Double metallocyanide the catalysts for production of polyether polyols

 

(57) Abstract:

This invention relates to a new dual metallocyanide the catalysts for production of polyether polyols and to a process for the preparation of polyether polyols by polyaddition of alkalisation to the original substances with active hydrogen atoms, with a catalyst includes: a) double metallocene compounds of General formula (III) Mx[M’x,(CN)y]z(III) where M is chosen from the metals 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); M’ is selected from metals 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); x, x’, y and z are equal to integers, and they are chosen so to double metallocyanide the compound had an electric neutrality; (b) bile acids or their salts, esters or amides, and (C) organic complex ligands. The method of obtaining DMC-catalyst includes the following stages: (i) interaction in aqueous solution ) of metal salts with salts of cyanide metals ) organic complex ligands, which differ from bile acids or their salts, esters or amides, and the bile acids or their salts, esters or amides, (ii) the separation, washing and with the high activity upon receipt of polyether polyols 3 N. and 6 C.p. f-crystals.

This invention relates to a new dual metallocyanide catalysts (DMC) to obtain polyether polyols by polyaddition of alkalisation to the original compounds with active hydrogen atoms.

Double metallocene catalysts (DMC) for the polyaddition of alkalisation to the original compounds with active hydrogen atoms are known (for example, see U.S. patent US-A 3 404 109, US-A 3 829 505, US-A 3 941 849 and US-A 5 158 922). Ispolzovanie such DMC-catalysts for production of polyether polyols reduces the content of monofunctional polyethers with terminal double bonds, so-called Manolov, compared with the traditional receipt of polyether polyols using alkaline catalysts, for example, hydroxides of alkali metals. Thus obtained polyether polyols and can be recycled into high-quality polyurethanes (for example, elastomers, foams, coatings). DMC-catalysts are usually obtained by a method in which an aqueous solution of metal salts is subjected to contact with an aqueous solution metallocyanide salts in the presence of organic complex ligands, for example, ethers. In the usual method of preparation katagamuwa dimethoxyethane (glyme) to form a suspension. After filtration and washing of the catalyst aqueous glyme solution get active catalyst of General formula

Zn3[CO(JV)6]2xZnCl2University2O z glyme

(for example, see European patent application EP-A 700 949).

In Japanese patent application JP-A 4145123, U.S. patent US-A 5 470 813, European patent applications EP-A 700 949, EP-a 743 093, EP-A 761 708, and international application WO 97/40086 described DMZ-catalysts, which also reduces the content of multi-functional polyethers with terminal double bonds upon receipt of polyether polyols using tert-butanol as the organic complex ligand (alone or in combination with polyester (European patent application EP-A 700 949, EP-A 761 708, international application WO 97/40086)). In addition, through the use of such DMC-catalysts decreases the induction time in the polyaddition reaction of alkalisation with the corresponding parent compounds, and increased activity of the catalysts.

The objective of the invention is to obtain improved DMC-catalysts for politicoeconomic of alkalisation to the corresponding source connections, which are compared with the hitherto known types of catalysts demo the profitability of the production of polyether polyols. In the ideal case, due to the high activity of the catalyst, it is possible to use in such a low concentration (25 parts per million or less), in order to avoid costly catalyst separation from the product, and the product could be directly used to obtain polyurethane.

It has been unexpectedly found that DMC-catalysts, which contain bile acid or its salt, ester or amide as complex ligands, have a very high activity upon receipt of the polyether polyols.

The object of this invention is the dual metallicity catalyst (DMC), which contains

a) one or more, preferably one double metallocyanide connection

b) one or more, preferably one bile acid or its salt, ester or amide, and

c) one or more, preferably one organic complex ligand, different from b).

According to this invention, the catalyst, if necessary, may contain (d) water, preferably 1-10 wt.% and/or e) one or more water-soluble metal salts, preferably 5-25 wt.%, formula (I) M(X)n from receiving double metallocyanide compounds a).r(III). Most preferred is a Zn(II), Fe(II), Co(II) and Ni(II). The anions X are the same or different, preferably identical, and are preferably chosen from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates, n is 1, 2 or 3.

