Highly active double metallocyanide catalysts

 

(57) Abstract:

Revealed highly active double metallocyanide (DMC) catalysts. Catalysts include DMC complex, organic complexing agents and from 5 to 80 wt. percent, calculated on the amount of catalyst polyether having srednekamennogo molecular weight less than 500. The above-mentioned catalysts will polimerizuet the propylene oxide with the speed, if the metal is cobalt, more than 1 kg/g With min 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC. the above-Mentioned catalysts are easy to obtain, allow to obtain the polyether polyols with very low degrees of unsaturation. 5 S. and 9 C. p. F.-ly, 1 Il. 2 table.

The present invention relates to a double metallocyanide (DMC) complex catalysts suitable for the polymerization of epoxy compounds. In particular, DMC catalysts corresponding to the present invention, which include a simple polyester, can be easily obtained and have an extremely high activity.

Double metallocyanide (DMC) complexes are well known as catalysts for the polymerization of epoxiconazole, 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 polyether, a complex of the polyester and simple and complex polyether polyols. The above-mentioned polyols can be used in polyurethane coating materials, elastomers, sealants, foams, and adhesive substances.

DMC catalysts usually get by reaction of aqueous solutions of salts of metals and cyanides of metals from sediment DMZ connection. In the process of obtaining catalysts include complexing agents of low molecular weight, usually a simple ether or alcohol. Other known complexing agents include ketones, esters, amides, urea, etc., Cm. for example, the U.S. patents 4477589, 3829505 and 5158922. Traditional preferred complexing agents is glyme (dimethoxyethane), which receive DMC catalysts having activity in the range from 0.1 to 0.5 kg) (propylene oxide)/g of Co (cobalt) per minute at 100 parts per million (ppm) catalyst, calculated on the weight of finished polyether, at 105oC.

Recently, thanks to the inclusion along with organic complexing agents from 5 to 80 wt. % polyether, srednekislye molecular mass of which exceeds 500. The catalysts, which include both organic complexing agents (for example, tert-butyl alcohol), and polyetherpolyols, can promote the polymerization of propylene oxide with a speed of more than 2 kg/g With min 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC. In contrast, the catalyst composed of the polyol, but was absent tert-butyl alcohol, was devoid of activity, at that time, as a catalyst obtained by using only the tert-butyl alcohol, had a lower level of activity. In our initial work has suggested that polyethers having a molecular weight less than 500, and glycols were, in General, unsuitable or produces catalysts possessing a lower level of activity.

The possibility of obtaining very active DMC catalysts using polyethers of low molecular weight would be a valuable acquisition, as polyethers of low molecular weight are often cheaper and more legkostup the service DMC catalysts would provide benefits possessed by the catalysts described in patent '908. For example, they would get the polyether polyols with low unsaturation and are sufficiently active to provide the latest in very low concentrations, preferably in concentrations low enough to eliminate any need for subsequent removal of the above-mentioned catalyst from the polyol.

The present invention offers a solid double metallocyanide (DMC) catalyst for polymerization of epoxy compounds. The composition of the above-mentioned catalyst is DMC compound, an organic complexing agents and from 5 to 80 wt. percent, calculated on the weight of the catalyst, polyether, srednekislye molecular weight is less than 500. The above-mentioned catalyst has a high activity: it promotes polymerization of propylene oxide at a rate greater than 1 kg/d With in a minute, 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC. As mentioned catalyst is so active, it can be used in very low concentrations, which ensures effective elimination of the need to stage the of aiolou with extremely low degrees of unsaturation. The present invention includes methods for obtaining the above-mentioned catalyst.

Drawing the curve of dependence of rate of propylene oxide from time to time during the polymerization reaction with one of the catalysts of the present invention, when the content of the last 50 ppm. The activity of the above catalyst (in the present application is usually expressed as pounds of propylene oxide /gram of cobalt per minute) is determined at the point of maximum steepness of the slope of the above curve.

Double metallocyanide (DMC) compounds used in this invention are the reaction products of water-soluble metal salt and water-soluble metal cyanide. Water-soluble salt of the metal, in the preferred embodiment, 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, is an anion selected from the group which includes a halide, hydroxide, sulfate, carbonate, cyanide, the valence state of M. Suitable metal salts are, however, not limited to, zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, cobalt (II) chloride, cobalt (II) thiocyanate, Nickel (II) formate, Nickel (II) nitrate, and mixtures thereof.

