The catalyst based on zinc/metal-hexacyanocobaltate to obtain polyether polyols and process for its manufacture

 

(57) Abstract:

The invention relates to the production of catalysts for production of polyether polyols. Proposed catalyst for more polyether polyols having a composition

Zn3-vMv[Co(CN)6]2w(H2O)(x(L)y[Zn(X)n]z[M(Y)m],

where M, X, Y, L, v, w, x, y, z, m, n bvt.n have the meanings specified in paragraph 1 of the claims. A method of manufacturing a catalyst to obtain polyether polyols. The method is realized by means of interaction between 1-90% (wt.) an aqueous solution of the zinc salt of the formula Zn(X)n and a metal salt of the formula M(Y)mfrom 0.5-50% (wt.) aqueous solution of cyanide salts of cobalt (III) of the formula M'3[Co(JV)6]rwhere r = 1 or 2 and M is alkali metal, in the presence of the organic complex ligand L. the Technical result: using catalyst reduces the induction time. 2 S. p. f-crystals.

The present invention relates to the technology of production of polyether polyols (simple esters of polyols, in particular to a catalyst based on zinc/metal-hexacyanocobaltate to obtain polyether polyols and to a method of its manufacture.

Known catalyst to obtain political is e(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), W(VI) or W(IV);

M' is Fe(II), Fe(III), Co(II), Co(IV), Cr(II) Cr(III), Mn(II), Mn(IV), V(IV) or V(V);

R is tert-butanol;

a, b, x and y independently of one another is a positive number, depending on the valence and coordination number of the metal;

c and d independently of one another is a positive number that depends on the coordination number of the metal.

(see JP 4145123 But, 1992).

Known catalyst was prepared by exposing aqueous solutions of metal salts interaction in the presence of tert-butanol, followed by the separation of the resulting catalyst in a known manner, i.e. by filtering and washing.

The disadvantage of this catalyst is that significant to the cycle time of receipt of polyetherpolyols induction time by polyaddition reaction of alkalisation to the corresponding compounds initiator is not quite satisfactory.

The present invention is the creation of a catalyst based on zinc/metal-hexacyanocobaltate to obtain polyether polyols (ethers of polyols), that reduce the time of induction when politicoeconomic of alkalisation to the corresponding connection initiator and the most, the present invention is to achieve the maximum narrow molecular weight distribution of the obtained polyether polyols. Most narrow molecular weight distribution polyols very important for processing into high-quality polyurethanes (e.g., elastomers).

The problem is solved by a catalyst according to the present invention based on the zinc/metal-hexacyanocobaltate to obtain polyether polyols (ethers of polyols) having the composition

Zn3-vMv[Co(CN)6]2w(H2O)(x(L)y[Zn(X)n]z[M(Y)m],

where M is divalent metal selected from the group of cadmium(II), mercury(II), palladium(II), platinum(II), vanadium(II), magnesium(II), calcium(II) and barium(II);

X and Y is a halogen, in particular chlorine or bromine;

L - organic complex ligand selected from the group of alcohols, ketones or ethers;

v = 0,012,99;

w = 0,110;

x = 0,0110;

y = 0,0013,0,

z = 0.001 to 3.0 and

m and n = 2.

As the ligands L with (simple) ether compounds are suitable, in particular, such compounds, which are capable of forming chelates with metals. For example, the ligands can be considered methanol, ethanol, propanol, isopropanol, butanol, GE is Dion, 2,4-hexandione, m-dioxane, p-dioxane, trioxymethylene, paraldehyde is recommended, diethyl ether, 1-ethoxyphenol, bis((-chloroethyl)ether, bis((-ethoxyethyl)ether, disutility ether, ethylpropyl ether, bis((-methoxyethyl)ether, dimethoxyethane (glyme), diethylethylenediamine ether (diglyme), triethylenemelamine ether, dimethoxymethane, methylpropyloxy ether, polyalkyleneglycol.

The preferred catalyst composition

Zn3-VMv[Co(JV)6]2w(H2O)x(L)(y(ZnCl2)z(MCl2)

where v = 0,012,99;

w = 0,110;

x = 0,0110 and

y and z = 0,0013,0.

Particularly preferred catalyst composition

Zn3-vCDv[Co(JV)6]2w(H2O)(x(tert-butanol)y(ZnCl2)z(CdCl2), with the above values for v, w, x, y and z.

