KR102324285B1 - Double metal cyanide catalyst, preparation method thereof and polyol preparation method - Google Patents

Abstract

The present invention relates to a double metal cyanide catalyst comprising a carbonate compound as a complexing agent, a method for preparing the same, and a method for preparing a polyol. The double metal cyanide catalyst of the present invention includes a compound represented by the following formula (1).
[Formula 1]
M _a [M'(CN) ₆ ] _b L _c L' _d
In Formula 1, M and M' is independently a transition metal ion, L comprises a carbonate compound as a complexing agent, L' is a co-complexing agent, and a, b, c and d are positive numbers.

Description

Double metal cyanide catalyst, preparation method thereof, and polyol preparation method {Double metal cyanide catalyst, preparation method thereof and polyol preparation method}

The present invention relates to a double metal cyanide catalyst comprising a carbonate compound as a complexing agent, a method for preparing the same, and a method for preparing a polyol.

A double metal cyanide salt or a multimetal cyanide complex is a known catalyst for epoxide polymerization, and is known to be effective in polymer polymerization reaction by epoxide ring-opening reaction. These catalysts have high activity, low unsaturation, narrow molecular weight distribution, and consequently provide polyols with low polydispersity.

As an example, in the prior art, potassium hydroxide such as soluble basic metal hydroxide has been widely used as a catalyst for producing polyether polyol, but when an alkali metal hydroxide is used to prepare polyether polyol, a coherent polyether having a terminal double bond ( There is a problem that the content of so-called mono) increases, which adversely affects the production of polyols.

In order to solve this problem, a double metal cyanide catalyst having excellent physical properties such as a higher molecular weight, a higher hydroxyl group and a lower degree of unsaturation compared to the conventional alkali catalyst is used to prepare a polyalkylene ether polyol.

Polyester polyol and polyether polyol can be prepared by using the double metal cyanide catalyst, and the prepared polyol is used for the production of polyurethane, which can be used for construction, fibers, foams, elastomers, and the like.

In general, the double metal cyanide catalyst may be prepared by a water-soluble metal salt, a water-soluble metal cyanide salt, a complexing agent and a co-complexing agent. It can be expressed as Ma[M'(CN)a]bLcL'd, where M and M' represent a metal component, and L and L' represent a complexing agent and a co-complexing agent.

Complexing agents used in conventional bimetallic cyanide catalysts are, for example, ethylene glycol, dimethyl ether disclosed in US Pat. No. 4,477,589, US Pat. No. 3,821505, US Pat. No. 5,158,922 or US Pat. No. 5,158,992. The disclosed alcohols, aldehydes, ketones, ethers, esters, amides, ureas and the like are known.

However, as a large amount of tertiary butyl alcohol is used as a complexing agent, the catalyst price increases, and there are problems in that environmental pollution occurs due to the use of volatile organic chemicals.

One object of the present invention is to provide a double metal cyanide catalyst comprising a carbonate compound as a complexing agent and a method for preparing the same.

Another object of the present invention is to provide a method for preparing a polyol using the catalyst.

The double metal cyanide catalyst according to an embodiment of the present invention may include a compound represented by the following formula (1).

[Formula 1]

M _a [M'(CN) ₆ ] _b L _c L' _d

In Formula 1, M and M' is independently a transition metal ion, L comprises a carbonate compound as a complexing agent, L' is a co-complexing agent, and a, b, c and d are positive numbers.

In this case, it is preferable that the solubility of the carbonate compound in water is 10 g/l or more, and the catalyst including the carbonate compound having a solubility in water of 10 g/l or more may exhibit high activity when preparing a polyol.

In one embodiment, the carbonate compound of the present invention may include any one or more selected from compounds represented by the following Chemical Formulas 2 to 6.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

In the present invention, since a carbonate compound is used as the complexing agent, the attractive force between the complexing agent and the metal is appropriately controlled, and the complexing agent is properly coordinated in the catalyst matrix to exhibit excellent activity.

Specifically, the carbonate compounds represented by Chemical Formulas 2 to 6 include an electron-donating carbonyl group (C=O), and the attractive force with the metal active site is appropriately regulated, thereby increasing the activity of the catalyst. .

Meanwhile, in Formula 1, M is a metal ion of a metal salt, zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II) , lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II) and chromium (III), wherein M' is a metal ion of a metal cyanide, iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III) ), manganese (II), manganese (III), iridium (III), nickel (II), rhodium (III), ruthenium (II), vanadium (V) and vanadium (IV) is preferably any one selected.

The double metal cyanide catalyst of the present invention is used for the production of polyether-based or polycarbonate-based polyols, and the carbonate complexing agent is properly coordinated into the catalyst matrix, so that it has a monoclinic plate-like form or an amorphous form having a low crystallinity. do. This structure can increase the surface area of the catalyst, thereby increasing the catalytic activity.

In addition, the catalyst includes a co-complexing agent in order to increase the surface area and activity of the catalyst by reducing the size and crystallinity of the catalyst.

In this case, the co-complexing agent is polypropylene glycol, polyethylene glycol, polytetrahydrofuran, poly(oxyethylene-block-propylene) copolymer, poly(oxyethylene-block-tetrahydrofuran) copolymer, poly(oxypropylene- It may include at least one selected from a block-tetrahydrofuran) copolymer and a poly(oxyethylene-block-oxypropylene-block-oxyethylene) copolymer.

On the other hand, the method for preparing a double metal cyanide catalyst according to another embodiment of the present invention comprises the steps of preparing a first solution comprising a carbonate-based complexing agent, a metal salt, and distilled water; Preparing a second solution containing a metal cyanide and distilled water; preparing a third solution comprising a carbonate-based complexing agent and a co-complexing agent; a first step of mixing the first solution and the second solution; and a second step of adding and mixing the third solution to the mixed solution.

Specifically, the carbonate-based complexing agent preferably includes at least one selected from the compounds represented by Chemical Formulas 2 to 6.

In one embodiment, when the solubility of the carbonate-based complexing agent in water is 40 g/l or more and the dielectric constant is similar to that of water (78), washing and drying the precipitate obtained after the second step It is preferable to prepare a double metal cyanide catalyst by carrying out.

In this case, the carbonate-based complexing agent used may include any one or more selected from the compounds represented by Chemical Formulas 2 to 4.

As described above, when a carbonate-based complexing agent having high solubility in water and having a dielectric constant close to that of water 78 is used, a sufficient amount is applied to the metal surface even if a double metal cyanide catalyst is prepared through the second step. It is coordinated, and as the washing process is reduced because the coordination process is not repeated several times, the catalyst yield is rather increased.

In addition, when preparing the double metal cyanide catalyst through the second step, it is preferable that the molar ratio of the metal salt and the metal cyan salt contained in the mixed solution is 1.5 to 10: 1, which is, when the molar ratio exceeds 10, the inside of the catalyst This is because the catalyst activity is lowered due to the inclusion of unreacted metal, and when it is less than 1.5, the amount of the metal having an active site is insignificant and the catalyst activity is lowered. Most preferably, the molar ratio of the metal salt and the metal cyanide may be 4:1. However, even when the minimum molar ratio is about 1.5, it has a desirable activity for polyether polyol synthesis.

Since the present invention prepares the catalyst by shortening the preparation step compared to the conventional preparation method, it is possible to prepare a catalyst with high activity while using a small amount of the complexing agent and the metal salt used. This can be expected to increase productivity in commercialization.

In another embodiment, when the solubility of the carbonate-based complexing agent in water is 10 g/l or more, after the second step, a solution containing distilled water and a carbonate-based complexing agent is added to the mixed solution obtained in the second step and mixed a third step; and a fourth step of adding and mixing the third solution to the mixed solution obtained in the third step.

The third step and the fourth step may be performed in at least two cycles or more, and in this case, the carbonate-based complexing agent used may include any one or more selected from the compounds represented by Formulas 2 to 6 above.

In particular, when a complexing agent having a solubility in water of 10 g/l or more and less than 40 g/l is used, higher activity is exhibited during catalyst preparation including the third and fourth steps.

On the other hand, the mixing can be carried out at a temperature of 30 °C to 90 °C, most preferably carried out at a temperature of 50 °C.