Water-soluble cyanides of the metals used to obtain double metallocyanide compounds, in the preferred embodiment, have 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), lr(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 one of the above-mentioned water-soluble metal cyanide may include one or more of these metals. In the above formula, Y is an ion of an alkali metal or alkali earth metal ion. And ion selected from the group which consists of 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 saradananda (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III), lithium hexacyanocobaltate (III).

Examples of dual metallocyanide compounds which can be used in the present invention include, for example, zinc hexacyanocobaltate (III), zinc hexacyanoferrate (III), Nickel hexacyanoferrate (II), cobalt hexacyanocobaltate (III), etc. Additional examples of suitable double metallocyanide complexes are listed in U.S. patent 5158922, the description of which is included in the present description by reference. Preference is given to zinc to hexacyanocobaltate (III).

The composition of the solid DMC catalysts of the present invention includes an organic complexing agents. Complexing agents, in General, should be relatively soluble in water. The number of suitable complexing agents include complexing agents, well known in the art, for example, described in U.S. patent 5158922. The above-mentioned complexing agents added either in the process of receiving, either directly after deposition of the catalyst. As a rule, use excessive amounts of complexing agents. Predpochtitelnye can form a complex with 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. Particular preference is given to tert-butyl alcohol.

The composition of the solid DMC catalysts of the present invention is from 5 to 80 wt. percent, calculated on the amount of catalyst polyether having srednekamennogo molecular weight of about less than 500. In the preferred composition of the catalyst is from 10 to 70 wt. % polyether; a part of the most preferred catalysts consist of 15 to 60 wt. % polyether. You can significantly improve the activity of the catalyst is necessary, at least about 5 wt. % polyether compared with the catalyst, obtained in the absence of a polyether. The catalysts, which include more than 80 wt. % polyether, activity, in General, not the s, instead of powdered solids.

Polyethers suitable for use in obtaining catalysts of the present invention have srednekislye molecular weight (Mn) of less than 500. The number of suitable polyethers include polyesters obtained by the polymerization of cyclic ethers with opening cycle, and polyepoxide with low molecular weight, polioksidony, polytetrahydrofuran. To obtain polyethers can be used any way catalysis. Part of polyethers may include any necessary end groups, including, for example, hydroxyl groups, amino groups, ester groups, ether groups, etc.

Among the preferred polyethers include polyether polyols having an average of from 1 to 8 hydroxyl functional groups and srednekislye molecular weight in the range from 150 to 500, in a more preferred embodiment, from 200 to 400. They can be obtained by polymerization of epoxides in the presence of an active hydrogen-containing initiators and basic, acid or ORGANOMETALLIC catalysts (including DMC catalysts). Among the suitable polyether polyols include the mixed, ethylenoxy-propenenitrile, the polymers of butilenica, copolymers of butilenica with ethylene oxide and/or propylene oxide, glycols polytetramethylene ether, etc., To the number of suitable polyethers include, for example, tripropyleneglycol, triethylene glycol, tetrapropylene, tetraethylene glycol, onomatology broadcast dipropyleneglycol, onomatology broadcast tripropyleneglycol, monoalkyl and disciline ethers of glycols and polyalkylene glycols, etc., Most preferred are polypropylenglycol and glycols having srednekislye molecular weight in the range from 150 to 500. The author found that double metallocyanide catalyst should include both organic complexing agents, and simple polyester. The inclusion of polyether, in addition to organic complexing agents, significantly increases the activity of the catalyst compared with the activity of the same catalyst, but obtained without the participation of the polyether (see examples 1-5 and comparative example 9). The required organic complexing agents: the catalyst, obtained in the presence of the polyether, but without organic complexing agents, such as tert-butyl alcohol, tactic catalysts, relevant to the present invention, is accomplished by any acceptable means. Simple polyester and organic complexing agents are usually identified and quantified, for example, by using thermogravimetric and mass spectrometric analyses. The number of metals can easily be determined using elemental analysis.

