RU2248241C2 - Double metal cyanide catalysts for production of polyetherpolyols - Google Patents

Abstract

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

Description

The present invention relates to new double metal cyanide catalysts (DMC catalysts) for the preparation of polyether polyols by polyaddition of alkylene oxides to the starting compounds containing active hydrogen atoms.

Binary metal cyanide catalysts (DMC catalysts) for the polyaddition of alkylene oxides to the starting compounds containing active hydrogen atoms are known (see, for example, US Pat. Nos. US-A 3404109, US-A 3829505, US-A 3941849 and US-A 5158922). The use of such DMC catalysts for the production of polyether polyols allows, in particular, to reduce the proportion of monofunctional polyethers with terminal double bonds, the so-called monools, in comparison with the generally known method for producing polyether polyols using alkaline catalysts such as alkali metal hydroxides. Thus obtained polyether polyols can be processed into high-quality polyurethanes (for example, elastomers, foams, coatings). DMC catalysts are usually prepared by reacting an aqueous solution of a metal salt with an aqueous solution of a metal cyanide salt in the presence of an organic complex ligand, for example, an ether. A typical catalyst preparation method involves, for example, mixing aqueous solutions of zinc chloride (in excess) and potassium hexacyanocobaltate, followed by the addition of dimethoxyethane (glime) to the resulting suspension. After filtering and washing the catalyst with an aqueous solution of glime, an active catalyst of the general formula is obtained

Zn ₃ [Co (CN) ₆ ] ₂ × ZnCl ₂ yH ₂ O z

(see European patent application EP-A 700949).

From Japanese patent application JP-A 4145123, US 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 thanks to the use of tert-butanol as an organic complex ligand (alone or in combination with polyether (EP-A 700949, EP-A 761708, WO 97/40086)), the proportion of monofunctional polymers with terminal double bonds is further reduced in the preparation of polyether polyols . In addition, the use of such DMC catalysts reduces the induction time during the polyaddition of alkylene oxides with the corresponding starting compounds and increases the activity of the catalyst.

The objective of the present invention is to provide even more improved DMC catalysts for the polyaddition of alkylene oxides to the corresponding starting compounds, which have increased activity compared to the types of catalysts known so far. The use of such catalysts increases the efficiency of the process of producing polyether polyols due to the reduction of alkoxylation time. In the ideal case, due to its higher activity, the catalyst can be used in such low concentrations (25 ppm or less) that the very laborious separation of the catalyst from the product is no longer required, and the product can be used directly to produce polyurethane.

Unexpectedly, it was found that DMC catalysts containing an ester of α, β-unsaturated carboxylic acid as a complex ligand have a fairly high activity in the production of polyether polyols.

An object of the present invention is a dual metal cyanide catalyst (DMC catalyst) comprising

a) one or more, preferably one double metal cyanide compound,

b) one or more, preferably one other than c) an organic complex ligand, and

c) one or more esters of α, β-unsaturated carboxylic acids, preferably one ester of 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 from 5 to 25 wt.%, Of the formula (I) M (X) _n from the step of producing double metallocyanide compounds a). In the formula (I) M, zinc Zn (II), iron Fe (II), nickel Ni (II), manganese Mn (II), cobalt Co (II), tin Sn (II), and lead Pb (II) are selected from metals: , 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), Cu (II) copper and Cr (III) chromium. The most preferred metals are Zn (II), Fe (II), Co (II) and Ni (II). X may be the same or different, preferably the same, and denote an anion, preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. Values for n are 1, 2, or 3.

The double metal cyanide compounds contained in the proposed catalysts a) are reaction products of water-soluble metal salts and water-soluble metal cyanide salts.

Water-soluble metal salts suitable for the preparation of double metal cyanide compounds a) preferably have the general formula (I) M (X) _n , M being selected from 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). Anions X are the same or different, preferably the same, and are preferably selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. Values for n are 1, 2, or 3.

Examples of suitable water soluble metal salts include zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron (II) sulfate, iron (II) bromide, iron (II) chloride, cobalt (II) chloride, cobalt thiocyanate (II), nickel (II) chloride and nickel (II) nitrate. Mixtures of various water-soluble metal salts may also be used.

