KR100908351B1 - Bimetallic cyanide catalyst for the production of random polyols - Google Patents

Abstract

The present invention relates to a bimetal cyanide catalyst for producing a random polyol, and the bimetal cyanide catalyst according to the present invention uses a complexing agent comprising a mixture of an ether having a molecular weight of less than 200 and a polyether polyol having a molecular weight of 1,000 to 4,000. As such, it is possible not only to have improved catalytic activity, but also to produce low viscosity transparent random polyols, especially when used in random copolymerization reactions of propylene oxide and ethylene oxide, with reduced production of unsaturated polyols.

Description

Bimetallic cyanide catalyst for random polyol production {DOUBLE METAL CYANIDE CATALYSTS FOR PREPARING RANDOM POLYOL}

The present invention relates to a highly active bimetal cyanide catalyst for producing polyol, and more particularly to a bimetal cyanide catalyst suitable for the production of random polyols in which propylene oxide (PO) and ethylene oxide (EO) are randomly copolymerized. It is about.

Polyols, together with isocyanate compounds, are used to make polyurethanes used in the fields of automotive interiors, furniture, elastomers, coatings, and the like. Generally, the production of flexible polyurethanes involves relatively high molecular weight polyols having a molecular weight of 3,000 to 6,000. And low molecular weight polyols having a molecular weight of 150 to 1,000 are used for the production of rigid polyurethanes. In addition, polyols produced by random copolymerization of PO and EO have been widely used to prepare polyurethane in the form of slab foam.

Generally, polyols are prepared by epoxide polymerization of hydrocarbon-based oxides and polymerization initiators under alkaline or basic catalysts such as KOH, whereby side reactions produce unsaturated polyols. Since unsaturated polyols have only one double bond and one hydroxyl group in one molecule of polyol, they do not form a three-dimensional network structure when polymerizing the polyurethane by the reaction of the polyol and isocyanate, and thus the mechanical properties of the polyurethane, in particular The elasticity is sharply lowered.

Thus, in order to lower the concentration of unsaturated polyols caused by side reactions of epoxide polymerization, the use of double metal cyanide (DMC) catalysts instead of KOH catalysts has been proposed. DMC catalysts have been used to minimize side reactions to reduce the concentration of unsaturated polyols in total polyols to 0.005 meq / g or less and to produce polymer products such as high molecular weight polyethers, polyesters and polyetheresters.

Such DMC catalysts are typically prepared by mixing a metal salt, a metal cyan salt and a complexing agent, whereby M _a [M '(CN) ₆ ] _b L _c L' _d where M and M 'are A metal element, L and L 'are complexing agents, a, b, c and d are integers, and the sum of a, b, c and d is equal to the sum of the number of charges of M and M'.

The complexing agent is to improve the activity of the catalyst, ethylene glycol, dimethyl ether, alcohol aldehyde ketone, ether, ester, amide, urea, nitrile and the like have been used. For example, US Pat. Nos. 4,477,589, 3,821,505, and 5,158,922 disclose ethylene glycol or dimethyl ether as complexing agents for the preparation of bimetal cyanide catalysts, and US Pat. No. 5,158,922 further discloses alcohols, aldehydes, Ketones, ethers, esters, amides, urea, nitriles are disclosed, US Pat. No. 5,780,584 tert-butyl alcohol and US Pat. Nos. 5,482,908 and 5,789,626 polyethers.

However, when preparing random polyols of PO and EO using the DMC catalyst using the complexing agent as described above, EO monomers having relatively low molecular weight in the polyol matrix are distributed unevenly to form self-bonding. As a result of crystallization and precipitation at room temperature, the polyol obtained is opaque at room temperature and has a high viscosity, making it impossible to use commercially.

The present invention has been made to solve the above problems, and an object of the present invention is to produce a high viscosity bimetal cyanide, which can produce a transparent random polyol of low viscosity while reducing the production of unsaturated polyol during epoxide copolymerization. To provide a catalyst.

