Double metal cyanide-based catalysts for production of polyether(ester)polyols

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

 

The invention relates to new catalysts based on double metallocyanide (DMC-catalysts) to obtain polyether polyols by polyaddition of alkalisation to the original compounds with active hydrogen atoms.

Known DMC-catalysts for the polyaddition of alkalisation to the original compounds with active hydrogen atoms (see, for example, U.S. patent US-A 3404109, US-A 3829505, US-A 3941849 and US-A 5158922). The use of these catalysts for production of polyether polyols and contributes, in particular, reduction of the proportion of monofunctional polyethers with terminal double bonds, so-called Manolov, compared with the conventional receiving polyether polyols in the presence of basic catalysts such as 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 reacting an aqueous solution of metal salt with the aqueous salt solution metallocyanide in the presence of the organic complex ligand, such as simple air. A typical example of obtaining DMC-catalyst is mixing excessive amounts of an aqueous solution of zinc chloride with an aqueous solution of hexacyanocobaltate potassium and then add dimethoxyethane (glima) to arr is Savasana suspension. After filtration and washing of the catalyst with an aqueous solution of glima get active catalyst of General formula

Zn3[Co(CN)6]2xZnCl2the H2O z (glyme)

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

From Japanese patent application JP-A 4145123, U.S. patent US-A 5470813, European patent applications EP-A 700949, EP-A 743093, EP-A 761708 and international application WO 97/40086 known DMC-catalysts that with the introduction of their composition tert-butanol (alone or in combination with easy polyester) as the organic complex ligand (European patent application EP-A 700949, EP-A 761708, international application WO 97/40086) provide additional decrease in the proportion of monofunctional polyethers with terminal double bonds upon receipt the polyether polyols. Along with this, when using such DMC-catalysts reduced the induction period of the reaction of polyaddition of alkalisation to the original compounds and increases the catalyst activity.

The present invention was based on the task of creating advanced advanced DMC-catalysts for the polyaddition of alkalisation to the corresponding source compounds, which possess higher catalytic activity in comparison with the known still types of catalysts and provide more than the high efficiency of the production of polyether polyols by reducing the duration of the stage of alkoxysilane. In the ideal case due to the increased activity of such catalysts can be used in such low concentrations (25 ppm or less)that will eliminate the need for expensive separation from the reaction products polyaddition, which can be used for the direct synthesis of polyurethanes.

It was unexpectedly found that DMC-catalysts containing three or more different komleksoobrazuyuschee component, upon receipt of the polyether polyols exhibit much higher activity compared to catalysts containing only one complexing component.

The object of the present invention, therefore, is the catalyst based on double metallocyanide (DMC-catalyst)containing:

a) one or more, preferably one, double metallocyanide connection

b) one or more, preferably one that is different from the (C) organic complex ligand, and

c) two or more, preferably two, different from b) complexing component selected from the following classes of polymers with functional groups: simple or complex polyesters, polycarbonates, esters of polyalkyleneglycols, simple polyalkyleneglycol esters, polyacrylamide, copolymers of acrylamide with acrylic acid, Poliak the sludge acid, copolymers of acrylic and maleic acids, polyacrylonitrile, polyalkylacrylate, polyalkylacrylate, simple polivinilbutilovy ether, simple polivinilbutilovy ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone, copolymers of N-vinylpyrrolidone and acrylic acid, polyvinylacetate, poly-4-vinylphenol, copolymers of acrylic acid with styrene, polymers of oxazoline, polyalkylimide, copolymers of maleic acid and maleic anhydride, acetylcellulose and Polyacetals, or simple glycidyloxy ethers, glycosides, esters of carboxylic acids and polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, esters α,βunsaturated carboxylic acids or ionic surfactants or ionic surfactants on the phase boundary.

In the composition of the catalyst according to the invention can, if necessary, log d) water, preferably in amounts of 1-10% of the mass. and/or e) one or more water-soluble metal salts of the formula (I) M(X)nused to get double metallocyanide compounds (a), preferably in the amount of 5-25 wt%. In the formula (I), "M" selected from the following group of metals: zinc(II), iron(II), Nickel(II), manganese(II), cobalt(II), tin(II), lead(II), iron(II), molybdenum(VI), molybdenum(VI), aluminum(III), vanadium(V)vanadium(IV), strontium(II), tungsten(IV), tungsten(VI), copper(II) and chromium(III). Particularly preferred zinc(II), iron(II), cobalt(II) and Nickel(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" means 1, 2 or 3.

Double metallocyanide compounds (a)included in the composition of the catalysts according to the invention are products of the interaction of water-soluble metal salts and water-soluble salts of metallocyanide.

Water-soluble metal salt, suitable for double metallocyanide compounds a)preferably have the General formula (I) M(X)nand "M" are selected from the following group of metals: zinc(II), iron(II), Nickel(II), manganese(II), cobalt(II), tin(II), lead(II), iron(III), molybdenum(IV), molybdenum(VI), aluminum(III), vanadium(V)vanadium(IV), strontium(II), tungsten(IV), tungsten(VI), copper(II) and chromium(III). Particularly preferred zinc(II), iron(II), cobalt(II) and Nickel(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, is solanto, isothioscyanates, carboxylates, oxalates or nitrates; "n" means 1, 2 or 3.

Examples of suitable water-soluble metal salts are the chloride, bromide, acetate, acetylacetonate, benzoate or zinc nitrate, sulfate, bromide, or chloride of iron(II)chloride cobalt(II)thiocyanate, cobalt(II)chloride Nickel(II) nitrate, Nickel(II). Can also be used mixtures of different water-soluble metal salts.

Water-soluble salts metallocyanide, suitable for double metallocyanide compounds a)preferably have the General formula (II): (Y)aM'(CN)b(A)cand M' are selected from the following group of metals: iron(II), iron(III), cobalt(II), cobalt(III), chromium(II)chromium(III), manganese(II)manganese(III), iridium(III), Nickel(II), rhodium(III)and ruthenium(II), vanadium(IV) and vanadium(V). Especially preferred choice of M' from the following group of metals: cobalt(II), cobalt(III), iron(II), iron(III), chromium(III), iridium(III) and Nickel(II). Water-soluble salt of metallocyanide may contain one or more atoms of these metals. Cations "Y" are the same or different, preferably identical, and are selected from the group of alkali and alkaline-earth metals. Anions "A" are the same or different, preferably identical, and are selected from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanate is in, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates. The indices "a", "b" and "C" correspond to integer values, chosen so as to conform to electroneutrality salt metallocyanide. The index "a" is preferably correspond to the values 1,2,3 or 4, "b" - 4,5 or 6 "C" is 0. Examples of suitable water-soluble salts of metallocyanide are hexacyanocobaltate(III)hexacyanoferrate(II) or hexacyanoferrate(III) potassium hexacyanocobaltate(III) calcium and hexacyanocobaltate(III) lithium.

Preferred dual metallocyanide compounds)present in the catalysts according to the invention are compounds of General formula (III)

MxM'x'(CN)y]z,

in which M means the same as in the formula (I),

M' means the same as in the formula (II)

x, x', y and z are integers selected so that was observed electroneutrality double metallocyanide connection.

Preferred the following values:

x is 3, x is 1, y is 6, and z is 2,

M means the zinc(II), iron(II), cobalt(II) or Nickel(II)

M' means the cobalt(III), iron(III), chromium(III) or iridium(III).

Examples of suitable double metallocyanide compounds a) are hexacyanocobaltate(III), hexacyanoferrate(III) or hexacyanoferrate(III) zinc, gexas anomalitet(III) cobalt(II). Other examples of suitable double metallocyanide compounds represented, for example, in U.S. patent 5158922. Especially preferably using hexacyanocobaltate(III) zinc.