The present invention does not use tertiary butyl alcohol, and uses a carbonate compound as a complexing agent to prepare a double metal cyanide catalyst. It is possible to reduce the content of the complexing agent and heavy metal used by reducing the amount, and as the final catalyst yield increases, the catalyst production cost can be reduced, and furthermore, the production cost of the polyol can be reduced.

On the other hand, in another embodiment of the present invention, in the presence of a double metal cyanide catalyst, there may be mentioned a polyol production method comprising the step of ring-opening polymerization reaction of an epoxy compound.

In this case, the epoxy compound may include any one or more selected from the following formulas.

In another embodiment, in the polyol production method, carbon dioxide may be additionally injected to copolymerize carbon dioxide and an epoxy compound to prepare a polycarbonate polyol.

According to the present invention, since the carbonate compound is included as a complexing agent, the catalyst can exhibit good activity by donating electrons to metal ions in the catalyst, and the complexing agent is properly coordinated in the catalyst matrix to exhibit an amorphous or monoclinic plate shape catalytic activity is increased.

In addition, the catalyst of the present invention contains a carbonate compound having a solubility in water of 10 g/l or more as a complexing agent, and particularly, exhibits excellent activity in the preparation of polyols, and thus, until the polymerization reaction is activated during preparation of polyols. There is an effect that the induction time, which is a time, is shortened to less than several tens of minutes.

In addition, without using tertiary butyl alcohol and using a carbonate compound as a complexing agent to prepare a double metal cyanide catalyst, it is environmentally friendly and when using a carbonate compound with high water solubility, the manufacturing step is reduced Thus, it is possible to reduce the content of the complexing agent and heavy metal used, and there is an advantage in that the final catalyst yield is increased. Therefore, according to the present invention, it is possible to reduce the production cost of the catalyst, and furthermore, the production cost of the polyol can also be reduced.

1 is a view showing X-ray diffraction analysis spectra of catalysts according to Examples 1-5, Example 8 and Comparative Example 1. FIG.
FIG. 2 is a view showing X-ray diffraction analysis spectra of catalysts according to Example 1 (PC-3step), Example 34, Examples 41-47, and Comparative Example 1. FIG.
3 to 12 are high-resolution images and forms of Examples 1 and 8, Examples 2 and 3, Example 4, Example 5, Example 34, Example 43, Example 45, Example 47, and Example 51, respectively. It is a figure showing the analysis result.
12 to 15 are graphs showing FT-IR analysis results of catalysts according to Examples 1-3, 9-14, and 16-19.
16 to 26 are graphs showing the consumption of PO over time during a polymerization reaction using catalysts according to an embodiment of the present invention.
27 is a graph showing the amount of PO consumption according to time during the polymerization reaction using Example 55(1), Example 77(2), and Examples 86-89(3-6).

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. Since the present invention can have various changes and can have various forms, specific embodiments are illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to the specific disclosed form, it should be understood to include all modifications, equivalents and substitutes included in the spirit and scope of the present invention. In describing each figure, like reference numerals have been used for like elements.

The terms used in the present application are used only to describe specific embodiments and are not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as “comprise” or “have” are intended to designate that a feature, step, operation, component, part, or combination thereof described in the specification is present, and includes one or more other features or steps. , it should be understood that it does not preclude the possibility of the existence or addition of , operation, components, parts, or combinations thereof.

Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not

The double metal cyanide catalyst according to an embodiment of the present invention includes a compound represented by the following formula (1).

[Formula 1]

M _a [M'(CN) ₆ ] _b L _c L' _d

In Formula 1, M and M' is independently a transition metal ion, L comprises a carbonate compound as a complexing agent, L' is a co-complexing agent, and a, b, c and d are positive numbers.

The complexing agent in the double metal cyanide catalyst imparts the activity of the catalyst by donating electrons to the metal ion of the metal salt. By using , the attractive force between the complexing agent and the metal is properly controlled, and the complexing agent is properly coordinated in the catalyst matrix to exhibit excellent activity.

The complexing agent is not particularly limited as long as it includes a chain or cyclic carbonate compound, for example,

dialkyl carbonates; dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate,

5-membered ring carbonate; Ethylene carbonate, propylene carbonate, glycerol carbonate, styrene carbonate, cyclohexene carbonate, isobutylene carbonate, trifluoromethylethylene carbonate, vinylethylene carbonate, butadiene monocarbonate, butadiene dicarbonate, chloromethyl carbonate, pinene carbonate, tetracyano Ethylene carbonate, tetra-dimethyl-yl, tri-dioxolane-ion, tetra, o-dimethyl-yl, tri-dioxolan-ion, tetra, tetra, o-trimethyl-yl, tri-dioxolane -I-one, yl, di-butylene carbonate, epichlorohydrin carbonate, aryl glycidyl carbonate, tetra-butyl-yl, tri-dioxolan-ion, tetra-ethyl-o-methyl-yl, 3-dioxolane-i-one, yl, di-hexylene carbonate, octylene carbonate, dodecene carbonate, vinyl ethylene carbonate, tetra-methyl-tetra-vinyl-yl, 3-dioxolane-i-one, tetra- (3-Buten-yl-yl)-yl, 3-dioxolan-ion, tetra-((vinyloxy) methyl)-yl, 3-dioxolan-ion, tetra-((aryloxy) methyl) )-yl, 3-dioxolan-ion, tetra-((ethynyloxy) methyl)-yl, 3-dioxolan-ion, tetra-(fluoromethyl)-yl, 3-dioxolane- I-one, tetra-(chloromethyl)-yl, 3-dioxolan-ion, tetra-(di-chloromethyl)-yl, 3-dioxolan-ion, tetra-(bromomethyl)- 1-, 3-dioxolane-ion, tetra-methoxy-yl, 3-dioxolan-ion, tetra-(trifluoromethyl)-yl, 3-dioxolan-ion, di-oxo -yl, tri-dioxolane-tetra-carboxamide, tetra-(hydroxymethyl)-o-propyl-yl, tri-dioxolan-ion, tetra-(isobutoxymethyl)-yl, tri-diox Solan-ion, tetra-(isopropoxymethyl)-yl, 3-dioxolan-ion, tetra-(tertiary-butoxymethyl)-yl, 3-dioxolane-ion, tetra- (Butoxymethyl)-yl, tri-dioxolan-ion, methyl-ii-oxo-yl, tri-dioxolane-tetra-carboxylate, ethyl-ii-oxo-yl, tri-dioxolane-tetra- Carboxylate, methyl di-(di-oxo-yl, tri-dioxolan-tetra-yl) acetate, methyl tetra-methyl-di-oxo-yl, tri-dioxolane-tetra-carboxylate, tetra-(oxirane) -2-yl)-yl, 3-dioxolan-ion, tetra-methyl-o-phenyl-yl, 3-dioxolan-ion, tetra-(tetra-fluorophenyl)-yl, 3- Dioxolane-I-On, Sa- benzyl-yl, tri-dioxolane-ion, cyclopentene carbonate,

6-membered ring carbonate; 1-, 3-dioxane-ion, tetra-phenyl-yl, 3-dioxane-ion, o, o-dimethyl-yl, tri-dioxane-ion, o, o-dimethoxy- One, three-dioxane-ion, three-phenyl-yl, five, eight, ten-cetraoxaspiro [oh, five] undecane-gu-one, hexahydrobenzo [d] [one, three] -dioxol-ion-one,

7-membered ring carbonate; tetra-methyl-yl, tri-dioxepen-i-one, yl, o-dihydrobenzo [e] [yl, three] dioxepin-three-one, tetra, seven-dihydro-yl, tri-dioxepin -ion,

8-membered ring carbonate; Hex-methyl-yl, 3-dioxocan-i-one, hexamethyl-yl, hex, hex-dioxazocan-ion, etc. can be used.

Specifically, it is preferable that the solubility of the carbonate compound in water is 10 g/l or more, and the catalyst including the carbonate compound having a solubility in water of 10 g/l or more may exhibit high activity when preparing a polyol.