Characteristics of the catalysts of the present invention, can also be determined using x-ray powder diffraction. The above-mentioned catalysts exhibit a broad line centered with the characteristic interplanar distances. For example, the catalyst of zinc hexacyanocobaltate obtained using tert-butyl alcohol and of polyethylene glycol having a molecular weight of 300, has two broad signal centered with an average interplanar distances, accounting for roughly of 5.75 and 4,82 Angstrom, and a somewhat more narrow signal, centered with an average interplanar distance, constituting approximately 3,76 Angstrom. (See table 2). This diffraction pattern is also characterized by the absence of sharp lines corresponding to vysokobarotermicheskogo zinc to hexacyanocobaltate the Present invention includes a method of obtaining a solid DMC catalysts, suitable for polymerization of epoxy compounds. The above method includes obtaining DMC catalyst in the presence of a polyether having srednekamennogo molecular weight less than 500, and in the composition of solid DMC catalyst is from 5 to 80 wt. % polyether.

In General, the above mentioned method is carried out by conducting the reaction in aqueous solution, a metal salt (excess) and the metal cyanide in the presence of a polyether and an organic complexing agents. Use this simple polyester, which ensures obtaining solid DMC catalyst, which comprises from 5 to 80 wt. % mentioned polyether. The catalysts obtained according to the method corresponding to the present invention, have an increased activity towards the polymerization of epoxy compounds compared with similar catalysts, however, received no simple polyester.

In one of the methods of the present invention (illustrated by the following examples 1-5), aqueous solutions of metal salt (e.g. zinc chloride) and cyanide metal (e.g. potassium hexacyanocobaltate) initially react in the presence of organicheskoi catalyst. Salt of the metal used in excess. The above suspension of the catalyst comprises the reaction product of metal salt and metal cyanide, which is a double metallocyanide connection. There is also an excess of metal salt, water and organic complexing agents; part of each of them are included in the structure of the catalyst.

Mentioned organic complexing agents can be included with any or both of aqueous solutions of salts or added to a suspension of the catalyst immediately after deposition DMZ connection. Preference is usually given prior to mixing the complexing agents with either or with both aqueous solutions before combining reactive substances.

Aqueous solutions of metal salt and metal cyanide (or DMC product of the reaction) must be effectively mixed with complexing agents to obtain the most active forms of the above-mentioned catalyst. To ensure effective mixing is used, as a rule, a homogenizer or mixer with a high shear force.

The suspension of the catalyst obtained in the first stage, subsequently mixed with simple polyester having srednekamennogo mania with low shear force if necessary to minimise foaming. In the case of use at this stage is very effective mixing of the above-mentioned mixture may thicken or coagulate, which complicates the selection of the above-mentioned catalyst. In addition, in the above-mentioned catalyst may not be necessary increased activity.

In the third stage solid polimersoderzhashchie the catalyst separated from the above-mentioned suspension of the catalyst. This operation is performed by any acceptable means, such as filtration, centrifugation, etc.

After that, the selected solid polimersoderzhashchie the catalyst is washed with an aqueous solution, which includes additional organic complexing agents. Washing is typically carried out by resuspendable catalyst in an aqueous solution of the organic complexing agents with the next stage of the selection of the catalyst. The specified washing step is used to remove pollutants from the above-mentioned catalyst, such as COP1, which, being undeleted, deprive the catalyst activity. In a preferred embodiment, the amount of organic complexing agent used in the above-mentioned aqueous solution, is the La certain amount of polyether. The amount of polyether to be included in the wash solution is, in the preferred embodiment, approximately from 0.1 wt. % to 8 wt. %. The inclusion of polyether in the washing step generally increases the activity of the catalyst.

Despite the fact that to obtain a catalyst of high activity sufficient there is one washing step, preference is given to more than one washing the above-mentioned catalyst. Subsequent rinsing may be a repetition of the first. In a preferred embodiment, subsequent rinsing is carried out without water, i.e. in the drilling environment include only organic complexing agents or a mixture of organic complexing agents and polyether.

After washing of the catalyst, preference is usually given to drying the latest in vacuum (from 88 to 102 kPa (26 to 30 inches Hg)) to achieve the said catalyst constant weight. The catalyst may be dried at temperatures 40-90oC.

