KR101129344B1 - The preparation method of nano-sized double metal or multi metal cyanide catalysts - Google Patents

Abstract

The present invention relates to a method for preparing a double metal or multimetal cyanide catalyst,

a) homogeneously mixing and then adding an aqueous solution of a water-soluble metal cyan salt in the presence of a polyether polyol as a flocculent to obtain an aqueous mixture containing a water-insoluble DMC and an MMC catalyst;

b) adding the organic complexing agent to uniformly mix and separating the catalyst after the reaction for a predetermined time;

c) washing and drying the catalyst using a mixture of an organic complexing agent and water.

Cyan salt, catalyst

Description

The preparation method of nano-sized double metal or multi metal cyanide catalysts

The present invention is a double-metal cyanide useful for ring-opening polymerization of epoxy-based monomers, such as ethylene oxide (EO), propylene oxide (propylene oxide; PO), cyclohexane oxide (CHO), DMC) catalyst and a multi-metal cyanide (MMC) catalyst and a method for preparing the same, and in particular, characterized in that the particle size of the catalyst is controlled to a small size to nanometer. Polyols prepared using this catalyst exhibit extremely low unsaturation and high molecular weight.

Polyether polyols are raw materials produced in industrial quantities in large quantities and are generally used together with polyisocyanates as starting materials for polyurethane production. The catalyst used is generally soluble basic metal hydroxides such as potassium hydroxide (KOH), but when the alkali metal hydroxide is used for the production of polyether polyols, a monofunctional polyether having a terminal double bond, so-called monool is increased, It is very disadvantageous in urethane production. On the other hand, using DMC catalyst or MMC catalyst can not only reduce the content of monool, but also increase the reaction rate of PO addition, and the polyether polyols thus obtained can be used as high-quality polyurethanes (e.g. coatings, elastomers, sealants, Foams and adhesives).

However, a high activity catalyst is still required, since a small amount of catalyst can be used, thereby eliminating the catalyst removal process after the preparation of the polyether polyol.

In the prior art WO-A-97 / 26080 describes a process for preparing a paste comprising at least about 90% by weight of particles having a particle size in the range of 0.1 to 10 microns as a paste consisting of a DMC catalyst, an organic complexing agent and water. However, the paste has a disadvantage in that it is difficult to transport and handle in the process.

US-A-5900384 discloses a production method for producing sludge of DMC catalyst particles and drying the particles by spray drying, but the process is complicated and energy is concentrated in spray drying, resulting in high cost.

PCT / EP2006 / 060872 describes a process for preparing a catalyst having a particle size of at least 95% by volume and less than 50 microns.

However, in order to obtain such a catalyst, it is cumbersome to disperse the catalyst in polypropylene, and then stand still for 1 to 72 hours, and then extract the upper layer. Not.

PCT / US2004 / 016394 describes a process for preparing DMC catalysts in the form of particles having an average particle size of about 20 to about 500 nm showing improved ability in forming EO capping on secondary hydroxy terminated polyethers. have.

However, the catalyst has improved ability, but hydrochloric acid, petroleum ether, and various surfactants are added during the preparation of the catalyst, making the manufacturing process complicated and unfavorable for the environment.

Therefore, there is a need for an improved method for the preparation of DMC and MMC catalysts that overcomes the disadvantages of the prior arts.

An object of the present invention is to firstly develop a high activity catalyst having a relatively short induction time in the polymerization process. Induction time is a time taken for the catalyst to be activated, and polymerization does not occur at all at this time. Extreme heat dissipation can lead to uncontrolled temperature rise during catalyst activation, resulting in defects due to overexposure to the product. There is also a risk that catalyst activity is weakened due to accelerated heat aging. Highly active catalysts can be polymerized even at low catalyst concentrations, and even if the catalyst remains in the resulting polyether polyol product, it does not affect product quality.

Second, the catalyst manufacturing process is to develop environmentally friendly, industrially feasible and efficient methods.

Third, to develop a catalyst capable of obtaining a polyether polyol having a relatively high molecular weight, a narrow molecular weight distribution, and a significantly low monool content.

In the present invention, a polyether having a number average molecular weight of 500 or more (US Pat. No. 5,482,908) or a polyether (US Pat. No. 5,789,626) of 500 or less is used as an adhesive in the catalyst manufacturing process. In addition to the role of the adhesion agent to increase the activity as well as controlling the size of the catalyst particles it was possible to prepare a catalyst having a particle distribution of the DMC catalyst of 80nm to 600nm, the average particle size of 150nm to 300nm. In particular, it is characterized by first reacting with such a polyether polyol tackifier before reacting with the organic complexing agent.

The remaining amount of Zn and Co in the polyol produced by the catalyst of the present invention is less than 5 ppm each before undergoing purification of the polyol. When the purity of the product needs to be high, simple filtration can be used to remove trace catalyst from the polyol product. This is because the catalyst is present in the product in a heterogeneous state. In general, most commercial polyether polyols produced by conventional KOH catalysts require a catalyst removal step, so it is an important advantage to be able to omit this process in the polyols.