In one embodiment, the carbonate compound, which is a complexing agent of the catalyst, preferably includes at least one selected from compounds represented by the following Chemical Formulas 2 to 6.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

On the other hand, the transition metal ion M contained in the catalyst of the present invention is zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), tin (II), lead (II), molybdenum (IV), molybdenum (VI), aluminum (III), vanadium (V), vanadium (IV), strontium (II), tungsten (IV), tungsten (VI), copper (II) and chromium (III), for example, zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate, iron bromide (II), cobalt chloride (II), cobalt thiocyanate (II), nickel formate (II), may be a metal ion contained in a metal salt such as nickel nitrate (II).

In addition, the transition metal M 'is iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III) , nickel (II), rhodium (III), ruthenium (II), vanadium (V) and any one selected from vanadium (IV), for example, potassium hexacyanocobaltate (III), potassium hexacyanoferrite ( II), potassium hexacyanoferrite (III), calcium hexacyanocobaltate (II), lithium hexacyanoferrite (II), zinc hexacyanocobaltate (II), zinc hexacyanoferrite (II), It may be a metal ion contained in a metal cyanide salt such as nickel hexacyanoferrite (II) and cobalt hexacyanocobaltate (III).

The double metal cyanide catalyst as described above is used for the production of polyether-based or polycarbonate-based polyols, and the catalyst of the present invention has a monoclinic plate shape having a low crystallinity by properly coordinating a complexing agent into the catalyst matrix. or have an amorphous form.

The co-complexing agent is for increasing the surface area and activity of the catalyst by reducing the size and crystallinity of the catalyst, for example, polypropylene glycol, polyethylene glycol, polytetrahydrofuran, poly (oxyethylene-block-propylene) selected from copolymers, poly(oxyethylene-block-tetrahydrofuran) copolymers, poly(oxypropylene-block-tetrahydrofuran) copolymers and poly(oxyethylene-block-oxypropylene-block-oxyethylene) copolymers It may include any one or more, preferably, may include polypropylene glycol, but is not limited thereto.

In one embodiment, the weight ratio of the complexing agent and the co-complexing agent of the catalyst is preferably 1 to 10:1. Since the co-complexing agent itself is an oligomer or a polymer, if an excessive amount is used, it completely surrounds the active site of the catalyst, making activation difficult, and the catalyst may be a solid having viscosity instead of a fine powder. It is most preferable to include

On the other hand, the method for preparing a double metal cyanide catalyst according to another embodiment of the present invention comprises the steps of preparing a first solution comprising a carbonate-based complexing agent, a metal salt, and distilled water; Preparing a second solution containing a metal cyanide and distilled water; preparing a third solution comprising a carbonate-based complexing agent and a co-complexing agent; a first step of mixing the first solution and the second solution; and a second step of adding and mixing the third solution to the mixed solution.

First, a first solution containing a carbonate-based complexing agent, a metal salt, and distilled water, a second solution containing a metal cyanide salt and distilled water, and a third solution containing a carbonate-based complexing agent and a co-complexing agent can be prepared, respectively have.

Here, as the carbonate-based complexing agent, metal salt, and metal cyan salt, the same materials as described above may be used, and a description thereof will be omitted.

Thereafter, a first step of mixing the first solution and the second solution may be performed, and a second step of mixing the third solution by adding the third solution may be performed.

In one embodiment, when the solubility of the carbonate-based complexing agent in water is 40 g/l or more and the dielectric constant is similar to that of water (78), washing and drying the precipitate obtained after the second step It is preferable to prepare a double metal cyanide catalyst by carrying out, in this case, the carbonate-based complexing agent used may include any one or more selected from the compounds represented by Chemical Formulas 2 to 4.

In addition, when preparing the double metal cyanide catalyst through the second step, the molar ratio of the metal salt and the metal cyan salt contained in the mixed solution is preferably 1.5 to 10: 1, and most preferably, the molar ratio of the metal salt and the cyan metal salt. may be 4:1.

In another embodiment, when the solubility of the carbonate-based complexing agent in water is 10 g/l or more, after the second step, a solution containing distilled water and a carbonate-based complexing agent is added to the mixed solution obtained in the second step and mixed third step; and a fourth step of adding and mixing the third solution to the mixed solution obtained in the third step.

The third step and the fourth step may be performed in at least two cycles or more, and in this case, the carbonate-based complexing agent used may include any one or more selected from the compounds represented by Formulas 2 to 6 above.

In addition, the mixing can be carried out at a temperature of 30 to 90 ℃, most preferably carried out at a temperature of 50 ℃.

On the other hand, in another embodiment of the present invention, in the presence of the double metal cyanide catalyst, there may be mentioned a polyol production method comprising the step of a ring-opening polymerization reaction of an epoxy compound.

Specifically, after introducing the double metal cyanide catalyst according to the embodiment of the present invention to the high-pressure reactor and purging the inside of the high-pressure reactor using nitrogen, the initiator (eg, polypropylene glycol) and the epoxy compound are introduced into the reactor. It can be injected, and at this time, it is preferable to continuously supply the epoxy compound so that the pressure is maintained.

Thereafter, the unreacted epoxy compound may be removed through a vacuum drying process after the reaction to obtain a polyether polyol.

In another embodiment, the inside of the high-pressure reactor is purged using carbon dioxide, an initiator (eg, polypropylene glycol) and an epoxy compound are injected into the reactor, and carbon dioxide is additionally injected into the reactor to provide carbon dioxide and an epoxy compound By copolymerizing reaction, polycarbonate polyol can be obtained.

In this case, the epoxy compound may include any one or more selected from the following formulas, but is not limited thereto.

That is, as the epoxy compound, ethylene oxide, propylene oxide, di, di-dimethyloxirane, di, tri-dimethyloxirane, di, di, trimethyloxirane, di-ethyloxirane, di-ethyl- 3-methyloxirane, di-pentyloxirane, di-butyloxirane, di-hexyl oxirane, di-vinyloxirane, di-methyl-i-vinyloxirane, di-(but-3-en-yl -yl)oxirane, di-((vinyloxy)methyl)oxirane, di-((allyloxy)methyl)oxirane, di-((prop-i-yn-yl-inoxy)methyl)oxirane , di-fluoromethyl)oxirane, di-(chloromethyl)oxirane, di-(di-chloroethyl)oxirane, di-(bromomethyl)oxirane, oxirane-i-ylmethanol, di- Methoxyoxirane, di-trifluoromethyl)oxirane, oxirane-i-carboxamide, (3-propyloxiran-i-yl)methanol, di-(isobutoxymethyl)oxirane, di-(iso Propoxymethyl)oxirane, di-(tertiary-butoxymethyl)oxirane, di-butoxymethyl)oxirane, methyloxirane-i-carboxylate, ethyloxirane-i-carboxylate, ethyl- (oxirane-i-yl)acetate, methyl di-meoxirane-i-carboxylate, i,2'-bioxirane, di-phenyloxirane, di-methyl-tri-phenyloxirane, di-( tetra-fluorophenyl)oxirane, di-benzyloxirane, sigma-oxabicyclo[3.yl.young]hexane, yl-methyl-sigma-oxabicyclo[3.yl.young]hexane, sigma-oxa -Three-diabicyclo[3.yl.young] hexanesam, 3-dioxide, 7-oxabicyclo[4.yl.young]heptane, 3-oxatricyclo[3.2.yl.young^2, tetra]octane, seven-oxabiㅣchloro[f.yl.young]hept-e-ene, tri-vinyl-chil-oxabicyclo-[f.yl.young]heptane, seven-oxabicyclo[g. 1.young]heptane-ion, pal-oxabicyclo[o.yl.young]octane, old-oxabicyclo[six.yl.young]nonane, (jet)-gu-oxabicyclo[six. Japanese.English]non-sa-en may be used, but the present invention is not limited thereto.

Hereinafter, various embodiments and experimental examples of the present invention will be described in detail. However, the following examples are only some examples of the present invention, and the present invention should not be construed as being limited to the following examples.