In accordance with the second manner consistent with the present invention, contaminants are removed from the above-mentioned catalyst in the process of its receipt by the method of the farming, through which plexopathies.

First, aqueous solutions of metal salt (excess) and the metal cyanide react in the presence of organic complexing agents in the implementation of effective mixing (as mentioned previously) to obtain a suspension of the catalyst. Secondly, the above mentioned mixture of the catalyst is effectively mixed with the diluent, which comprises an aqueous solution of an additional organic complexing agents. The above-mentioned diluent is used in an amount to provide effective dissolution of contaminants (i.e., excess reactant, KCl, and so on ) in the aqueous phase.

After dilution with water complexing agents, the suspension of catalyst combined with a simple polyester having srednekamennogo molecular weight less than 500. At this stage, as a rule, prefer to apply mixing with low shear force. After this solid polimersoderzhashchie catalyst separated from said suspension using any suitable method (as mentioned previously), including filtration, centrifugation, etc., After selecting the above-mentioned catalyst, in a preferred embodiment, washed with an additional quantity of organizesactivities. This washing step may be carried out without resuspendable solids in the wash solvent. And finally, there are the solid DMC catalyst, which comprises from 5 to 80 wt. % polyether.

The above-mentioned catalysts corresponding to the present invention have significantly higher activity compared with most DMC catalysts previously known in the art. For example, traditional DMC catalysts obtained by using complexing agents of glima without polyether (as described, for example, in U.S. patents 4477589, 3829505 and 5158922), have activity in the range of 0.1-0.5 kg/g With min 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC. In contrast, the above-mentioned catalysts corresponding to the present invention, will polimerizuet the propylene oxide with a speed of more than 1 kg/d With in a minute, 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC. These catalysts have high activity similar to the activity of catalysts I, previously described in U.S. patent 5482908 that use polyethers of higher molecular weight. Previously believed that Pro the inventor has found, what polyethers having a molecular weight less than 500, can actually be used to obtain olefinsoderzhashchikh DMC catalysts with high activity. As examples 1-5 and comparative example 9, the above-mentioned catalysts in accordance with the present invention have the activity exceeds the activity of a complex of zinc hexacyanocobaltate/tert-butyl alcohol, obtained in the absence of a polyether.

The above-mentioned catalysts corresponding to the present invention, active enough to be used in very low concentrations, for example, 25 ppm or less (see example 10 below). With such low levels of catalyst, the said catalyst can often be left in polyetherpolyols the product without exerting a negative influence on the quality of the product. For example, the residual quantity of Zn and Co in the polyol obtained by using the catalyst of zinc hexacyanocobaltate corresponding to the present invention, may be within the specifications for the product (<5 ppm each) before carrying out any cleaning polyol. When the demand of a product of higher purity, removal of the latter from the flock filtering; the above-mentioned catalyst appears to be heterogeneous. Elimination of the need for removal of the catalyst from the polyol is an important advantage, because at the present time in the way for most industrial polyether polyols (obtained, as a rule, using CON) includes the step of removal of the catalyst.

Presented in the following examples serve as a simple illustration of the present invention. Specialists in the art will be apparent, numerous variations within the spirit of the present invention and scope of the attached claims.

Example 1

Getting polimersoderzhashchie DMC catalyst (PEG (polyethylene glycol) -300)

Potassium hexacyanocobaltate (7.5 g) dissolved in distilled water (300 ml) and tert-butyl alcohol (50 ml) in a beaker (Solution 1). In the second beaker dissolve zinc chloride (76 g) in distilled water (76 ml) (Solution 2). In the third beaker is Solution 3: a mixture of distilled water (200 ml), tert-butyl alcohol (2 ml) and polyol (8 g of PEG-300 (polyethylene glycol, molecular weight 300), obtained from Aldrich).

Solution 2 is added to Solution 1 is emisiune. The intensity of mixing is increased to 40% for 10 minutes Homogenizer off. Add a Solution of 3, and the mixture using a magnetic stirrer stirred for 3 minutes. The resulting mixture was filtered under pressure (gauge pressure of 276 kPa (gauge pressure of 40 pounds/inch2)) through the filter 20x10-6m (20 microns).

