Double metallicity catalyst, process for its production and a method of producing polyether polyols

 

(57) Abstract:

This invention relates to a dual metallocyanide catalyst containing (a) one or more double metallocyanide compounds of formula (I): Mx[M’x’(CN)y]zin which M stands for a metal selected from the group comprising Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III), M’ is a metal selected from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), x, x’, y, and z each is an integer and they are chosen so that the double metallocyanide the compound had an electric neutrality, in one or more than) organic complex ligands and (C) one or more phospholipids or derivatives of amino acids, which can be used to obtain polyether polyols by polyaddition of alkalisation to the original compounds with active hydrogen atoms. The invention also relates to a method for obtaining a specified catalyst. The technical result - the assortment of highly active double metallocyanide catalysts. 3 N. and 4 C.p. f-crystals.

The invention relates to a new catalyst is containing a series of active hydrogen atoms, more specifically to dual metallocyanide catalysts, method of its production and process for the preparation of polyether polyols.

Double metallocene catalysts (DMC) for the polyaddition of alkalisation to the original compounds containing active hydrogen atoms are known (see for example U.S. patent No. 3404109, 3829505, 3941849 and 5158922). The use of such DMC-catalysts for production of polyether polyols reduces the content of monofunctional polyethers with terminal double bonds, so-called Manolov, compared with the traditional receipt of polyether polyols using alkaline catalysts 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 a method in which an aqueous solution of metal salts is subjected to contact with an aqueous solution of salts of metallocyanide in the presence of organic complex ligands, such as ethers. In a typical method of preparation of the catalyst, for example, a mixed aqueous solutions of zinc chloride (in excess) and hexacyanocobaltate potassium and then add dimethoxy get active catalyst of General formula

Zn3[CO(JV)6]2x ZnCl2the H2O z dimethoxyethane

(for example, see European patent application No. 700949).

In Japanese patent application No. 4145123, U.S. patent No. 5470813, European patent applications No. 700949, 743093, 761708 and international application WO 97/40086 described DMZ-catalysts, which also reduces the content of monofunctional polyethers with terminal double bonds upon receipt of polyether polyols using tert-butanol as the organic complex ligand (alone or in combination with polyester (European patent application No. 700949, 761708, international application WO 97/40086)). In addition, through the use of such DMC-catalysts decreases the induction time in the polyaddition reaction of alkalisation with the corresponding parent compounds and increases the catalyst activity.

The closest analogue is the dual metallicity catalyst for U.S. patent No. 5714428, sumeragi double metallocene compound, an organic complex ligand and non-polyether functionalliteracy polymer or water-soluble salt.

Object of the invention is the expansion of the range of highly active double bedroom problem is solved, we offer double metallocyanide catalyst, containing

a) one or more double metallocyanide compounds of formula (I)

Mx[M'x,(CN)y]z,

in which M stands for a metal selected from the group comprising 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,

M' is a metal selected from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V)

x, x', y and z each is an integer, and they are chosen so that the double metallocyanide the compound had an electric neutrality (II) and Cr(III)

C) one or more than C), organic integrated Li gang Dov and

C) one or more phospholipids or derivatives of amino acids.

The catalyst according to this invention may contain (d) water, preferably 1-10 wt.%, and/or e) one or more water-soluble metal salts, preferably 5-25 wt.%, formula (II) M(X)nused when getting double metallocyanide compounds a). In the formula (II) M stands for a metal selected from the group comprising 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), preferably Zn(II), Fe(II), Co(II) and Ni(II), X is the same the oxides, sulfates, carbonates, cyanate, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates or nitrates, and the index n is 1, 2 or 3.

Double metallocene compound (a) contained in the catalyst according to the invention, are products of the interaction of water-soluble metal salts with water-soluble salts of the metal cyanide.

Suitable for double metallocyanide compounds and water-soluble metal salts have the above General formula (II) M(X)nand M, X and n have the above significance.

Suitable water-soluble metal salts are, for example, 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). Is also possible to use mixtures of different water-soluble metal salts.

Suitable for double metallocyanide compounds and water-soluble salts metallocyanide have the General formula (III) (Y)aM'(CN)b(A)cin which M' is a metal selected from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), R is denotes a cation, selected from the group comprising ions of alkali and alkaline earth metals, And is the same or different and denotes an anion selected from the aforementioned group a, b, and C are integers, with values for a, b and C is chosen so that the salt metallocyanide had electrical neutrality; and preferably is 1, 2, 3 or 4; b is preferably 4, 5 or 6; preferably 0. Water-soluble salt of metallocyanide may contain one or more metals M'. Suitable water-soluble salts of metallocyanide are, for example, caligen-satyanarayana (III), caliecaciones (II), caliecaciones (III), calorigenically (III) and litigationrelated (III).

