Double metal cyanide catalysts for production of polyetherpolyols

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

 

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

Double metallocyanide catalysts (DMC-catalysts for polyaddition of alkalisation to the original compounds containing active hydrogen atoms are known (see, for example, U.S. patent US-A 3404109, US-A 3829505, US-A 3941849 and US-And 5158922). The use of such DMC-cialization to obtain polyether polyols allows, in particular, to reduce the proportion of monofunctional polyethers with terminal double bonds, so-called Manolov, in comparison with obsesity a method of producing polyether polyols using alkaline 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 conducting the interaction of 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 way to obtain the catalyst includes, for example, a mixture of aqueous solutions of zinc chloride (in excess) and hexacyano is Baltata potassium followed by the addition of dimethoxyethane (glima) to the resulting suspension. After filtration and washing of the catalyst with an aqueous solution of glima get active catalyst of General formula

Zn3[Co(JV)6]2×ZnCl2yH2O z

(see European patent application EP-A 700949).

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 patent application WO 97/40086 known DMC-catalysts, which are due to the use of tert.-butanol as the organic complex ligand (alone or in combination with a simple polyester (EP-A 700949, EP-A 761708, WO 97/40086)) further reduce the proportion of monofunctional polyethers with terminal double bonds upon receipt of the polyether polyols. In addition, the use of such DMC-catalysts reduces the induction time by polyaddition reaction of alkalisation with the corresponding parent compounds and increases the activity of the catalyst.

The present invention is to offer a more superior DMC-catalysts for the polyaddition of alkalisation to the corresponding source compounds with increased activity in comparison with known still types of catalysts. The use of such catalysts increases the efficiency of the production of polyether polyols by C the time alkoxysilane. In the ideal case, the catalyst with higher activity can be used in such low concentrations (25 ppm or less)that do not require a very time-consuming selection of the catalyst from the product, and the product can be used directly to obtain polyurethane.

Unexpectedly, it was found that DMC-catalysts containing ether α ,β unsaturated carboxylic acid as a complex ligand, have a fairly high activity upon receipt of polyetherpolyols.

The object of the present invention is a dual metallocyanide catalyst (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) one or more esters α ,β unsaturated carboxylic acids, preferably one ether α ,β unsaturated carboxylic acid.

The proposed catalyst may optionally contain (d) water, preferably in an amount of from 1 to 10 wt.%, and/or e) one or more water-soluble metal salts, preferably in an amount of 5 to 25 wt.%, formula (I) M(X)nfrom the stage to receive dual metallocyanide compounds a). In the formula (I) M viber which is made of metal zinc Zn(II), iron Fe(II), Nickel Ni(II), manganese MP(II), cobalt(II), tin Sn(II), lead Pb(II), iron Fe(III), molybdenum Mo(IV), molybdenum Mo(VI), aluminum Al(III), vanadium V(V), vanadium V(IV), strontium Sr(II), tungsten W(IV), tungsten W(VI), copper cu(II) and chromium CR(III). The most preferred metals are Zn(II), Fe(II), Co(II) and Ni(II). X may be the same or different, preferably identical, and represent an anion, preferably selected from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, carboxylates, oxalates or nitrates. Values for n equal to 1, 2 or 3.

Contained in the proposed catalysts double metallocyanide compounds (a) are the reaction products of water-soluble metal salts and water-soluble salts of metallocyanide.

Water-soluble metal salts, suitable for double metallocyanide compounds a)preferably have the General formula (I) M(X)nand M is selected 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). The most preferred metals are 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, isothiocyanate is, carboxylates, oxalates or nitrates. Values for n equal to 1, 2 or 3.