Organic complex ligands b)included in DMC-catalysts according to the invention, in principle known and described in the patent literature, the relevant prior art (for example, in U.S. patent US-A 5158922, US-A 3404109, US-A 3829505, US-A 3941849, European patent applications EP-A 700949, EP-A 761708, Japanese patent application JP-A 4145123, U.S. patent US-A 5470813, European patent application EP-A 743093 and international application WO 97/40086). Preferred organic complex ligands are water-soluble organic compounds containing heteroatoms such as oxygen, nitrogen, phosphorus or sulfur, are capable of forming complexes with double metallocyanide soedinenii). Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, carbamides, NITRILES, sulfides and mixtures of these compounds. Preferred organic complex ligands are water-soluble aliphatic alcohols as ethanol, isopropanol, n-butanol, Isobutanol, sec-butanol and tert-butanol. Especially preferred tert-butanol.

The organic complex ligand added is because in the process of preparation of the catalyst, either directly after loss of double metallocyanide compounds in the sediment. Usually use an excess of the organic complex ligand.

DMC-catalysts according to the invention contain double metallocyanide connection (a) in an amount of from 20 to 90 wt. -%, preferably from 25 to 80 wt. -%, regarding the number of finished catalyst and organic complex ligands b) in an amount of from 0.5 to 30 wt. -%, preferably from 1 to 25 wt. -%, relative quantity of the finished catalyst. DMC-catalysts according to the invention usually contain from 1 to 79.5 wt. -%, preferably from 1 to 50 wt. -%, regarding the number of finished catalyst, of a mixture of complexing components C).

Complexing components C), suitable for the preparation of catalysts according to the invention are the above-mentioned polymers with functional groups, simple goldglove ethers, glycosides, esters of carboxylic acids and polyhydric alcohols, bile acids or their salts, esters or amides, cyclodextrins, phosphorus compounds, esters α,βunsaturated carboxylic acids or ionic surfactants or ionic surfactants on the phase boundary.

Polymers with functional groups suitable for receiving the catalyst is in accordance with the invention, in principle known and described in detail in European patent application EP-A 700949, international applications WO 97/40086, WO 98/16310 and German patent applications 19745120.9, 19757574.9, 19810269.0, 19834573.9 and 19842382.9. Suitable polymers with functional groups are, for example, simple and complex polyesters, polycarbonates, esters of polyalkyleneglycols, simple polyalkyleneglycol esters, polyacrylamide, copolymers of acrylamide with acrylic acid, polyacrylic acid, copolymers of acrylic and maleic acids, polyacrylonitrile, polyalkylacrylate, polyalkylacrylate, simple polivinilbutilovy ether, simple polivinilbutilovy ether, polyvinyl acetate, polyvinyl alcohol, poly-N-vinyl pyrrolidone, copolymers of N-vinylpyrrolidone and acrylic acid, polyvinylacetate, poly-4-vinylphenol, copolymers of acrylic acid with styrene, polymers of oxazoline, polyalkylimide, copolymers of maleic acid and maleic anhydride, acetylcellulose and Polyacetals.

Preferably used polymers with functional groups are simple and complex polyesters, polycarbonates, esters of polyalkyleneglycols and simple polyalkyleneglycol esters.

Preferably used is a simple polyol include polyether polyols containing from 1 to 8, especially before occhialino from 1 to 3 hydroxyl groups and having srednekamennogo molecular weight of from 150 to 10 7, particularly preferably from 200 to 5·104. The polyether polyols generally produced by polymerization of epoxides with disclosure cycle in the presence of the corresponding parent compounds with active hydrogen atoms and basic, acidic or coordination-ion catalysts (e.g., DMC-catalysts). Suitable polyether polyols are, for example, polyoxypropyleneamine, polyoxyethyleneglycol with ethylenoxide links polyoxypropyleneamine, a mixture of polyoxyethyleneglycol with polyoxypropyleneamine, polymers of butilenica, copolymers of butilenica with ethylene oxide and/or propylene oxide, and polyoxyethyleneglycol.

Preferably used complex polyesters are linear or partially branched polyesters with terminal hydroxyl groups, having srednekamennogo molar mass of less than 10,000, which are described in more detail in the German patent application 19745120.9. Especially preferably the use of polyesters with srednekamennogo molar mass of from 400 to 6000 and a carboxyl number of from 28 to 300 mg KOH/g, suitable for the synthesis of polyurethanes. Suitable complex polyesters are, for example, polyethyleneglycoladipinate, polydiethyleneglycoladipinate, polypropylenglycol, polydiethyleneglycoladipinate, branched group is a rotary of trimethylolpropane, polytetramethylene or poly-2-methyl-1,3-propylenglykol.

Preferably used polycarbonates are aliphatic polycarbonates with terminal hydroxyl groups, having srednekamennogo molar mass of less than 12000, which are described in more detail in the German patent application 19757574.9. Especially preferably the use of diols aliphatic polycarbonates with srednekamennogo molar mass of from 400 to 6000. Suitable dialami polycarbonates are, for example, poly(1,6-hexanediol)carbonate, poly(diethylene glycol)carbonate, poly(dipropyleneglycol)carbonate, poly(triethylene glycol)carbonate, poly(1,4-bis-hydroxymethylcellulose)carbonate, poly(1,4-butanediol)carbonate, or poly(dipropyleneglycol)carbonate.

Preferred esters of polyalkyleneglycols are esters polietilenglikolsuktsinata (Polysorbate), described in more detail in German patent application 19842382.9. Particularly preferred complex of mono-, di - and treatery polietilenglikolsuktsinata and fatty acids with 6 to 18 carbon atoms containing from 2 to 40 ethylenoxide links.

Preferably used simple polyalkyleneglycol esters are mono - and diglycidyl esters of polypropylenglycol and polyethylene glycol, are described in more detail in it is ckoi the patent application 19834573.9.

In addition, the compounds preferably used for the preparation of catalysts according to the invention as component C), are simple glycidyloxy ester monomer or polymer containing at least two Monomeric link) aliphatic, aromatic or arylaliphatic, mono-, di-, tri-, Tetra - or polyfunctional alcohols.

Preferred simple glycidyloxy esters of the following mono-, di-, tri-, Tetra - or polyfunctional aliphatic alcohols: butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol, 1,2-propane diol, 1,3-propane diol, 1,4-butanediol, 2,2-dimethyl-1,3-propane diol, 1,2,3-propane diol, 1,6-hexandiol, 1,1,1-Tris-hydroxymethylamino, 1,1,1-Tris-hydroxymethylpropane, tetrakis-hydroxymethylamino, sorbitol, polyethylene glycol and polypropylenglycol, and can be used as mono-, di-, tri - and tetraglycidyl, and polyglycerol esters.

Particularly preferable to use a mono - or diglycidyl esters butanol, hexanol, octanol, decanol, dodecanol, tetradecanol, ethanediol or 1,4-butanediol, and polypropyleneglycol or polyethylene glycol, in particular, with degree of polymerization from 2 to 1000 Monomeric units.

Simple glycidyloxy esters are usually obtained by interaction of mono-, di-, tri-, Tetra - or polyfun the national alcohols with epichlorohydrin in the presence of Lewis acids, for example, tin tetrachloride or boron TRIFLUORIDE, and the subsequent dehydrohalogenation formed chlorhydrins base (e.g. sodium hydroxide).

Methods of obtaining simple glycidyloxy esters are well known and are described, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", Band 9, 4. Edition, 1994, S. 739 ff.; "Ullmann''s Encyclopedia of Industrial Chemistry", Band A9, 5. Edition, Weinheim/New York, 1987, p. 552.

Simple glycidyloxy ether used for the preparation of the catalyst according to the invention, may be present in the finished catalyst in the source or chemically modified, for example gidrolizovannogo, state.