According to this invention a double metallocyanide compounds (a), which contain the proposed catalysts are the reaction products of water-soluble metal salts and water-soluble salts of cyanide metals.

To obtain double metallocyanide compounds (a) suitable water-soluble metal salts preferably have the General formula (I) M(X)n, where M is chosen from the metals 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). Most preferred is a Zn(II), Fe(II), Co(II) and Ni(II). The anions X are the same or different, preferably identical, and are preferably chosen from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates, n is 1, 2 or 3.

Suitable water-soluble salts of the metal is NSV, sulphate of iron (II) bromide, iron (II) chloride iron (II) chloride cobalt (II) thiocyanate, cobalt (II) chloride Nickel (II) nitrate, Nickel (II). Is also possible to use mixtures of different water-soluble metal salts.

To obtain double metallocyanide compounds (a) suitable water-soluble salts of cyanide metals preferably have the General formula (II) (Y)aM’(CN)b(A)cand M’ are selected from metals 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). Most preferably M’ is selected from metals Co(II), Co(III), Fe(II), Fe(III), Cr(III), Ir(III) and Ni(II). Water-soluble salt of the metal cyanide may contain one or more of such metals. Cations Y are the same or different, preferably identical, and they are chosen from the group consisting of ions of alkaline and alkaline-earth metals. Anions And are the same or different, preferably identical, and are selected from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates. Values as a and b and C are integers, with values for a, b and C is chosen so that the salt of cyanide metals obeditelna 0. Suitable water-soluble salts of cyanide metals are, for example, hexacyanocobaltate (III), potassium hexacyanoferrate (II) potassium hexacyanoferrate (III) potassium hexacyanocobaltate (III) calcium and hexacyanocobaltate (III) lithium. Preferred dual metallocyanide compounds (a), which contain the proposed catalysts are compounds of General formula (III)

Mx[M’x,(CN)y]z,

moreover, the value of M is as in the formula (I), and

M’ is the same as in the formula (II), and

x, x’, y and z are equal to integers, and they are chosen so that the double metallocyanide the compound had an electric neutrality.

Preferably

x=3, x’=1, y=6 and z=2,

M=Zn (II), Fe(II), CO(II) or Ni(II) and

M’=Co(III), Fe(III), Cr(III) or Ir(III).

Suitable double metallocyanide compounds a) are hexacyanocobaltate (III) zinc, hexacyanoferrate (III), zinc hexacyanoferrate (III), zinc and hexacyanocobaltate (III) cobalt (II). Suitable double metallocene compounds described, for example, in U.S. patent US-A 5 158 922. Most preferred is hexacyanocobaltate (III) zinc.

Organic complex ligands) that contain predlog 158 922, US-A 3 404 109, US-A 3 829 505, US-A 3 941 849, European patent application EP-A 700 949, EP-A 761 708, Japanese patent application JP-A 4145123, U.S. patent US-A 5 470 813, European patent application EP-A 743 093, and international application WO 97/40086). Preferred organic complex ligands are water-soluble, organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which can form complexes with the connection of the double cyanides of metals). Suitable organic complex ligands are, for example, water-soluble, aliphatic alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Preferred organic complex ligands are water-soluble, aliphatic alcohols, for example ethanol, isopropanol, n-butanol, Isobutanol, sec-butanol and tert-butanol. Most preferred is tert-butanol.

Organic complex ligands are added to or during preparation of the catalyst directly or after separation of double-IU-tallandini compounds a). Usually organic complex ligands used in excess.

Proposed DMC-catalysts contain double MEA the finished catalyst, and organic complex ligands) in an amount of from 0.5 to 30 wt.%, preferably from 1 to 25 wt.%, relative quantity of the finished catalyst. Proposed DMC-catalysts usually contain 1-74,5 wt.%, preferably 1-40 wt.%, regarding the number of finished catalyst, bile acid or its salt of ester or amide.