[Preparation of double metal cyanide catalyst according to type of complexing agent]

Example 1

A first solution was prepared by mixing 2.05 g of zinc chloride, 2.5 ml of distilled water, and 0.8 ml of propylene carbonate (PC) in a first beaker, and 2.5 ml of 0.5 g of potassium hexacyanocobaltate (III) in a second beaker. A second solution was prepared by dissolving in distilled water. In addition, a third solution was prepared by mixing 1 ml of propylene carbonate (PC) and Pluronic P123 (Wyandotte Chemicals Corp.) in a third beaker.

Thereafter, the second solution was added to the first solution and stirred at 50° C. for 30 minutes, and then 1.1 ml of the third solution was further added and stirred at 50° C. for 10 minutes (first step).

Next, the solid was separated using a centrifugal separator, and 5 mL of distilled water and 0.8 mL of propylene carbonate (PC) were additionally injected into the separated catalyst slurry, followed by stirring at 50° C. for 30 minutes. Then, 1.1 mL of the third solution was further added and stirred at 50° C. for 10 minutes (second step).

Thereafter, the solid was separated using a centrifuge, and 5 mL of distilled water and 0.8 mL of propylene carbonate (PC) were additionally injected into the separated catalyst slurry, stirred at 50° C. for 30 minutes, and 1.1 mL of the third solution was added. and stirred at 50° C. for 10 minutes (3rd step).

Thereafter, the solid was separated using a centrifuge, and the separated catalyst slurry was washed several times with 10 mL of distilled water and separated by a centrifugal separator, and then the separated solid catalyst was dried at 85° C. A salt catalyst (Example 1) was prepared.

Example 2

Example 1 except that 0.5 g of ethylene carbonate (EC) was used as the complexing agent in the first solution, the second step and the third step, and 1 g of ethylene carbonate (EC) was used as the complexing agent in the third solution. A double metal cyanide catalyst was prepared in the same manner as described above.

Example 3

Example 1 except that 0.5 mL of glycerol carbonate (GC) was used as the complexing agent in the first solution, the second step and the third step, and 1 mL of glycerol carbonate (GC) was used as the complexing agent in the third solution. A double metal cyanide catalyst was prepared in the same manner as described above.

Example 4

0.1 mL of 1,2-butylene carbonate (BC) as the complexing agent in the first solution, the second step and the third step, and 1 mL of 1,2-butylene carbonate (BC) as the complexing agent in the third solution ) was used, and a double metal cyanide catalyst was prepared in the same manner as in Example 1.

Example 5

Example 1 except that 0.05 mL of dimethyl carbonate (dmc) was used as the complexing agent in the first solution, the second step and the third step, and 1 mL of dimethyl carbonate (dmc) was used as the complexing agent in the third solution A double metal cyanide catalyst was prepared in the same manner as described above.

Example 6

Implemented except that 0.05 mL of diethyl carbonate (dec) was used as the complexing agent in the first solution, the second step and the third step, and 1 mL of diethyl carbonate (dec) was used as the complexing agent in the third solution. A double metal cyanide catalyst was prepared in the same manner as in Example 1.

Example 7

0.05 mL of epichlorohydrin carbonate (ehc) was used as the complexing agent in the first solution, the second step and the third step, and 1 mL of epichlorohydrin carbonate (ehc) was used as the complexing agent in the third solution. A double metal cyanide catalyst was prepared in the same manner as in Example 1, except that.

[Preparation of double metal cyanide catalyst according to change in complexing agent content]

Example 8

A double metal cyanide catalyst was prepared in the same manner as in Example 1, except that 0.05 mL of propylene carbonate (PC) was used in the first solution, the second step, and the third step.

Example 9

A double metal cyanide catalyst was prepared in the same manner as in Example 1, except that 0.1 mL of propylene carbonate (PC) was used in the first solution, the second step, and the third step.

Example 10

A double metal cyanide catalyst was prepared in the same manner as in Example 1, except that 0.3 mL of propylene carbonate (PC) was used in the first solution, the second step, and the third step.

Example 11

A double metal cyanide catalyst was prepared in the same manner as in Example 1, except that 0.5 mL of propylene carbonate (PC) was used in the first solution, the second step, and the third step.

Example 12

A double metal cyanide catalyst was prepared in the same manner as in Example 2, except that 0.05 g of ethylene carbonate (EC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 13

A double metal cyanide catalyst was prepared in the same manner as in Example 2, except that 0.1 g of ethylene carbonate (EC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 14

A double metal cyanide catalyst was prepared in the same manner as in Example 2, except that 0.3 g of ethylene carbonate (EC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 15

A double metal cyanide catalyst was prepared in the same manner as in Example 2, except that 0.8 g of ethylene carbonate (EC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 16

A double metal cyanide catalyst was prepared in the same manner as in Example 3, except that 0.1 mL of glycerol carbonate (GC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 17

A double metal cyanide catalyst was prepared in the same manner as in Example 3, except that 0.3 mL of glycerol carbonate (GC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 18

A double metal cyanide catalyst was prepared in the same manner as in Example 3, except that 1.0 mL of glycerol carbonate (GC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 19

A double metal cyanide catalyst was prepared in the same manner as in Example 3, except that 2.0 mL of glycerol carbonate (GC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 20

A double metal cyanide catalyst was prepared in the same manner as in Example 4, except that 0.2 mL of 1,2-butylene carbonate (BC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 21

A double metal cyanide catalyst was prepared in the same manner as in Example 5, except that 0.1 mL of dimethyl carbonate (dmc) was used as a complexing agent in the first solution, the second step, and the third step.

Example 22

A double metal cyanide catalyst was prepared in the same manner as in Example 5, except that 0.5 mL of dimethyl carbonate (DMC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 23

A double metal cyanide catalyst was prepared in the same manner as in Example 5, except that 1.0 mL of dimethyl carbonate (DMC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 24

A double metal cyanide catalyst was prepared in the same manner as in Example 5, except that 2.0 mL of dimethyl carbonate (DMC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 25

A double metal cyanide catalyst was prepared in the same manner as in Example 6, except that 0.1 mL of diethyl carbonate (DEC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 26

A double metal cyanide catalyst was prepared in the same manner as in Example 7, except that 0.1 mL of epichlorohydrin carbonate (EHC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 27

A double metal cyanide catalyst was prepared in the same manner as in Example 7, except that 0.2 mL of epichlorohydrin carbonate (EHC) was used as a complexing agent in the first solution, the second step, and the third step.

Example 28

A double metal cyanide catalyst was prepared in the same manner as in Example 7, except that 0.3 mL of epichlorohydrin carbonate (EHC) was used as a complexing agent in the first solution, the second step, and the third step.

[Preparation of a double metal cyanide catalyst according to the complexing agent preparation step]

Example 29

A first solution was prepared by mixing 2.05 g of zinc chloride, 2.5 ml of distilled water, and 0.8 ml of propylene carbonate (PC) in a first beaker, and 2.5 ml of 0.5 g of potassium hexacyanocobaltate (III) in a second beaker. A second solution was prepared by dissolving in distilled water. In addition, a third solution was prepared by mixing 1 ml of propylene carbonate (PC) and 0.1 g of Pluronic P123 (Wyandotte Chemicals Corp.) in a third beaker.

Thereafter, the second solution was added to the first solution and stirred at 50° C. for 30 minutes, and then 1.1 ml of the third solution was further added and stirred at 50° C. for 10 minutes (first step).

Next, the solid was separated using a centrifugal separator, and 5 mL of distilled water and 0.8 mL of propylene carbonate (PC) were additionally injected into the separated catalyst slurry, followed by stirring at 50° C. for 30 minutes. Then, 1.1 mL of the third solution was further added and stirred at 50° C. for 10 minutes (second step).

Next, the solids are separated using a centrifuge, the separated catalyst slurry is washed several times with 10 mL of distilled water, separated by a centrifugal separator, and the separated solid catalyst is dried at a temperature and vacuum conditions of 85° C. A cyanide catalyst (Example 29) was prepared.

Example 30

A first solution was prepared by mixing 2.05 g of zinc chloride, 2.5 ml of distilled water, and 0.8 ml of propylene carbonate (PC) in a first beaker, and 2.5 ml of 0.5 g of potassium hexacyanocobaltate (III) in a second beaker. A second solution was prepared by dissolving in distilled water. In addition, a third solution was prepared by mixing 1 ml of propylene carbonate (PC) and 0.1 g of Pluronic P123 (Wyandotte Chemicals Corp.) in a third beaker.