Solid catalyst resuspending in tert-butyl alcohol (130 ml) and distilled water (56 ml) and homogenized at 40% intensity mixing for 10 minutes Add PEG-300 (2 g) and a magnetic stirrer was stirred for 3 minutes. The resulting mixture was filtered under pressure, as mentioned before. Solid catalyst resuspending in tert-butyl alcohol (185 ml) and homogenized as previously indicated. Add PEG-300 (1 g) and a magnetic stirrer was stirred for 3 minutes. The resulting mixture is filtered under pressure. Obtained on the catalyst filter cake is dried at 60oC in vacuum (102 kPa (30 inches Hg) to a constant mass.

Example 2

Getting polimersoderzhashchie DMC catalyst (PEG-300)

Zinc chloride (75 g) dissolved in distilled water (275 ml) and tert-butyl alcohol (50 ml) for receiving the de (100 ml) (Solution 2). In the third beaker is Solution 3: a mixture of distilled water (50 ml), tert-butyl alcohol (2 ml) and polyol (8 g of PEG-300).

Solution 2 is added to Solution 1 for 30 min at 50oWith stirring using a homogenizer, set at 20% of the intensity of mixing. The intensity of mixing is increased to 40% for 10 minutes Homogenizer off. Add a Solution of 3, and the mixture using a magnetic stirrer stirred for 3 minutes. The resulting mixture was filtered under pressure (gauge pressure of 276 kPa (gauge pressure of 40 pounds/inch2)) through the filter 5x10-6m (5 microns).

Solid catalyst resuspending in tert-butyl alcohol (130 ml) and distilled water (55 ml) and homogenized at 40% intensity mixing for 10 minutes Homogenizer off. Add PEG-300 (2 g) and a magnetic stirrer was stirred for 3 minutes. The resulting mixture was filtered under pressure, as mentioned before. Solid catalyst resuspending in tert-butyl alcohol (185 ml) and homogenized as previously indicated. Add PEG-300 (1 g) and a magnetic stirrer was stirred for 3 minutes. The resulting mixture was filtered polucheniya constant weight.

Example 3

Getting polimersoderzhashchie DMC catalyst (PPG-425)

Repeat the procedure of example 1, except that instead of PEG-300 used PPG-425 (polypropylenglycol, molecular weight 400, received KOH catalysis and catalyst, instead of the 30oTo get at the 50oC. the Resulting catalyst is isolated and dried as described earlier.

Example 4

Getting polimersoderzhashchie DMC catalyst (PPG-425)

In a glass reactor with a volume of 1 gallon (there are 3,785 l) prepare a solution (Solution 1) zinc chloride (252 g), distilled water (924 ml) and tert-butyl alcohol (168 ml). Potassium hexacyanocobaltate of 25.2 g) dissolved in distilled water (336 ml) in a beaker (Solution 2). In another beaker is Solution 3: a mixture of distilled water (160 ml), tert-butyl alcohol (6,7 ml) and polyol (26,9 g PPG-425).

Solution 2 is added to Solution 1 for 1 hour at 50oWith stirring (450 rpm). After complete addition, the stirring speed was increased to 900 rpm for 1 hour in a nitrogen atmosphere at a pressure of 10 pounds/inch2(0,703 kg/cm2). The mixing speed is reduced to 200 rpm Add a Solution of 3, and the mixture is stirred for 3 m is through the filter of 10 x 10-6m (10 microns).

Solid catalyst resuspending in the same reactor in tert-butyl alcohol (437 ml) and distilled water (186 ml) and mixed at 900 rpm for 1 hour. The mixing speed is reduced to 200 rpm Add PPG-425 (6.7 g) and the resulting mixture was stirred at 200 rpm for 3 minutes. The resulting mixture was filtered under pressure, as mentioned before. Solid catalyst resuspending in tert-butyl alcohol (622 ml) and stirred, as mentioned previously. The mixing speed is again reduced to 200 rpm Add PPG-425 (3.4 g) and stirred for 3 minutes. The resulting mixture is filtered under pressure. Obtained on the catalyst filter cake is dried at 60oC in vacuum (102 kPa (30 inches Hg) to a constant mass.