In order to achieve the above object, the present invention provides a bimetal cyanide catalyst for preparing a random polyol having a structure of Formula 1 below:

M _a [M '(CN) ₆ ] _b L _c L' _d

Where

M is Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI ), Al (II), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II) and Cr (III) ;

M 'is 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 (V) and V (IV);

L is an alcoholic ligand, L 'is a ligand in which an ether having a molecular weight of less than 200 and a polyether polyol having a molecular weight of 1,000 to 4,000 are combined.

a, b, c and d are integers, the sum of which is equal to the sum of the charge numbers of M and M '.

The present invention also comprises the steps of 1) mixing and reacting an aqueous solution of a metal (M) salt, an aqueous solution of a metal (M ') cyan salt and some alcoholic complexing agent (L) to obtain a catalyst slurry;

2) To the slurry obtained in step 1), a co-complexing agent (L ') consisting of a mixture of ethers having a molecular weight of less than 200 and polyether polyols having a molecular weight of 1,000 to 4,000 is added, and then the remaining amount of the alcohol complexing agent ( Adding L) and mixing; And

3) providing a method for preparing a bimetal cyanide catalyst for preparing a random polyol having the structure of Chemical Formula 1, comprising the step of separating the solid catalyst by filtration or centrifugation of the mixture obtained in step 2).

Hereinafter, the present invention will be described in detail.

The bimetal cyanide catalyst according to the present invention is characterized by containing an alcohol-based ligand and a ligand in which an ether having a molecular weight of less than 200 and a polyether polyol having a molecular weight of 1,000 to 4,000 are combined.

The alcoholic ligand is derived from ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol or mixtures thereof.

In the present invention, the ether-polyether polyol ligand is an ether having a molecular weight of less than 200, such as diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether or mixtures thereof, and polyethers having a molecular weight of 1,000 to 4,000. Derived from a mixture of polyols, it is possible to shorten the activation time of the catalyst and increase the catalytic reactivity, thereby lowering the viscosity of the resulting polyol by inhibiting the crystallization of the EO monomers in the matrix at room temperature in the production of random polyols.

The ether and the polyether polyol are preferably combined at 1: 9 to 9: 1, with a particularly preferred mixing ratio of 1: 1.

In addition, it is preferable that ethylene oxide, butylene oxide, styrene oxide, etc. are addition-polymerized at the terminal of the said polyether polyol.

The bimetal cyanide catalyst of the present invention is prepared by 1) mixing and reacting an aqueous solution of a metal salt, an aqueous solution of a metal cyan salt and a part of an alcohol complexing agent to obtain a catalyst slurry, and 2) ether-to the obtained slurry. It can be prepared by adding and mixing the complexing agent of the polyether polyol and the remaining amount of the alcoholic complexing agent, and then 3) separating the solid catalyst from the slurry by filtration or centrifugation.

The metal salt has a general formula of M (X) _n , where M is Zn (II), Fe (II), Ni (II), Mn (II), Co (II), as defined in Formula 1 , Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI), Al (II), V (V), V (IV), Sr (II), W (IV) , Metals such as W (VI), Cu (II) and Cr (III), X is a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, An anion selected from thiocyanate, isocyanate, isothiocyanate, carboxylate, nitrate, etc., n is 1 to 3, which satisfies the valence of the metal. Value.

Suitable examples of metal salts that can be used in the present invention include zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt (II) chloride, thiocyanate Cobalt (II), nickel (II) formate, nickel (II) nitrate, and the like, of which zinc zinc chloride is particularly preferred.