Examples of suitable water-soluble metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, sulfate, iron(II)bromide, iron(II)chloride 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 metals iron Fe(II), Fe(III), cobalt(II), Co(III), chromium CR(II)Cr(III), manganese MP(II), Mn(III), iridium Ir(III), Nickel Ni(II), rhodium Rh(III), ruthenium Ru(II), vanadium 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 metallocyanide may contain one or more of such metals. Cations Y are the same or different, preferably identical, and are selected from the group comprising alkali metal ions and alkaline earth metal ions. Anions And are the same or different, preferably identical, and are selected from the group of halides, hydroxides, sulfates, carbonates, tiantou, thiocyanates, isocyanates, isothioscyanates, to the of rboxylic, oxalates or nitrates. As a and b and take the integer value, with values for a, b and C are chosen so as to ensure electroneutrality salt metallocyanide; and preferably equal to 1,2,3 or 4; b is preferably 4, 5 or 6; C preferably has the value 0. Examples of suitable water-soluble salts of metallocyanide include hexacyanocobaltate(III), potassium hexacyanoferrate(II) potassium hexacyanoferrate(III) potassium hexacyanocobaltate(III) calcium and hexacyanocobaltate(III) lithium.

Preferred dual metallocyanide compound (a)contained in the proposed catalysts are compounds of General formula (III)

Mx[M'x·(CN)y]z,

where M has the same meaning as in the formula (I), and

M' has the same meaning as in the formula (II), and

x, x', y, and z are an integer value and is selected so as to ensure electroneutrality double metallocyanide connection.

Preferably:

x=3, x'=1, y=6 and z=2,

M represents Zn (II), Fe (II), Co (II) or Ni (II) and

M' denotes Co (III) Fe (III), Cr (III) or Ir (III).

Examples of suitable double metallocyanide compounds (a) include hexacyanocobaltate(III) zinc, hexacyanoferrate(III), zinc hexacyanoferrate(III), zinc and hexacyanocobaltate(III) cobalt(II). Other examples of suitable double metal is anenih compounds are, for example, in patent US-A 5158922. Most preferred is the use of hexacyanocobaltate(III) zinc.

Contained in the proposed DMC-catalysts organic complex ligands b) in principle known and described in detail in the literature relating to the prior art (for example, in US-A 5158922, US-A 3404109, US-A 3829505, US-A 3941849, EP-A 700949, EP-A 761708, JP-A 4145123, US-A 5470813, EP-A 743093 and WO 97/40086). Preferred organic complex ligands are water-soluble organic compounds with heteroatoms, such as oxygen, nitrogen, phosphorus or sulfur, which are capable of forming double metallocyanide compound (a) complexes. Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, urea, NITRILES, sulfides and mixtures thereof. Preferred organic complex ligands are water-soluble aliphatic alcohols, such as ethanol, isopropanol, n-butanol, Isobutanol, sec.-butanol and tert-butanol. The most preferred tert-butanol.

The organic complex ligand added either during the preparation of the catalyst, either directly after the deposition of the double metallocyanide connection). The organic complex ligand is usually used in excess.

Offer DMC-catalysts contain double the e metallocyanide connection (a) in quantities of from 20 to 90 wt.%, preferably from 25 to 80 wt.%, in terms of the number of finished catalyst, and the organic complex ligand b) in quantities of from 0.5 to 30 wt.%, preferably from 1 to 25 wt.%, in terms of the number of finished catalyst. Offer DMC-catalysts typically contain from 1 to 79.5 wt.%, preferably from 1 to 50 wt.%, in terms of the number of finished catalyst, ester α ,β unsaturated carboxylic acids (C).

Ethers α ,β unsaturated carboxylic acid), suitable for the proposed catalysts are, for example, mono-, di-, tri - or polyesters of acrylic acid and alkyl-, alkoxy-, alkoxycarbonyl and alkoxycarbonylmethyl acids and alcohols containing from 1 to 30 carbon atoms, or polyether polyols.

As the alcohol component suitable one-, two-, three - or polyhydric aryl, kalkilya, alkoxyalkyl and alkyl alcohols with 1-30 carbon atoms, preferably 1 to 24 carbon atoms, most preferably 1-20 carbon atoms, preferably kalkilya, alkoxyalkyl and alkyl alcohols, most preferably alkoxyalkyl and alkyl alcohols.

Further, as an alcohol component suitable polyalkylene glycols and polyalkylene glycol ethers, preferably polypropylenglycol and polietilenglikol is or their ethers with molecular mass of from 200 to 10000, preferably from 300 to 9000, most preferably from 400 to 8000.