Water-soluble salts of metallocyanides suitable for the preparation of double metallocyanide compounds a) preferably have the general formula (II) (Y) _a M ′ (CN) _b (A) _c , M ′ being selected from metals iron Fe (II), Fe (III ), cobalt Co (II), Co (III), chromium Cr (II), Cr (III), manganese Mn (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). The water-soluble salt of the metallocyanide may contain one or more of these metals. Cations Y are the same or different, preferably the same, and are selected from the group consisting of alkali metal ions and alkaline earth metal ions. Anions A are the same or different, preferably the same, and are selected from the group of halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates. Both a, b and c take an integer value, and the values for a, b and c are chosen so as to ensure the electroneutrality of the metal cyanide salt; and preferably equal to 1,2,3 or 4; b is preferably 4, 5 or 6; c is preferably 0. Examples of suitable water-soluble salts of metallocyanides include potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), calcium hexacyanocobaltate (III) and lithium hexacyanocobaltate (III).

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

M _x [M ' _x · (CN) _y ] _z ,

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

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

x, x ', y, and z are integer values and are selected so as to ensure the electroneutrality of the double metal cyanide compound.

Preferably:

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

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

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

Examples of suitable double metallocyanide compounds a) include zinc hexacyanocobaltate (III), zinc hexacyaniriridate (III), zinc hexacyanoferrate (III) and cobalt (II) hexacyanocobrate (III). Other examples of suitable double metal cyanide compounds are given, for example, in US Pat. No. 5,158,922. The use of zinc hexacyanocobaltate (III) is most preferred.

The organic complex ligands contained in the proposed DMC catalysts are in principle known and described in detail in the literature related 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 complexes with the double metallocyanide compound a). Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, ethers, esters, amides, ureas, 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. Most preferred is tert-butanol.

The organic complex ligand is added either during the preparation of the catalyst or immediately after the precipitation of the double metallocyanide compound a). Organic complex ligand is usually used in excess.

The proposed DMC catalysts contain double metal cyanide compounds a) in amounts from 20 to 90 wt.%, Preferably from 25 to 80 wt.%, Calculated on the amount of the finished catalyst, and organic complex ligands b) in amounts from 0.5 to 30 wt.%, preferably from 1 to 25 wt.%, in terms of the amount of finished catalyst. The proposed DMC catalysts usually contain from 1 to 79.5 wt.%, Preferably from 1 to 50 wt.%, Calculated on the amount of the finished catalyst, α, β-unsaturated carboxylic acid ester c).

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

Suitable alcohol components are mono-, di-, tri- or polyhydric aryl, aralkyl, alkoxyalkyl and alkyl alcohols with 1-30 carbon atoms, preferably with 1-24 carbon atoms, most preferably with 1-20 carbon atoms, preferably aralkyl, alkoxyalkyl and alkyl alcohols, most preferably alkoxyalkyl and alkyl alcohols.

Further, polyalkylene glycols and polyalkylene glycol ethers, preferably polypropylene glycols and polyethylene glycols or their ethers with molecular weights from 200 to 10,000, preferably from 300 to 9000, most preferably from 400 to 8000, are suitable as the alcohol component.

Acrylic acid and alkyl-, alkoxy- and alkoxycarbonylalkylacrylic acids with 1-20 carbon atoms, such as 2-methylacrylic acid (methacrylic acid), 3-methylacrylic acid (crotonic acid), trans can be considered as α, β-unsaturated carboxylic acids. -2,3-dimethylacrylic acid (tiglinic acid), 3,3-dimethylacrylic acid (senic acid) or 3-methoxyacrylic acid, preferably acrylic acid, 2-methylacrylic acid, 3-methylacrylic acid and 3-methoxyacrylic acid, most preferred itelno acrylic acid and 2-methyl acrylic acid.

The esters of α, β-unsaturated carboxylic acid used to obtain the proposed catalysts are usually obtained by esterification of mono-, di-, tri-, tetra- or polyhydroxy compounds with 1-30 carbon atoms such as methanol, ethanol, ethanediol (ethylene glycol ), 1-propanol, 2-propanol, 1,2-propanediol, 1,3-propanediol, 1,2,3-propanetriol (glycerol), 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-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-dodecanol , 1-tridecanol, 1-tetradecanol, 1- exadecanol, 1-heptadecanol, 9-octadecanol, 1,1,1-tris (hydroxymethyl) propane, pentaerythritol, methoxymethanol, ethoxymethanol, propoxymethanol, butoxymethanol, 2-ethoxyethanol, 2-propoxyethanol, 2-butoxyethoxyethanol, methyl 2-butoxyethanol, methyl hydroxyacetic acid ester, hydroxyacetic acid propyl ester, hydroxypropionic acid methyl ester, hydroxypropionic acid ethyl ester, hydroxypropionic acid propyl ester, or polyether polyols such as polyethylene glycols and polypropylene glycols, respectively favoring α, β-unsaturated carboxylic acids, if appropriate in the presence of catalysts.