Example 5

Getting polimersoderzhashchie DMC catalyst (nanometrology ether tripropyleneglycol)

Repeat the procedure of example 2, except that instead of PEG-300 used onomatology broadcast tripropyleneglycol (company Aldrich). The resulting catalyst is isolated and dried as described earlier.

Comparative example 6

Getting polimersoderzhashchie DMC katalysator (7.5 g) and PEG-300 (8.0 g) is dissolved in distilled water (300 ml) in a beaker (Solution 1). In the second beaker dissolve zinc chloride (76 g) in distilled water (76 ml) (Solution 2). Solution 2 is added to Solution 1 for 30 min at 30oWith stirring using a homogenizer, set at 20% of the intensity of mixing. The intensity of mixing is increased to 40% for 10 minutes the mixture is filtered under pressure (gauge pressure of 276 kPa (40 lb/in2)) through the filter 5x10-6m (5 microns).

Solid catalyst resuspending in distilled water (200 ml) and homogenized at 40% intensity stirring for 10 minutes the mixture is filtered under pressure, as mentioned before. Obtained on the catalyst filter cake is dried at 60oC in vacuum (102 kPa (30 inches Hg) to a constant mass.

Comparative example 7

Getting polimersoderzhashchie DMC catalyst: PPG-425 polyol; without complexing agents tert-butyl alcohol.

Repeating the process of comparative example 6, except that instead of PEG-300 polyol used PPG-425 polyol. The resulting catalyst is isolated and dried as described earlier.

Comparative example 8

Getting politilogija the chloride (75 g) and PEG-300 (39 g) dissolved in distilled water (275 ml) in a beaker (Solution 1). In the second beaker dissolve potassium hexacyanocobaltate (7.5 g) in distilled water (100 ml) (Solution 2). In the third beaker in distilled water (50 ml) dissolve PEG-300 (8 g) (Solution 3).

Solution 2 is added to Solution 1 for 30 min at 50oWith stirring using a homogenizer, set at 20% of the intensity of mixing. The intensity of mixing is increased to 40% for 10 minutes Homogenizer off. Add a Solution of 3, and the mixture using a magnetic stirrer stirred for 3 minutes. The resulting mixture was filtered under pressure (gauge pressure of 276 kPa (40 lb/in2)) through the filter 5x10-6m (5 microns). Solid catalyst resuspending in distilled water (75 ml) and PEG-300 (75 g) and homogenized at 40% intensity mixing for 10 minutes Homogenizer off. Add PEG-300 (2 g) and a magnetic stirrer was stirred for 3 minutes. The resulting mixture was filtered under pressure, as mentioned before. Obtained on the catalyst filter cake is dried at 60oC in vacuum (102 kPa (30 inches Hg) to a constant mass.

Comparative example 9

Getting DMC catalyst with tert-butyl who stillyoung water (450 ml) in a beaker (Solution 1). Zinc chloride (60 g) dissolved in distilled water (90 ml) in a second beaker (Solution 2). Solutions 1 and 2 are combined using a mixing homogenizer. Directly after mixing, slowly add a mixture of tert-butyl alcohol and water (50/50 volume ratio, 600 ml) and the resulting suspension is homogenized for 10 minutes. The suspension is centrifuged, the liquid portion is decanted. Solids resuspended in a mixture of tert-butyl alcohol and water (70/30 volume ratio, 600 ml) and the resulting mixture is homogenized for 10 minutes, then centrifuged and decanted as described earlier, to highlight the washed solids. Mentioned solids resuspending 100% tert-butyl alcohol (600 ml), the mixture is homogenized for 10 minutes, centrifuged and decanted. The solid catalyst is dried in a vacuum oven (50oWith, 102 kPa (30 inches Hg) to a constant mass.

The results of the elemental, thermogravimetric and mass spectrometric analyses of the solid catalyst: tert-butyl alcohol= a 14.1 wt. percent; (polyol= 0 wt. %).

An example of a

Determination of the activity of the catalyst and synthesis of polyetherpolyols.

Catalysts, receiving is as follows.

