Double metal cyanide catalyst

Abstract

The present application relates to a bimetallic cyanide (DMC) catalyst having a fast reaction rate and a high conversion rate.

Description

Technology Field

[0001] The present application relates to a bimetallic cyanide catalyst. Specifically, the present application relates to a bimetallic cyanide catalyst, a catalyst composition, and a method for manufacturing polyethers, polyether carbonates, polycarbonate polymers, or polyols. Background Technology

[0002] Polyols can be used in the manufacture of general-purpose polymers. For example, polyols can react with isocyanates to produce polyurethanes, which are widely used in fields such as elastomers, automotive interiors, and coatings. Double metal cyanide (DMC) catalysts are used in the manufacture of these polyols.

[0003] Generally, DMC catalysts are prepared by mixing or reacting metal salts, metal cyanide salts, and complexing agents. The complexing agent is a component intended to enhance the activity of the catalyst, and it is known that substances such as alcohols, ethylene glycol, amides, and nitriles can be used as complexing agents. However, it is difficult to expect a fast reaction rate and high conversion rate using only conventionally known complexing agents. The problem to be solved

[0004] One objective of the present application is to provide a bimetallic cyanide catalyst having a fast reaction rate and a high conversion rate.

[0005] Another objective of the present application is to provide a polymer, a polyol, and a method for producing the same, prepared using a bimetallic cyanide catalyst.

[0006] The above-mentioned purpose of the present application and other other purposes can all be resolved by the present application described in detail below. means of solving the problem

[0007] According to a specific embodiment of the present application, a double metal cyanide (DMC) catalyst, a double metal cyanide (DMC) catalyst composition, a method for manufacturing the same, and a method for manufacturing a polyol or polymer using the catalyst are provided.

[0008] In this specification, unless specifically defined otherwise, the term “alkyl group” may be an alkyl group having 1 to 40 carbon atoms. For example, the alkyl group may be an alkyl group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. In this case, the alkyl group may be a straight-chain, branched-chain, or cyclic alkyl group. Additionally, the alkyl group may optionally be substituted by one or more substituents.

[0009] In this specification, unless specifically defined otherwise, the term “haloalkyl group” may mean a compound in which a hydrogen atom of an alkyl group is substituted with a halogen atom. In this case, the alkyl group may be used with the same meaning as described above.

[0010] In this specification, unless specifically defined otherwise, the term “alkenyl group” may be an alkenyl group having 2 to 40 carbon atoms. For example, the alkenyl group may be an alkenyl group having 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. In this case, the alkenyl group may be a straight-chain, branched-chain, or cyclic alkenyl group. Additionally, the alkenyl group may optionally be substituted by one or more substituents.

[0011] In this specification, unless specifically defined otherwise, the term “alkynyl group” may be an alkynyl group having 2 to 40 carbon atoms. For example, the alkynyl group may be an alkynyl having 2 to 36 carbon atoms, 2 to 32 carbon atoms, 2 to 28 carbon atoms, 2 to 24 carbon atoms, 2 to 20 carbon atoms, 2 to 16 carbon atoms, 2 to 12 carbon atoms, 2 to 8 carbon atoms, or 2 to 4 carbon atoms. In this case, the alkynyl group may be a straight-chain, branched-chain, or cyclic alkynyl group. Additionally, the alkynyl may optionally be substituted by one or more substituents.

[0012] In this specification, unless specifically defined otherwise, the term “aryl group” may mean a monovalent residue derived from a compound or a derivative thereof comprising a structure in which one benzene ring structure, or two or more benzene rings are connected by sharing one or two carbon atoms or by any linker. For example, the aryl group may be an aryl group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the aryl group may optionally be substituted by one or more substituents.

[0013] In this specification, unless specifically defined otherwise, the term “heteroaryl group” may mean an aryl group comprising one or more of O, N, Si, and S. For example, the aryl group in the heteroaryl group may be used with the same meaning as described above. Alternatively, the number of carbon atoms in the heteroaryl group may be 2 to 30.

[0014] In this specification, unless specifically defined otherwise, the term “aryloxy group” may mean a group RO- where R is an aryl group. In this case, the allyl group may be used with the same meaning as described above.

[0015] In this specification, unless specifically defined otherwise, the “alkoxy group” may be an alkoxy group having 1 to 40 carbon atoms. For example, the alkoxy group may be an alkoxy group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkoxy group may be a straight-chain, branched-chain, or cyclic alkoxy group. Additionally, the alkoxy group may optionally be substituted by one or more substituents.

[0016] In this specification, unless specifically defined otherwise, "aliphatic structure" may refer to a cyclic hydrocarbon structure that is not an aromatic ring structure and is represented by -Y. Unless specifically defined otherwise, the aliphatic ring structure may be, for example, an aliphatic ring structure having 3 to 30 carbon atoms, 3 to 25 carbon atoms, 3 to 21 carbon atoms, 3 to 18 carbon atoms, or 3 to 13 carbon atoms. The aliphatic structure may optionally be substituted by one or more substituents.

[0017] In this specification, unless specifically defined otherwise, "heterocycloniform structure" may mean acycloniform structure comprising one or more of O, N, Si, and S. For example, acycloniform structure may be used with the same meaning as described above.

[0018] In this specification, unless specifically defined otherwise, “alkylthio group” may mean RS- where R is an alkyl group. In this case, the alkyl group may be used with the same meaning as described above.

[0019] In this specification, unless specifically defined otherwise, "arylthio group" may mean RS- where R is an aryl group. In this case, the aryl group may be used with the same meaning as described above.