As α ,β unsaturated carboxylic acids can be considered an acrylic acid and alkyl-, alkoxy - and alkoxycarbonylmethyl acid with 1-20 carbon atoms, such as 2-methylacrylate acid (methacrylic acid), 3-methylacrylate acid (crotonic acid), TRANS-2,3-dimethylacrylic acid (Tihonova acid), 3,3-dimethylacrylic acid (senecia acid) or 3-ethoxyacrylate acid, preferably acrylic acid, 2-methylacrylate acid, 3-methylacrylate acid and 3-ethoxyacrylate acid, most preferably acrylic acid and 2-methylacrylate acid.

Ethers α ,β unsaturated carboxylic acid used to obtain the proposed catalysts are usually obtained by the esterification of mono-, di-, tri-, Tetra - or polyhydroxybenzenes with 1-30 carbon atoms, such as methanol, ethanol, ethanediol (ethylene glycol), 1-propanol, 2-propanol, 1,2-propandiol, 1,3-propandiol, 1,2,3-propantriol (glycerine), butanol, 2-butanol, isobutyl alcohol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2,3-butanetriol, 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-hexadecanol, 1-heptadecanol, 9-octadecanol, 1,1,1-Tris(hydroxymethyl)propane, p is starfrit, methoxymethanol, ethoxyethanol, propoxyethanol, butoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethanol, methyl ester hydroxyoctanoic acid, ethyl ester hydroxyoctanoic acid, propyl ester hydroxyoctanoic acid, methyl ester hydroxypropionic acid, ethyl ester hydroxypropionic acid, propyl ester hydroxypropionic acid, or politicolegal, such as glycols and polypropylenglycol, with the appropriate α ,β unsaturated carboxylic acids, optionally in the presence of catalysts.

Preferred are mono-, di - and treatery acrylic and methacrylic acid with ethanediol, 1,2-propane diol, 1,3-propane diol, 1,4-butanediol, 1,6-hexanediol, 1,2,3-propantriol (glycerine), 1,1,1-Tris(hydroxymethyl)propane, 1,1,1-Tris(hydroxymethyl)propanecarboxylate, 1,1,1-Tris(hydroxymethyl)provenprobable, glycols and polypropylenglycol.

The most preferred esters α ,β unsaturated carboxylic acids are polietilenglikolsuktsinata, polietilenglikolsuktsinata, polietilenglikolsuktsinata, polietilenglikolmonostearat, polypropylenglycol, polypropyleneglycol, polypropyleneglycol, polypropyleneglycol, 1,2,3-propertiesvaries is, 1,2,3-proportionately, 1,2,3-proportionality, 1,2,3-propantriol-1,3-(2-hydroxypropoxy)-diacrylate, 1,2,3-propanetricarboxylate, 1,4-potentiality, 1,4-butanedioldiglycidylether, 1,6-hexanediamine, 2-hydroxypropylmethacrylate, 1,1,1-Tris(hydroxymethyl)prophetically, 1,1,1-Tris(hydroxymethyl)propanedinitrile, 1,1,1-Tris(hydroxymethyl)propagateactivity, 1,1,1-Tris(hydroxymethyl)properpropertyoffice or 1,1,1-Tris(hydroxymethyl)properpropertyoffice.

Methods of obtaining esters α ,β unsaturated carboxylic acids are well known and are described in detail in the literature: see, for example, Kirk-Othmer: Encylopedia of Chemical Technology", Band 1, 4. Edition, 1991, p. 291ff.; "Rompp: Lexikon Chemie", Band 1, 10. Edition, Stuttgart/New York 1996, S. 49, Band 4, 10. Edition, Stuttgart/New York 1998, S. 2629 ff.; "Ullmanns Encyclopedia of Industrial Chemistry", Band A1, 5. Edition, 1995, p. 161 ff.

Can be used also any mixtures of the aforementioned esters α ,β unsaturated carboxylic acid.

Analysis of the composition of the catalyst is carried out in the usual way by using elemental analysis, thermogravimetry or extractive removal of the ether fraction α ,β unsaturated carboxylic acids with subsequent gravimetric determination.

The proposed catalysts may be crystalline, partially crystalline or amorphous. Analysis of cristalli the activities carried out in the usual way using the powder roentgendifractometric.