Preferred are mono-, di- and triesters of acrylic and methacrylic acid with ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,2,3-propanetriol (glycerol) 1,1,1-tris (hydroxymethyl) propane, 1,1,1-tris (hydroxymethyl) propaneethoxylates, 1,1,1-tris (hydroxymethyl) propane propoxylates, polyethylene glycols and polypropylene glycols.

The most preferred esters of α, β-unsaturated carboxylic acid are polyethylene glycol acrylates, polyethylene glycol diacrylates, polyethylene glycol dimethacrylates, polypropylene glycol acrylates, polypropylene glycol diacrylates, polypropylene glycol methacrylates, 1,2-di-acrylates, 1,2-1,2-dimethryl acrylates 1,2,3-propanetriol-1,3- (2-hydroxypyroxylate) diacrylates, 1,2,3-propanetriolpropoxylate triacrylates, 1,4-butanediol acrylates, 1,4-b tanediol dimethacrylates, 1,6-hexanediol diacrylates, 2-hydroxypropyl methacrylates, 1,1,1-tris (hydroxymethyl) propane triacrylates, 1,1,1-tris (hydroxymethyl) propane ethoxyl triacrylates, 1,1,1-tris (hydroxymethyl) propane ethoxyl trimethacrylates, 1,1-tris (hydroxymethyl) propane propoxylate triacrylates or 1,1,1-tris (hydroxymethyl) propane propoxylate trimethacrylates.

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

Any mixtures of the above esters of α, β-unsaturated carboxylic acid may also be used.

The analysis of the composition of the catalyst is carried out in the usual way using elemental analysis, thermogravimetry or extractive removal of the ether fraction of α, β-unsaturated carboxylic acid, followed by gravimetric determination.

The proposed catalysts can be crystalline, partially crystalline or amorphous. Crystallinity analysis is carried out in the usual way using powder x-ray diffractometry.

Catalysts of the invention are preferred.

a) zinc hexacyanocobaltate (III),

b) tert.-butanol; and

c) an ester of α, β-unsaturated carboxylic acid.

The proposed DMC catalysts are usually prepared in an aqueous solution by reacting a) metal salts, in particular formula (I), with metal cyanide salts, in particular formula (II), β) of organic complex ligands b) other than α, β-unsaturated esters carboxylic acid, and γ) ester of α, β-unsaturated carboxylic acid.

In this case, first, aqueous solutions of a metal salt (for example, zinc chloride used in a stoichiometric excess (at least in a 50% molar, based on a metal cyanide salt)) and a metal cyanide salt (for example, potassium hexacyanocobaltate) are reacted in the presence of an organic complex ligand b) (for example, tertbutanol), obtaining a suspension containing a double metal cyanide compound a) (for example, zinc hexacyanocobaltate), water a), excess metal salt e) and an organic complex ligand b).

The organic complex ligand b) may be present in an aqueous solution of a metal salt and / or a metal cyanide salt, or it may be added to the suspension obtained immediately after precipitation of the double metallocyanide compound a). It turned out to be appropriate to mix aqueous solutions and the organic complex ligand b) with vigorous stirring. The resulting suspension is usually then treated with an ester of α, β-unsaturated carboxylic acid c). The α, β-unsaturated carboxylic acid ester c) is used predominantly in a mixture with water and the organic complex ligand b).

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

The amount of the organic complex ligand b) in the aqueous wash solution is preferably in the range of 40 to 80% by weight, based on the total solution. It is further advisable to add a little α, β-unsaturated carboxylic acid ester to the aqueous wash solution, preferably in the range of 0.5 to 5% by weight, based on the total solution.

In addition, it is advisable to wash the catalyst more than once. For this, for example, the first water wash can be repeated. However, for subsequent washes, it is preferable to use not aqueous solutions, but a mixture of organic complex ligands and an ester of α, β-unsaturated carboxylic acid.

The washed catalyst is then, if necessary, after spraying, dried at temperatures generally ranging from 20 to 100 ° C and pressures generally ranging from 0.1 mbar to normal (1013 mbar).

Another object of the present invention is the use of the proposed DMC catalysts in the method of producing polyether polyols by polyaddition of alkylene oxides to the starting compounds containing active hydrogen atoms.