DMC or MMC catalyst production method of the present invention is significantly simpler than the process of DMC or MMC catalyst prepared using the tertiary butyl alcohol (t-butyl alcohol) most commonly used in the existing catalyst, the organic used during the catalyst synthesis process The amount of the complexing agent is small and, in particular, the manufacturing process is environmentally friendly in that environmentally friendly lactate is used as the complexing agent instead of tertiary butyl alcohol, and the produced catalyst is also a relatively environmentally friendly product. In addition, all the catalyst manufacturing processes are performed in one reactor, which can reduce the catalyst production time and cost, thereby eliminating the need for economic and complicated steps, thereby obtaining a relatively high yield of catalyst.

In addition, in the present invention, the polymerization activity was shown even if the content of transition metal salts such as zinc chloride was significantly reduced, and in particular, the content of transition metal salts decreased the exposure to risk during the operation of the equipment, the risk of corrosion of the equipment, and the cost of catalyst production. The reduction can lead to economic effects.

The present invention is to provide a method for producing a DMC and MMC catalyst comprising the following steps:

a) homogeneously mixing and then adding an aqueous solution of a water-soluble metal cyan salt in the presence of a polyether polyol as a flocculent to obtain an aqueous mixture containing a water-insoluble DMC and an MMC catalyst;

b) adding the organic complexing agent to uniformly mix and separating the catalyst after the reaction for a predetermined time;

c) washing the catalyst using a mixture of an organic complexing agent and water and drying the catalyst.

The process of the present invention allows the particle size of the DMC and MMC catalysts to be reduced to nano size, while maintaining the amorphous or crystalline structure of these DMC and MMC catalysts.

The present invention also relates to a catalyst obtained by such a method and a polyether polyol obtained using the catalyst.

The catalyst according to the present invention achieves two goals of improving the activity of the catalyst and controlling the particle size of the catalyst by using an adhesive agent. In the case of the DMC-TBA catalyst synthesized using only the t-butyl alcohol complexing agent without the addition of a tackifier, irregular and wide particle distribution catalyst particles were formed. However, a white suspension was easily formed in the cobalt hexavalent salt aqueous solution mixed with an excess of an aqueous zinc chloride solution with a tackifier. When t-butyl alcohol was added to the prepared catalyst slurry and reacted, and then washed several times with a mixture of butyl alcohol and distilled water, catalyst particles having a much smaller particle size of less than 300 nm and a narrow particle distribution could be prepared ( 2, 3). As a result, it was found that the oxygen atom of the hydroxyl portion of the polyether polyol as an adhesion agent during the nucleation and growth phase of the catalyst weakly forms coordination bonds with zinc and cobalt ions (FIG. 1). In addition, the catalyst according to the present invention is very simple in the synthesis process, using environmentally friendly lactates as an organic complexing agent is environmentally friendly and economical.

DMC to MMC catalyst prepared by the method of the present invention has the formula:

For example, in the case of DMC catalyst prepared by adding an organic complexing agent after the reaction of a zinc chloride (excess) aqueous solution with an aqueous solution of potassium cyanide cobalt salt (1)

Zn ₃ [Co (CN) ₆ ] ₂ ZnCl ₂ yH ₂ O z Complexing Agent

For example, in the case of the MMC catalyst manufactured by adding an organic complexing agent after adding the potassium hexacyanide aqueous solution to the manufacturing method of 1;

Zn ₃ [Co (CN) ₆ ] ₂ Zn ₂ [Fe (CN) ₆ ] ZnCl ₂ yH ₂ O z Complexing Agent

DMC or MMC catalysts are the reaction products of water soluble metal salts and water soluble metal cyan salts.

Metal salts soluble in water generally have the general formula M (X) _n 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) or Cr (III). Among them, Zn (II), Fe (II), Co (II), Ni (II) and the like are more suitable.

X is a halide, hydroxide, sulfate, carbonate, cyanide, oxalate, thiocyanate, isocyanate, isothiocyanate It is an anion selected from carboxylate and nitrate. The value of n is 1 to 3 and satisfies the valence of M.

Examples of suitable metal salts are zinc chloride, zinc bromide, zinc acetate, zinc acetonylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II), formic acid And compounds such as nickel (II), nickel nitrate (II) and the like.

Metal cyanide salts that are soluble in water used to prepare MMC catalysts generally have the formula (Y) _a M'C (N) _b (A) _c . 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), V (IV) and so on. Among these, Co (II), Co (III), Fe (II), Fe (III), Cr (III), Ir (III), Ni (II) and the like are more suitable. Metal cyanide salts that are soluble in water may contain one or more of these metals. Y is an alkali metal ion or an alkali metal ion. A is an ion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates, nitrates and the like. a and b are integers greater than one. The sum of the charges a, b and c balances the charge of M '.