Thereafter, the second solution was added to the first solution and stirred at 50° C. for 30 minutes, and then 1.1 ml of the third solution was further added and stirred at 50° C. for 10 minutes (first step).

Next, the solids are separated using a centrifuge, the separated catalyst slurry is washed several times with 10 mL of distilled water, separated by a centrifugal separator, and the separated solid catalyst is dried at a temperature and vacuum conditions of 85° C. A cyanide catalyst (Example 30) was prepared.

Example 31

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that 0.05 mL of propylene carbonate (PC) was used in the first solution.

Example 32

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that 0.5 g and 1 g of ethylene carbonate (EC) was used as a complexing agent in the first solution and the third solution, respectively.

Example 33

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that 0.05 ml and 1 ml of dimethyl carbonate (DMC) were used as the complexing agent in the first solution and the third solution, respectively.

Example 34

In the third solution, 3 ml of propylene carbonate (PC) and 0.3 g of Pluronic P123 (Wyandotte Chemicals Corp.) were used (Zn : Co = 10 : 1) in the same manner as in Example 30, except that cyanide double metal A salt catalyst was prepared.

Example 35

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.1 ml of propylene carbonate (PC) was used in the first solution.

Example 36

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.3 ml of propylene carbonate (PC) was used in the first solution.

Example 37

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.1 ml and 3 ml of 1,2-butylene carbonate (BC) were used in the first solution and the third solution, respectively.

[Preparation of double metal cyanide catalyst according to reaction temperature]

Example 38

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that the stirring reaction temperature was carried out at 30°C.

Example 39

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that the stirring reaction temperature was performed at 70°C.

Example 40

A double metal cyanide catalyst was prepared in the same manner as in Example 30, except that the stirring reaction temperature was carried out at 90°C.

[Preparation of double metal cyanide catalyst according to molar ratio of metal salt and metal cyanide]

Example 41

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 1.635 g (0.012 mol) of zinc chloride was used in the first solution (Zn:Co=8:1).

Example 42

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 1.227 g (0.009 mol) of zinc chloride was used in the first solution (Zn:Co=6:1).

Example 43

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.818 g (0.006 mol) of zinc chloride was used in the first solution (Zn:Co=4:1).

Example 44

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.409 g (0.003 mol) of zinc chloride was used in the first solution (Zn:Co=2:1).

Example 45

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.306 g (0.00225 mol) of zinc chloride was used in the first solution (Zn:Co=1.5:1).

Example 46

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.245 g (0.0018 mol) of zinc chloride was used in the first solution (Zn:Co=1.2:1).

Example 47

A double metal cyanide catalyst was prepared in the same manner as in Example 37, except that 0.204 g (0.0015 mol) of zinc chloride was used in the first solution (Zn:Co = 1:1).

Example 48

A double metal cyanide catalyst was prepared in the same manner as in Example 37, except that 1.635 g (0.012 mol) of zinc chloride was used in the first solution (Zn:Co=8:1).

Example 49

A double metal cyanide catalyst was prepared in the same manner as in Example 37, except that 1.227 g (0.009 mol) of zinc chloride was used in the first solution (Zn:Co=6:1).

Example 50

A double metal cyanide catalyst was prepared in the same manner as in Example 37, except that 0.818 g (0.006 mol) of zinc chloride was used in the first solution (Zn:Co=4:1).

Example 51

A double metal cyanide catalyst was prepared in the same manner as in Example 34, except that 0.409 g (0.003 mol) of zinc chloride was used in the first solution (Zn:Co=2:1).

Comparative Example 1

As Comparative Example 1, a double metal cyanide catalyst prepared without using a complexing agent and a co-complexing agent was prepared.

1) Comparison of catalyst properties according to types of complexing agents

In order to check the activity of the catalyst in preparing the polyol according to the solubility of the complexing agent in water, catalysts were prepared using carbonate complexing agents having different solubility in water (Examples 1 to 8).

Specifically, the solubility in water for each type of carbonate complexing agent used in the present invention is 240 g/l in Examples 1 and 8 (propylene carbonate (PC)), and in Example 2 (epylene carbonate (EC)). having high solubility values, high solubility values for Example 3 (GC), 33.8 g/l for Example 4 (BC), 13.9 g/l for Example 5 (DMC), and Examples 6 and 7 Insoluble in water.

In addition, the dielectric constant of each type of carbonate complexing agent is 64.9 in Examples 1 and 8, 95.3 in Example 2, 109.7 in Example 3, 56.1 in Example 4, 3 in Example 5, 2.82 in Example 6, and 2.82 in Example 6. 7 has a value of 22.

1 shows X-ray diffraction analysis spectra of catalysts including different complexing agents and Comparative Example 1 catalyst, respectively.

Referring to FIG. 1 , in the case of Examples 1 to 5 having a solubility in water of 10 g/l or more, a peak indicating a monoclinic plate-like structure or an amorphous structure having a lower crystallinity than Comparative Example 1 can be observed, and this Through this, it can be confirmed that a catalyst with high activity was made during polyol production.

On the other hand, in the case of Examples 6 and 7 in which diethyl carbonate (dec) and epichlorohydrocarbonate (ehc) were used as complexing agents, the solubility in water was very low or due to the property insoluble in water, common double metal cyanide It was not prepared in the powder state of the salt catalyst.

On the other hand, in the case of the catalyst of Comparative Example 1 in which the complexing agent and the co-complexing agent were not used, the crystallinity was very high as a cubic structure, and a sharp and high concentration peak was shown. this drops significantly.

Therefore, in order to prepare a highly active catalyst for polyol production, it is preferable to use a carbonate complexing agent having a solubility in water of 10 g/l or more.

2) Comparison of catalyst properties according to molar ratio of metal salt and metal cyanide

2 shows Example 1 (PC-3 step) prepared in the third step, Example 34, Examples 41-47, and Comparative Example 1 prepared only in the first step, in which the molar ratio of the metal salt and the metal cyanide was variously changed. It is a diagram showing the X-ray diffraction analysis spectrum of the catalyst according to

Referring to FIG. 2 , the catalyst of Comparative Example 1 has a cubic structure and very high crystallinity, and thus exhibited a sharp and high-concentration peak shape.

Specifically, as shown in FIGS. 1 and 2, the catalyst of Comparative Example 1 has a main peak showing high crystallinity of the cubic phase (Fm-3m) characterized by reflection at 2θ = 14.9°, 17.1°, 24.3°, 35.1° was observed.

On the other hand, in the case of the catalysts according to the embodiments, since the complexing agent and the co-complexing agent are incorporated on the catalyst matrix to interfere with the growth of crystals, 2θ = 14,9˚, which is a part of the main peak that appears when crystallinity is very high, 24.5° disappeared, or peak concentrations at 2θ = 17.1°, 24.3°, 35.1°, 39.1°, and 43.1° were greatly reduced. In addition, it can be seen that 2θ = 17.1° and 24.3° decrease the peaks, and at the same time as the newly appearing monoclinic peaks 2θ = 16.1°, 20.1° to 23.8° are wide, the crystallinity is greatly reduced.

Among the catalysts, in Example 1, compared with Comparative Example 1, the complexing agent was sufficiently incorporated into the catalyst matrix to reduce the particle size, at the same time, the degree of exposure of the catalyst surface was increased, and the concentration corresponding to the main peak of crystallinity was decreased as a whole. It was. This is because the coordinated complexing agent is sufficiently incorporated on the catalyst matrix to fragment the bulky pure double metal cyanide catalyst, thereby effectively controlling the particle size and reducing the crystallinity of the catalyst.

Therefore, in the case of the catalysts according to the embodiments of the present invention, compared to the catalyst of Comparative Example 1, a monoclinic plate-shaped structure or an amorphous structure having a lower crystallinity may be exhibited.