Preferred are catalysts containing

a) hexacyanocobaltate(III) zinc,

b) tert.-butanol and

c) ether α ,β unsaturated carboxylic acid.

Offer DMC-catalysts are usually obtained in aqueous solution by reacting (a) metal salts, in particular of the formula (I), salts metallocyanide, in particular of the formula (II), β ) organic complex ligands b)other than esters α ,β unsaturated carboxylic acid, and γ ) ether α ,β unsaturated carboxylic acid.

First preferably subjected to interaction of aqueous solutions of metal salt (e.g. zinc chloride, used in stoichiometric excess (at least 50%by mole, in terms of salt metallocyanide)) and salts metallocyanide (for example, hexacyanocobaltate potassium) in the presence of the organic complex ligand b) (for example, tertbutanol), obtaining a suspension containing double metallocyanide connection a) (for example, hexacyanocobaltate zinc), water (a), excess metal salt (e) and the organic complex ligand b).

The organic complex ligand b) may be in an aqueous solution of metal salt and/or salt metallocyanide, or it is added to the suspension obtained after precipitation of the double metallocyanide what about the connection). Turned out to be expedient to mix the aqueous solutions and organic complex ligand b) with vigorous stirring. The resulting suspension is then usually treated with ether α ,β unsaturated carboxylic acid). Ether α ,β unsaturated carboxylic acid) is used mainly mixed with water and the organic complex ligand b).

Then known methods, such as centrifugation or filtration, the catalyst was separated from the suspension. In a preferred embodiment of the invention, the selected catalyst is then washed with an aqueous solution of an organic complex ligand b) (for example, by re-suspension and subsequent re-allocation by filtration or centrifugation). Thus, the proposed catalyst can be removed, for example, water-soluble by-products, such as potassium chloride.

The amount of organic complex ligand b) in the aqueous wash solution is preferably in the range from 40 to 80 wt.% in terms of the whole solution. The next step would be to add in an aqueous wash solution with a little ether α ,β unsaturated carboxylic acid, preferably in the range from 0.5 to 5 wt.%, in terms of the whole solution.

In addition, the washing of the catalyst, it is advisable to spend more than the underwater times. For this example, the first water washing can be repeated. However, for subsequent leaching, it is preferable to use aqueous solutions, and the complex mixture of organic ligands and ether α ,β unsaturated carboxylic acid.

The washed catalyst is then, if necessary, after comminution, dried at temperatures generally in the range from 20 to 100° and pressures generally in the range from 0.1 mbar to normal (1013 mbar).

Another object of the present invention is the application of the proposed DMC-catalysts in the method of producing polyether polyols by polyaddition of alkalisation to the original compounds containing active hydrogen atoms.

As alkalisation preferably used are ethylene oxide, propylene oxide, butylenes, and mixtures thereof. Synthesis of polyester chains by allotriophagy can be produced, for example, only using Monomeric epoxide or statistically or block using 2 or 3 different Monomeric epoxides. See "Ullmanns Encyclopedie der industiellen Chemie", Band A21,1992, S. 670ff.

As a source of compounds containing active hydrogen atoms, are preferably used compounds with (srednekislye) molecular weights from 18 to 2000, containing from one to eight hydroxyl groups. Examples of the same, the compounds include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethyleneimine, bisphenol a, trimethylolpropane, glycerin, pentaerythritol, sorbitol, cane sugar, degraded starch or water.

Preferably used such source compounds containing active hydrogen atoms which are derived, for example, by conventional alkaline catalysis of the above low molecular weight initiators and represent oligomeric products alkoxysilane with (srednekislye) molecular mass of from 200 to 2000.

Polyprionidae of alkalisation catalyzed proposed catalysts, to the original compounds containing active hydrogen atoms occurs at temperatures of in General from 20 to 200° C, preferably in the range from 40 to 180° S, most preferably at temperatures from 50 to 150° C. the Reaction can be carried out with a total pressure of from 0.001 to 20 bar. Polyprionidae can be conducted in bulk or in an inert organic solvent such as toluene and/or tetrahydrofuran. The amount of solvent is usually from 10 to 30 wt.% in terms of the mass of receivable of polyetherpolyols.