In the above formula (I) m, M', x, x', y and z have the following preferred meanings:

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

M'=Co(III), Fe(III), CR(III) or Ir(III)

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

Examples of suitable double metallocyanide compounds a) are linkexecute (III), linkextend (III), cinchers-cyanoferrate (III) and cobalt(II)hexacyanocobaltate (III). It is preferable to linkexecute (III).

The organic complex ligand is key (see U.S. patents№№5158922, 3404109, 3829505, 3941849, European patent application No. 700949, 761708, Japanese patent application No. 4145123, U.S. patent No. 5470813, European patent application No. 743093 and international application WO 97/40086). Preferred organic complex ligands are water-soluble, organic compounds with heteroatoms, such as, for example, oxygen, nitrogen, phosphorus or sulfur, which can form complexes with double metallocyanide connection). Suitable organic complex ligands are, for example, alcohols, aldehydes, ketones, simple esiri, complex esiri, amides, urea, NITRILES, sulfides and mixtures thereof. Preferred organic complex ligands are water-soluble aliphatic alcohols, for example ethanol, ISO-propanol, n-butanol, ISO-butanol, sec-butanol and tert.-butanol. Most preferred is tert.-butanol.

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

DMC catalyst according to soobramoney contains a double metallocyanide connect the ora, organic complex ligands b) in an amount of from 0.5 to 30 wt.%, preferably from 1 to 25 wt.%, regarding the number of finished catalyst and from 1 to 79.5 wt.%, preferably from 1 to 40 wt. -%, regarding the number of finished catalyst, of one or more phospholipids or derivatives of amino acids).

Analysis of the catalyst composition is usually carried out by elemental analysis, thermogravimetry and extractive separation of the content of the component (C) with subsequent gravimetric determination.

The catalysts according to the invention can be crystalline, partially crystalline or amorphous. Analysis of crystallinity is usually carried out by x-ray diffraction powder.

Getting DMC-catalysts according to the invention is usually carried out in aqueous solution by interaction ) metal salts of the formula (II) salts metallocyanide formula (III), ( ) is different from component (C) organic complex ligands b) and ) phospholipids or derivatives of amino acids as component (C).

Preferably do so that aqueous solutions of metal salts (e.g. zinc chloride, used in stoichiometric excess (at least 50 mol.%, otnosica potassium), in the presence of organic complex ligands b) (for example, tert-butanol), and get the suspension, which contains a compound double metallocyanide a) (for example, hexacyanocobaltate zinc), water (d), excess metal salt (e) and the organic complex ligand b).

The organic complex ligand b) may already be present in the aqueous solution of metal salts and/or salts metallocyanide, or directly injected into the suspension obtained after separation of the double metallocyanide connection). Preferably mixed aqueous solutions and organic complex ligands b) under vigorous stirring. The resulting suspension is usually treated with component (C), which is preferably used in the form of a mixture with water and the organic complex ligand b).

Directly after this, carry out the allocation of the catalyst from the suspension by known means, such as centrifugation or filtration. In accordance with a preferred embodiment of the present invention, the selected catalyst is washed with an aqueous solution of an organic complex ligand b) (e.g., re-suspension and re-selection by filtering or centrifugation"ptx2">The preferred amount of organic complex ligands b) in an aqueous rinse solution is between 40 and 80 wt.%, in relation to the entire solution. Also preferably in an aqueous wash solution add a small amount of component C), preferably in amounts of between 0.5 and 5 wt.%, in relation to the entire solution.

In addition, the catalyst is preferably washed more than once. This may, for example, the repetition of the first washing process. However, preferably the next stages of washing do not use aqueous solutions, as for example, mixtures of organic complex ligands and phospholipids or derivatives of amino acids.

Then the washed catalyst, if necessary, after the dispersion is dried at a temperature of usually from 20 to 100 C and at a pressure of generally from 0.1 mbar to normal pressure (1013 mbar).

The above method is a second object of the present invention.

The third object of this invention is a method of producing polyether polyols by polyprionidae of alkalisation to the original compounds containing active hydrogen atoms, in the presence of the catalyst according to the invention.

As accelerated predpochtu alkoxysilane can be for example, only Monomeric epoxide or statistically or in blocks with 2 or 3 different Monomeric epoxides. Details are given in "Ullmanns der industriellen Chemie", BandA21, 1992, S. 670f.

As a source of compounds containing active hydrogen atoms, it is preferable to use compounds with a molecular weight (average number) from 18 to 2000 and 1 to 8 hydroxyl groups. As examples can be mentioned: ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, hexamethyleneimine, bisphenol a, trimethylolpropane, glycerin, pentaerythritol, sorbitol, sucrose, split starch or water.

Preferably use the original compounds containing active hydrogen atoms, which receive, for example, a standard alkaline catalysis of the above low molecular weight starting compounds and represent oligomeric products alkoxysilane (srednekislovsky) molecular weight from 200 to 2000.