Suitable metal cyanide salts that are soluble in water include potassium hexacyanocobaltate (III), potassium hexacyanoferrate (II), potassium hexacyanoferrate (III), and calcium hexavalent cobalt salt. (calcium hexacynocobaltate) (II) and lithium hexacyanoferrate (II).

Examples of the MMC catalyst used in the present invention include zinc hexacynocobaltate (III), hexacyanoferrate (III) and zinc hexacyanoco, which are composed of Zn, Co, and Fe. Zinc hexacynocobaltate (III), hexacyanoferrate (II), and the like.

The DMC or MMC catalyst invented in the present invention contains an organic complexing agent. In general, complexing agents should be well soluble in water. Suitable complexing agents conventionally used are US Patents 3,278,457, 3,278,459, 3,289,505, 3,427,256, 4,477,589, 5,158,922, 5,470,813, 5,482,908, 5,545,601, 5,627,122, 6,423,662, WO 01/04180, WO 02/09875. As well as in patents.

Existing patented complexing agents are added after the preparation of the catalyst or after precipitation has taken place. Generally excess complexing agents are used. More suitable complexing agents are organic compounds containing heteroatoms that are soluble in water that can be mixed with the DMC catalyst. Suitable organic complexing agents include alcohols, aldehydes, ketones, ethers, esters, amides, urea, nitriles, sulfates and mixtures thereof. When synthesizing the existing DMC or MMC catalyst, ether type such as dimethoxyethane and diglyme or water-soluble aliphatic alcohols were preferred. Among them, alcohols that are well soluble in water such as ethanol, isopropanol, normal butanol, isobutanol, sec-butanol, and tert-butanol are more suitable. In particular, tert-butanol is the most suitable and widely used to make DMC or MMC catalyst.

As the organic complexing agent used in the present invention, all of the above-mentioned general complexing agents may be used, but particularly preferred organic complexing agents of the present invention are lactate species having both ester and alcohol groups which are completely different from the existing organic complexing agents. It has the same form as 1, wherein R includes both alkyl groups. Ethyl lactate was used to synthesize DMC or MMC catalyst. Lactate paper used includes both lactate and a mixture of the lactate and the complexing agent in the existing patent, when it contains only one lactate. In particular, the preferred lactate species in the present invention is ethyl lactate, which has little toxicity and is certified as a food additive from the FDA by the US Food and Drug Administration. It is a more suitable organic solvent than butyl alcohol.

Chemical structure of lactate

The DMC or MMC catalyst of the present invention contains about 10-60 mmol of polyether polyols such as PTMEG. More preferred are catalysts containing about 10-40 mmol. The best is to add 20-40 mmol. Catalysts containing 80 mmol or more of polyether polyols are not effective in improving the activity, and are generally difficult to store and use because they are not sticky solids but sticky dough.

The PTMEG used to make the DMC or MMC catalyst in the present invention has a number average molecular weight of 500 or more. Although PTMEG is suitable, other polyether polyols may be used. Suitable polyethers include those produced by ring-opening polymerization of cyclic ether compounds, low molecular weight epoxy polymers, oxetane polymers and the like. Such polymers can be prepared by various methods. The terminal groups of these polymers may be hydroxyl groups, amine groups, ester groups, ether groups and the like. Particularly suitable polyethers are polyethers having a hydroxyl functional degree of about 1 to 8. Useful polyethers include poly (propylene glycol), poly (ethylene glycol), poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) terpolymers, EO-capped poly (oxypropylene ) Polyols, EO-PO polyols, butylene oxide polymers and copolymers thereof. Although the molecular weight is much higher than those listed above, overly branched glycerol (molecular weight 4000) and copolymers thereof having hydroxyl groups are also available as complexing agents.

The present invention is characterized in that a DMC catalyst or an MMC catalyst is prepared by first adding an attaching agent such as PTMEG and using an organic complexing agent such as ethyl lactate. In case of DMC catalyst synthesized using t-butyl alcohol and PTMEG, which are well described in the existing patent, as an organic complexing agent, the induction time was 3 hours at any time, but it was derived when the new DMC or MMC catalyst prepared by the preparation method of the present invention. The time could be advanced by at least 78 minutes.

1 illustrates a catalyst preparation process according to the present invention. A white suspension easily formed in the case of an aqueous solution of cobalt cyanide salt mixed with an excess of an aqueous zinc chloride solution added with an adjuvant. When t-butyl alcohol was added to the prepared catalyst slurry and reacted, and then washed several times with a mixture of t-butyl alcohol and distilled water, a much smaller and narrower particle distribution than 300 nm could be prepared. From this result, it can be seen that during the nucleation and growth of the catalyst, the oxygen atom in the hydroxyl portion of the polyether polyol, which is an adsorbent, forms weakly coordination bonds with zinc and cobalt ions.