A further object of the present invention is a method of producing the catalyst according to the invention based on the zinc/metal-hexacyanocobaltate by the interaction of aqueous solutions of metal salts in the presence of the organic complex ligand, followed by the separation of the obtained catalyst, consisting in the fact that 1-90% (wt.) an aqueous solution of the zinc salt of the formula Zn(X)nand a metal salt of the formula M(Y)mput UB>]r,

where r = 1 or 2 and

M' = alkali metal,

in the presence of the organic complex ligand L, and salt Zn(X)nM(Y)mand cyanide salt of cobalt(III) is used in such quantities that the molar ratio of zinc and the metal M to cobalt is from 2:1 to 10:1, the complex ligand L is used in such quantities that the molar ratio of zinc and the metal M to L is from 1:100 to 100:1 and the molar ratio of the zinc salt of Zn(X)nand metal salt M(Y)m is in the range from 500:1 to 1:500.

As the alkali metal M' can be considered, in particular, sodium, potassium and lithium, especially preferred potassium.

The value of X, Y and L in the above formulas described above.

Preferably use 5-70% (wt.) a solution of salts of zinc (Zn(X)n) and metal (M(Y)m). An aqueous solution of cyanide salts of cobalt(III) is preferably used in a concentration of from 1 to 30 wt.%.

The molar ratio of zinc and metal to cobalt is preferably from 2.25:1 to 8:1. Complex ligand L is preferably used in molar amounts of from 1: 50 to 50:1 in terms of the zinc and the metal M. the Molar ratio of zinc salt and a metal salt of predpochtitel zinc, the zinc bromide, zinc iodide, zinc acetate, zinc acetylacetonate, carbonatehydroxide zinc, zinc fluoride, zinc nitrate, zinc sulfate, zinc benzoate, zinc carbonate, zinc citrate, zinc formate, zinc thiocyanate. Especially preferred, zinc chloride and zinc bromide. Can also be used mixtures of different zinc salts.

As the metal salt M(Y)mpreferably use cadmium chloride, mercury chloride, palladium chloride, platinum chloride, vanadium chloride, calcium chloride, barium chloride, bromide, cadmium, or magnesium chloride. Particularly preferred metal halide, in particular chloride and bromide. Can also be used mixtures of different metal salts. As cyanide salts of cobalt(III) of the formula M'3[Co(JV)6]rpreferably use hexacyanocobaltate(III) lithium, hexacyanocobaltate(III) sodium, hexacyanocobaltate(III) potassium and hexacyanocobaltate(III) calcium. Particularly preferred hexacyanocobaltate(III) potassium.

Can be used mixtures of different cyanide salts of cobalt(III).

As complex ligands L used above, i.e., alcohols, ketones and ethers. The ligands can be used separately or in combination the above-mentioned metal salts at 10-80oC, preferably at 20 to 60oC. While the aqueous solution of the above zinc salts Zn(X)nand metal salts M(Y)madded to aqueous solution of cyanide salts of cobalt(III). Fundamentally it is also possible to add an aqueous solution of cyanide salts of cobalt(III) to aqueous solution of zinc salts and metal salts.

For the method according to the invention proved to be particularly favorable intensive mixing with each other both above-mentioned aqueous solutions. Further it is desirable to pass an aqueous solution of cyanide salts of cobalt(III) prior to its mixing with the combined aqueous solution of zinc and metal salts through ion-exchange column with an acidic ion exchanger (H-form).

After mixing both aqueous solutions mixed zinc/metal-hexacyanocobaltate catalyst precipitates. Phase precipitate the catalyst is treated then one or more of the above-mentioned complex ligands L.

You can also add organic ligands L to aqueous solutions of the aforementioned metal salts or organic ligands to add to the suspension obtained after mixing aqueous solutions of metal salts.

To improve the activity of katalizatoriai, the catalyst with water or the above-mentioned organic ligands, optionally in the presence of water. Thus, the catalyst according to the invention can be removed, for example, water-soluble by-products, such as potassium chloride, having a negative impact on the reaction of polyaddition.

The treated water and/or appropriate organic ligands, the catalyst is then dried, if necessary, after comminution, at temperatures from 20 to 100oC and at pressures from 0.1 mbar to normal (1013 mbar).