Catalyzed by the catalysts according to the invention, polyprionidae of alkalisation to the original compounds containing active hydrogen atoms, carried out usually at a temperature of from 20 to 200, preferably from 40 to 180 C, most preferably at the to be carried out in the absence or presence of an inert, organic solvent, such as, for example, toluene and/or tetrahydrofuran. The amount of solvent is usually 10 to 30 wt.%, regarding the number of received polyetherpolyols.

The concentration of catalyst is chosen so that under the given reaction conditions was possible for the reliable control of the polyaddition reaction. The concentration of catalyst is usually from 0.0005 to 1 wt.%, preferably from 0.001 to 0.1 wt.%, most preferably from 0.001 to 0.0025 wt.%, regarding the number of received polyetherpolyols.

(Srednetsenovoj) molecular weight of the obtained polyether polyols ranges from 500 to 100,000 g/mol, preferably from 1000 to 50000 g/mol, most preferably from 2000 to 20,000 g/mol.

Polyprionidae may be performed continuously or periodically, for example, in a periodic or properities mode.

Due to its high activity catalysts according to the invention can be used in very low concentrations (25 parts per million or less, relative to the amount of polyetherpolyols). If the polyether polyols are used, for example, to obtain polyurethanes, it is possible refusal of the Department of catalysis is SS="ptx2">Preparation of catalyst

Example A. Obtaining DMC-catalyst using sodium salt holeva acid (catalyst A).

To a solution of 2 g (6 mmol) of hexacyanocobaltate potassium in 35 ml of distilled water with vigorous stirring (24000 rpm) add a solution of 6.2 g (45,75 mmol) of zinc chloride in 10 ml of distilled water. Directly after the last operation add a mixture of 25 g of tert-butanol and 25 g of distilled water to form a suspension and then within 10 minutes intensively mixed (24 rpm). Then add a mixture of 0.5 g of sodium salt holeva acid (Fluka Chemie AG, CH-9471 Buchs), 0.5 g of tert-butanol and 50 g of distilled water and within 3 minutes, stirred (1000 rpm). The solid is separated by filtration, and then within 10 minutes, stirred with a mixture of 35 g of tert-butanol, 15 g of distilled water and 0.5 g of sodium salt holeva acid (10,000 rpm) and again filtered. Then once again stirred with a mixture of 50 g of tert-butanol and 0.25 sodium salt holeva acid (10000 rpm) for 10 minutes. After filtration, the catalyst is dried at a temperature of 50 C and normal pressure until weight constancy.

The yield of dried, powdered catalyst: 2,1 is tanol = 10.9 wt.%, sodium salt holeva acid = 4.3 wt.% The remainder to 100%: the content of linked in hexacyanocobaltate cyanide, water and chlorine.

Example B. Obtaining DMC-catalyst using L - a-lecithin (catalyst B).

Repeat example A, but instead of the sodium salt holeva acid from the sample And use L - a-lecithin (from egg yolk, Fluka Chemie AG, CH-9471 Buchs).

The yield of dried, powdered catalyst: 2.0 g

Elemental analysis, thermogravimetric analysis and extraction: cobalt = 13.7 wt.%, zinc = 25,6 wt.%, tert-butanol = 7.5 wt.%, L - a-lecithin = 12.0 wt.%.

The remainder to 100%: the content of linked in hexacyanocobaltate cyanide, water and chlorine.

Example Century. Getting DMC-catalyst using N-lauroylsarcosine in the form of sodium salt (catalyst).

Repeat example A, but instead of the sodium salt holeva acid from the sample And use the sodium salt of N-lauroylsarcosine (Fluka Chemie AG, CH-9471 Buchs).

The yield of dried, powdered catalyst: 1,95, Elemental analysis, thermogravimetric analysis and extraction: cobalt = 13,2 wt.%, zinc = 28,6 wt.%, tert-butanol = 9.5 wt.%, N-lauroylsarcosine-sodium salt = 6.2 wt.% The remainder to 100%: the content of svasand catalyst using tert-butanol without using component (C) phospholipids or derivatives of amino acids (catalyst G, the synthesis of the Japan patent No. 4145123).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 75 ml of distilled water with vigorous stirring (24000 rpm) add a solution of 10 g (73,3 mmol) of zinc chloride in 15 ml of distilled water. Directly after the last operation add a mixture of 50 g of tert-butanol and 50 g of distilled water to form a suspension and then within 10 minutes intensively stirred (24000 rpm). The solid is separated by filtration, and then within 10 minutes, stirred with 125 g of a mixture of tert-butanol and distilled water (ratio 70/30) (10,000 rpm) and again filtered. Then once again stirred with 125 g of tert-butanol (10000 rpm) for 10 minutes. After filtration, the catalyst is dried at a temperature of 50°C and normal pressure until weight constancy.