As alkylene oxides, ethylene oxide, propylene oxide, butylene oxide, and mixtures thereof are preferably used. The synthesis of polyester chains by alkoxylation can be carried out, for example, only using monomeric epoxide or also statistically or blockwise using 2 or 3 different monomeric epoxides. For more details see Ullmanns Encyclopedie der industiellen Chemie, Band A21,1992, S. 670ff.

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

Preferred are such starting compounds containing active hydrogen atoms, which were obtained, for example, by conventional alkaline catalysis from the above low molecular weight initiators and are oligomeric alkoxylation products with (number average) molecular weights from 200 to 2000.

The polyaddition of alkylene oxides catalyzed by the proposed catalysts to the starting compounds containing active hydrogen atoms occurs at temperatures generally from 20 to 200 ° C, preferably in the range from 40 to 180 ° C, most preferably at temperatures from 50 to 150 ° C. The reaction can be carried out at a total pressure of from 0.001 to 20 bar. The polyaddition can be carried out 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 weight of the polyester polyol to be obtained.

The concentration of the catalyst is chosen so that, under the given reaction conditions, the polyaddition reaction can be well controlled. The concentration of the catalyst is usually in the range from 0.0005 wt.% 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. %, calculated on the amount to be obtained polyether polyol.

The number average molecular weights of the polyether polyols obtained by the proposed method are in the range of 500 to 100,000 g / mol, preferably in the range of 1000 to 50,000 g / mol, most preferably in the range of 2000 to 20,000 g / mol.

The polyaddition can be carried out continuously or periodically, for example, in a portioned or semi-portioned manner. Due to their markedly higher activity, the proposed catalysts can be used at very low concentrations (25 ppm or less, based on the amount of polyether polyol to be prepared). If polyether polyols obtained in the presence of the proposed catalysts are used to produce polyurethanes (Kunststoffhandbuch, Band 7, Polyurethane, 3. Auflage, 1993, S. 25-32 and 57-67), it is possible to abandon the stage of removal of the catalyst from polyether polyol without sacrificing quality the resulting product is polyurethane.

Examples

Catalyst Preparation

Example A. Obtaining DMC catalyst using polyethylene glycol diacrylate (catalyst A).

To a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 70 ml of distilled water, a solution of 12.5 g (91.5 mmol) of zinc chloride in 20 ml of distilled water is added with vigorous stirring. Immediately thereafter, a mixture of 50 g of tert-butanol and 50 g of distilled water is added to the resulting suspension, and then vigorously stirred (24,000 rpm) for 10 minutes. Then, a mixture consisting of 1 g of polyethylene glycol diacrylate with a number average molecular weight of 575 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim), 1 g of tert-butanol and 100 g of distilled water is added, and stirred for 3 minutes (1000 rpm). The solid was isolated 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 polyethylene glycol diacrylate (10,000 rpm) and filtered again. In conclusion, mix again for 10 minutes with a mixture of 100 g of tertbutanol and 0.5 g of the above polyethylene glycol diacrylate (10,000 rpm). After filtration, the catalyst is dried at 50 ° C and normal pressure until the weight is constant.

The yield of dried powder catalyst: 5.4 g. Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 10.9 wt.%, Zinc = 22.8 wt.%, Tert-butanol = 6.2 wt.%, Polyethylene glycol diacrylate = 19.5 wt.%, Cl = 5.1 wt.%, CN = 28 9 wt.%, Water = 6.6 wt.%.

Example B. Obtaining a DMC catalyst using polyethylene diol dimethacrylate (catalyst B).

The experiment was carried out as in Example A, however, instead of the polyethylene glycol diacrylate from Example A, polyethylene glycol dimethacrylate with a number average molecular weight of 875 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim) was used.

The yield of dried powder catalyst: 5.4 g.

Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 11.2 wt.%, Zinc = 24.3 wt.%, Tertbutanol = 4.9 wt.%, Polyethylene glycol dimethacrylate = 18.5 wt.%, Cl = 6.1 wt.%, CN = 29.79 wt.%, water = 5.3 wt.%.

Example C. Obtaining DMC catalyst using polypropylene glycol methacrylate (catalyst C).

The experiment was carried out as in Example A, however, instead of the polyethylene glycol diacrylate from Example A, polypropylene glycol methacrylate with a number average molecular weight of 375 was used (Sigma Aldrich Chemie GmbH, D-89552 Steinheim).