The metal cyan salt has a general formula of (Y) _a M '(CN) _b (A) _c , wherein Y is an alkali or alkaline metal, M' is as defined in Formula 1, Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ir (III), Ni (II), Rh Metal elements such as (III), Ru (II), V (V), and V (IV), and A is a halide, hydroxide, sulfate, carbonate, cyanate, oxalate, thiocyanate, isocyanate, iso It is an ion which forms the salt chosen from thiocyanate, carboxylate, nitrate, etc., a and b are integers larger than 1, and the sum of a, b, and c balances the charge of M '.

Specific examples of metal cyanide salts that may be used in the present invention include potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (potassium hexacyanoferrate (III)), and Calcium hexacyanocobaltate (II), lithium hexacyanoferrate (II), zinc hexacyanocobaltate (II), zinc hexacyanoferrate (III), hex Nickel hexacyanoferrate (II), cobalt hexacyanocobaltate (III), and the like, of which potassium hexacyanocobalate (III) is particularly preferable.

In the catalyst preparation process as described above, the alcohol-based complexing agent is used in an amount of 10 to 90% by weight, preferably 10 to 80% by weight, based on the total amount of the total used material, and the conjugate of the ether-polyether polyol The topical agent is used in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of the total used material.

 In addition, the content of the alcohol complexing agent used in step 1) is preferably in the range of 10 to 30% by weight of the total alcohol complexing agent, and in step 2) a milling process may be performed for homogeneous mixing of the mixture, At this time, a ceramic ball mill (capacity 500 ml, 5 balls of 2.3 cm diameter, and 10 balls of 1.3 cm diameter) can be used.

The solid catalyst separated by step 3) may optionally be subjected to an additional purification process, which may be, for example, an aqueous solution containing from 60 to 80% by weight of an organic complexing agent such as tert-butyl alcohol. Washed, then separated by filtration or centrifugation, washed again with an aqueous solution containing 80 to 95% by weight of an organic complexing agent, and then 40 until the weight of the catalyst remained constant under vacuum of 600 to 800 mmHg. It may be carried out by drying in a temperature range of 90 ° C.

The catalyst of the present invention has a significantly higher activity than the existing catalyst, and can shorten the activation time of the existing catalyst from 1 to 4 hours to almost 1 hour, and the existing catalyst is 0.1 to 0.5kg- at a catalyst concentration of 100 ppm. While having a PO / g-Cat / min activity, the catalyst of the present invention has a high activity of 1 kg-PO / g-Cat / min or more even at a very low catalyst catalyst concentration of 25 ppm, thus eliminating the need for a residual catalyst removal process. ("kg-PO / g-Cat / min" is a unit representing the activity of the catalyst, which means the amount of propylene oxide (PO) polymerized per 1 g of the constituent of the catalyst in 1 minute).

In addition, the bimetal cyanide catalyst of the present invention is used in the random copolymerization reaction of propylene oxide (PO) and ethylene oxide (EO), having an unsaturation of 0.002 to 0.0055 meq / g, transparent at room temperature and low viscosity of 1000 cps or less. It is possible to prepare a random polyol having, in particular, in the preparation of a random polyol copolymerized in a mixing ratio of 2 to 6 OH functional groups per molecule of polyol, molecular weight of 1,000 to 10,000, PO and EO in the ratio of 9.5: 0.5 to 8: 2 Suitable.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

<Production of Double Metal Cyanide Catalyst>

Example 1

63 g of an aqueous zinc chloride solution (50%), 78 ml of distilled water, and 21 ml of tert-butanol were mixed to obtain Solution 1. Separately, 2 g of potassium cobalt hexadecate was dissolved in 42 ml of distilled water to obtain Solution 2. Solution 2 was added dropwise to Solution 1 at 50 ° C. for 1 hour and mixed using a mechanical stirrer. After the dropwise addition, the mixture was further stirred for 1 hour to form a slurry.