Based on the following examples and comparative examples, the ratio of Zn and CO was 10: 1 when the catalyst was synthesized, the synthesis temperature was 50 ° C, the amount of PTMEG added as an adhesion agent was 20 mmol, and the amount of ethyl lactate added as an oil lubricant was 50 ml. The highest activity was observed and the polymerized polyols also showed extremely low monool content.

The following examples illustrate the invention but do not limit the scope of the invention.

Preparation Example 1 Preparation of Nano-Sized Catalyst (DMC-PT1) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

A 500 ml Erlenmeyer flask was equipped with a mechanical stirrer, thermostat and thermometer. 200 mL of distilled water was added to a beaker with 2.7258 g of zinc chloride, and the solution was sufficiently dissolved by stirring (mixture 1). In a second beaker, 0.6595 g of potassium hexacyanocobaltate is dissolved in 20 mL of distilled water (mixture 2). Mixed solution 1 and 2.9244 g (40 mmol) of PTMEG were added, followed by heating to 50 ° C. until the entire solid dissolved, and the mixture was stirred at 400 rpm for 20 minutes. Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. 50 mL of t-butyl alcohol is added to the catalyst slurry thus obtained, followed by reaction at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. The obtained catalyst slurry is separated by high-speed centrifugation, and the remaining impurities are removed by washing and centrifuging three times using a mixture of 50 mL of distilled water and 50 mL of t-butyl alcohol. Finally the separated catalyst cake is dried under 60 ^o C, 30in.Hg vacuum until it has a constant weight

Preparation Example 2 Preparation of Nano-Sized Catalyst (DMC-PT2) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Preparation Example 1 was repeated except that the amount of zinc chloride added was reduced from 2.7258 g to 1.3629 g.

Preparation Example 3 Preparation of Nano-Sized Catalyst (DMC-PT1a) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Repeat Preparation Example 1 except adding 35 mL of t-butyl alcohol and 15 mL distilled water mixture instead of 50 mL of t-butyl alcohol.

Preparation Example 4 Preparation of Nano-Sized Catalyst (DMC-PT1b) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Repeat Preparation Example 1 except adding 25 mL of t-butyl alcohol and 25 mL distilled water mixture instead of 50 mL of t-butyl alcohol.

Preparation Example 5 Preparation of Nano-Sized Catalyst (DMC-PT1c) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Repeat Preparation Example 1 except adding 15 mL of t-butyl alcohol and 35 mL distilled water mixture instead of 50 mL of t-butyl alcohol.

Preparation Example 6 Preparation of Nano-Sized Catalyst (DMC-PTS1) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Preparation Example 1 is repeated except that 0.7311 g (10 mmol) is added instead of 2.9244 g (40 mmol) of PTMEG.

Preparation Example 7 Preparation of Nano-Sized Catalyst (DMC-PTS2) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Preparation Example 1 is repeated except that 1.4622 g (20 mmol) is added instead of 2.9244 g (40 mmol) of PTMEG.

Preparation Example 8 Preparation of Nano-Sized Catalyst (DMC-PTS3) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Preparation Example 1 is repeated except that 4.3866 g (60 mmol) is added instead of 2.9244 g (40 mmol) of PTMEG.

Preparation Example 9 Preparation of Nano-Sized Catalyst (DMC-PEG) Containing t-Butyl Alcohol and PEG as Organic Complexing Agent

A 500 ml Erlenmeyer flask was equipped with a mechanical stirrer, thermostat and thermometer. 200 mL of distilled water was added to a beaker with 2.7258 g of zinc chloride, and the solution was sufficiently dissolved by stirring (mixture 1). In a second beaker, 0.6595 g of potassium hexacyanocobaltate is dissolved in 20 mL of distilled water (mixture 2). After the addition of 0.88 g of the mixed solution 1 and PEG, the mixture was heated to 80 ° C. until the whole solid was dissolved, and the mixture was stirred at 400 rpm for 20 minutes. Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. 50 mL of t-butyl alcohol is added to the catalyst slurry thus obtained, followed by reaction at 80 ^° C. for 3 hours while mixing using a mechanical stirrer. The obtained catalyst slurry is separated by high-speed centrifugation, and the remaining impurities are removed by washing and centrifuging three times using a mixture of 50 mL of distilled water and 50 mL of t-butyl alcohol. Finally, the catalyst cake is dried until it has a constant weight under 60 ^° C and 30mmHg vacuum.

Preparation Example 10 Preparation of Nano-Sized Catalyst (DMC-PPG) Containing t-Butyl Alcohol and PPG as Organic Complexing Agent

Preparation Example 9 is repeated except that 0.92 g (20 mmol) of PPG is added instead of 0.88 g (20 mmol) of PEG.

Preparation Example 11 Preparation of Nano-sized Catalyst (DMC-PTG) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

Preparation Example 9 is repeated except that 1.462 g (20 mmol) of PTMEG is added instead of 0.88 g (20 mmol) of PEG.

Preparation Example 12 Preparation of Nano-Sized Catalyst (DMC-P123) Containing t-Butyl Alcohol and P123 as an Organic Complexing Agent

Preparation Example 9 is repeated except that P123 1 g (20 mmol) is added instead of 0.88 g (20 mmol) of PEG.