Proposed according to the present invention, the zinc/metal-hexacyanocobaltate-catalyst is used to retrieve polyether polyols by polyaddition of alkalisation to containing active hydrogen atoms to the connection initiator. As alkalisation it is preferable to use ethylene oxide, propylene oxide, butylenes, and mixtures thereof. Synthesis of polyester chains by alkoxysilane may be performed, for example, with one epoxide or statistically or block with 2 or 3 different Monomeric epoxides. For more information, see "Ullmanns Encyclopdie der industriellen Chemie", English-language edition, 1992, volume A21, pages 670-671.

As the source is -8 hydroxyl groups, for example, ethylene glycol, diacylglycerol, 1,2-propylene glycol, 1,4-butanediol, hexamethyleneimine, bisphenol a, trimethylolpropane, glycerin, pentaerythritol, sorbitol, cane sugar, degraded starch and water.

It is advisable to use such containing active hydrogen compound initiator, which were obtained, for example, by conventional alkaline catalysis of the above low molecular weight initiators and which are oligomeric products alkoxysilane with molecular mass of from 200 to 2000.

Polyprionidae to contain active hydrogen atoms of the compounds initiator catalyzed proposed according to the present invention the catalyst occurs when 20-200oC, preferably at 40-180oS, particularly preferably at 50-150oC. the Reaction can be carried out at normal pressure or at pressures from 0 to 20 bar (absolute). Polyprionidae can be conducted in bulk or in an inert organic solvent such as toluene and/or tetrahydrofuran. The amount of solvent is usually 10 to 30 wt.%, in terms of the amount receivable of polyetherpolyols.

The concentration of the catalyst vybere the th polyaddition. The concentration of the catalyst generally is in the range of 0.0005 to 1 wt.%, preferably in the range 0.001-0.1 wt.%, in terms of the amount receivable of polyetherpolyols.

The polyaddition reaction are in the range from several minutes to several days, preferably they comprise a few hours.

The molecular weight of the polyether polyols obtained by using the catalyst according to the invention, are 500-100000 g/mol, preferably 1000-50000 g/mol, particularly preferably 2000-20000 g/mol.

Polyprionidae may be continuous, periodic, or semi-continuous manner.

Using the proposed according to the present invention the catalyst induction period is reduced by approximately 30% in comparison with the known catalyst. Molecular mass distribution Mw/Mnthe polyether polyols obtained by using the catalyst according to the invention is approximately from 1.01 to 1.07, and thus is considerably narrower than the molecular weight distribution of polyether polyols obtained with a known catalyst (see examples).

Examples

Preparation of catalyst

is as organic complex ligand (catalyst A, the synthesis according to JP 4145123).

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

The output of the dried powdered catalyst: is 3.08,

Elementary analysis: cobalt = 13.6 per cent; zinc = 27,35%.

Example 1

Obtaining zinc/cadmium-hexacyanocobaltate(III) catalyst with tert-butanol as the organic complex ligand and 0.9% cadmium (catalyst B).

To a solution of 4 g (12 mmol) of hexacyanocobaltate potassium in 75 ml of distilled water was added with vigorous stirring a solution of 9 g (66 mmol) of zinc chloride and 1.34 g (7.3 mmol) of cadmium chloride is tert-butanol and 50 ml of distilled water and then stirred for 10 minutes

The solid is filtered off, then within 10 min stirred with 125 ml of a mixture of tert-butanol and distilled water (70/30;./about.) and again filtered. In conclusion, again within 10 min, washed with 125 ml of tert-butanol. After filtration, the catalyst was dried at 50oC and normal pressure until constant weight.

The output of the dried powdered catalyst of the formula

Zn2,93Cd0,07[Co(CN)6] 22(H2O)1(tert-butanol)of 0.58[ZnCl2] 0,01[CdCl2] :2.83 g

Elementary analysis: cobalt = 11.8 per cent; zinc = 22,9%; cadmium = 0,9%.

Example 2

Obtaining zinc/cadmium-hexacyanocobaltate(III) catalyst with tert-butanol as the organic complex ligand and 7.1% cadmium (catalyst).