Glycosides suitable for use as component (C)are compounds consisting of carbohydrates (sugars) and nasarov (aglycones), in which the aglycone is connected by means of the oxygen atom through a glycosidic bond with polyacetylene carbon atom of the carbohydrate to the full acetal.

As the carbohydrate component (sugar) suitable monosaccharides: glucose, galactose, mannose, fructose, arabinose, xylose or ribose, disaccharides: sucrose or maltose, and oligo - or polysaccharides, in particular starch.

As for the non-sugar component, we are talking about hydrocarbon radicals with 1-30 carbon atoms, in particular aryl, arylalkyl and alkyl radicals, preferably aralkyl the x and alkyl radicals, especially preferably about alkyl radicals with 1-30 carbon atoms.

Preferred glycosides are the so-called alkylpolyglucoside, which typically is produced by the interaction of carbohydrates with such alcohols as methanol, ethanol, propanol and butanol, or by paracetalmol short chain of Alkylglucoside fatty alcohols with 8 to 20 carbon atoms in the presence of acids.

Particularly preferred alkylpolyglycoside with glucose as a repeating unit link and 8-16 carbon atoms in the alkyl chain, having an average degree of polymerization of from 1 to 2.

Methods of obtaining glycosides are well known and are described, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", Band 4, 4. Edition, 1992, S. 916 ff.; "Lexikon Chemie", Band 2, 10. Edition, Stuttgart/New York, 1996, S. 1581 ff.; Angewandte Chemie 110, S. 1394-1412 (1998).

Suitable esters of carboxylic acids and polyhydric alcohols are, for example, esters of carboxylic acids with 2 to 30 carbon atoms and aliphatic or alicyclic alcohols containing two or more hydroxyl groups in the molecule, which include ethylene glycol, 1,2-propandiol, 1,3-propandiol, diethylene glycol, triethylene glycol, 1,2,3-propantriol (glycerine), 1,3-butanediol, 1,4-butanediol, butanetriol, 1,6-hexanediol, 1,1,1-trimethyloctane, 1,1,1-trimethylolpropane, pintaric is it carbohydrates (sugar) or such polyhydric alcohols like sorbitol or sorbitan becoming the oxidation into monosaccharides. As sugars are suitable monosaccharides: glucose, galactose, mannose, fructose, arabinose, xylose or ribose, disaccharides: sucrose or maltose, and oligo - or polysaccharides, in particular starch.

As the carboxylic acid to obtain the corresponding esters suitable acid with 2-30 carbon atoms, such as aryl-, arylalkyl and alkalicarbonate, preferably arylalkyl and alkalicarbonate, particularly preferably alkalicarbonate acid, for example acetic, butyric, isovalerianic, Caproic, Caprylic, capric, lauric, myristic, palmitic, stearic, oleic, linoleic or linolenic acid.

Preferred esters of carboxylic acids and polyhydric alcohols are esters of 1,2,3-propantriol (glycerine), 1,1,1-trimethylolpropane, pentaerythritol, maltose or sorbitan and alkylcarboxylic acids with 2-18 carbon atoms.

Particularly preferred esters of carboxylic acids and polyhydric alcohols are mono-, di-, tri - or terrafire 1,2,3-propanetriol (glycerol, pentaerythritol or sorbitan and alkylcarboxylic acids with 2-18 carbon atoms.

Methods of obtaining esters of carboxylic acids and a lot of the languid spirits or separated from the fat of well-known and described in detail, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", Band 9, 3. Edition, 1980, S. 795 ff.; "Lexikon Chemie", 8. Edition, Stuttgart/New York, 1981; "Ullmann''s Encyclopedia of Industrial Chemistry", Volume A10, 5 th Edition, 1987,S. 173-218.

Bile acids suitable for use as component C), are steroid carboxylic acids with 24 carbon atoms - degradation products of cholesterol, generally representing derivatives 5β-Holan-24-OIC acid obtained by introducing hydroxyl groups in α-position relative to the carbon atoms 3, 6, 7 and 12 of this acid.

Preferred bile acids have the General formula

moreover, the radicals R1, R2, R3and R4independently from each other mean a hydrogen atom or a hydroxy-group, and the radical R5means a hydroxy-group, 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 free bile acids or their salts, preferably salts of alkaline or alkaline-earth metals, as well as the corresponding esters, preferably containing alkyl radicals with 1-30 carbon atoms, and amides, predpochtitelnei alkyl radicals or sulfoalkyl, sulfoalkylation, sulfogalactosylceramide and carboxyl residues in acid or salt form.

Examples of suitable bile acids or their salts, esters or amides are cholic acid (3α,7α,12α-trihydroxy-5β-Holan-24-OIC acid; R1=R3=R4=R5=HE, R2=N), sodium salt holeva acid (Holt sodium), holati lithium and potassium, glikoholeva acid (N-[carboxymethyl]amide 3α,7α,12α-trihydroxy-5β-Holan-24-OIC acid; R1=R3=R4=HE, R2=H, R5=NH-CH2-COOH), glycocholate sodium, human beings need it to acid (N-[2-sulfoethyl]amide 3α,7α,12α-trihydroxy-5β-Holan-24-OIC acid; R1=R3=R4=HE, R2=H, R5=NH-CH2-CH2-SO3N); taurocholate sodium, desoxycholic acid (3α,12α-dihydroxy-5β-Holan-24-OIC acid; R1=R4=R5=HE, R2=R3=H), desoxycholate sodium, potassium and lithium, glikogenofiksiruta acid (N-[carboxymethyl]amide 3α,12α-dihydroxy-5β-Holan-24-OIC acid; R1=R4=HE, R2=R3=H, R5=NH-CH2-COOH), glycometabolic sodium, taurodeoxycholic acid (N-[2-sulfoethyl]amide 3α,12α-dihydroxy-5β-Holan-24-OIC acid; R1=R4=HE, R2=R3=H, R5=NH-CH2CH 2-SO3N), taurodeoxycholate sodium, chenodesoxycholic acid (3α,7α-dihydroxy-5β-Holan-24-OIC acid; R1=R3=R5=HE, R2=R4=H), chenodesoxycholic sodium, glyconanoparticles acid (N-[carboxymethyl]amide 3α,7α-dihydroxy-5β-Holan-24-OIC acid; R1=R3=HE, R2=R4=H, R5=NH-CH2-COOH), glyconanoparticles sodium, taurochenodeoxycholate acid (N-[2-sulfoethyl]amide 3α,7α-dihydroxy-5β-Holan-24-OIC acid; R1=R3=HE, R2=R4=H, R5=NH-CH2-CH2-SO3N), taurochenodeoxycholate sodium, lithocholic acid (3α-hydroxy-5β-Holan-24-OIC acid; R1=R5=HE, R2=R3=R4=H), lithocholate sodium and potassium, Gogoleva acid (3α,6α,7α-trihydroxy-5β-Holan-24-OIC acid, R1=R2=R3=R5=HE, R4=H), geopolity sodium, lithium and potassium, hyodesoxycholic acid (3α,6α-dihydroxy-5β-Holan-24-OIC acid; R1=R2=R5=HE, R3=R4=H), hyodesoxycholic sodium, lithium and potassium, methyl and ethyl esters holeva acid, ethyl and methyl esters geoholiday acid.

Especially preferably using sodium, lithium or potassium salt holeva acid methyl or ethyl ester Ho is eve glycocholate, human beings need it, deoxycholic, glycometabolic, taurodeoxycholate, chenodesoxycholic, glockengiesserwall, taurochenodeoxycholate, lithocholic, geoholiday, hyodesoxycholic acids or mixtures thereof.

In addition, suitable following bile acids: orthology (3α,7β,12α-trihydroxy-5β-Holan-24-OIC), ursodesoxycholic (3α,7β-dihydroxy-5β-Holan-24-OIC), 7-oxalidaceae (3α-hydroxy-7-oxo-5β-Holan-24-OIC), 3-saltatricula (3-sulfate 3α-hydroxy-5β-Holan-24-OIC), Koroleva and generalia acid or their salts, esters or amides.