Preparation Example 13 Preparation of Nano-Sized Catalyst (DMC-HBP) Containing t-Butyl Alcohol and Polyglycidol Excessly Branched as Organic Complexing Agent

Preparation 9 is repeated except that 1.48 g (20 mmol) of excessively branched polyglycidol is added instead of 0.88 g (20 mmol) of PEG.

Preparation Example 14

Preparation of Nano-sized Catalyst (DMC-PE1) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

A 500 ml Erlenmeyer flask was equipped with a mechanical stirrer, thermostat and thermometer. 200 mL of distilled water was added to a beaker with 2.7258 g of zinc chloride, which was sufficiently dissolved by stirring (mixture 1). In a second beaker, 0.6595 g of potassium hexacyanocobaltate is dissolved in 20 mL of distilled water (mixture 2). After the addition of 1.4622 g of the mixed solution 1 and PTMEG, the mixture was heated to 50 ° C until the whole solid was dissolved, and the mixture was stirred at 400 rpm for 20 minutes. Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. 50 mL of ethyl lactate was added to the catalyst slurry thus obtained, followed by reaction at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. The obtained catalyst slurry is separated by high-speed centrifugation, and the remaining impurities are removed by washing and centrifuging three times using a mixture of 50 mL of distilled water and 50 mL of ethyl lactate. Finally, the separated catalyst cake is dried at 60 ^o C and 30 mmHg vacuum until constant weight.

Preparation Example 15 Preparation of Nano-Sized Catalyst (DMC-PE1) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation 14 is repeated except that the amount of zinc chloride is reduced to 1.908 g.

Preparation Example 16 Preparation of Nano-Sized Catalyst (DMC-PE2) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation 14 is repeated except that the amount of zinc chloride is reduced to 1.363 g.

Preparation Example 17 Preparation of Nano-Sized Catalyst (DMC-PE3) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation 14 is repeated except that the amount of zinc chloride is reduced to 0.818 g.

Preparation Example 18 Preparation of Nano-Sized Catalyst (DMC-PES1) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation 14 is repeated except that 0.7311 g (10 mmol) is added instead of 1.4622 g (20 mmol) of PTMEG.

Preparation Example 19 Preparation of Nano-Sized Catalyst (DMC-PES3) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation 14 is repeated except that 2.9244 g (40 mmol) is added instead of 1.4622 g (20 mmol) of PTMEG.

Preparation Example 20 Preparation of Nano-Sized Catalyst (DMC-PE1a) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Preparation Example 14 was repeated except that 50 mL of ethyl lactate was added to 25 mL.

Preparation Example 21 Preparation of Nano-Sized Catalyst (DMC-PET8) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Production Example 14 was repeated except that the catalyst synthesis temperature was increased from 50 ° C. to 80 ° C.

Preparation Example 22 Preparation of Nano-Sized Catalyst (DMC-PET11) Containing Ethyl Lactate and PTMEG as Organic Complexing Agent

Production Example 14 was repeated except that the catalyst synthesis temperature was increased from 50 ° C. to 110 ° C.

Comparative Production Example 1 Preparation of Catalyst (DMC-5) Containing t-Butyl Alcohol and PTMEG as Organic Complexing Agent

In a beaker mix 30 g of zinc chloride, 69 mL of distilled water, 115.5 mL of t-butyl alcohol. (Mixed solution 1). Dissolve 3.15 g of potassium hexacyanocobaltate in 42 mL of distilled water in a second beaker (mixture 2). In a third beaker, 3.5 g of PTMEG is dissolved in 20 mL of t-butyl alcohol and 20 mL of distilled water (mixture 3). Mixing solution 2 is added dropwise to the mixing solution 1 at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. A mixed solution 3 is added thereto and reacted for 3 minutes. After the reaction, the solid is separated using high-speed centrifugation. 46 mL of distilled water and 104 mL of t-butyl alcohol were mixed in the catalyst slurry thus obtained, followed by reaction at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. After 1 hour of reaction, 0.85 g of PTMEG was added to the reactor and stirred for 3 minutes. Solids are separated using high speed centrifugation. 77.75 mL of t-butyl alcohol was mixed with the catalyst slurry thus obtained, followed by reaction at 50 ^° C. for 1 hour while mixing using a mechanical stirrer. After the reaction for 1 hour, 0.45 g of PTMEG was added to the reactor and stirred for 3 minutes. The obtained catalyst cake was then centrifuged three times using 100 mL of distilled water and 50 mL of t-butyl alcohol to remove the remaining impurities. Finally, the catalyst cake is dried until it has a constant weight under 60 ^° C and 30mmHg vacuum.

2 and 3 are the results of analyzing the average particle size and particle distribution of the catalyst using the particle shape and size and particle size analyzer analyzed by the electron scanning microscope (SEM) of the catalyst according to the present invention.