The yield of dried powder catalyst: 6.2 g. Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 10.2 wt.%, Zinc = 23.9 wt.%, Tert-butanol = 6.6 wt.%, Polypropylene glycol methacrylate = 20.6 wt.%, Cl = 7.2 wt.%, CN = 27 , 0 wt.%, Water = 4.5 wt.%.

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

The experiment was carried out as in Example A, however, instead of the polyethylene glycol diacrylate from Example A, 1,6-hexanediol dimethacrylate was used.

The yield of dried powder catalyst: 5.5 g. Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 10.0 wt.%, Zinc = 23.3 wt.%, Tert-butanol = 10.2 wt.%, 1,6-hexanediol dimethacrylate = 15.5 wt.%, Cl = 7.2 wt.% , CN = 26.5 wt.%, Water = 7.3 wt.%.

Example E. Obtaining DMC catalyst using 1,1,1-trishydroxymethyl) propanetriacrylate (catalyst E).

The experiment is carried out as in example A, however, instead of the polyethylene glycol diacrylate from example A, 1,1,1-tris (hydroxymethyl) propanetriacrylate is used.

The yield of dried powder catalyst: 5.0 g. Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 11.8 wt.%, Zinc = 27.7 wt.%, Tert-butanol = 11.8 wt.%, 1,1,1-tris (hydroxymethyl) propanetriacrylate = 2.4 wt.%, Cl = 8.8 wt.%, CN = 31.3 wt.%, Water = 6.2 wt.%.

Example F. Preparation of DMC catalyst using 1,1,1-tris- (hydroxymethyl) propaneethoxylate triacrylate (catalyst F).

The experiment is carried out as in example A, however, instead of the polyethylene glycol diacrylate from example A, 1,1,1-tris (hydroxymethyl) propane ethoxylate (14/3 EO / OH) triacrylate (EO / OH denotes the ratio of ethylene oxide groups to hydroxyl groups) with the number average a molecular weight of about 912 (Sigma Aldrich Chemie GmbH, D-89552 Steinheim).

The yield of dried powder catalyst: 6.1 g. Elemental analysis, thermogravimetric analysis and extraction:

Cobalt = 10.9 wt.%, Zinc = 24.9 wt.%, Tert-butanol = 5.1 wt.%, 1,1,1-tris (hydroxymethyl) propaneethoxylate (14/3 ЕО / ОН) -triacrylate = 5.7 wt.%, Cl = 7.4 wt.%, CN = 28.9 wt.%, Water = 17.1 wt.%.

Example G. Obtaining DMC-catalyst using 2-hydroxypropylmethacrylate (catalyst G).

The experiment was carried out as in Example A, however, instead of the polyethylene glycol diacrylate from Example A, 2-hydroxypropyl methacrylate was used.

The yield of dried powder catalyst: 4.9 g. 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). Obtaining a DMC catalyst without using an α, β-unsaturated carboxylic acid ester (catalyst H, synthesis according to JP-A-4145123).

To a solution of 4 g (12 mmol) of potassium hexacyanocobaltate in 75 ml of distilled water, a solution of 10 g (73.3 mmol) of zinc chloride in 15 ml of distilled water is added with vigorous stirring. Immediately thereafter, a mixture of 50 g of tertbutanol and 50 g of distilled water is added to the resulting suspension, and then vigorously stirred (24000 rpm) for 10 minutes. The solid was isolated by filtration, then stirred (10,000 rpm) for 10 minutes with 125 g of a mixture of tert-butanol and distilled water (70/30 by weight) and filtered again. In conclusion, mix again (10,000 rpm) for 10 minutes with 125 g of tertbutanol. After filtration, the catalyst is dried at 50 ° C and normal pressure until the weight is constant.

The yield of dried powder catalyst: 3.08 g

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.%.

Obtaining Polyester Polyols

General methodology

In a 500 ml pressure reactor, 50 g of a polypropylene glycol initiator (with a number average molecular weight of 1000 g / mol) and 4-5 mg of catalyst (25 ppm, based on the amount to be obtained) are charged under a protective gas (argon) atmosphere. polyether polyol) and heated with stirring to 105 ° C. Then, propylene oxide (about 5 g) is immediately added until the total pressure rises to 2.5 bar. Re-addition of propylene oxide is carried out only if an accelerated pressure drop in the reactor is observed. This accelerated pressure drop in the reactor indicates that the catalyst is activated. Then, a residual amount of propylene oxide (145 g) was continuously added at a constant pressure of 2.5 bar. Upon completion of the addition of propylene oxide and 2 hours after the start of the reaction proceeding at 105 ° C, the volatile components are distilled off at 90 ° C (1 mbar), after which they are cooled to room temperature.