Bile acids and their salts, esters or amides are well known and are described, for example, "Nachr. Chem. Tech. Lab. 43 (1995), 1047; Setchell et al., The Bile Acids", Bd. 4, Plenum, New York 1998; "Lexikon Naturstoffe, Stuttgart, New York 1997, p. 248 ff.

The cyclodextrins suitable for use as component C)are, for example, unsubstituted cyclodextrins or their esters, simple alkalemia, hydroxyalkyloxy, alkoxycarbonylmethyl and carboxyaniline esters or their salts.

Cyclodextrins are cyclohexa-, cyclohepta or cyclooctanone with 6, 7 or 8 repeating fragments of glucose linked in the 1,4-position. Cyclodextrins, for example, α-, β-, γor δ-cyclodextrin,are formed in the degradation of starch in prisutstvie Bacillus macerans or Bacillus circulans under the influence tsiklodekstringlyukanotransferazy.

As carboxylic acids to obtain the esters of cyclodextrin suitable aryl-, arylalkyl and alkalicarbonate acid with 2 to 30, preferably 2-24, particularly preferably from 2 to 20, carbon atoms, and preferable are arylalkyl and alkalicarbonate acid, and particularly preferred alkalicarbonate acid.

As the alkyl components in the simple alilovic, hydroxyalkyloxy, alkoxycarbonylmethyl and carboxyhaemoglobin ethers of cyclodextrin suitable linear or branched alkyl group with 1-30, preferably 1 to 24, particularly preferably from 1 to 20, carbon atoms.

Preferably used cyclodextrins are α-, β- and γ-cyclodextrins and their simple mono-, di - and treatery, complex di - and treatery or complex monetary/simple diesters, which are usually obtained by etherification α-, β- and γ-cyclodextrin such alkylating agents as, for example, dimethylsulfate or alkylhalogenide with 1-30 carbon atoms, in particular methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, heptyl-, artilharia, bromides or alkylated with the same alkyl substituents and/or esterification of acetic or succinic acid in the presence of acids.

Especially preferred methyl-α-, methyl-β-, methyl-γ-, ethyl-β-, butyl-1 -, butyl-β-, butyl-γ-, 2,6-dimethyl-α-, 2,6-dimethyl-β-, 2,6-dimethyl-γ-, 2,6-diethyl-β-, 2,6-dibutil-β-, 2,3,6-trimethyl-α-, 2,3,6-trimethyl-β-, 2,3,6-trimethyl-γ-, 2,3,6-trioctyl-α-, 2,3,6-trioctyl-β-, 2,3,6-triacetyl-α-, 2,3,6-triacetyl-β-, 2,3,6-triacetyl-γ-, 2-hydroxypropyl-α-, 2-hydroxypropyl-β-, 2-hydroxypropyl-γ-cyclodextrin, partially or fully acetylated or succinylcholine α-, βor γ-cyclodextrin, 2,6-dimethyl-3-acetyl-β- or 2,6-dibutil-3-acetyl-β-cyclodextrin.

Methods for producing cyclodextrins are well known and are described, for example, "Lexikon Chemie", 10. Edition, Stuttgart/New York 1997, S. 845 ff; Chemical Reviews 98 (1998) 1743.

Phosphorus compounds suitable for the preparation of the catalyst according to the invention as component C)are organic phosphates such as, for example, complex mono-, di - or truefire phosphoric acid, complex mono-, di-, tri - or terrafire pyrophosphoric acid and a complex of mono-, di-, tri-, Tetra - or polyesters polyphosphoric acid and alcohols with 1-30 carbon atoms.

Suitable organic phosphites are complex mono-, di - or truefire phosphorous acid and alcohols with 1-30 carbon atoms.

Suitable for use as component (C) organic phosphonates are, for example, is one mono - or diesters of phosphonic acid, alkylphosphonate, arylphosphonate, alkoxycarbonylmethyl, alkoxycarbonylmethyl, cyanoacrylates and cyanophosphonate acids, or complex of mono-, di-, tri - or terrafire alkilirovannami acids and alcohols with 1-30 carbon atoms.

The phosphonites, suitable as component C)are complex diesters fashonistas or arylphosphonate acids and alcohols with 1-30 carbon atoms.

Phosphinate suitable for the preparation of catalysts according to the invention as component C)are esters of phosphinic acid, alkylphosphonic, dialkylphosphinate or arylphosphine acids and alcohols with 1-30 carbon atoms.

Phosphinite suitable for the preparation of catalysts according to the invention as component C)are esters alkylphosphonate, dialkylphosphinate or arylphosphonate acids and alcohols with 1-30 carbon atoms.

As the alcohol component suitable one - or polyhydric aromatic, arylalkylamine, alkoxyalkyl and alkalemia alcohols from 1-30, preferably 1 to 24, particularly preferably from 1 to 20, carbon atoms, preferably aromatic, alkoxyalkyl and alkalemia, and especially preferred alkoxyalkyl and alkalemia alcohols.

Organic phosphates, phosphites, phosphonates, phosphonites, phosphinate or phosphinate, the use of which has been created for the preparation of catalysts according to the invention, receive, as a rule, by reacting phosphoric, pyrophosphoric, polyphosphoric, phosphonic, alkylphosphonate, arylphosphonate, alkoxycarbonylmethyl, alkoxycarbonylmethyl, cyanoacrylates acids, cyanophosphonate acid, alkilirovannami, fashonistas, phosphide, phosphine and phosphinite acids, or their halogenated derivatives, or oxides of phosphorus with the following hydroxyl-containing compounds with 1-30 carbon atoms: methanol, ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, heptanol, octanol, nonanol, decanola, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanone, methoxymethanol, ethoxyethanol, propoxyethanol, butoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, phenol, ethyl ester hydroxyoctanoic acid, propyl ester hydroxyoctanoic acid, ethyl ester hydroxypropionic acid, propyl ester hydroxypropionic acid, 1,2-ethanediol,1,2-propane diol, 1,2,3-trihydroxypropane, 1,1,1-trimethylolpropane or pentaerythritol.

Preferred are triethyl-, tributyl-, trioctyl-, Tris-(2-ethylhexyl) -, or Tris-(2-butoxyethyl)phosphate, disutility ether butylphosphonic acid, dioctyloxy ether Fe is infostroy acid, tritely ether of phosphonopropionic acid, timetravel and tritely esters phosphonooxy acid, timetravel, tritely, Tripropylamine and tributylamine esters of 2-phosphonopropionic acid, tritely ether 3-phosphonopropionic acid, tributyl, dilauryl-, Tris-(3-atmlocator-3-methyl)- or heptanes-(dipropyleneglycol)FOSFA.

Methods of obtaining esters of phosphoric, phosphorous, phosphonic, fashonistas, phosphine and phosphinite acids are known and are described in detail in Kirk-Othmer, Encyclopedia of Chemical Technology", Band 18, 4. Edition, 1996, S. 737 ff., "Lexikon Chemie", Band 4, 10. Edition, Stuttgart/New York, 1998, S. 3280 ff.; "Ullmann''s Encyclopedia of Industrial Chemistry", Band A19, 5. Edition, 1991, S. 545 ff.; "Houben-Weyl: Methods der organischen Chemie", Band XII/1 und XII/2, Stuttgart 1963/1964.

Esters α, βunsaturated carboxylic acids suitable for the preparation of catalysts according to the invention as component C)are, for example, mono-, di-, tri - or polyesters formed by acrylic acid or alkyl-, alkoxy-, alkoxycarbonyl and alkoxycarbonylmethyl acids and alcohols with 1-30 carbon atoms or polyether polyols.