The yield of dried, powdered catalyst: is 3.08 g

Elemental analysis:

cobalt = 13,6 wt.%, zinc = 27,4 wt.%, tert-butanol = 14.2 wt.% The remainder to 100%: the content of linked in hexacyanocobaltate cyanide, water and chlorine.

Getting polyether polyols

General methodology

In a pressure reactor with a capacity of 500 ml serving 50 g polypropyleneglycol (average molecular weight = 1000 g/m in the presence of a protective gas (argon) and heated at a temperature of 105 C with stirring. Then add the propylene oxide (about 5 g). The total pressure is increased up to 2.5 bar. Then, if the reactor see accelerated pressure drop, then again add the propylene oxide. This rapid pressure drop indicates that the catalyst is activated. Then continuously add the remaining propylene oxide (145 g) at constant total pressure of 2.5 bar. After complete dispensing of propylene oxide and endurance after reaction for 2 hours at a temperature of 105 With volatile components are distilled off at a temperature of 90 C (1 mbar) and then cooled to room temperature.

The resulting polyether polyols are characterized by hydroxyl number, the content of double bonds and viscosity.

Over the course of the reaction is monitored by using the curve of the time-conversion (consumption of propylene oxide [g] relative response time [min]). The point of intersection of the tangent at the steepest point of the curve the time-transformation with the extended base line of the curve determine the induction time. Time propoxycarbonyl essential for the activity of the catalyst corresponds to the time interval between activation of the catalyst (the end of the induction period) and the end of the dosing of propylene oxide. The total time re epipolae using catalyst A (15 parts per million)

Induction time: 230 min

Time propoxycarbonyl: 95 min

The total reaction time: 325 min

Polyetherpolyols:

hydroxyl number (mg KOH/g): 28,9

the content of double bonds (mmol/kg): 4

the viscosity at 25°C (mPas): 982

Without separation of the catalyst metal content in the polyol is:

Zn = 4 parts per million, SD = 2 parts per million

Example 2

Getting polyetherpolyols using catalyst B (25 parts per million)

Induction time: 125 min

Time propoxycarbonyl: 140 min

The total reaction time: 265 minutes

Polyetherpolyols

hydroxyl number (mg KOH/g): 29,5

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

the viscosity at 25°C (mPas): 921

Example 3 Obtaining polyetherpolyols using catalyst (25 parts per million)

Induction time: 350 min

Time propoxycarbonyl: 40 min

The total reaction time: 390 minutes

Polyetherpolyols: number of HE (mg KOH/g): 30,4

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

the viscosity at 25°C (mPas): 842

Example 4 (control example)

Catalyst G (15 parts per million) under the above reaction conditions is inactive even last 9 hours. Time propoxycarbonyl is more than 12 hours, and during the reaction deactivation of the catalyst.

Examples 1-3 demonstrate that due to their increased activity DMC-catalysts according to the invention can be used to obtain polyetherpolyols in such low concentrations that it is possible to abandon the separation of the catalyst from the resulting polyol.

1. Double metallicity catalyst containing (a) one or more double metallocyanide compounds of formula (I)

Mx[M’x’(CN)y]z,

in which M stands for a metal selected from the group comprising Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III);

M’ is a metal selected from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V);

x, x’, y, and z each is an integer

and they are chosen so that the double metallocyanide the compound had an electric neutrality; C) one or more non-C) organic complex ligands and (C) one or more phospholipids or derivatives of amino acids.

2. Double metallicity catalyst under item 1, the hydrated catalyst p. 1 or 2, in which the double metallocyanide connection is hexacyanocobaltate (III) zinc.

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

5. Double metallicity catalyst according to one of paragraphs. 1-4, which contains 1-79,5 wt.% one or more phospholipids or derivatives of amino acids.

6. The method of obtaining dual metallocyanide catalyst, which comprises the following stages: i) interaction in aqueous solution ) metal salts of the formula M(X)nin which M stands for a metal selected from the group comprising: Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III), X is identical or different and denotes an anion selected from the group comprising halides, hydroxides, sulfates, carbonates, cyanate, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates and nitrates, and n = 1, 2, or 3, with salts of metallocyanide formula (Y)aM’(SP)b(A)within which M’ is a metal selected from the group comprising Fe(II), Fe(III), Co(II), Co(III), Cr(II) Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV) and V(V), Y is the same or different and denotes a cation selected from the group cluanie of the above groups; a, b, and C are integers, with values for a, b and C is chosen so that the salt metallocyanide had electrical neutrality; ) organic complex ligands and ) phospholipids or derivatives of amino acids; (ii) the separation, washing and drying of the catalyst obtained in stage i).

7. The method of producing polyether polyols by polyprionidae of alkalisation to the original compounds containing active hydrogen atoms, in the presence of one or more catalysts, one of PP. 1-5.

 

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