The concentration of catalyst is chosen so that under these conditions the reaction could well control the polyaddition reaction. To ncentrate catalyst is, typically, in the range from 0.0005 wt.% up to 1 wt.%, preferably in the range from 0.001 wt.% to 0.1 wt.%, most preferably in the range from 0.001 to 0.0025 wt.%, in terms of the amount receivable of polyetherpolyols.

Srednekanskaya molecular weight of the polyether polyols obtained by the proposed method are in the range from 500 to 100,000 g/mol, preferably in the range from 1000 to 50,000 g/mol, most preferably in the range from 2000 to 20,000 g/mol.

Polyprionidae may be performed continuously or periodically, for example, portions or proportionem way. Due to their clearly higher activity proposed catalysts can be used at very low concentrations (25 ppm or less, in terms of the amount receivable of polyetherpolyols). If produced in the presence of the proposed catalysts politically used to produce polyurethanes (Kunststoffhandbuch, Band 7, Polyurethane, 3rd. Edition, 1993, S. 25-32 und 57-67), you can withdraw from the stage of removal of the catalyst from polyetherpolyols, without compromising the quality of the product is polyurethane.

Examples

Preparation of catalyst

Example A. Obtaining DMC-catalyst using polietilenglikolsuktsinata (catalyst A).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 70 ml disti the profiled water is added with vigorous stirring (about 24000./min) a solution of 12.5 g (from 91.5 mmol) of zinc chloride in 20 ml of distilled water. Directly thereafter, to the resulting suspension was added a mixture of 50 g of tert-butanol and 50 g of distilled water and then strongly stirred (about 24000./min) for 10 minutes Then add the mixture consisting of 1 g of polietilenglikolsuktsinata with srednetsenovoj molecular weight of 575 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim), 1 g of tertbutanol and 100 g of distilled water, and stirred for 3 minutes (1000 rpm./min). Solid allocate by filtration, then stirred for 10 min with a mixture of 70 g of tertbutanol, 30 g of distilled water and 1 g of the above polietilenglikolsuktsinata (about 10000./min) and again filtered. In conclusion, once again stirred for 10 min with a mixture of 100 g of tertbutanol and 0.5 g of the above polietilenglikolsuktsinata (about 10000./min). After filtration, the catalyst was dried at 50° and normal pressure until constant weight.

The output of the dried powdered catalyst: 5,4, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=10.9 wt.%, zinc=22,8 wt.%, tert-butanol=6.2 wt.%, polietilenglikolmonostearat=19.5 wt.%, Cl=5,1 wt.%, CN=28,9 wt.%, water=6.6 wt.%.

Example Century. Getting DMC-catalyst using polietilentireftalat (catalyst).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata from the example And apply polietilenglikolmonostearat with srednetsenovoj molecular weight of 875 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim).

The output of the dried powdered catalyst: 5,4,

Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=11,2 wt.%, zinc=24,3 wt.%, tertbutanol=4.9 wt.%, polietilenglikolmonostearat=18,5 wt.%, Cl=6,1 wt.%, CN=RUR 29.79 wt.%, water=5.3 wt.%.

Example C. Obtaining DMC-catalyst using polypropylenglycol (catalyst C).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata of example And use polypropyleneglycol with srednetsenovoj molecular weight of 375 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim).

The output of the dried powdered catalyst: 6,2, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=10,2 wt.%, zinc=23,9 wt.%, tert-butanol=6.6 wt.%, polypropyleneglycol=20,6 wt.%, Cl=7.2 wt.%, CN=to 27.0 wt.%, water=4.5 wt.%.

Example D. Obtaining DMC-catalyst using 1,6-hexandioldiacrylate (catalyst D).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata of example And use 1,6-hexaniacinate.

The output of the dried powdered catalyst: 5,5, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=10.0 wt.%, zinc=23,3 wt.%, tert-butanol=10,2 wt.%, 1,6-hexaniacinate=15.5 wt.%, Cl=7.2 wt.%, CN=26.5 wt.%, water=7,Mas.%.

The example that is Getting DMC-catalyst using 1,1,1-trihydroxyphenyl)preventionrelated (catalyst E).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata of example And use 1,1,1-Tris(hydroxymethyl)proventricular.