As alcohols suitable one-, two-, three - or polyhydric aromatic, arylalkylamine, alkoxyalkyl and alkalemia alcohols from 1-30, preferably 1 to 24, particularly preferably from 1 to 20, carbon atoms, and pre is respectful are aromatic, alkoxyalkyl and alkalemia alcohols, and particularly preferred alkoxyalkyl and alkalemia alcohols.

In addition, as the alcohols suitable polyalkylene glycols and ethers of polyalkylene glycols, preferably are polypropylenglycol, polyethylene glycol or corresponding ethers with molecular weight from 200 to 10,000, preferably from 300 to 9000, particularly preferably from 400 to 8000.

As α,βunsaturated carboxylic acids suitable acrylic acid and alkyl-, alkoxy - and alkoxycarbonylmethyl acid with 1-20 carbon atoms: 2-methylacrylate (methacrylic), 3-methylacrylate (CROTONALDEHYDE), TRANS-2,3-dimethylacrylamide (Tihonova), 3,3-dimethylacrylate (senecia) or 3-ethoxyacrylate acid. Preferred are acrylic, 2-methylacrylate, 3-methylacrylate and 3-ethoxyacrylate acid. Especially preferred acrylic and 2-methylacrylate acid.

Used for preparation of catalysts according to the invention esters α,βunsaturated carboxylic acids normally produced by the esterification of mono-, di-, tri-, Tetra - and poly-functional hydroxyl-containing compounds with 1-30 carbon atoms: methanol, ethanol, ethanediol (ethylene glycol), 1-propanol, 2-propanol, 1,2-propane diol, 1,3-propane diol, 1,2,3-propantriol (glyceri is a), butanol, 2-butanol, Isobutanol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2,3-butanetriol, 1-pentanol, 1-hexanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-hexadecanol, 1-heptadecanol, 9-octadecanol, 1,1,1-Tris(hydroxymethyl)propane, pentaerythritol, methoxymethanol, ethoxyethanol, propoxyethanol, butoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl, ethyl and propyl esters hydroxilase (glycolic) acid, methyl, ethyl and propyl esters hydroxypropionic acid or polyether polyols such as polyethylene glycol and polypropylenglycol by relevant α,βunsaturated carboxylic acids, optionally in the presence of catalysts.

The preferred complex of mono-, di - and treatery acrylic and methacrylic acid and ethanediol, 1,2-propane diol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, 1,2,3-propanetriol, 1,1,1-Tris(hydroxymethyl)propane, 1,1,1-Tris(hydroxymethyl)propanetriol, 1,1,1-Tris(hydroxymethyl)papandropoulos, polyethylene glycol and polypropylenglycol.

Particularly preferred esters α,βunsaturated carboxylic acids are acrylic, diacrylate, methacrylic and dimethacrylate esters of polyethylene glycol, AK is silt, diacrylate, methacrylic and dimethacrylate esters of polypropylenglycol, diacrylate, dimethacrylate and triacrylate esters of 1,2,3-propantriol, diacrylates ester of 1,2,3-propantriol-1,3-(2-hydroxypropoxy), triacrylate ester of 1,2,3-propanetricarboxylate, acrylic and dimethacrylates ethers of 1,4-butanediol, diacrylates ether of 1,6-hexandiol, 2-hydroxypropylmethacrylate ether, triacrylate ether 1,1,1-Tris(hydroxymethyl)propane, triacrylate and trimethacrylate esters of 1,1,1-Tris(hydroxymethyl)propanecarboxylate or triacrylate and trimethacrylate esters of 1,1,1-Tris(hydroxymethyl)provenprobable.

Methods of obtaining esters α,βunsaturated carboxylic acids are well known and are described, for example, in "Kirk-Othmer, Encyclopedia of Chemical Technology", Band 18, 4. Edition, 1996, S. 737 ff.; "Lexikon Chemie", Band 4, 10. Edition, Stuttgart/New York, 1998, S. 3286 ff.; "Ullmann''s Encyclopedia of Industrial Chemistry", Band A19, 5. Edition, 1991, S. 545 ff.; "Houben-Weyl: Methods der organischen Chemie", Band XII/1 und XII/2, Stuttgart 1963/1964.

The peculiarity of molecules-ionic surfactants or ionic surfactants on the phase boundary, suitable for the preparation of catalysts according to the invention is an amphiphilic structure, i.e. they contain at least one ionic hydrophilic group (or one ionic hydrophilic part of the molecule) and at least the bottom of the hydrophobic group or a hydrophobic portion of the molecule). Examples of the ionic compounds of this kind can be found among the surfactants, Soaps, emulsifiers, detergents and dispersants.

Hydrophilic ionic group may have anionic, cationic or zwitterionic (amphoteric) nature. For example, are anionic carboxylate, sulphonate, sulphate, thiosulfate, phosphonate, phosphinate, phosphate or dithiophosphate group. Examples of cationic groups are Quaternary ammonium, postname or sulfonate group. An example of zwitter-ionic groups are betainovuyu, sulfobetaine or aminoxide group.

Hydrophobic groups are preferably hydrocarbon (aromatic, and alkylaromatic alkyl) radicals with 2 to 50 carbon atoms, but is also suitable fluorine-, silicon-, thio - or oxacillin group.

Examples of suitable classes of compounds containing anionic hydrophilic groups include carboxylates, such as alkylcarboxylic (soap), ethers, carboxylic acids (carboxymethyloxime) and polycarboxylate: malonate and succinate; salts of bile acids, amides such as bile acids with sulfoalkyl and carboxialkilnuyu substituents in salt form; derivatives of amino acids, such as sarcosine (alkanolamine), sulfamethoxine; sulphates: alkyl sulphates, sulfonic ethers, e.g. the R sulfonic ethers of fatty alcohols, aromatic sulfonic ethers or amidosulfuron, sulfated carboxylates, glycerides, esters and amides of carboxylic acids; sulfonates, such as alkyl-, aryl - and alkylarylsulfonates, sulphonated carboxylates, esters and amides of carboxylic acids, carboxylesterases, for example esters α-califoirnia acids, carboxamidotryptamine, esters sulfonterol acids, ethers, sulphonic acids, thiosulfate; phosphates, such as alkylphosphate or glycerophosphate, phosphonates, phosphonate and dithiophosphate.

Examples of suitable classes of compounds containing hydrophilic cationic groups are primary, secondary, tertiary and Quaternary ammonium salts with alkyl, aryl and alcylaryl substituents, alkoxysilane ammonium salts, esters of Quaternary ammonium bases, salts of benzylamine, alkanolamine, pyridine, imidazoline, oxazoline, thiazoline, aminoxide, sulfone, quinoline, isoquinoline and trapelia.

Examples of suitable classes of compounds containing hydrophilic zwitter ion (amphoteric) groups are aminoxide, imidazoline derivatives, for example, imidazoline carboxylates, betaines such as alkyl-, amidopropyl and sulfobetaine, aminocarbonyl acids and phospholipids, such as phosphatidylcholine (lecithin).

Ionogen the e surfactant or ionic surfactant on the phase boundary can be a mixture of several hydrophilic (anionic and/or cationic and/or zwitter-ionic) groups or parts molecules.

Ionic surfactants or ionic surfactants on the phase boundary, suitable for the preparation of catalysts according to the invention, are well known and are described, for example, in "Ullmann''s Encyclopedia of Industrial Chemistry, 5thEdition, Vol. A25, S. 747-817, VCH, Weinheim, 1994; "Kirk-Othmer, Encyclopedia of Chemical Technology, 4thEdition, Vol. 23, S. 477-541, John Wiley & Sons, New York, 1997; "Tensid-Taschenbuch", 2nd. Edition, H. Stache (Hrsg.), Carl Hanser Verlag,1982; "Surfactant Science Series", Vol. 1-74, M.J. Schick (Consulting Editor), Marcel Decker, New York, 1967-1998; "Methods in Enzymology", Vol. 182, M.P. Deutscher (Ed), S. 239-253, Academic Press, San Diego, 1990.