Bile acids suitable for receipt of the proposed catalysts are24-steroid-carboxylic acid, which are degradation products of cholesterol, which is usually derived from 5-Holan-24-acid activating hydroxyl groups at position C-3, C-6, C-7 and C-12.

Preferred bile acids have the General formula

and R1, R2, R3and R4independently of one another are hydrogen or hydroxy and5is hydroxy, NH-CH2-COOH, NH-CH2-CH2-SO3N, NH-(CH2)3-N+(CH3)2-CH2-CHOH-CH2-SO3- or NH-(CH2)3-N+(CH3)2-(CH2)3-SO3-.

Suitable are the free acids or their salts, preferably salts of alkaline and alkaline-earth metals and their esters, predpochtitelnei, sulfoalkylation, sulfogalactosylceramide and carboxialkilnuyu remains in the form of acids or salts.

Suitable bile acids or their salts, esters or inorganic salts are cholic acid (3 ,7 ,12 trihydroxy-5-Holan-24-acid; R1=R3=R4=R5=hydroxy, R2=hydrogen), sodium salt holeva acid (Holt sodium), Holt lithium Holt potassium, glycol-holeva acid (3 ,7 ,12 trihydroxy-5-Holan-24-acid-N-[carboxymethyl]amide; R1=R3=R4=hydroxy, R2=hydrogen, R5=NH-CH2-COOH), glycocholate sodium, human beings need it to acid (3 ,7 ,12 trihydroxy-5-Holan-24-acid-N-[2-sulfoethyl]amide; R1=R3=R4=hydroxy, R2=hydrogen, R5=NH-CH2-CH2-SO3N), taurocholate sodium, desoxycholic acid (3 ,12-dihydroxy-5-Holan-24-acid; R1=R4=R5=hydroxy, R2=R3=hydrogen), sodium deoxycholate, dezoksiholatom potassium, dezoksiholatom lithium glycometabolic acid (3 ,12 trihydroxy-5-Holan-24-acid-N-[carboxymethyl]amide; R1=R4=hydroxy, R2=R3=hydrogen, R5=NH-CH2-COOH), glycolytically sodium, taurodeoxycholic acid (3 ,12-dihydroxy-5-hone2-SO3N), taurodeoxycholate sodium, chenodesoxycholic acid (3 ,7-dihydroxy-5-Holan-24-acid; R1=R3=R5=hydroxy, R2=R4=hydrogen), chenodesoxycholic sodium, glockengiesserwall acid (3 ,7-dihydroxy-5-Holan-24-acid-N-[carboxymethyl]amide; R1=R3=hydroxy, R2=R4=hydrogen, R5=NH-CH2-COOH), glyconanoparticles sodium, taurochenodeoxycholate acid (3 ,7-dihydroxy-5-Holan-24-acid-N-[2-sulfoethyl]amide; R1=R3=hydroxy, R2=R4=hydrogen, R5=NH-CH2-CH2-SO3N), taurochenodeoxycholate sodium, lithocholic acid (3-hydroxy-5-Holan-24-acid; R1=R5=hydroxy, R2=R3=R4=hydrogen), lithocholic sodium, lithocholate potassium, Gogoleva acid (3 ,6 ,7 trihydroxy-5-Holan-24-acid; R1=R2=R3=R5=hydroxy, R4=hydrogen), geopolit sodium, geopolit lithium geopolit potassium, hyodesoxycholic acid (3 , 6-dihydroxy-5-Holan-24-acid; R1=R2=R5=hydroxy, R3=R4=hydrogen), hyodesoxycholic sodium, hyodesoxycholic lithium hyodesoxycholic potassium, methyl ester holeva acid complex ethyl ester holeva acid complex is or their salts, esters or amides can be used individually or as mixtures.