Meanwhile, in order to compare the catalytic activity according to the molar ratio of the metal salt and the metal cyan salt of the catalyst prepared only in the first step, the lattice spacing d was calculated by Bragg's Law with reference to FIG. 2 .

Interplanar spacing (d) = Order of Reflection (n) x Wavelength (λ) / 2 × Sinθ

In the peaks corresponding to Examples 34 and 41 to 45 in which the molar ratio of Zn:Co is 1.5 to 10: 1, the concentration of the peak is significantly reduced compared to Comparative Example 1, and the lattice spacing d values are 5.1 A° and 3.6, respectively. It increased from A° to 5.5 A°, 4.5 A°, and 3.8 A°. It is determined that the particle size of the catalysts of Examples 34 and 41-45 was decreased and the degree of fragmentation was large compared to Comparative Example 1, and the interplanar distance between the particles was increased.

However, in the case of Example 46 and Example 47 in which the molar ratio of Zn:Co is 1 to 1.2: 1, the peak shape of the increased d values was very sharp and large, which resulted in a decrease in particle size but still high crystallinity. means that

Therefore, when the catalyst is prepared only in the first step, when the molar ratio of the metal salt: the metal cyan salt is 1.5 to 10: 1, it can be seen that a catalyst with high activity is prepared during the preparation of the polyol.

3) Comparison of forms of catalysts according to Examples

In order to compare the catalyst types of the examples, after selecting the catalysts of Examples 1-5, Example 8, Example 34, Example 43, Example 45, Example 47 and Example 51 among the synthesized catalysts, each sample High-resolution images and morphological analyzes of the surface were performed. Here, for the analysis, an electron beam writing process device and a scanning electron microscope FE-SEM (with EDS) device were used, and an electron beam was scanned into the sample to detect secondary electrons and X-rays generated from the sample, thereby analyzing the morphology of the sample surface. carried out.

Fig. 3 shows Embodiments 1 and 8, Fig. 4 shows Embodiments 2 and 3, Fig. 5 shows Embodiment 4, Fig. 6 shows Embodiment 5, Fig. 7 shows Embodiment 34, Fig. 8 shows Embodiment 43, Fig. 9 shows Embodiment Example 45 and FIG. 10 are diagrams showing high-resolution images and shape analysis results of Example 47 and Example 51;

As shown in FIG. 10 , in the case of the catalyst of Example 47 prepared in a molar ratio of Zn:Co of 1:1, the complexing agent and the co-complexing agent did not flow into the matrix of the catalyst, so that it was not fragmented from the bulky structure. It can be seen that there is no catalyst activity.

On the other hand, referring to FIGS. 3-9 and 11 , the complexing agent and the co-complexing agent are introduced into the matrix of the catalyst according to each embodiment, so that the pure DMC catalyst has a cubic (cubic) form or a monoclinic plate form or Changes in the amorphous shape were confirmed. Such a monoclinic plate shape or amorphous shape means that the area that the catalyst can contact with the monomer and the initiator increases during polyol polymerization, which is observed in catalysts with high activity.

4) Comparison of catalyst structures according to changes in complexing agent content

12 to 15 are graphs showing FT-IR analysis results of catalysts according to Comparative Example 1 and Examples 1-3, 9-14, and 16-19 in which the contents of PC, EC and GC were changed. .

12 to 15 , in Comparative Example 1, a C≡N peak appears at 2177 cm ⁻¹ , and as the complexing agent and the co-complexing agent are properly coordinated, the C≡N peak moves toward a longer wavelength. That is, in FIG. 12, DMC 2 shows the FT-IR peak of propylene carbonate (PC), and as propylene carbonate (PC) is properly coordinated to pure DMC, in Examples 1, 9, 10, and 11 to propylene carbonate (PC) The corresponding peak could be observed. In addition, in Examples 1, 9, 10, and 11, it can ^{be seen that the peaks corresponding to C≡N shifted to 2193 cm -1} , respectively, indicating that the catalysts according to Examples had a structural change due to fragmentation.

Referring to FIG. 13 , as EC is properly coordinated to pure DMC as a complexing agent, peaks corresponding to EC can be observed in Examples 12, 13, 14, and 2. Also, in Examples 12, 13, 14, and 2, ^{it can be seen that the peak corresponding to C≡N shifted to 2193 cm −1} , respectively, indicating that a structural change occurred due to fragmentation of the catalysts according to Examples.

In addition, DMC 1 shown in FIG. 14 is a peak of FT-IR of glycerol carbonate (GC), and as glycerol carbonate (GC) as a complexing agent is properly coordinated to pure DMC, glycerol carbonate in Examples 3, 16, 18, and 19 A peak corresponding to (GC) was observed. In addition, in Examples 3, 16, 18, and 19, the peaks corresponding to C≡N shifted to 2192 cm ^-1 , 2189 cm ^-1 , 2192 cm ^-1 , 2193 cm ^-1 , respectively, the catalyst according to the embodiment It can be seen that structural changes occurred due to fragmentation.

15 also similarly, the peak (DMC 4) corresponding to dimethyl carbonate (DMC) was observed in Examples 21 to 24, and the peak corresponding to C≡N was 2191 cm ^-1 , 2183 cm ^-1 , 2183 cm, respectively. ^-1 , 2184 cm ^-1 , it was confirmed that the catalysts according to the examples had a structural change due to fragmentation.

Preparation of polyether polyols

Example 52

20 g of an initiator polypropylene glycol (PPG) (Mw = 400 g/mol (functional group 2)) and 0.1 g of the catalyst according to Example 1 were added to the high-pressure reactor, and at 100 rpm to remove moisture that may remain in the solution While stirring, the temperature was raised to 115° C., purged with nitrogen several times, and then maintained in a vacuum state for 1 hour.

Next, after injecting 15 g of propylene oxide (PO) monomer into the reactor, when the pressure drop and temperature rise indicating catalyst activation, the monomer was additionally injected. Specifically, while maintaining the pressure at 0.2 bar, it was injected until 200 g of PO was consumed.

Thereafter, a polyoxypropylene polyol (Example 52) was prepared by maintaining a vacuum state for 30 minutes to remove unreacted PO.

Examples 52-89

The same method as in Example 52, using the catalysts according to Examples 1-5, Examples 8-17, Examples 19-20, Examples 29-45, and Examples 48-51 instead of the catalyst according to Example 1, respectively to prepare polyoxypropylene polyols (Examples 53-89).

Preparation of polycarbonate polyol

Example 90

After carbon dioxide was injected into the reactor at a pressure of 10 bar or more, 1 mL of 50 mg polypropylene glycol (PPG) 978 (functional group 4) and 10 mL of toluene were added to the catalyst of Example 1, and then purged for 30 minutes under a pressure of about 30 bar. Thereafter, the reactor was heated to 105° C. for 50 minutes to remove the initiator and moisture in the reactor as much as possible.

Then, after cooling the temperature of the reactor to 30 ℃ or less, a trace amount of carbon dioxide gas, 20 mL of propylene oxide (PO) was added, and then the vent line and the inlet were closed.

After heating the reactor to 105 °C, carbon dioxide gas was injected to increase the carbon dioxide pressure in the reactor to 30 bar, and when the temperature and pressure were stabilized, stirring was started and polymerization was carried out for 3 hours.

After 3 hours, after stopping the injection of carbon dioxide gas and heating, the residual carbon dioxide gas in the reactor was removed, the reactor was disconnected, and a reactant was obtained.

After diluting the reactant in chloroform, filtering it through filter paper to remove the catalyst, and then performing a purification process using chloroform and distilled water to remove unreacted products and by-products, and using a rotary evaporator, chloroform and toluene as solvents 2 Removal over time yielded a polycarbonate polyol.

Example 91

A polycarbonate polyol was prepared in the same manner as in Example 90, except that the catalyst of Example 43 was used instead of the catalyst of Example 1.

16 to 27 are graphs showing the consumption of PO over time during a polymerization reaction using catalysts according to an embodiment of the present invention.

Table 1 below is a table showing the physical properties and polymerization results of the polyoxypropylene polyols prepared according to Examples 52 to 89.

