (hexacyanocobaltate zinc) in General adhere to the method described in U.S. patent 5482908. Organic complexing agent is tert-butyl alcohol. As the polyester component in the composition of the above-mentioned catalyst is approximately 20 wt. % polyoxypropylene (molecular weight 1000). Alkalinity mentioned of zinc chloride used to produce each of the catalyst is changed as shown in table 1, or by using different sources of chloride of zinc, or by adding zinc oxide in an aqueous solution of zinc chloride to bring the alkalinity to the desired values.

Preparative method for example 7

A solution of zinc chloride

50% solution of zinc chloride is prepared by adding in parts 175 g technical chloride of zinc to 175 g of ice deionized water so as to minimize the possible impact of atmospheric CO2. The solution obzharivayut, then add 1.5 g of zinc oxide and stirred the mixture at 55oC for 105 min for complete dissolution of the oxide. Before using rastle, equipped with a mechanical stirrer, thermocouple and mounting rubber membrane, load 152 g of a 50% aqueous solution of zinc chloride prepared in the above stage, 200 g of deionized water and 39 g of tert. -butyl alcohol. The flask contents are heated to 50oWith under stirring. Prepare a second solution containing 7.4 g hexacyanocobaltate of potassium in 100 g of deionized water. The solution hexacyanocobaltate potassium is added to a solution of zinc chloride for one hour with a syringe. After complete addition, continue stirring for another 60 min at 50oC. Prepare a third solution containing 7.9 g of polyoxypropylene with a molecular weight of 1000, 27,1 g of tert.-butyl alcohol and 14.9 g of water, and add it to the mass in the flask at the end of the 60-minute period. Mix the contents of the flask for another 3 minutes and separate the solids by filtration. The precipitate from the filter again suspended in the reaction vessel with 156 g of a mixture of tert.-butyl alcohol with deionized water (70:30 wt.h.). The suspension is stirred for 60 min at 50oC. is Added to a suspension of 2.0 g of polyoxypropylene with a molecular weight of 1000 and continue stirring for another 3 minusinsi stirred for 60 min at 50oC. and Then added to a suspension of 1.0 g of polyoxypropylene with a molecular weight of 1000 and continue mixing for another 3 minutes the Mixture is filtered and the precipitate is dried overnight in a vacuum drying Cabinet at a temperature of 40-50oC.

This General methodology used in the other examples presented in table 1, except that the installation of alkalinity using zinc oxide is not produced, and the reaction was carried out in a larger scale installation with a capacity of 200 gallons - 0.75 m3). To achieve the target values of alkalinity used a mixture of solutions of zinc chloride, obtained from the suppliers (table. 1).

Each catalyst is used to obtain polyoxypropylene (molecular weight 8000) as follows: to a reactor with a volume of 2 gallons (7,571 liters) make polypropylenglycol starter (molecular weight 750, 618 g) and hexacyanocobaltate zinc (0.16 g); said reactor is blown dry with nitrogen. Referred to the stirred mixture is heated to a temperature of 130oWith minor depression. Add the propylene oxide (72 g) and activation of the catalyst was checked by a rapid decrease in pressure. Pay an additional amount of propylene oxide (5810 g) Sri temperature 130oC for 1 h Residual amount of propylene oxide is removed from the reactor under vacuum. The resulting polyol is cooled and drained. In table. 2 presents the results of determination of the infrared spectrum, the degree of unsaturation and a viscosity polyols obtained with each catalyst.

EXAMPLES 9-10 and COMPARATIVE EXAMPLE 11

Getting hexacyanocobaltate zinc using zinc chloride different alkalinity and receiving polyetherdiol having a molecular weight of 8000, with the help of the mentioned catalysts

Complex catalyst hexacyanocobaltate zinc/tert-butyl alcohol is prepared as follows. In a round bottom flask, equipped with a mechanical stirrer, additional funnel and a thermometer, make distilled water (302 g), hexacyanocobaltate potassium (7,4 g) and tert-butyl alcohol (39 g). The resulting mixture was stirred to dissolve all of the potassium salt. The resulting solution is heated to a temperature of 30oC. To the above mixed solution was added 50 wt.% aqueous solution of zinc chloride (152 g). Alkalinity chloride zinc used for each catalyst for change, as shown in table 2, or by using different sources of chlorine is to the required values. Stirring is continued for 30 minutes at a temperature of 30oC. the resulting white suspension is filtered under positive pressure of 30 lb/inch2(2,109 kg/cm2). A portion of the filter pressey cakes (8.0 g) resuspension by vigorous stirring in a solution of tert-Botafogo alcohol (110 g) and water (60 g). After suspending all solids in the above-mentioned washing solution, the stirring is continued for 30 minutes the mixture is filtered, as described earlier. Filter pressnow cake in full resuspension 99.5% tert-butyl alcohol (144 g) and was isolated as described earlier. The resulting filter pressnow cake is dried at a temperature of 45oWith overnight under vacuum. The resulting catalyst is used, as described in the preceding examples to obtain polyoxypropylene (molecular weight 8000). Properties diols (molecular weight 8000) are given in table. 3.