Most preferred are salts of sodium, lithium or potassium, or a complex of methyl or ethyl esters holeva acid, glycocholic acid, human beings need it to acid, deoxycholic acid, glycometabolic acid, taurodeoxycholic acid, chenodeoxycholic acid, glockengiesserwall acid, taurochenodeoxycholate acid, lithocholic acid, geoholiday acid, hyodesoxycholic acid or mixtures thereof.

Also suitable bile acids are, for example, ourside-Saxicola acid (3 ,7-dihydroxy-5-Holan-24-acid), 7-oxalidaceae acid (3-hydroxy-7-oxo-5-Holan-24-acid, lithocholic acid 3-sulfate (3-hydroxy-5-Holan-24-acid-3-sulfate), Nord-cholic acid and bisnor-cholic acid, or their salts, esters or amides.

Bile acids and their salts, esters or amides are known and, for example, described in detail in Nachr. Chem. Tech. Lab. 43 (1995) 1047 and , Stuttgart, New York 1997, S. 248ff.

It is also possible to use any mixtures of the aforementioned bile acids or their salts, esters or amides.

Analysis of the catalyst composition is usually done with the help of the elemental is or amides, followed by gravimetric determination.

The proposed catalysts may be crystalline, partially crystalline or amorphous. Analysis of crystallinity is usually carried out by roentgendifractometric powder.

The proposed catalysts preferably contain

a) hexacyanocobaltate (III) zinc

b) bile acid or its salt, ester or amide and

c) tert-butanol.

Getting proposed DMC-catalysts usually carried out in aqueous solution by interaction ) metal salts, preferably of the formula (I) cyanide salts of metals, preferably of the formula (II ) organic complex ligands) that are different from a bile acid or salt of ester or amide and the bile acid or salt of ester or amide.

First, preferably the interaction of aqueous solutions of metal salts (e.g. zinc chloride, used in stoichiometric excess of at least 50 mole%, relative to the salt of the metal cyanide) and cyanide salts of the metal (for example, hexacyanocobaltate potassium), and get the suspension, which contains a double metallocyanide connection a) (for example, hexacyanocobaltate zinc), water (d), excess metal salt (e), and organic completelv and/or salts of cyanide, metals, or to be directly added to the suspension obtained after separation of the double metallocyanide connection). Preferably the mixing of aqueous solutions and organic complex ligands (C) under vigorous stirring. The resulting suspension is usually treated with bile acid or its salt, complex ether or Amida). Bile acid or its salt, ester or amide) is preferably used in a mixture with water and organic complex ligands with).

In conclusion, spend the allocation of the catalyst from the suspension in the usual way, for example, such as centrifugation or filtration. In accordance with a preferred embodiment of the present invention, the selected catalyst is washed with an aqueous solution of an organic complex ligands (for example, re-suspended and then re-allocate by filtration or centrifugation). Thus, for example, can be removed from the proposed catalyst by-products, such as potassium chloride.

The preferred amount of organic complex ligands) in an aqueous rinse solution is between 40 and 80 wt.%, in relation to the entire solution. Also preferably Appendix is but in amounts of between 0.5 and 5 wt.%, in relation to the entire solution.

In addition, the catalyst is preferably washed more than once. This may, for example, the repetition of the first washing process. However, preferably the next stages of washing do not use aqueous solutions, and, for example, a mixture of organic complex ligands and bile acid or its salt of ester or amide. Then the washed catalyst, if necessary, after comminution is dried at a temperature of usually from 20 to 100 C and at a pressure of generally from 0.1 mbar to normal pressure (1013 mbar).

It is also an object of this invention is the application of the proposed DMC-catalysts in the method of producing polyether polyols by polyprionidae of alkalisation to the original substances with active hydrogen atoms.

As accelerated it is preferable to use ethylene oxide, Pro-pileated, butylenes, and mixtures thereof. Synthesis of polyester chains by alkoxysilane can be, for example, only Monomeric epoxide or statistically or in blocks with 2 or 3 different Monomeric epoxides. Details are given in "Ullmanns Encyclopadie der industriellen Chemie", Band A21, 1992, S. 670f.