In a 1 l reactor with stirring contribute 70 g of polyol-starter (polyoxypropylene, molecular weight 700) and 0,014 g-0,057 g of zinc hexacyanocobaltate/tert-butyl alcohol/polyetherpolyols catalyst (25 to 100 ppm of catalyst in the final polyol as one product, see notes to table. 1). This mixture was intensively stirred and heated to 105oC in vacuum for about 30 minutes to remove residual traces of water. In the reactor add the propylene oxide (PO) (approximately 10-11 g), and the excess pressure in the reactor increased from vacuum to about 28 kPa (4 lb/in2). Soon in the reactor is observed accelerated pressure drop, indicating the activation of the catalyst. After checking the initiation of catalyst in the reactor slowly add the additional amount of propylene oxide (in total, 500 g) to maintain a positive pressure in the reactor at a level of about 69 kPa (gauge pressure of 10 pounds/inch2).

The catalyst is determined at the point of maximum steepness of the slope of the conversion of propylene oxide over time (see curve is represented as an example in the drawing and the rate of polymerization in the table. 1). When you are finished adding Propylenediamine about the conversion of propylene oxide is completed. The said mixture is subjected to evaporation in a vacuum at a temperature of from 60 to 80oC for 0.5 hour to remove from the reactor for any traces of unreacted propylene oxide. The product is cooled and isolated. The said product is of polyoxypropylene having a hydroxyl number of about 30 mg KOH/g (see table. 1).

The example IN

Characterization of the catalyst by x-ray powder diffraction

In table. 2 presents typical results of x-ray diffraction for a number of catalysts (zinc hexacyanocobaltate). X-ray diffraction pattern of comparative examples 6-9 (catalysts obtained in the presence of polyol, but without complexing agents (tert-butyl alcohol)) resemble the diffraction pattern for vysokobarotermicheskogo hydrate zinc hexacyanocobaltate, which was obtained without the polyol or organic complexing agents. All these "catalysts" are devoid of activity towards the polymerization of epoxy compounds.

The catalysts corresponding to the present invention (examples 1-5), obtained in the presence of tert-butyl alcohol, or polyol, demonstrate shirtsthat the catalyst, obtained using tert-butyl alcohol, but without the polyol (comparative example 9). The catalysts of examples 1-5 and comparative example 9 actively polimerizuet the propylene oxide, however, the catalysts prepared using tert-butyl alcohol and polyol (examples 1-5), have a higher activity (see table. 1).

Example 10

Getting polyoxypropylene (molecular weight 8000) with 25 ppm of catalyst

This example shows that the catalysts corresponding to the present invention have sufficient activity, allowing to obtain the polyether polyols with low concentrations of catalyst. This ensures effective elimination of the need for removal of catalyst in many cases, end-use of the polyol.

Using a sample of the catalyst obtained in example 4. In a 1 l reactor with stirring contribute catalyst (0,0166 g, 25 ppm in the finished polyol) and polyoxypropylene (65 g, molecular weight 785) obtained in the traditional way of propylene glycol, KOHN and propylene oxide. The resulting mixture was well stirred and heated to 105oC in vacuum for about 30 minutes to remove residual traces of water. The temperature of the mass is raised to a 14 kPa (gauge pressure of 2 lb/in2). There is an accelerated pressure drop, indicating the activation of the catalyst. After checking the initiation of catalyst into the reactor continuously for 6 hours at a rate of 1.7 g/min add an additional amount of propylene oxide (in total, 600 g). The temperature of the reactor is kept on level 130oC for 30-45 min until reaching a constant pressure, which suggests that the conversion of propylene oxide is completed. The said mixture is subjected to evaporation in a vacuum at a temperature of 60oC for 30 minutes to remove any traces of unreacted propylene oxide. The product is cooled and isolated. The resulting polypropyleneoxide (molecular weight 8000) has a hydroxyl number of 14.9 mg KOH/g, an unsaturation 0,0055 IEC/g and Mw/Mn= l, 22.

The preceding examples are given only as illustrations. Scope of the present invention presents the following claims.

1. Solid double metallocyanide (DMC) catalyst suitable for the polymerization of epoxy compounds and providing for the polymerization of propylene oxide (PO) with the speed, if the metal is cobalt, more than 1 kg/g With min 100 ppm CA who concludes: (a) double metallocyanide connection; (b) an organic complexing agents; and (c) from 5 to 80 wt. percent, calculated on the amount of catalyst, polyether, characterized in that the polyester has srednekamennogo molecular weight less than 500.