The output of the dried powdered catalyst: 5,0, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=11,8 wt.%, zinc=27,7 wt.%, tert-butanol=11,8 wt.%, 1,1,1-Tris(hydroxymethyl)proventricular=2.4 wt.%, Cl=8.8 wt.%, CN=31,3 wt.%, water=6.2 wt.%.

Example F. Obtaining DMC-catalyst using 1,1,1-Tris(hydroxymethyl)propanedinitrile (catalyst F).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata of example And use 1,1,1-Tris(hydroxymethyl)-propanecarboxylate(14/3 EO/OH)triacrylate (EA/HE refers to the ratio of ethyleneoxide groups to hydroxyl groups) with srednetsenovoj molecular weight of about 912 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim).

The output of the dried powdered catalyst: 6,1, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=10.9 wt.%, zinc=24,9 wt.%, tert-butanol=5.1 wt.%, 1,1,1-Tris(hydroxymethyl)propanecarboxylate(14/3 EO/OH)-triacrylate=5.7 wt.%, Cl=7.4 wt.%, CN=28,9 wt.%, water=17,1 wt.%.

Example G. Obtaining DMC-catalyst using 2-is hydroxymethylglycinate (catalyst G).

The experiment is carried out as in example a, but instead of polietilenglikolsuktsinata of example And use 2-hydroxypropylmethacrylate.

The output of the dried powdered catalyst: 4,9, Elemental analysis, thermogravimetric analysis and extraction:

Cobalt=12.4 wt.%, zinc=24,8 wt.%, tert-butanol=11,7 wt.%, 2-hydroxypropylmethacrylate =9.1 wt.%, Cl=4.5 wt.%, CN=32.9 wt.%, water=4.6 wt.%,

Example H (comparative). Getting DMC-catalyst without the use of ether α ,β unsaturated carboxylic acid (catalyst H, the synthesis according to JP-A-4145123).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 75 ml of distilled water is added with vigorous stirring (about 24000./min) a solution of 10 g (73,3 mmol) of zinc chloride in 15 ml of distilled water. Directly thereafter, to the resulting suspension was added a mixture of 50 g of tertbutanol and 50 g of distilled water and then strongly stirred (about 24000./min) for 10 minutes, the Solid is allocate by filtration, then stirred (about 10000./min) for 10 min with 125 g of a mixture of tert-butanol and distilled water (70/30 by weight) and again filtered. In conclusion, once again stirred (about 10000./min) for 10 min with 125 g of tertbutanol. After filtration, the catalyst was dried at 50° and normal pressure until constant weight.

The output of the dried poroshkoobraz the CSOs catalyst: is 3.08,

Elemental analysis:

Cobalt=13,6 wt.%, zinc=27,4 wt.%, tert-butanol=14.2 wt.%, CI=5.2 wt.%, CN=36,0 wt.% and water=3.6 wt.%.

Getting polyether polyols

General methods

In a 500-ml reactor operating under pressure, load in a protective gas atmosphere (argon) 50 g polypropylenglycol initiator (with srednetsenovoj molecular weight 1000 g/mol) and 4-5 mg of catalyst (25 ppm, in terms of the amount receivable polyaminopropyl) and heated with stirring to 105° C. Then immediately added propylene oxide (about 5 g), until the total pressure will not increase to 2.5 bar. Repeated addition of propylene oxide is produced only in the case when there has been a rapid pressure drop in the reactor. This rapid pressure drop in the reactor shows that the catalyst is activated. Then continuously add the residual quantity of propylene oxide (145 g) at constant pressure of 2.5 bar. After the addition of propylene oxide and 2 hours after start of the reaction proceeding at 105° C, volatile components are distilled off at 90° (1 mbar), after which produce cooling to room temperature.

Received preferability characterized by determining the hydroxyl number, the content of double bonds and viscosity.

Over the course of the reaction is observed on the curve of the time-conversion (races of the od of propylene oxide [g] reaction time [min]). From the point of intersection of the tangent at the steepest point of the curve the time-conversion with a continuation of the baseline curve determine the induction time. Times propoxycarbonyl, which are decisive for the activity of the catalyst, correspond to the period of time between activation of the catalyst (the end of the induction period) and the end of the addition of propylene oxide. The total reaction time is the amount of time induction time and propoxycarbonyl.