As a source of substances with active taxiline groups, for example, ethylene glycol, di-ethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethyleneimine, bisphenol a, trimethylolpropane, glycerol, Penta-aritra, sorbitol, sucrose, split starch or water.

Preferably use such source materials with active hydrogen atoms, which, for example, conventionally receive alkaline catalysis of the above low molecular weight starting compounds, and get oligomeric products alkoxysilane molecular weight (average number) from 200 to 2000.

Catalyzed proposed catalysts, polyprionidae of alkalisation to the original substances with active hydrogen atoms is conducted usually at a temperature of from 20 to 200, preferably from 40 to 180 C, most preferably at a temperature of from 50 to 150 C. the Reaction can be provodina with a total pressure of from 0.001 to 20 bar.

Carrying out polyaddition possible substance or inert, organic solvent, such as toluene and/or THF. The amount of solvent is usually 10 to 30 wt.%, regarding the number of received polyetherpolyols.

The concentration of catalyst is chosen so that under the given reaction conditions was vozmojnym.%, preferably from 0.001 to 0.1 wt.%, most preferably from 0.001 to 0.0025 wt.%, regarding the number of received polyetherpolyols.

Molecular weight (average number) of polyether polyols obtained according to the proposed in accordance with this invention, is from 500 to 100,000 g/mol, preferably from 1000 to 50000 g/mol, most preferably from 2000 to 20,000 g/mol.

Carrying out polyaddition may continuously or periodically, for example at periodic or properities mode.

Due to its high activity proposed in accordance with this invention, the catalysts can be used in very low concentrations (25 parts per million or less, relative to the amount of polyetherpolyols). The polyether polyols obtained in the presence of the proposed in accordance with this invention catalysts used to produce polyurethanes (Kunststoffhandbuch, Bd. 7, Polyurethane, 3rd.Aufl., 1993, S. 25-32 und 57-67), possible rejection of the separation of the catalyst from polyetherpolyols without negative impact on the quality of the resulting polyurethanes.

Examples

Preparation of catalyst

Example A. Obtaining DMC-catalyst with ispolzovanie in 35 ml of distilled water with vigorous stirring (24000 rpm) add a solution of 6.2 g (45,75 mmol) of zinc chloride in 10 ml of distilled water. Immediately after you add a mixture of 25 g of tert-butanol and 25 g of distilled water to form a suspension and then within 10 minutes intensively mixed (24 rpm). Then add a mixture of 0.5 g of sodium salt holeva acid (Fluka Chemie AG, CH-9471 Buchs), 0.5 g of tert-butanol and 50 g of distilled water and within 3 minutes, stirred (1000 rpm). The solid is separated by filtration, and then within 10 minutes, stirred with a mixture of 35 g of tert-butanol, 15 g of distilled water and 0.5 g of sodium salt holeva acid (10,000 rpm) and again filtered. Then once again stirred with a mixture of 50 g of tert-butanol and 0.25 sodium salt holeva acid (10000 rpm) for 10 minutes. After filtration, the catalyst is dried at a temperature of 50 C and normal pressure until weight constancy.

The yield of dried, powdered catalyst: 2,1 g

Elemental analysis, thermogravimetric analysis and extraction: cobalt=of 12.6 wt.%, zinc=27,3 wt.%, tert-butanol = 10.9 wt.%, sodium salt holeva acid=4.3 wt.%, cyanide of 33.4 wt.%, chloride of 6.9 wt.%, water of 4.6 wt.%.

Example Century. Getting DMC-catalyst using sodium salt hyodesoxycholic acid (catalyst).

I repeat the example And, on the s (Firma Sigma-Aldrich Chemie GmbH, D-82041 Deisenhofen).