In the case of the DMC-TBA catalyst synthesized using only the t-butyl alcohol complexing agent without the addition of a tackifier, irregular and wide particle distribution catalyst particles were formed. However, a white suspension was easily formed in the cobalt hexavalent salt aqueous solution mixed with an excess of an aqueous zinc chloride solution with a tackifier. When t-butyl alcohol was added to the prepared catalyst slurry and reacted, and then washed several times with a mixture of butyl alcohol and distilled water, the catalyst particles were able to prepare catalyst particles having a much smaller particle size of less than 300 nm and having a narrow particle distribution.

The X-ray diffraction trends of the catalyst prepared without addition of an organic complexing agent (DMC-PB), and the catalyst prepared by Comparative Preparation Example (DMC 5) and Preparation Example are shown in Table 1 below.

TABLE 1

 catalyst Characteristics of DMC Catalyst X-ray Diffraction Trends
(d-spacings, angstroms) 5.83 5.07 4.82 3.76 3.59 2.54 2.28 DMC 5 X O O O X X X DMC-PB O O X X O O O DMC-PT1 O O O O O O O DMC-PT2 O O X O O O O DMC-PT1a O O X O O O O DMC-PT1b O O X O O O O DMC-PT1c O O X O O O O DMC-PTS1 O O X O O O O DMC-PTS3 O O X O O O O DMC-PTS4 O O X O O O O DMC-PEG X O X O O X X DMC-PPG X O X O O O O DMC-PTG X O X O O O O DMC-P123 X X X O X X X DMC-HBP X O X O O O O DMC-PE1 X O X O O X X DMC-PE2 X O X O O X X DMC-PE3 X O X O O X X DMC-PE4 X O X O O X X DMC-PES1 X O X O O X X DMC-PES3 X O X O O X X DMC-PET8 X O O O O X X DMC-PET11 O X X X O O O

 (O mark indicates X-ray diffraction peak, X mark indicates that X-ray diffraction peak does not exist)

11 to 17 show X-ray diffraction graphs of the catalyst of the present invention, a catalyst prepared without adding an organic complexing agent (DMC-PB), and a catalyst prepared without adding an tackifier (DMC-TPA). Indicated. It can be seen from the above table and graph that the catalyst of the present invention has a crystal structure completely different from that of the conventional catalyst.

Comparative Example 1 Preparation of Polyol Using DMC-5 Catalyst (1): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

Into a 1 L high-pressure reactor is introduced 70 g of PPG having a molecular weight of 400 g as a starter polyol and 0.3 g of the catalyst prepared (250 ppm catalyst based on the last polyol product). After raising the mixture to 115 ^o C with good stirring. Hold under vacuum for 2 hours to remove moisture remaining in the mixture. About 15 g of PO is injected into the reactor. At this time, the pressure in the reactor increases from vacuum to 4 psig. After some time (induction time), a pressure drop appears in the reactor. This shows that the activity of the catalyst is shown. When the activity of the catalyst appears, PO (400 g total) is continuously injected into the reactor to maintain a pressure of 10 psig.

The activity of the catalyst is measured at the steepest point in the graph of PO consumption versus time (see polymerization rates in FIGS. 3-7 and Table 1). After injection of PO is maintained at 115 ^° C. until a constant pressure is maintained, ie the polymerization of PO is complete. The vacuum is maintained at 60-80 ^o C for 30 minutes to remove unreacted PO in the reactor. The polymer is cooled and recovered. The effects of the catalyst on the polymerization rate, activation induction time, and unsaturation are summarized in Table 1.

Comparative Example 2 Preparation of Polyol Using DMC-5 Catalyst (2): Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Saturation

The order of the comparative example 1 is followed. Only the catalyst usage of DMC-5 is reduced from 0.3g to 0.1g. The product is recovered in the same way.

Comparative Example 3 Preparation of Polyol Using DMC-5 Catalyst (3): Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the catalyst usage of DMC-5 is reduced from 0.3g to 0.05g. The product is recovered in the same way.

Example 1 Preparation of Polyol Using DMC-PT1 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the catalyst of DMC-PT1 is used. The product is recovered in the same way.

Example 2 Preparation of Polyols Using DMC-PT2 Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the catalyst of DMC-PT2 is used. The product is recovered in the same way.

Example 3 Preparation of Polyols Using DMC-PT1a Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, and Saturation

The order of the comparative example 1 is followed. Only the catalyst of DMC-PT1a is used. The product is recovered in the same way.

Example 4 Preparation of Polyols Using DMC-PT1b Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the catalyst of DMC-PT1b is used. The product is recovered in the same way.

Example 5 Preparation of Polyols Using DMC-PT1c Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only DMC-PT1c catalyst is used. The product is recovered in the same way.