2. The catalyst p. 1, characterized in that the double metallocyanide compound is zinc hexacyanocobaltate.

3. Catalyst under item 1 or 2, characterized in that the organic complexing agents is tert-butyl alcohol.

4. Catalyst according to any of the preceding paragraphs. 1-3, characterized in that the above simple polyester is polyetherpolyols with srednekamennogo molecular weight in the range from 150 to 500.

5. The catalyst p. 1, characterized in that it includes: (a) connection of zinc hexacyanocobaltate; (b) tert-butyl alcohol; and (c) from 10 to 70 wt. percent, calculated on the amount of catalyst, polyetherpolyols with srednekamennogo molecular weight in the range from 150 to 500, and the above-mentioned catalyst provides the polymerization of propylene oxide with speed, if the metal is cobalt, more than 2 kg/g With min 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oC.

7. Catalyst under item 5 or 6, characterized in that it has an x-ray diffraction pattern (interplanar distance, in angstroms): 5,75 (wide band), 4,82 (wide band), 3,76, and has no detectable signals corresponding vysokobarotermicheskogo zinc to hexacyanocobaltate if (interplanar distances in angstroms): 5,07, 3,59, 2,54, 2,28.

8. A method of producing a catalyst suitable for the polymerization of epoxy compounds and providing for the polymerization of propylene oxide (PO) with the speed, if the metal is cobalt, more than 1 kg/g With min 100 ppm of catalyst, calculated on the weight of finished polyether, at 105oSince, moreover, the aforementioned method includes obtaining a solid double metallocyanide (DMC) catalyst in the presence of organic complexing agents and from 5 to 80 wt. percent, calculated on the amount of catalyst, polyether, characterized in that the polyester has srednekamennogo molecular weight less than 500.

9. A method of obtaining a solid double metallocyanide (DMC) catalyst suitable for the polymerization of epoxy compounds and providing Poltu at 100 ppm catalyst, in recalculation on weight of finished polyether, at 105oSince, moreover, the said method comprises: (a) obtaining a suspension of the catalyst by reaction of aqueous solutions of metal salt (excess) and the metal cyanide in the presence of organic complexing agents using the effective mixing; (b) combining the suspension of the catalyst with a simple polyester; (c) the allocation of solid polimersoderzhashchie catalyst from the suspension; (d) washing the solid polimersoderzhashchie catalyst aqueous solution, which includes an additional amount of organic complexing agents; and (e) the allocation of solid DMC catalyst, which comprises from 5 to 80 wt. percent, calculated on the amount of solid DMC catalyst, polyether, characterized in that the polyester has srednekamennogo molecular weight less than 500.

10. A method of obtaining a solid double metallocyanide (DMC) catalyst suitable for the polymerization of epoxy compounds and providing for the polymerization of propylene oxide (PO) with the speed, if the metal is cobalt, more than 1 kg/g With min 100 ppm of catalyst, calculated on the weight of the finished simple is the your response aqueous solutions of metal salt (excess) and the metal cyanide in the presence of organic complexing agents using the effective mixing; (b) effective mixing a suspension of the catalyst diluent, which comprises an aqueous solution of an additional organic complexing agents; (c) combining the above suspension of the catalyst of step (b) with a simple polyester; (d) allocation polimersoderzhashchie catalyst from the suspension; and (e) the allocation of solid DMC catalyst, which comprises from 5 to 80 wt. percent, calculated on the amount of solid DMC catalyst, polyether, characterized in that the polyester has srednekamennogo molecular weight less than 500.

11. The method according to any of the preceding paragraphs. 8 to 10, characterized in that DMC catalyst is zinc hexacyanocobaltate.

12. The method according to any of the preceding paragraphs. 8 to 11, characterized in that the organic complexing agents is tert-butyl alcohol.

13. The method according to any of the preceding paragraphs. 8 to 12, characterized in that the above simple polyester is polyetherpolyols with srednekamennogo molecular weight in the range from 150 to 500.

14. The method of polymerization of epoxysilane, and the above-mentioned method includes the response epoxysilane and initiator, including hydroxyl is according to any one of the preceding paragraphs. 1 - 7 or obtained by the method according to any of the preceding paragraphs. 8 - 13.

 

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