The yield of dried, powdered catalyst: 2,0,

Elemental analysis, thermogravimetric analysis and extraction: cobalt = 13,8 wt.%, zinc = 28,3 wt.%, tert-butanol = 7.3 wt.%, sodium salt hyodesoxycholic acid = 6.2 wt.%, cyanide of 36.5 wt.%, chloride and 5.8 wt.%, water of 2.1 wt.%.

Example (test case). Getting DMC-catalyst using tert-butanol without the use of a bile acid or its salt of ester or amide (catalyst, the conversion according to Japanese patent application JP-A 4145123).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 75 ml of distilled water with vigorous stirring (24000 rpm) add a solution of 10 g (73,3 mmol) of zinc chloride in 15 ml of distilled water. Immediately after you add a mixture of 50 g of tert-butanol and 50 g of distilled water to form a suspension and then within 10 minutes intensively stirred (24000 rpm). The solid is separated by filtration, and then within 10 minutes, stirred with 125 g of a mixture of tert-butanol and distilled water (70/30, w/w) (10,000 rpm) and again filtered. Then once again stirred with 125 g of tert-butanol (10000 rpm) for 10 minutes. After filtering the cat is, poroshkoobraznogo catalyst: is 3.08,

Elemental analysis:

cobalt = 13,6 wt.%, zinc = 27,4 wt.%, tert-butanol = 14.2 wt.%, cyanide 36,0 wt.%, chloride of 5.2 wt.%, water of 3.6 wt.%.

Getting polyetherpolyols

General methodology

In a 500 ml reactor under pressure is placed 50 g of educt - polypropyleneglycol (average molecular weight = 1000 g/mol) and 3-5 mg of catalyst (15-25 h/m, relative to the amount of poly-eticholeve) in the presence of a protective gas (argon) and heated at a temperature of 105 C with stirring. Then once added propylene oxide (about 5 g) and the total pressure is increased up to 2.5 bar. Then, if the reactor see accelerated pressure drop, again add the propylene oxide. This rapid pressure drop indicates that the catalyst is activated. Then add the remaining propylene oxide (145 g) continuously at a constant total pressure of 2.5 bar. After complete dispensing of propylene oxide and endurance after reaction for 2 hours at a temperature of 105 With water portion is distilled at a temperature of 90 C (1 mbar) and then cooled at room temperature.

The resulting polyether polyols characterized by hydroxyl number, the content of double bonds and vascostylis reaction time [min]). From the point of intersection of the tangent at the vertical point of the curve the time-transformation with the extended base line of the curve determine the induction time. Time propoxycarbonyl playing essential for the activity of the catalyst corresponds to the temporal space between the activation of the catalyst (the end of the induction period) and the end of the dosing of propylene oxide. The total reaction time is the sum of the time of induction and propoxycarbonyl.

Example 1. Getting polyetherpolyols using catalyst A (25 parts per million).

Induction time: 217 min

Time propoxycarbonyl: 33 min

The total response time: 250 min

Polyetherpolyols: hydroxyl number (mg KOH/g): 29,6

the content of double bonds (mmol/kg): 6

viscosity 25 C (MPa s): 855

Example 2. Getting polyetherpolyols using catalyst A (15 parts per million).

Induction time: 387 minutes

Time propoxycarbonyl: 168 min

The total reaction time: 555 min

Polyetherpolyols: hydroxyl number (mg KOH/g): 30,1

the content of double bonds (mmol/kg): 6

viscosity 25 C (MPa s): 993

Without separation of the catalyst metal content in the polyol extending t).

Induction time: 371 min

Time propoxycarbonyl: 40 min

The total reaction time: 411 min

Polyetherpolyols: hydroxyl number (mg KOH/g): 30,2

the content of double bonds (mmol/kg): 6

viscosity 25 C (MPa s): 902

Example 4 (control example).

The catalyst (15 parts per million) under the above reaction conditions demonstrates the absence of activation after induction for 14 hours.

When using 50 parts per million of catalyst With the induction time is about 9 hours. Time propoxycarbonyl is less than 12 hours, and during the reaction causes the activation of the catalyst.