Example 6 Preparation of Polyols Using DMC-PTS1 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PTS1 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 7 Preparation of Polyols Using DMC-PTS2 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Saturation

The order of the comparative example 1 is followed. Only the amount of DMC-PTS2 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 8 Preparation of Polyols Using DMC-PTS3 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PTS3 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 9 Preparation of Polyols Using DMC-PTS4 Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PTS4 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 10 Preparation of Polyols Using DMC-PEG Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PEG catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 11 Preparation of Polyols Using DMC-PPG Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Saturation

The order of the comparative example 1 is followed. Only the amount of DMC-PPG catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 12 Preparation of Polyols Using DMC-PTG Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PTG catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 13 Preparation of Polyol Using DMC-P123 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-P123 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 14 Preparation of Polyols Using DMC-HBP Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-HBP catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 15 Preparation of Polyols Using DMCPE1 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE1 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 16 Preparation of Polyols Using DMC-PE2 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE2 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 17 Preparation of Polyols Using DMC-PE3 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE3 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 18 Preparation of Polyols Using DMC-PE4 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE4 catalyst used is reduced from 0.3 g to 0.1 g. The product is recovered in the same way.

Example 19 Preparation of Polyols Using DMC-PES1 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, and Saturation

The order of the comparative example 1 is followed. Only the amount of DMC-PES1 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 20 Preparation of Polyols Using DMC-PES2 (DMC-PE1) Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PES2 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 21 Preparation of Polyols Using DMC-PES3 Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PES3 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 22 Preparation of Polyols Using DMC-PE1a Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE1a catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 23 Preparation of Polyols Using DMC-PET5 (DMC-PE1) Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PE1 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 24 Preparation of Polyols Using DMC-PET8 Catalyst: Effect of Catalyst on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PET8 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

Example 25 Preparation of Polyols Using DMC-PET11 Catalysts: Effect of Catalysts on Polymerization Rate, Activation Induction Time, Unsaturation

The order of the comparative example 1 is followed. Only the amount of DMC-PET11 catalyst used is reduced from 0.1 g to 0.05 g. The product is recovered in the same way.

The results of the above Examples and Comparative Examples are shown in Table 2 and FIGS. 4 to 10.

Table 2

Run No. catalyst catalyst
density
(ppm) Molecular Weight
(M _n ) Molecular Weight
Distribution
(PDI) Judo
time
(min) Polymerization speed
(g POP / g-cat h) Unsaturation
(meq / g) KOH 2000 2000 0.02608 KOH 3000 3000 0.03591 Comparative Example 1 DMC-5 750 6500 1.26 169 6393 0.00507 Comparative Example 2 DMC-5 250 6200 1.13 160 15000 0.00475 Comparative Example 3 DMC-5 125 5700 1.14 207 70800 0.00462 Example 1 DMC-PT1 750 7300 1.23 48 11788 0.00451 Example 2 DMC-PT2 750 7000 1.22 44 12687 0.00359 Example 3 DMC-PT1a 750 7300 1.23 63 18181 0.00234 Example 4 DMC-PT1b 750 6800 1.23 65 5394 0.00155 Example 5 DMC-PT1c 750 6500 1.23 89 2397 0.00143 Example 6 DMC-PTS1 250 6300 1.23 150 18000 0.00272 Example 7 DMC-PTS2
(DMC-PT1) 250 7000 1.23 32 35400 0.00201 Example 8 DMC-PTS3 250 7400 1.27 38 23400 0.00341 Example 9 DMC-PTS4 250 6400 1.29 41 4800 0.00512 Example 10 DMC-PEG 250 6300 1.26 120 30000 0.00219 Example 11 DMC-PPG 250 6500 1.21 123 25200 0.00151 Example 12 DMC-PTG 250 6000 1.08 116 40200 0.00318 Example 13 DMC-P123 250 6600 1.14 92 39400 0.00299 Example 14 DMC-HBP 250 6400 1.12 116 33000 0.00173 Example 15 DMC-PE1 250 6900 1.21 68 10200 0.00267 Example 16 DMC-PE2 250 6500 1.23 96 9600 0.00393 Example 17 DMC-PE3 250 6000 1.21 115 4800 0.00517 Example 18 DMC-PE4 250 5500 1.28 232 1800 0.00710 Example 19 DMC-PES1 125 - - - - - Example 20 DMC-PES2
(DMC-PE1)
125 5300 1.23 78 8400 ** Example 21 DMC-PES3 125 - - - - - Example 22 DMC-PE1a 125 6400 1.32 193 3000 0.00393 Example 23 DMC-PET5
(DMC-PE1) 125 5300 1.23 78 8400 ** Example 24 DMC-PET8 125 - - - - - Example 25 DMC-PET11 125 - - - - -

** indicates that unsaturation value is too low to be measured (measured by ASTM D2847 method)

4 to 10 graph the consumption of PO versus time during the polymerization using the catalyst according to the invention. The activity of the catalyst is expressed in kg / cobalte g / min of propylene oxide and is determined by the slope at the steepest point in the graph. It was found that the activity of the catalyst according to the present invention was much better than that of the catalyst of the comparative example.

1 illustrates a catalyst preparation process according to the present invention.