Subsequently, 8 g of ethylene glycol monomethyl ether and 8 g of polyether polyol having a molecular weight of 1,000 and ethylene oxide addition-polymerized at the end were mixed to obtain a coagulant, and then a solution obtained by mixing 80 ml of tert-butanol was prepared as described above. To a slurry prepared beforehand. The product was placed in a high speed centrifuge to separate solid catalyst components. To the separated solid was added a mixed solution of tert-butanol 100ml and 40ml of distilled water to make a slurry again, mixed with stirring for 1 hour, and centrifuged at high speed. To the separated solid, 130 ml of tert-butanol and 10 ml of distilled water were added again to form a slurry, mixed with stirring for 1 hour, and dried under vacuum at 60 ° C. and 762 mmHg until a constant weight was obtained. A cyan catalyst was obtained.

Example 2

Upon formation of the co-culling agent, a bimetal cyanide catalyst was obtained in the same manner as in Example 1 except that 8 g of diethylene glycol dimethyl ether was used instead of ethylene glycol monomethyl ether.

Example 3

Upon formation of the co-culling agent, a bimetal cyanide catalyst was obtained in the same manner as in Example 1 except that 8 g of ethylene glycol dimethyl ether was used instead of ethylene glycol monomethyl ether.

Example 4

At the time of formation of the complexing agent, except that 8 g of a polyether polyol having a molecular weight of 2,000 and an ethylene oxide addition polymerization at the terminal is used instead of a polyether polyol having a molecular weight of 1,000 and an ethylene oxide addition polymerization at the terminal. The bimetal cyanide catalyst was obtained by the same method as in Example 1.

Example 5

In the formation of the co-culling agent, except that 8 g of a polyether polyol having a molecular weight of 4,000 and an ethylene oxide addition polymerization at the terminal is used instead of a polyether polyol having a molecular weight of 1,000 and the ethylene oxide addition polymerization at the terminal. The bimetal cyanide catalyst was obtained by the same method as in Example 1.

Example 6

At the time of formation of the complexing agent, 8 g of a polyether polyol having a molecular weight of 1,000 and a butylene oxide addition polymerization at the terminal is used, instead of a polyether polyol having a molecular weight of 1,000 and an ethylene oxide addition polymerization at the terminal, The double metal cyanide catalyst was obtained by the same method as in Example 1.

Example 7

At the time of formation of the complexing agent, 8g of a polyether polyol having a molecular weight of 1,000 and a styrene oxide addition polymerization at the terminal is used instead of a polyether polyol having a molecular weight of 1,000 and an ethylene oxide addition polymerization at the terminal, The double metal cyanide catalyst was obtained by the same method as in Example 1.

Comparative Example 1

Except not using a complexing agent, it was carried out in the same manner as in Example 1 to obtain a bimetal cyanide catalyst.

<Production of PO / EO Random Polyols>

Example 8

460 g of glycerolpropoxylate having a molecular weight of 550 as a starter polyol and 0.14 g of the catalyst obtained in Example 1 were added to a 4 L high pressure reactor, and then the temperature was heated to 115 DEG C while stirring and maintained in a vacuum state. Here, after about 100 g of a 9: 1 mixture of propylene oxide (PO) monomer and ethylene oxide (EO) monomer was injected, the pressure of the reactor was increased to 4 psig. When the reaction started and a pressure drop occurred, the reactor temperature was maintained at 115 ° C. while again injecting 2250 g of a 9: 1 mixture of PO and EO at a rate of 8 g / min. After the completion of the dosing, wait until a constant pressure was maintained, and then maintained in a vacuum at 115 ℃ for 30 minutes to remove the unreacted monomer to prepare a PO / EO random polyol.

Examples 9-14 and Comparative Example 2

A PO / EO random polyol was prepared in the same manner as in Example 8 except that the catalysts obtained in Examples 2 to 7 and Comparative Example 1 were used as catalysts, respectively.

The physical properties of the random polyol prepared above were measured and shown in Table 1 below.