Example catalyst
(Example) yield maximum temperature 　　
Judo
hour
(min) 　
total reaction time
(min) catalyst
activation Polyol Characteristics maximum
speed polyol
Molecular Weight
Mn (g/mol) polydispersity
Indices Unsaturation
(meq/g) functional radix Viscosity
(cp) 57 PC -0.05(8) 0.65 164 26.5 57 3780 5200 1.18 0.0121 2.8 890 58 PC-0.1(9) 0.60 160 34 65 3658 5500 1.17 0.0116 2.6 628 59 PC-0.3(10) 0.70 167 31 58 4200 5700 1.16 0.0176 2.9 682 60 PC-0.5(11) 0.57 169 30 58 4007 6300 1.17 0.0180 2.7 792 52 PC-0.8(1) 0.76 170 21.5 49 4167 5900 1.16 0.0153 3.1 604 53 EC -0.5(2) 0.70 168 20 52 3525 4400 1.18 0.0122 2.7 748 61 EC-0.05(12) 0.74 164 13 58 2493 5700 1.19 0.0086 2.9 717 62 EC-0.1(13) 0.73 163 30 64 3300 5800 1.18 0.0090 2.9 737 63 EC-0.3(14) 0.74 163 17 56 2876 5500 1.18 0.0086 3.1 621 64 EC-0.8(15) 0.80 166 15 66 2221 4800 1.20 0.0079 3.0 541 54 GC-0.5(3) 0.70 152 32 65 3400 5700 1.16 0.0119 3.0 980 65 GC-0.1(16) 0.34 165 17 56 2769 5600 1.22 0.0043 2.6 872 66 GC-0.3(17) 0.82 173 22 55 3309 5500 1.20 0.0096 2.9 715 67 GC-2.0(19) 0.30 182 11.5 47 3228 6200 1.20 0.0186 2.9 859 56 DMC-0.05(5) 0.65 142 19 65 2374 5400 1.20 0.0096 2.8 997 - DMC-0.1(21) 0.70 - - - - - - - - - - DMC-0.5(22) 0.71 - - - - - - - - - - DMC-1.0(23) 0.75 - - - - - - - - - - DMC-2.0(24) 0.75 - - - - - - - - - 69 PC 0.8+1 mL (2 steps)
(29) 0.73 161 13.5 66 2217 70 PC 0.8+1 mL (1 step) - 50℃
(30) 0.70 140 29 2h 30 min 907 71 PC 0.05+1mL
(1 step)
(31) 0.60 121 44 more than 2h - 72 EC 0.5+1mL
(1 step)
(32) 0.60 143 20 more than 3h - 73 DMC 0.05+1mL
(1 step)
(33) 0.56 135 22 more than 3h - 75 PC 0.1+3mL
(1 step)
(35) 0.85 122 40 2h30 min - 76 PC 0.3+ 3mL
(1 step)
(36) 0.89 149 30 55 4320 78 PC 0.8+1 mL (1 step) - 30℃ (38) 0.50 - - - - 79 PC 0.8+1 mL (1 step) - 70℃ (39) 0.68 126 31 more than 3 hours - 80 PC 0.8+1 mL (1 step) - 90℃
(40) 0.66 126 38 3hours - 74 PC-0.8
+3
step 1 Zn : Co = 10 : 1
(34) 0.9 161 30 50 5280 5700 1.15 0.0096 3.7 754 81 Zn : Co = 8 : 1
(41) 0.86 182 25 41 6750 4700 1.14 0.0133 3.6 598 82 Zn : Co = 6 : 1
(42) 0.83 186 20 35 7200 5300 1.15 0.0159 3.1 633 83 Zn : Co = 4 : 1
(43) 0.85 184 19 34 7280 4700 1.15 0.0033 3.6 557 84 Zn : Co = 2 : 1
(44) 0.84 181 21 36 7240 4800 1.14 0.0133 3.0 438 85 Zn:Co = 1.5:1
(45) 0.65 162 31 55 4475 4100 1.14 0.0170 2.7 496 68 BC-0.2(20) 1.13 175 17 42.5 4117 4200 1.17 0.0096 3.0 539 55 BC-0.1(4) 1.06 174 17 35 5966 4300 1.16 0.0113 2.5 457 77 BC-0.1 +3
step 1 Zn : Co = 10 : 1
(37) 0.76 147 36 1h 25min 2338 4400 1.16 0.0089 3.1 451 86 Zn : Co = 8 : 1
(48) 1.13 123 40 more than 2h - 3400 1.18 0.0076 3.0 200 87 Zn : Co = 6 : 1
(49) 1.26 122 47 more than 2h - 2800 1.17 0.0079 2.9 193 88 Zn : Co = 4 : 1
(50) 0.8 126 34 1h 35min 1790 4400 1.17 0.0103 2.8 454 89 Zn : Co = 2 : 1
(51) 0.7 126 39 more than 2h - 3500 1.17 0.0056 3.0 195

1) Comparison of catalytic activity according to carbonate content and reaction temperature

In order to compare the catalytic activity according to the carbonate content and the reaction temperature, the catalytic activity of the Examples in which the carbonate content and the reaction temperature were respectively changed were compared.

24 shows the consumption of PO over time during the polymerization reaction using the catalyst of Examples 34-36 prepared in one step and prepared by changing the amount of PC, and Example 37 prepared using BC as a complexing agent It is a graph.

As shown in Figure 24 and Table 1, among the catalysts prepared in the first step, it was found that the catalyst of Example 34 (Example 74) in which the amount of PC was contained in the first solution in a content of 0.8 mL had the highest catalyst activity. and it exhibited similar activity to the catalyst of Example 1 prepared in three steps (Example 52, see FIG. 16).

And, referring to FIG. 25, among the catalysts of Examples 38-40 prepared by changing the temperature, it can be seen that the catalyst of Example 49 (Example 70) prepared at a temperature of 50° C. exhibits the highest activity.

2) Comparison of catalytic activity according to the complexing agent preparation step

In order to compare the catalytic activity according to the complexing agent preparation step, the catalytic activity of Examples 52 and 74 in which the content was the same and only the preparation step was changed, and the results are shown in Table 1 and FIG. 26 .

26, in the case of propylene carbonate (PC) among the various carbonates used as complexing agents, the content of PC is the same, but in Example 52 (PC = 3Step) and 3 steps in which the production step was performed in 3 steps Even when comparing Example 74 (Zn: Co = 10: 1) reduced to one step, there is little difference in activity, and it can be seen that a catalyst exhibiting sufficient catalytic activity is prepared even in one step. This is because the solubility of propylene carbonate (PC) in water is very high as 240 g/L, and the dielectric constant is 64.9, which is similar to that of water (78).

In addition, referring to Table 1, the catalyst yield of Example 34, in which the DMC catalyst was prepared in one step, was 0.9 g (PC-1 step), and the yield of Example 1 prepared in three steps was 0.76 g (PC) -3 step) rather than increasing.

On the other hand, 1,2-butylene carbonate (BC) has a lower solubility in water than propylene carbonate (PC), but has a dielectric constant similar to that of water. When this BC catalyst was prepared in three steps (Example 4), as shown in FIG. 27, Example 4 had higher activity in PO ring-opening polymerization than propylene carbonate (PC) (Example 55), but in one step When prepared with , the activity was somewhat decreased in all Examples regardless of the molar ratio of the amount of metal (Examples 77, 86-89).

Therefore, in the case of 1,2-butylene carbonate (BC), it is preferable to prepare in three steps because the solubility in water is low.

3) Comparison of catalytic activity according to the molar ratio of metal salt and metal cyanide

Meanwhile, when preparing the DMC catalyst in one step, in order to confirm the desired amount of metal added, a polyol polymerization reaction was carried out using a catalyst prepared by changing the molar ratio of a metal salt and a metal cyanide to 1 to 10: 1, respectively (Example 74) , 81-85), and the results are shown in FIG. 26 and Table 1.

Referring to FIG. 26 and Table 1, when preparing the DMC catalyst in one step, the Zn:Co molar ratio is within the range of 1.5 to 10:1, and as the Zn:Co ratio decreases, the amount of unreacted Zn decreases. It can be seen that the catalytic activity is increased. In particular, the most preferable Zn:Co molar ratio was 4:1.