Usually, the composition of the catalysts determined by the method of elemental analysis, thermogravimetry or removal of the complexing components extraction with subsequent gravimetric determination.

The catalysts according to the invention can be crystalline, partially crystalline or amorphous substances. The degree of crystallinity is usually analyzed by x-ray diffraction of powders.

Particularly preferred catalysts according to the invention, containing:

a) hexacyanocobaltate(III) zinc,

b) tert-butanol and

c) two or more complexing component of the above type.

DMC-catalysts according to the invention are usually obtained in aqueous solution by interaction of metal salts, cha is in the surrounding area, formula (I) with salts of metallocyanide, in particular, formula (II), carried out in the presence of organic complex ligands b), which are not polymers with functional groups, simple glycidyloxy esters, glycosides, esters of carboxylic acids and polybasic alcohols, bile acids or their salts, esters or inorganic salts, cyclodextrins, phosphorus compounds, esters α,βunsaturated carboxylic acids or ionic surfactants or ionic surfactants on the phase boundary, and in the presence two or more complexing components C).

While it is preferable to first carry out the interaction of the aqueous solution of metal salt (e.g. zinc chloride, taken in excess to salt metallocyanide of not less than 50 mol%. compared with the stoichiometric ratio) with an aqueous salt solution metallocyanide (for example, hexacyanocobaltate potassium) in the presence of the organic complex ligand b) (for example, tert-butanol), forming a suspension, which contains a double metallocyanide connection a) (for example, hexacyanocobaltate zinc), water (d), excess metal salt (e) and the organic complex ligand b).

And the organic complex ligand b) may have Itsa in an aqueous solution of metal salt and/or salt metallocyanide, or add it directly after the drop of the suspension obtained double metallocyanide compounds in the sediment. Turned out to be advantageous intensive mixing of aqueous solutions of salts with organic complex ligand b). The formed suspension in the future, usually treated with a mixture of two or more complexing components C). The mixture of two or more complex-forming component is preferably introduced into the mixture of water and organic complex ligand b).

Then allocate the catalyst from the suspension of known methods, for example by centrifugation or filtration. Further, in accordance with the preferred embodiment of the method selected, the catalyst is washed with an aqueous solution of an organic complex ligand b) (for example, by resuspendable and subsequent re-allocation of the catalyst by filtration or centrifugation). Such treatment allows, in particular, to remove from the catalyst according to the invention the side of the water-soluble products, such as potassium chloride.

The preferred content of the organic complex ligand b) in General, the aqueous solution used for washing, is from 40 to 80% of the mass. In addition, this solution is advantageous to add a small amount of the mixture of two or more complexometry the components c), the preferred content of which in the total solution is from 0.5 to 5% of the mass.

In addition, it is advantageous to wash the catalyst more than once, which, for example, can be repeated initial washing process. However, for re-washing is preferable to use non-aqueous solutions, for example a mixture of organic complex ligand b) with a mixture of complexing components C).

The washed catalyst, in conclusion, if necessary, subjected to grinding to turn into powdery condition and subsequent drying at the temperature of in General from 20 to 100°C and a pressure of in General from 0.1 mbar to normal values (1013 mbar).

Another object of the present invention is the use of DMC-catalysts according to the invention for implementing the method of producing polyether polyols by polyaddition of alkalisation to the original compounds with active hydrogen atoms.

Preferably used acceleratedly are ethylene oxide, propylene oxide, butylenes, as well as mixtures of these compounds. Polymer chain, resulting from alkoxysilane, can consist, for example, only one epoxide as a repeating unit link or from 2-3 different, statistically or block distributed epoksidnyh links. More detailed information on this issue is presented in "Ullmann'sder industriellen Chemie", Band A21, 1992, S.670f.

As a source of compounds with active hydrogen atoms, preferably using products with srednekamennogo molecular weight of from 18 to 2000 and 1 to 8 hydroxyl groups. Such compounds are, for example, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethyleneimine, bisphenol a, trimethylolpropane, glycerin, pentaerythritol, sorbitol, cane sugar (sucrose), split starch or water.

Preferred is the use of such starting compounds with active hydrogen atoms, which are obtained, for example, by the usual basic catalysis of the above low molecular weight starting compounds and represent oligomeric products alkoxysilane with srednekamennogo molecular weight of from 200 to 2000.

Polyprionidae of alkalisation to the original compounds with active hydrogen atoms in the presence of catalysts according to the invention in the General case occurs at a temperature of from 20 to 200°C, preferably in the range from 40 to 180°C, particularly preferably at temperatures from 50 to 150°C. the Reaction can be carried out at total pressures of from 0.0001 to 20 bar. Polyprionidae can PROTEK shall be in bulk or in an inert organic solvent, such as toluene or tetrahydrofuran (THF). The amount of solvent relative to the amount of synthesized polyetherpolyols is preferably from 10 to 30% of the mass.

The concentration of the catalyst are selected so that under given reaction conditions it was possible convenient control of the polyaddition reaction. The concentration of catalyst in relation to sinteziruemy polyetherpolyols in General is in the range from 0.0005 to 1 wt. -%, preferably from 0.001 to 0.1 wt. -%, particularly preferably from 0.001 to 0.0025% of the mass.

Srednekislye molecular weight of the polyether polyols obtained by the process according to the invention, is in the range from 500 to 100,000 g/mol, preferably from 1000 to 50000 g/mol, particularly preferably from 2000 to 20,000 g/mol.

Polyprionidae can be continuous or intermittent, for example periodic or properities way.

Due to the extremely high activity of the catalysts according to the invention can be used in very low concentrations (25 ppm or less in relation to the number of synthesized polyetherpolyols). If the polyether polyols obtained in the presence of catalysts according to the invention, used for the synthesis of polyurethanes (Kunststoffhandbuch, Bd. 7, Polyurethane, 3rd. Aufl. 1993, S. 25-32 und 57-67), you can refuse removal is utilizator of these polyols, that will not lead to deterioration of quality indicators synthesized from them polyurethanes.

Examples

Sample preparation of catalyst

Example A. Obtaining DMC-catalyst containing TRICORONA glycerin and tritely ether 2-phosphonopropionic acid (catalyst A).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 70 ml of distilled water with vigorous stirring (24000 rpm) was added a solution of 12.5 g (from 91.5 mmol) of zinc chloride in 20 ml of distilled water. Directly following this, to the resulting suspension was added a mixture of 50 g of tert-butanol and 50 g of distilled water, followed by intensive mixing (24000 rpm) for 10 minutes. Then add a mixture consisting of 0.5 g of tricarinata of glycerol, 0.5 g teeterboro ether 2-phosphonopropionic acid, 1 g of tert-butanol and 100 g of distilled water, and carry out stirring for 3 minutes (1000 rpm). Solid allocate filtering, for 10 minutes, stirred with a mixture consisting of 70 g of tert-butanol, 30 g of distilled water, 0.5 g of tricarinata glycerol and 0.5 g teeterboro ether 2-phosphonopropionic acid (10000 rpm), and again produce filtering. Then within 10 minutes are repeated stirring with a mixture consisting of 100 g tert-butanol, 0.5 g of tricarinata glits the width and 0.5 g teeterboro ether 2-phosphonopropionic acid (10,000 rpm). After filtration of the catalyst is dried at 50°and normal pressure until constant weight.

The yield of dry powdered catalyst was 5.8,

The results of elemental analysis, thermogravimetry and extraction: cobalt =9.8% of mass., zinc=23,2% wt., tert-butanol=to 3.0 wt. -%, TRICORONA glycerol =11,4% wt., tritely ether 2-phosphonopropionic acid =16,9% of the mass...