From Table 1 above, the random polyols of Examples 8 to 14 were prepared using a complex metal cyanide catalyst containing a co-culling agent of an ether-polyether polyol, and thus prepared using a co-culling agent-free catalyst. Compared with the polyol of Comparative Example 2, the polymerization induction time, that is, the activation time by the catalyst is shortened, not only exhibits a very low viscosity of less than 1000 cps, but also an unsaturation of less than 0.005 meq / g. In addition, the random polyols prepared in Examples 8 to 14 according to the present invention exhibited an OH value in the range of 55 to 57 (KOH mg / g) (this range is usually the case where the molecular weight is about 3 OH functional groups per molecule of polyol). Polyether polyols of about 3000).

As described above, the bimetal cyanide catalyst according to the present invention has a short activation time and can produce a transparent random polyol having a low viscosity while reducing the production of unsaturated polyol during random copolymerization of PO and EO. Random polyols can also be usefully used in the production of polyurethane in the form of slab foam.

Claims (13)

A bimetal cyanide catalyst for preparing a random polyol having the structure of Formula 1 <Formula 1> M _a [M '(CN) ₆ ] _b L _c L' _d Where M is Zn (II), Fe (II), Ni (II), Mn (II), Co (II), Sn (II), Pb (II), Fe (III), Mo (IV), Mo (VI ), Al (II), V (V), V (IV), Sr (II), W (IV), W (VI), Cu (II) and Cr (III) ; M 'is 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 (V) and V (IV); L is an alcoholic ligand selected from the group consisting of ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and mixtures thereof, L 'is an ether having a molecular weight of less than 200 and a molecular weight of 1,000 to 4,000 A polyether polyol is a combined ligand, a, b, c and d are integers, the sum of which is equal to the sum of the charge numbers of M and M '. delete The method of claim 1, A bimetal cyanide catalyst for producing a random polyol, characterized in that the ether is diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, ethylene glycol monomethyl ether or a mixture thereof. The method of claim 1, A polymetal cyanide catalyst for producing a random polyol, wherein the polyether polyol is ethylene oxide, butylene oxide or styrene oxide addition-polymerized at the terminal. The method of claim 1, The ether and the polyether polyol is a complex metal cyanide catalyst for producing a random polyol, characterized in that combined in a ratio of 1: 9 to 9: 1. 1) an aqueous solution of a metal (M) salt; An aqueous solution of a metal (M ') cyan salt; And ethanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol and mixtures thereof, alcohol complexes in the range of 10 to 30% by weight of the total alcoholic complexing agent used. Mixing and reacting the agent (L) to obtain a catalyst slurry; 2) To the slurry obtained in step 1), a co-complexing agent (L ') consisting of a mixture of ethers having a molecular weight of less than 200 and polyether polyols having a molecular weight of 1,000 to 4,000 is added, and then the alcohol-based complex described in step 1) Adding and mixing an alcoholic complexing agent (L) in the range of 70 to 90% by weight of the total alcoholic complexing agent used, selected from topical agents; And 3) A method for preparing a bimetal cyanide catalyst for preparing a random polyol according to claim 1, comprising the step of separating the solid catalyst by filtration or centrifugation of the mixture obtained in step 2). The method of claim 6, Wherein the total alcohol complexing agent is used in an amount of 10 to 90% by weight based on the total amount of the total used material. The method of claim 6, Wherein the co-compounding agent of the ether-polyether polyol is used in an amount of 0.1 to 20% by weight based on the total amount of the total used material. delete The method of claim 6, The process of washing the separated solid catalyst with an aqueous solution of alcohol is further performed one or more times. A method of random copolymerization of propylene oxide (PO) and ethylene oxide (EO) using the bimetal cyanide catalyst for producing a random polyol of claim 1 as a polymerization catalyst. The method of claim 11, Wherein said PO and EO are used in a mixing ratio of 9.5: 0.5 to 8: 2. PO / EO random polyol polymer having a viscosity of 1000 cps or less at 25 ° C., prepared by the method of claim 11 or 12.