In addition, comparing Examples 52 and 74, when the excess metal amount (ie, Zn: Co = 10: 1) used in the three-step preparation is also used in the first-stage preparation, there is no reaction in the finally obtained catalyst. In the presence of Zn, the catalytic activity was rather decreased.

That is, as the ratio of the active sites inside the catalyst is relatively increased as the ratio of the amount of metal is decreased, the induction time and the total reaction time in PO polymerization are shortened.

According to these results, when propylene carbonate is used as a complexing agent in preparing the DMC catalyst in one step, there is no need to use an excess of metal, and thus, not only the manufacturing method is simplified, but also the manufacturing cost can be reduced. .

Meanwhile, referring to Table 1, in preparing the polyols according to Examples 52 to 87 of the present invention, propylene oxide (PO) as a monomer and PPG (Mn=400 g/mol (functional group 2)) were used as an initiator. The maximum velocity value was obtained using the formula [(200-initial PO amount)*60]/[(total reaction time-induction time)*0.1]. However, as the polymerization progresses, the activity decreases and when the total reaction time exceeds three hours, the maximum rate value is generally 1000 or less. The number of functional groups was indicated by measuring the hydroxyl value according to ASTM E 1899-97. In addition, for the viscosity, the average value of the values measured a total of three times was selected using a Brookfield DV-11+por Viscometer, and the molecular weight (Mn) and polydispersity index (PDI) of the polyol were expressed using gel permeation chromatography (GPC). It was.

As shown in Table 1, the induction time was from several minutes to several tens of minutes, and in the case of a preferred catalyst, it had a narrow PDI value and a low unsaturation value, and a very high functional group value.

In addition, by adjusting the functional group of the initiator of each catalyst, the functional group of the resulting polyol can be controlled, and the hard polyol and the soft polyol can be determined according to the use.

The degree of unsaturation value is a value obtained by calculating the degree of unsaturation when an alkene group due to a side reaction occurs at one end of the polyol when preparing a polyol. This means high. In the case of the catalysts according to the embodiment of the present invention, it can be seen that all exhibit a low unsaturation value, thereby maintaining high activity.

Table 2 below is a table showing the physical properties and polymerization results of the polycarbonate polyols prepared according to Examples 90 to 91.

Example ¹ H-NMR Yield (g) OHV
(mg Bu ₄ OH/g) polyol
hydroxyl prayer Mn (g/mol) Sco ₂
(%) 90 3100 25 7 33.8 2.2 91 2500 11 6.5 - -

In Table 2, S _CO2 (CO ₂ selectivity) and M _n (molecular weight) of the ^{prepared polyol are values calculated through the spectrum of 1} H-NMR 400 MHz spectrometer, and ^c OH value (hydroxylity value) is ASTM E It was measured by the titration method according to 1899-97. The yield is a value indicating the yield of only the polycarbonate polyol obtained after the purification process, and the conversion rate of the product from the monomer (propylene oxide) is 100%.

As shown in Table 2, polycarbonate polyols were prepared using the catalysts of Examples 1 and 43, and it can be confirmed that the catalyst of the present invention can be usefully used for copolymerization of carbon dioxide and PO.

Although the above has been described with reference to the preferred embodiments of the present invention, those skilled in the art can variously modify and change the present invention without departing from the spirit and scope of the present invention as set forth in the following claims. You will understand that you can.

Claims (20)

As a double metal cyanide catalyst for the preparation of polyols prepared in the absence of an alcohol complexing agent,
A double metal cyanide catalyst for polyol production, comprising a compound represented by the following Chemical Formula 1, and having a monoclinic plate shape or an amorphous form;
[Formula 1]
M _a [M'(CN) ₆ ] _b L _c L' _d
In Formula 1,
M and M' is independently a transition metal ion,
L is a complexing agent comprising a carbonate compound having a solubility in water of 10 g / l or more,
L' is a co-complexing agent,
a, b, c and d are positive numbers.
delete According to claim 1,
The carbonate compound is a double metal cyanide catalyst for polyol production, characterized in that it comprises at least one selected from compounds represented by the following Chemical Formulas 2 to 6.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

According to claim 1,
M is zinc (II), iron (II), iron (III), nickel (II), manganese (II), cobalt (II), molybdenum (IV), molybdenum (VI), vanadium (V), vanadium ( IV), tungsten (IV), tungsten (VI), copper (II), and any one selected from chromium (III),
M' is iron (II), iron (III), cobalt (II), cobalt (III), chromium (II), chromium (III), manganese (II), manganese (III), iridium (III), nickel (II), characterized in that any one selected from rhodium (III), ruthenium (II), vanadium (V) and vanadium (IV),
A double metal cyanide catalyst for the production of polyols.
delete delete According to claim 1,
The co-complexing agent is polypropylene glycol, polyethylene glycol, polytetrahydrofuran, poly(oxyethylene-block-propylene) copolymer, poly(oxyethylene-block-tetrahydrofuran) copolymer, poly(oxypropylene-block- Tetrahydrofuran) copolymer and poly (oxyethylene-block-oxypropylene-block-oxyethylene) copolymer, characterized in that it comprises at least one selected from the group consisting of
A double metal cyanide catalyst for the production of polyols.
delete In the method for preparing a double metal cyanide catalyst for polyol production carried out in the absence of an alcohol complexing agent,
preparing a first solution comprising a carbonate-based complexing agent having a solubility in water of 10 g/l or more, a metal salt, and distilled water;
Preparing a second solution containing a metal cyanide and distilled water;
preparing a third solution including the carbonate-based complexing agent and the co-complexing agent;
a first step of mixing the first solution and the second solution; and
a second step of adding and mixing the third solution to the mixed solution;
The catalyst is characterized in that it has a monoclinic plate-like form or an amorphous form,
A method for preparing a double metal cyanide catalyst for polyol production. 10. The method of claim 9,
The carbonate-based complexing agent is a method for preparing a double metal cyanide catalyst for polyol production, characterized in that it comprises at least one selected from compounds represented by the following Chemical Formulas 2 to 6.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

10. The method of claim 9,
When the solubility of the carbonate-based complexing agent in water is 40 g/l or more,
Washing and drying the precipitate obtained after the second step to obtain a catalyst; characterized in that it comprises,
A method for preparing a double metal cyanide catalyst for polyol production. 12. The method of claim 11,
The carbonate-based complexing agent is a method for preparing a double metal cyanide catalyst for polyol production, characterized in that it comprises at least one selected from compounds represented by the following Chemical Formulas 2 to 4.
[Formula 2]

[Formula 3]

[Formula 4]

12. The method of claim 11,
characterized in that the molar ratio of the metal salt and the metal cyan salt contained in the mixed solution is 1.5 to 10: 1,
A method for preparing a double metal cyanide catalyst for polyol production. 10. The method of claim 9,
a third step of adding distilled water and a solution containing the carbonate-based complexing agent to the mixed solution obtained in the second step and mixing; and
A fourth step of adding and mixing the third solution to the mixed solution obtained in the third step; characterized in that it further comprises,
A method for preparing a double metal cyanide catalyst for polyol production. 15. The method of claim 14,
The third and fourth steps are characterized in that performed in at least two or more cycles,
A method for preparing a double metal cyanide catalyst for polyol production. 16. The method of claim 15,
The carbonate-based complexing agent is a method for preparing a double metal cyanide catalyst for polyol production, characterized in that it comprises at least one selected from compounds represented by the following Chemical Formulas 2 to 6.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

17. The method according to any one of claims 9 to 16,
The mixing is characterized in that it is carried out at a temperature of 30 to 90 ℃,
A method for preparing a double metal cyanide catalyst for polyol production. In the presence of the double metal cyanide catalyst according to claim 1, comprising the step of ring-opening polymerization reaction of the epoxy compound,
A method for preparing polyols. 19. The method of claim 18,
The epoxy compound is a polyol production method, characterized in that it comprises any one or more selected from the following formula.

In the polyol production method according to claim 18, carbon dioxide is additionally injected to copolymerize the carbon dioxide and the epoxy compound, the polycarbonate polyol production method.

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