Example Century. Getting DMC-catalyst containing diglycidyl ether polypropylenglycol and triavir 2-phosphonopropionic acid (catalyst).

The catalyst was obtained by a method similar to that described in example a, but instead of tricarinata glycerol and Trevira 2-phosphonopropionic acid used diglycidyl ether polypropylenglycol with srednekamennogo molar mass of 640 and triavir 2-phosphonopropionic acid.

The yield of dry powdered catalyst was 6.8,

The results of elemental analysis, thermogravimetry and extraction: cobalt=10,3% wt., zinc= 3,4% wt., tert-butanol=1,3 wt. -%, diglycidyl ether polypropylenglycol = 20,5% wt., tritely ether 2-phosphonopropionic acid =8,5% of the mass...

Example C. Obtaining DMC-catalyst containing a complex of the polyester and the sodium salt holeva acid (catalyst C).

The catalyst was obtained by a method similar to that described in example a, but pax is tricarinata glycerol and Trevira 2-phosphonopropionic acid used sophisticated polyester of adipic acid and diethylene glycol, poorly ramified through trimethylolpropane, with srednekamennogo molar mass of 2300 (carboxyl number of 50 mg KOH/g) and sodium salt holeva acid.

The yield of dry powdered catalyst 4.8,

The results of elemental analysis, thermogravimetry and extraction: cobalt=12,7% wt., zinc=25,2% wt., tert-butanol=4,2% wt., complex polyester =12.8% wt., sodium salt holeva acid=3.7% of the mass.

Example D (comparative). Getting DMC-catalyst containing TRICORONA glycerol in the absence of Trevira 2-phosphonopropionic acid (catalyst D).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 75 ml of distilled water with vigorous stirring (24 000 rpm) was added a solution of 12.5 g (from 91.5 mmol) of zinc chloride in 20 ml of distilled water. Directly following this, to the resulting suspension was added a mixture of 50 g of tert-butanol and 50 g of distilled water, followed by vigorous stirring (24000 rpm) for 10 minutes. Then add a mixture consisting of 1 g of tricarinata glycerol (company Aldrich), 1 g of tert-butanol and 100 g of distilled water, and carry out stirring for 3 minutes (10,000 rpm). Solid allocate filtering, for 10 minutes, stirred with a mixture consisting of 70 g of tert-butanol, 30 g of distilled water and 1 g vishey is related of tricarinata glycerin, and again produce filtering. Then within 10 minutes are repeated stirring with a mixture of 100 g tert-butanol and 0.5 g of the above tricarinata glycerol (10,000 rpm). After filtration of the catalyst is dried at 50°and normal pressure until constant weight.

The yield of dry powdered catalyst was 5.3,

The results of elemental analysis, thermogravimetry and extraction: cobalt=12.3% of mass., zinc=27,0% wt., tert-butanol=7,2% wt., TRICORONA glycerol=3.7% of the masses..

Example E (comparative). Getting DMC-catalyst containing triavir 2-phosphonopropionic acid, in the absence of tricarinata glycerol (catalyst E).

The catalyst was obtained by a method similar to that described in example D (comparative), but instead of tricarinata glycerin used triavir 2-phosphonopropionic acid (firm Fluka).

The yield of dry powdered catalyst amounted to 5.9,

The results of elemental analysis, thermogravimetry and extraction: cobalt=10,2% wt., zinc=23.5% wt., tert-butanol=2,3 wt. -%, tritely ether 2-phosphonopropionic acid=26,1% of the mass...

Example F (comparative). Getting DMC-catalyst containing diglycidyl ether polypropylenglycol, in the absence of Trevira 2-phosphonopropionic acid (catalyst F).

The catalyst was obtained by the method of analogues of the figures described in example D (comparative), however, instead of tricarinata glycerin used diglycidyl ether polypropylenglycol with srednekamennogo molar mass of 640 (company Aldrich).

The yield of dry powdered catalyst was 6.0,

The results of elemental analysis, thermogravimetry and extraction: cobalt=8,7% wt., zinc=20,2% wt., tert-butanol=4,2% wt., diglycidyl ether polypropylenglycol (ligand)=30.5% of the mass.

Example G (comparative). Getting DMC-catalyst containing a complex of the polyester, in the absence of sodium salt holeva acid (catalyst G).

The catalyst was obtained by a method similar to that described in example D (comparative), but instead of tricarinata glycerin used sophisticated polyester of adipic acid and diethylene glycol, weakly branched by means of trimethylolpropane and having srednekamennogo molar mass of 2300 (carboxyl number of 50 mg KOH/g).

The yield of dry powdered catalyst was 3.9,

The results of elemental analysis, thermogravimetry and extraction: cobalt=12,2% wt., zinc=25,7% wt., tert-butanol=7,1% wt., complex polyester=12.3% of the mass.

Example H (comparative). Getting DMC-catalyst containing a complex of the polyester, in the absence of sodium salt holeva acid (catalyst H).

The catalyst was obtained by a method similar to that described in example D (compare Inom), however, instead of tricarinata glycerin used sodium salt holeva acid.

The yield of dry powdered catalyst was 4.2,

The results of elemental analysis, thermogravimetry and extraction: cobalt=12.6% wt., zinc=27,3% wt., tert-butanol=10,9% wt., sodium salt holeva acid=4,3% of the mass. The obtained catalysts correspond to the General formula

Zn3[Co(JV)6]2*aL1*bL*ZnCl2*dH2O.

Thus, these catalysts other than those mentioned in examples a to H of the ingredients also include chloride, cyano and water. The respective shares in % of the mass. shown in the table below.

ExampleAndInDEFGN
Cl7,56,84,47,17,16,25,96,9
CN26,027,333,632,627,023,132,3the 33.4
H2O2,21,9of 5.4the 10.1the 3.87,14,54,6

Getting Polief is Belyalov

General conditions for synthesis

In a reactor of 500 ml, intended for carrying out reactions under pressure, in an atmosphere of inert gas (under argon) were loaded with 50 grams of polypropyleneglycol with srednekamennogo molecular weight 1000 g/mol, is used as starting compound and 5 mg of catalyst (concentration of 25 parts per million based on the number of synthesized polyetherpolyols), which was heated with stirring to 105°C. Then simultaneously introduced about 5 g of propylene oxide, resulting in a total pressure in the reactor was increased up to 2.5 bar. Further feeding of propylene oxide produced just after he observed the rapid pressure drop in the reactor, indicating the activation of the catalyst. Continuous injection of the rest of the amount of propylene oxide (145 g) was carried out at constant total pressure of 2.5 bar. Upon completion of the introduction of propylene oxide and a two-hour aging the reaction mixture at 105°drove it contains volatile components at a temperature of 90°and a pressure of 1 mbar and cooled it to room temperature.

For characterization of the obtained polyether polyols used the results of determination of carboxylic number, the content of double bonds and viscosity.

Of the reaction was judged based on the kinetic curves, the construction of the authorized coordinates "time is the degree of transformation" (consumption of propylene oxide [g] depending on the reaction time [min]). The induction period was determined by the point of intersection of the tangent conducted to the kinetic curve at the point of maximum slope, with extended base line of this curve. Duration propoxycarbonyl determining the activity of the catalyst corresponds to the time interval between activation of the catalyst (the end of the induction period) and the completion of dosing of propylene oxide. The total duration of the reaction consists of the induction period and duration of propoxycarbonyl.

Example 1. Getting polyetherpolyols in the presence of a catalyst And the concentration of 25 parts per million).

The induction period (minutes):100
The duration of propoxycarbonyl (minutes):40
The total duration of the reaction (minutes):140

Properties polyetherpolyols:

carboxyl number (mg KOH/g):29,4
the content of double bonds (mmol/kg):9
the viscosity at 25°S (MPa):845

Example 2. Getting polyetherpolyols in the presence of catalyst (concentration of 25 parts per million).