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

Induction time: 87 min

Time propoxycarbonyl: 54 min

The total reaction time: 141 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 29,4

The content of double bonds (mmol/kg): 8

Viscosity 25° With (MPa· (C): 836

Without removing the catalyst metal content in the polyol is: Zn=6 parts per million, SD=3 parts per million.

Example 2. Getting polyetherpolyols using catalyst (25 ppm)

Induction time: 136 min

Time propoxycarbonyl: 98 min

The total reaction time: 234 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 31,3

The content of double bonds (mmol/kg): 11

Viscosity 25° With (MPa· (C): 832

Example 3. Getting polyetherpolyols with the use of the catalyst (25 ppm)

In EMA induction: 151 min

Time propoxycarbonyl: 209 min

The total reaction time: 360 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 30,1

The content of double bonds (mmol/kg): 8

Viscosity 25° With (MPa· (C): 937

Example 4. Getting polyetherpolyols using catalyst D (25 parts per million)

Induction time: 318 min

Time propoxycarbonyl: 511 min

The total reaction time: 829 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 30,0

The content of double bonds (mmol/kg): 7

Viscosity 25° With (MPa· (C): 1060

Example 5. Getting polyetherpolyols using catalyst E (25 ppm)

Induction time: 120 min

Time propoxycarbonyl: 87 min

The total reaction time: 207 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 29,8

The content of double bonds (mmol/kg): 7

Viscosity 25° With (MPa· (C): 922

Example 6 Obtaining polyetherpolyols using catalyst F (25 parts per million)

Induction time: 88 min

Time propoxycarbonyl: 99 min

The total reaction time: 187 min

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 30,0

The content of double bonds (mmol/kg): 8

Viscosity 25° With (MPa· (C): 889

Example 7 Getting polyetherpolyols using catalyst G (25 parts per million)

Induction time: 120 min

Time propoxy the simulation: 143 min

The total reaction time: 265 minutes

Polyetherpolyols:

Hydroxyl number (mg KOH/g): 29,9

The content of double bonds (mmol/kg): 7

Viscosity 25° With (MPa· (C): 990

Example 8 (comparative)

Catalyst H (25 ppm) does not show activity under the above described reaction conditions even after 10h of time of induction.

Examples 1-8 show that the new proposed according to the invention DMC-catalysts, due to their higher activity upon receipt of the polyether polyols can be used in such low concentrations that it is possible to avoid the stage of selection of the catalyst from the polyol.

1. Double metallocyanide catalyst (DMC-catalyst)containing

a) one or more double metallocyanide connections

b) one or more than)organic complex ligands and

c) one or more esters α,βunsaturated carboxylic acid.

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 or 2, 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 represents a tert-butanol.

5. DMC-rolled the ATOR according to one of claims 1 to 4, in which the catalyst contains from 1 to 79.5 wt.% ether α,βunsaturated carboxylic acid.

6. DMC catalyst according to one of claims 1 to 5, in which the ether α,βunsaturated carboxylic acid is polietilenglikolya, polietilenglikolmonostearat, polietilenglikolmonostearat, polietilenglikolmonostearat, polypropylenglycol, polypropyleneglycol, polypropyleneglycol, polypropyleneglycol, 1,2,3-propane-trilliaceae, 1,2,3-preventionbiomechanical, 1,2,3-propane-theatrical, 1,2,3-propantriol-1,3-(2-hydroxypropoxy)-diacrylate, 1,2,3-propanetricarboxylate, 1,4-batangyagit, 1,4-potentialtheorie, 1,6-hexanediamine, 2-hydroxy-propylbetaine, 1,1,1-Tris(hydroxymethyl)propane-acrylate, 1,1,1-Tris(hydroxymethyl)propanedinitrile, 1,1,1-Tris(hydroxymethyl)propanedinitrile, 1,1,1-Tris(hydroxymethyl)properpropertyoffice or 1,1,1-Tris(hydroxymethyl)properpropertyoffice.



 

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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.

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