Examples 1-3 demonstrate that due to their increased activity new, proposed in accordance with this invention DMC-catalysts, can be used to obtain polyether polyols in such low concentrations that it is possible to abandon the separation of the catalyst from the polyol.

1. Double metallicity catalyst (DMC), containing a) one double metallocene compound of General formula (III)

Mx[M’x,(CN)y]z(III)

where M is chosen from the metals Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V);

x, x’, y and z are equal to integers, and they are chosen so that the double metallocyanide the compound had an electric neutrality;

b) bile acid or its salt, ester or amide and (c) organic complex ligand, different from b).

2. DMC catalyst under item 1, which further comprises (d) water and/or e) a water-soluble salt of the metals of the General formula (I)

M(X)n(I)

where M is chosen from the metals 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);

X represents the same or different anions;

n = 1, 2, or 3.

3. DMC catalyst under item 1 or 2, in which the double metallocyanide compound (a) is hexacyanocobaltate (III) zinc.

4. DMC catalyst according to one of paragraphs.1-3, in which the organic complex ligand (C) is tert-butanol.

5. DMC catalyst according to one of paragraphs.1-4, which contain 1-80 wt.% bile acid or its salt of ester or amide.

6. DMC catalyst according to one of paragraphs.1-5, in which the bile acid has a General formula

and R1, R2, R3and R4independently of one another are hydrogen or hydroxy;

3)2-CH2-SNON-CH2-SO-3or NH-(CH2)3-N+(CH3)2-(CH2)3-SO-3.

7. DMC catalyst according to one of paragraphs.1-6, with the catalyst as salts of bile acids contains a salt of sodium, lithium or potassium holeva acid, glycocholic acid, human beings need it to acid, deoxycholic acid, glycometabolic acid, taurodeoxycholic acid, chenodeoxycholic acid, glockengiesserwall acid, taurochenodeoxycholate acid, lithocholic acid, geoholiday acid, hyodesoxycholic acid or mixtures thereof.

8. The method of obtaining DMC-catalyst in one of the paragraphs.1-7, which includes the following stages:

i) interaction in aqueous solution ) metal salts of General formula (I)

M(X)n(I)

where M is chosen from the metals 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);

X represents the same or different anions;

n = 1, 2, or 3,

with cyanide salts of metals of the General formula (II)

(Y)aM'(CN)b(A)c(II)

where M' is selected from metals 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);

Y means about who appoints the same or different anions from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates;

a, b and C are integers, with values for a, b and C is chosen so that the salt of cyanide metals had electrical neutrality;

) organic complex ligands, which differ from bile acids or their salts, esters or amides, and the bile acids or their salts, esters or amides,

ii) the separation, washing and drying of the catalyst obtained in stage i).

9. The method of producing polyether polyols by polyprionidae of alkalisation to the original substances with active hydrogen atoms in the presence of one or more DMZ-catalysts on one of the PP.1-7.

 

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The invention relates to polyetherpolyols, the method of its production, to polyetherpolyols mixture containing the polyol, and the hard polyurethane foam and can be used as insulating material for refrigerators, freezers in industrial plants, construction industry

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The invention relates to the production of PEAK that can be used as hardeners polymer compositions, varnishes, waxes, thickeners, reagents for the synthesis of surfactants, ion exchange polymers, flocculants water, floating agents, etc
The invention relates to the production of catalysts for production of polyether polyols

The invention relates to polyols, catalyzed double metallocyanide catalyst that get through improved method, in which the starter continuously added to the polymerization of epoxide

The invention relates to methods of producing double metallocyanide (DМС) catalysts for the polymerization of epoxy compounds

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 new substituted the phthalocyanine, which may find application as a dye, catalyst for various redox processes
The invention relates to methods for producing socialization for the polymerization of butadiene, occurring in the presence of cobalt containing catalysts, and may find application in the IC industry in the production of CIS-1,4-polybutadiene
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