As in example 1, but with the addition of a solution of 7 g (51,3 mmol) of zinc chloride and 4.0 g (22 mmol) of cadmium chloride in 15 ml of distilled water. The output of the dried powdered catalyst of the formula

Zn2,6Cdfor 0.4[Co(CN)6]23(H2O)2(tert-butanol)0,2[ZnCl2] 0,05[CdCl2] :3,32 g

Elementary analysis: cobalt = 16,5%; zinc = 25,2%; cadmium = 7,1%.

All other catalysts falling within the above formula, receive similar is thew 500 ml, working under pressure, load 50 g polypropylenglycol initiator (molecular weight = 1000 g/mol) and 20 mg of catalyst (100 ppm, in terms of the amount receivable polyol) in a protective gas atmosphere (argon) and heated with stirring to 105oC. Then immediately add the propylene oxide (about 5 g) until the pressure rises to 2.5 bar (absolute). Further dosing of propylene oxide is produced only when the reactor is observed accelerated pressure drop. This rapid pressure drop indicates that the catalyst is activated. Then slowly dispense the residual quantity of propylene oxide (145 g) at constant pressure of 2.5 bar (absolute). After using the total number of propylene oxide and 5 h polyreactive exposure at 105oWith distilled volatile components at 90o(1 mbar) and then cooled to room temperature.

The resulting polyether polyols are characterized by determining the Oh number, the content of double bonds, and average molecular mass and molecular mass distributions Mw/Mn(MALDI-TOF-MS).

Induction periods are determined by the curves of the time-transformation (consumption of propylene oxide [g] against vrutochka on the very steep section, with the continuation of the baseline curve.

Comparative example 2

Getting polyetherpolyols with catalyst (100 ppm).

The induction period, min - 290

Polyetherpolyols: IT is a number, mg KOH/g: - 28,5

The content of double bonds, (mmol/kg) - 6

Mn: - 3426

Mw/Mn: - 1,12

Example 3

Getting polyetherpolyols with catalyst B (100 ppm)

The induction period, min - 240

Polyetherpolyols: IT is a number, mg KOH/g: - 28,0

The content of double bonds, mmol/kg: - 7

Mn: - 3426

Mw/Mn: - 1,03

Example 4

Getting polyetherpolyols with catalyst (100 ppm).

The induction period, min - 195

Polyetherpolyols: IT is a number, mg KOH/g - 29,3

The content of double bonds, mmol/kg - 8

Mn- 3324

Mw/Mn- 1,06

Similar results are achieved when using all other catalysts falling within the above formula.

The comparison between examples 3, 4 and comparative example 2 clearly shows that the use of zinc/metal-hexacyanocobaltate(III) catalysts B and C according to the present invention upon receipt of polyether polyols leads to a noticeable reduction of the period in which the polyether polyols obtained with the catalyst according to the present invention have a significantly narrower molecular weight distribution in comparison with the corresponding polyether polyols obtained by using a known catalyst.

1. The catalyst based on zinc/metal-hexacyanocobaltate to obtain polyether polyols, characterized in that it has a composition

Zn3-vMv[Co(CN)6]2w(H2O)x(L)y[Zn(X)n]z[M(Y)m],

where M is divalent metal selected from the group of cadmium (II), mercury(II), palladium (II), platinum (II), vanadium (II), magnesium (II), calcium (II) and barium (II);

X and Y is a halogen, in particular chlorine or bromine;

L - organic complex ligand selected from the group of alcohols, ketones or ethers;

V IS 0.01 TO 2.99;

W - 0,1 10;

X - 0,01 10;

U - 0,001 3,0;

z is 0.001 to 3.0;

m and n - 2.

2. The method of producing catalyst according to p. 1 by conducting interaction of aqueous solutions of metal salts in the presence of the organic complex ligand, followed by the separation of the obtained catalyst, characterized in that the 1-90% (wt. ) aqueous solution of the zinc salt of the formula Zn(X)nand a metal salt of the formula M(Y)msubjected to interaction with 0.5-50% (wt.) water is BR> M' is an alkaline metal,

in the presence of the organic complex ligand L, and salt Zn(X)nM(Y)mand cyanide salt of cobalt (III) is used in such quantities that the molar ratio of zinc and the metal M to the cobalt is 2:1 to 10:1, the complex ligand L is used in such quantities that the molar ratio of zinc and the metal M to L is 1:100 to 100:1 and the molar ratio of the zinc salt of Zn(X)nand metal salt M(Y)mlies within 500:1 to 1:500.

 

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