The obtained polyether polyols are characterized by determining hydroxyl numbers, double bond content and viscosity.

The reaction is monitored by time-conversion curves (propylene oxide consumption [g] by reaction time [min]). From the point of intersection of the tangent at the steepest point of the time-conversion curve with the continuation of the baseline of the curve, the induction time is determined. The propoxylation times, which are decisive for the activity of the catalyst, correspond to the time period between the activation of the catalyst (end of the induction period) and the end of the addition of propylene oxide. The total reaction time is the sum of the induction time and the propoxylation time.

Example 1. Obtaining polyether polyol using catalyst A (25 ppm)

Induction time: 87 min

Propoxylation time: 54 min

Total reaction time: 141 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 29.4

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

Viscosity 25 ° C (MPa · s): 836

Without removal of the catalyst, the metal content in the polyol is: Zn = 6 ppm, Co = 3 ppm.

Example 2. Obtaining polyether polyol using catalyst B (25 parts per million)

Induction time: 136 min

Propoxylation time: 98 min.

Total reaction time: 234 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 31.3

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

Viscosity 25 ° C (MPa · s): 832

Example 3. Obtaining polyether polyol using catalyst C (25 parts per million)

Induction time: 151 min

Propoxylation time: 209 min

Total reaction time: 360 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 30.1

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

Viscosity 25 ° C (MPa · s): 937

Example 4. Obtaining polyether polyol using catalyst D (25 parts per million)

Induction time: 318 min

Propoxylation time: 511 min

Total reaction time: 829 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 30.0

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

Viscosity 25 ° C (MPa · s): 1060

Example 5. Obtaining polyether polyol using catalyst E (25 parts per million)

Induction time: 120 min

Propoxylation time: 87 min

Total reaction time: 207 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 29.8

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

Viscosity 25 ° C (MPa · s): 922

Example 6 Preparation of Polyester Polyol Using Catalyst F (25 ppm)

Induction time: 88 min

Propoxylation time: 99 min

Total reaction time: 187 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 30.0

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

Viscosity 25 ° C (MPa · s): 889

Example 7 Preparation of Polyether Polyol Using Catalyst G (25 ppm)

Induction time: 120 min

Propoxylation time: 143 min

Total reaction time: 265 min

Polyester Polyol:

Hydroxyl number (mg KOH / g): 29.9

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

Viscosity 25 ° C (MPa · s): 990

Example 8 (comparative)

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

Examples 1-8 show that the new DMC catalysts according to the invention, due to their markedly higher activity in the preparation of polyether polyols, can be used in such low concentrations that the stage of separation of the catalyst from the polyol can be omitted.

Claims (6)

1. Double metal cyanide catalyst (DMC catalyst) containing a) one or more double metallocyanide compounds, b) one or more than complex c) organic complex ligands and c) one or more esters of α, β-unsaturated carboxylic acid. 2. The DMC catalyst according to claim 1, further comprising d) water and / or e) a water-soluble metal salt. 3. The DMC catalyst according to claim 1 or 2, wherein the double metallocyanide compound is zinc hexacyanocobaltate (III). 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 from 1 to 79.5 wt.% Ester of α, β-unsaturated carboxylic acid. 6. The DMC catalyst according to one of claims 1 to 5, wherein the α, β-unsaturated carboxylic acid ester is polyethylene glycol acrylate, polyethylene glycol diacrylate, polyethylene glycol methacrylate, polyethylene glycol dimethacrylate, polypropylene glycol acrylate, polypropylene glycol diacrylate, polypropylene glycol acrylate, triol diacrylate, 1,2,3-propanetriol dimethacrylate, 1,2,3-propane-triol triacrylate, 1,2,3-propanetriol-1,3- (2-hydroxypoxylate) diacrylate, 1,2,3-propanetriolpropoxylate triacrylate, 1, 4-butanediolacre ylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate, 2-hydroxy-propyl methacrylate, 1,1,1-tris (hydroxymethyl) propanetri acrylate, 1,1,1-tris (hydroxymethyl) propane ethoxyl triacrylate, 1,1, 1-tris (hydroxymethyl) propaneethoxylatetrimethacrylate, 1,1,1-tris (hydroxymethyl) propane propoxylate triacrylate or 1,1,1-tris (hydroxymethyl) propane propoxylate trimethacrylate.