Figure 2 is a catalyst using a particle shape and size and particle size analyzer analyzed by electron scanning microscope (SEM) of the catalyst (DMC-PEG, DMC-PPG, DMC-PTG, DMC-P123, DMC-HBP) according to the present invention The average particle size and particle distribution of are analyzed.

3 is a particle shape and size and particle size analyzer analyzed by electron scanning microscope (SEM) of the catalyst (DMC-PES1, DMC-PES2, DMC-PES3, DMC-PET5, DMC-PET8, DMC-PET11) according to the present invention This is the result of analyzing the average particle size and particle distribution of the catalyst using.

FIG. 4 shows the consumption versus time of PO during polymerization using catalysts (DMC-PT1, DMC-PT2, DMC-PT1a, DMC-PT1b, DMC-PT1c) according to the present invention and the existing patented catalyst (DMC5). It's a graph.

FIG. 5 is a graph of consumption versus time of PO during the polymerization reaction using catalysts according to the invention (DMC-PTS1, DMC-PTS2, DMC-PTS3, DMC-PTS4) and the existing patented catalyst (DMC5). .

6 shows the consumption versus time of PO during the polymerization reaction using the catalysts (DMC-PEG, DMC-PPG, DMC-PTG, DMC-P123, DMC-HBP) according to the present invention and the existing patented catalyst (DMC5). It's a graph.

FIG. 7 is a graph of consumption versus time of PO during polymerization using catalysts according to the present invention (DMCPE1, DMCPE2, DMCPE3, DMCPE4) and the patented catalyst (DMC5).

8 is a graph of the consumption of PO versus time during the polymerization using catalysts (DMCPE1, DMCPE1a) according to the present invention.

9 is a graph of the consumption of PO versus time during the polymerization using catalysts according to the invention (DMCPES1, DMCPES2, DMCPES3).

10 is a graph of the consumption of PO versus time during the polymerization using catalysts according to the invention (DMCPET5, DMCPET8, DMCPET11).

11 is an X-ray diffraction of the catalyst (DMC-PT1, DMC-PT2, DMC-PT1a, DMC-PT1b, DMC-PT1c) according to the present invention and X-ray of DMC-PB prepared without the addition of an organic complexing agent The diffraction graph is shown.

FIG. 12 shows the X-ray diffraction graph of DMC-PB prepared without addition of an X-ray diffraction and organic complexing agent of the catalyst (DMC-PTS1, DMC-PTS2, DMC-PTS3, DMC-PTS4) according to the present invention. will be.

FIG. 13 shows silver prepared without addition of an adjuvant agent for controlling the X-ray diffraction and catalyst particle size of the catalyst (DMC-PEG, DMC-PPG, DMC-PTG, DMC-P123, DMC-HBP) according to the present invention. X-ray diffraction graph of DMC-TPA is shown.

Figure 14 shows the X-ray diffraction graph of the DMC-PB prepared without the X-ray diffraction and the organic complexing agent of the catalyst (DMCPE1, DMCPE2, DMCPE3, DMCPE4) according to the present invention.

FIG. 15 shows an X-ray diffraction graph of DMC-PB prepared without adding an X-ray diffraction and an organic complexing agent of the catalysts (DMCPE1 and DMCPE1a) according to the present invention.

Figure 16 shows the X-ray diffraction graph of the DMC-PB prepared without the X-ray diffraction and the organic complexing agent of the catalyst (DMCPES1, DMCPES2, DMCPES3) according to the present invention.

Figure 17 shows the X-ray diffraction graph of the DMC-PB prepared without the X-ray diffraction and the organic complexing agent of the catalyst (DMCPET5, DMCPET8, DMCPET11) according to the present invention.

Claims (7)

Method for preparing a double metal cyan salt (DMC) or multimetal cyan salt (MMC) catalyst comprising the following steps: a) homogeneously mixing and then adding an aqueous solution of a water-soluble metal cyan salt in the presence of a polyether polyol as a flocculent to obtain an aqueous mixture containing a water-insoluble DMC and an MMC catalyst; b) adding the organic complexing agent to uniformly mix and separating the catalyst after the reaction for a predetermined time; c) washing the catalyst using a mixture of an organic complexing agent and water and drying the catalyst. The method for preparing a DMC or MMC catalyst according to claim 1, wherein the organic complexing agent is lactate. The method of claim 2, wherein the lactate is at least one selected from the group consisting of methyl lactate, ethyl lactate, propyl lactate, and isopropyl lactate. The method for preparing a DMC or MMC catalyst according to claim 3, wherein the polyether polyol suspending agent is contained in 10 to 60 mmol. The polyether polyol of claim 4, wherein the polyether polyol is poly (propylene glycol), poly (ethylene glycol), poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) terpolymer, poly (tetramethylene ether glycol). ), A process for producing a DMC or MMC catalyst, characterized in that at least one selected from the group consisting of overly branched polyglycidol in dendrimer form. delete delete

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