The above examples are illustrative only; the scope of the present invention is defined by the claims.

1. The method of obtaining virtually non-crystalline double metallocyanide (D) catalyst for the lia in the presence of organic complexing agent, characterized in that the prepared aqueous solution of metal salt and regulate its alkalinity so that it ranged from 0.2 to 2.0 wt.% in terms of the metal oxide relative to the amount of metal salt.

2. The method according to p. 1, characterized in that the said metal salt is zinc chloride.

3. The method according to p. 1, characterized in that the said (LCA) catalyst is hexacyanocobaltate zinc.

4. The method according to p. 1, characterized in that the said organic complexing agent is tert-butyl alcohol.

5. The method according to p. 1, characterized in that said catalyst comprises from 2 to 80 wt.% functionalized polymer.

6. The method according to p. 5, wherein the functionalized polymer is polyetherpolyols.

7. The method according to p. 1, characterized in that the said metal salt has an alkalinity in the range of 0.3 to 1.0 wt.% in terms of the metal oxide relative to the amount of metal salt.

8. The method according to p. 1, characterized in that the said metal salt has an alkalinity in the range from 0.4 to 0.9 wt. % in terms of metal oxide relative to the amount of metal salt.

9. The method according to any of the previous is (b) identifying the importance of alkalinity of this water solution in the range of 0.2 to 2.0 wt.% in terms of the metal oxide relative to the amount of metal salt.

10. The method according to p. 9, characterized in that the alkalinity is adjusted by adding base to the aqueous solution in stage (b).

11. The method according to any of the preceding paragraphs, characterized in that the catalyst comprises from 2 to 8.0 wt.% functionalized polymer.

12. The method according to p. 2, characterized in that the zinc chloride has an alkalinity in the range of 0.3 to 1.0 wt.% in terms of zinc oxide with respect to the amount of zinc chloride.

13. The catalyst obtained by the method according to any of the preceding paragraphs, having a spectral absorption ability in the infrared range 640-645 cm-1from 0.2 to 2, and the measured absorption capacity normalized to the amendment on the cyanide content of metal in the catalyst samples.

14. The catalyst p. 13, wherein the normalized absorption ability in the infrared range 640-645 cm-1ranges from 0.3 to 0.8.

 

Same patents:

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

The invention relates to a double metallocyanide catalysts suitable for the polymerization of epoxy compounds

The invention relates to a method of obtaining polyoxyethyleneglycol with extremely low content of transition metal ions by catalyzed double metallocyanide complex polyoxyalkylene corresponding hydrogen initiator in the presence of 15 or less parts per million (ppm) double metallocyanide complex catalyst

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

The invention relates to the production of polyoxyethyleneglycol, in particular to a method for polytetrahydrofuran or complex monoamino monocarboxylic acids with 1 to 10 carbon atoms

The invention relates to chromium catalysts and methods for their preparation used for oxidation of organic compounds, hydrogen and carbon monoxide in the gas emissions from industrial productions

The invention relates to chromium catalysts and methods for their preparation used for oxidation of organic compounds, hydrogen and carbon monoxide in the gas emissions from industrial productions

The invention relates to a method for producing a catalyst for polymerization of olefins and method of polymerization of olefin monomers with its use

The invention relates to catalysts for the reductive alkylation of 4-aminodiphenylamine acetone and hydrogen to N-isopropyl-N-phenyl-p-phenylenediamine (diafana OP, IPPD) and methods for their preparation

The invention relates to catalysts for the reductive alkylation of 4-aminodiphenylamine acetone and hydrogen to N-isopropyl-N-phenyl-p-phenylenediamine (diafana OP, IPPD) and methods for their preparation

The invention relates to a catalyst, the method of its preparation and process for the catalytic purification method from the carbon monoxide-enriched hydrogen gas mixtures

The invention relates to a catalyst used for the synthesis of mercaptan from methanol and hydrogen sulfide, as well as to a method for producing this catalyst

The invention relates to methods of producing the catalyst for purification of exhaust gases of internal combustion engines

The invention relates to the field of catalysts

The invention relates to a catalyst for the synthesis of methylmercaptan and method thereof

The invention relates to an improved dual metallocyanide (DMC) catalysts and methods for their preparation

FIELD: polymerization catalysts.

SUBSTANCE: invention provides double metal cyanide catalysts for production of polyetherpolyols via polyaddition of alkylene oxides to starting compounds containing active hydrogen atoms, which catalysts contain double metal cyanide compounds, organic complex ligands, and α,β-unsaturated carboxylic acid esters other than above-mentioned ligands.

EFFECT: considerably increased catalytic activity.

6 cl, 16 ex

FIELD: polymerization catalysts.

SUBSTANCE: catalyst is composed of double metal cyanide compound, organic ligand, and two complexing components other than precedent organic ligand and selected from group including: polyethers and polyesters, glycidyl ethers, esters from carboxylic acids and polyatomic alcohols, bile acids, bile acid salts, bile acid esters, bile acid amides, and phosphorus compounds, provided that selected complexing components belong to different classes.

EFFECT: substantially increased catalytic activity.

5 cl, 1 tbl, 16 ex

Up!