The induction period (minutes):140
The duration of propoxycarbonyl (minutes):37
The total duration of the reaction (minutes):177

Properties polyetherpolyols:

carboxyl number (mg KOH/g):30,0
the content of double bonds (mmol/kg):7
the viscosity at 25°S (MPa):821

Example 3. Getting polyetherpolyols in the presence of the catalyst (concentration of 25 parts per million).

The induction period (minutes):80
The duration of propoxycarbonyl (minutes):27
The total duration of the reaction (minutes):107

Properties polyetherpolyols:

carboxyl number (mg KOH/g):30,1
the content of double bonds (mmol/kg):7
the viscosity at 25°S (MPa):863

The metal content in the polyol (without removal of the catalyst) is: zinc (Zn)=5 frequent ppm cobalt (Co)=2 parts per million.

Example 4 (comparative). Getting on epipolae in the presence of a catalyst D (concentration of 25 parts per million).

The induction period (minutes):166
The duration of propoxycarbonyl (minutes):291
The total duration of the reaction (minutes):457

Properties polyetherpolyols:

carboxyl number (mg KOH/g):30,9
the content of double bonds (mmol/kg):8
the viscosity at 25°S (MPa):874

Example 5 (comparative). Getting polyetherpolyols in the presence of catalyst E (concentration of 25 parts per million).

The induction period (minutes):99
The duration of propoxycarbonyl (minutes):110
The total duration of the reaction (minutes):209

Properties polyetherpolyols:

carboxyl number (mg KOH/g):29,9
the content of double bonds (mmol/kg):10
the viscosity at 25°S (MPa):862

Example 6 (comparative). Getting polyetherpolyols in the presence of catalyst F (concentration of 25 parts of the and million).

The induction period (minutes):154
The duration of propoxycarbonyl (minutes):37
The total duration of the reaction (minutes):191

Properties polyetherpolyols:

carboxyl number (mg KOH/g):30,7
the content of double bonds (mmol/kg):7
the viscosity at 25°S (MPa):809

Example 7 (comparative). Getting polyetherpolyols in the presence of catalyst G (concentration of 25 parts per million).

The induction period (minutes):130
The duration of propoxycarbonyl (minutes):150
The total duration of the reaction (minutes):280

Properties polyetherpolyols:

carboxyl number (mg KOH/g):29,5
the content of double bonds (mmol/kg):5
the viscosity at 25°S (MPa):861

Example 8 (comparative). Getting polyetherpolyols in the presence of catalyst H (concentration of 25 parts of the and million).

The induction period (minutes):217
The duration of propoxycarbonyl (minutes):33
The total duration of the reaction (minutes):250

Properties polyetherpolyols:

carboxyl number (mg KOH/g):29,6
the content of double bonds (mmol/kg):6
the viscosity at 25°S (MPa):855

Catalysts a-C, containing, along with tert-butanol two complexing component, in the above reaction conditions exhibit higher activity than catalysts D-H, except that tert-butanol contain only one ligand complex.

Thus, the catalyst containing as the complexing component and TRICORONA glycerin, and tritely ether 2-phosphonopropionic acid has a significantly higher activity than catalysts D and E, containing a complexing components, respectively TRICORONA glycerin or tritherapy ether 2-phosphonopropionic acid; in particular, in the presence of a catalyst And reduces the duration of propoxycarbonyl.

Examples 1-3 show is that due to significantly higher activity new DMC-catalysts according to the invention can be used in such low concentrations, what can opt out of their isolation from synthesized in the presence of polyether polyols.

1. The catalyst based on double metallocyanide (DMC-catalyst) to obtain polyether polyols containing a) double metallocyanide connection, (b) organic complex ligand other than C), c) two non-b) complexing component selected from the group including simple or complex polyesters, simple glycidyloxy esters, esters of carboxylic acids and polyhydric alcohols, bile acids, bile salts, esters of bile acids, amides of bile acids or phosphorus compounds, provided that the selected complexing components C) belong to different groups.

2. DMC catalyst according to claim 1, further containing (d) water and/or e) a water-soluble salt of the metal.

3. DMC catalyst according to claim 1, in which the double metallocyanide connection is hexacyanocobaltate (III)zinc.

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

5. DMC catalyst according to one of claims 1 to 4, in which the catalyst contains 1-80 wt.% a mixture of two complexing components C).



 

Same patents:

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: polymer production.

SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.

EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.

21 cl, 2 dwg, 2 tbl, 3 ex

The invention relates to polyether polyols with the content of primary hydroxyl groups of from 40 to 95 mol.% and General content oxyethylene blocks more than 25 wt.%, which are obtained in the presence of CBM - catalyst poly(oksietilenom/oxypropylene) - terminal block

The invention relates to hydrophilic processing of films made from styrene resins, and the use of modifiers to improve, for example, antistatic properties and sliding properties (slipperiness) films

The invention relates to a method for carrying out gas-liquid reactions, which proceed with participation of the mechanism of dispersion gas to liquid and liquid to gas

The invention relates to a semi-continuous method and system for producing Preductal of alkalisation by carrying out the reactions of addition of accelerated on the initiator growth macromolecular chain, which has at least one active hydrogen atom
The invention relates to methods of producing polyether of polyglycols (oligomers of 1,2-oxirane) and can be used in chemical industry for production of surfactants, plasticizers, binders, complexing agents, etc

The invention relates to an improved method for producing polyoxyethyleneglycol, in particular oxyalkylene, higher fatty alcohols, ALKYLPHENOLS, glycols, amines and carboxylic acids, highly effective nonionic surfactants

FIELD: organic chemistry, polymer materials.

SUBSTANCE: polyester-polyols are obtained by double metalcyanide catalyzed polyaddition of alkylenoxide to starting material containing active hydrogen atoms. Alkylenoxide is continuously fed into reactor during induction period while maintaining constant pressure in reactor.

EFFECT: method for polyester-polyol production with decreased induction time.

2 ex, 1 dwg

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: polymer production.

SUBSTANCE: polyoxyalkylene-polyols are obtained via direct polyoxyalkylenation of acid-sensitive low-molecular initiator with molecular weight below 400 Da in presence of double complex metal cyanide catalyst. Process comprises: (i) creation of appropriate conditions in reactor of polyoxyalkylenation in presence of double complex metal cyanide catalyst; (ii) continuously feeding into reactor alkylene oxide and above-mentioned initiator; and (iii) discharging polyether product. Loss of catalyst activity is reduced by performing at least one of the following operations: acidification of acid-sensitive low-molecular initiator before feeding it into reactor; and treatment of the same with effective amount of a substance other than acid, which reacts with base or absorbs base, before feeding it into reactor.

EFFECT: prevented catalyst from loosing its activity and essentially decreased high-molecular fraction and polydispersity of polyoxyalkylene-polyols.

21 cl, 2 dwg, 2 tbl, 3 ex

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

FIELD: polymerization catalysts.

SUBSTANCE: invention relates to novel organometallic compounds and to olefin polymerization catalytic systems including such organometallic compounds, and also to a method for polymerization of olefins conduct in presence of said catalytic system. Novel organometallic compound is prepared by bringing into contact (i) compound of general formula I: (I), where Ra, Rb, Rc, and Rd, identical or different, represent hydrocarbon groups; and (ii) Lewis acid of general formula MtR

13
, where Mt represents boron atom and R1, identical or different, are selected from halogen and halogenated C6-C30-aryl groups.

EFFECT: enabled preparation of novel olefin polymerization cocatalysts, which reduce use of excess cocatalyst relative to alkylalumoxanes, do not lead to undesired by-products after activation of metallocene, and form stable catalytic compositions.

14 cl, 1 tbl, 32 ex

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