[0020] In this specification, unless specifically defined otherwise, the “alkylene group” may be an alkylene group having 1 to 40 carbon atoms. For example, the alkylene group may be an alkylene group having 1 to 36 carbon atoms, 1 to 32 carbon atoms, 1 to 28 carbon atoms, 1 to 24 carbon atoms, 1 to 20 carbon atoms, 1 to 16 carbon atoms, 1 to 12 carbon atoms, 1 to 8 carbon atoms, or 1 to 4 carbon atoms. The alkylene group may be a straight-chain, branched-chain, or cyclic alkylene group. Additionally, the alkylene group may optionally be substituted by one or more substituents.

[0021] In this specification, unless specifically defined otherwise, a “heteroalkylene group” may be an alkylene group comprising one or more of O, N, Si, and S. In this case, the alkylene group may be used with the same meaning as described above.

[0022] In this specification, unless specifically defined otherwise, the “cycloalkylene group” is a divalent functional group derived from a cycloalkane and may have 3 to 20 carbon atoms. For example, the cycloalkylene group may be a cycloalkylene group having 3 to 15 carbon atoms, 3 to 10 carbon atoms, or 3 to 5 carbon atoms. Additionally, the cycloalkylene group may optionally be substituted by one or more substituents.

[0023] In this specification, unless specifically defined otherwise, "arylene group" may mean a divalent aromatic hydrocarbon group. For example, the arylene group may mean a divalent residue derived from a compound or a derivative thereof comprising a single benzene ring structure, or a structure in which two or more benzene rings are connected by sharing one or two carbon atoms or are connected by any linker. For example, the arylene group may be an arylene group having 6 to 30 carbon atoms, 6 to 25 carbon atoms, 6 to 21 carbon atoms, 6 to 18 carbon atoms, or 6 to 13 carbon atoms. In this case, the arylene group may optionally be substituted by one or more substituents.

[0024] In this specification, unless specifically defined otherwise, the term “hetero-arylene group” may be an arylene group comprising one or more of O, N, Si, and S. For example, the arylene group in the hetero-arylene group may be used with the same meaning as described above. Alternatively, the number of carbon atoms in the hetero-arylene group may be 2 to 30.

[0025] Although not specifically limited, the functional group described above may be a substituted or unsubstituted functional group. In this specification, the term “substituted or unsubstituted” may mean being substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium; halogen group; cyano group; nitro group; hydroxyl group; carbonyl group; ester group; imide group; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thioxy group; aryl thioxy group; alkyl sulfoxy group; aryl sulfoxy group; silyl group; boron group; alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; alkylaryl group; alkylamine group; aralkylamine group; heteroarylamine group; arylamine group; arylphosphine group; or heteroaryl containing one or more of N, O, and S atoms, or being substituted or unsubstituted with two or more of the exemplified substituents connected. For example, "a substituent with two or more substituents connected" can be a biphenyl group. That is, the biphenyl group can be an aryl group, or it can be interpreted as a substituent with two phenyl groups connected.

[0026] The present invention will be described in more detail below.

[0028] In one example relating to the present application, the present application relates to a double metal cyanide (DMC) catalyst. As confirmed by the experimental examples below, a catalyst of the following composition provides a fast reaction rate and a high conversion rate.

[0029] Specifically, the catalyst comprises (A) a bimetallic cyanide compound, (B) an organic complex ligand, and (C) a polysiloxane-containing polyol. That the catalyst comprises (A) to (C) may mean that the catalyst is a reactant of (A) to (C) or comprises a reactant thereof, or that the catalyst is formed from a composition comprising at least (A) to (C) components. In this regard, the DMC catalyst of the present application may be referred to as a DMC complex.

[0030] In a specific example of the present application, the (A) double metal cyanide compound may be a reaction product of (a1) a metal salt and (a2) a metal cyanide salt. In this case, the metal salt may be distinguished from the metal cyanide salt in that it does not contain cyanide. That is, the metal salt (a1) may be referred to as a cyanide-free (metal) compound, and the metal cyanide salt (a2) may be referred to as a (metal) cyanide compound.

[0031] According to a specific embodiment of the present application, the metal salt and metal cyanide salt may be water-soluble.

[0032] In one example, the (a1) metal salt used to form the above-mentioned double metal cyanide compound may be represented by the following chemical formula 1.

[0033] [Chemical Formula 1]

[0034] M(X) n

[0035] In the above chemical formula 1, M can be selected from Zn(II), Fe(II), Ni(II), Mn(II), Co(II), Sn(II), Pb(II), Fe(III), Mo(IV), Mo(VI), Al(II), Al(III), V(V), V(IV), Sr(II), W(IV), W(VI), Cu(II) and Cr(III), X can be an anion selected from halides, hydroxides, sulfates, carbonates, cyanates, oxalates, thiocyanates, isocyanates, isothiocyanates, carboxylates and nitrates, or an anion containing the same, and n can be a value of 1 to 3.

[0036] Although not specifically limited, the metal salt used to form the above-mentioned double metal cyanide compound may be, for example, zinc chloride, zinc bromide, zinc acetate, zinc acetylacetoate, zinc benzoate, zinc nitrate, iron sulfate (II), iron bromide (II), iron chloride (II), cobalt chloride (II), cobalt thiocyanate (II), nickel chloride (II), nickel formate (II), or nickel nitrate (II).

[0037] In one example, the (a2) metal cyanide salt used to form the above-mentioned double metal cyanide compound may be represented by the following chemical formula 2.

[0038] [Chemical Formula 2]

[0039] (Y) a M'(CN) b (A) c

[0040] In the above chemical formula 2, Y may be a cation selected from alkali metal ions and alkaline earth metal ions or a cation containing the same, M' may be selected from Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ir(III), Ni(II), Rh(III), Ru(II), V(IV), and V(V), A may be an anion selected from halides, hydroxides, sulfates, carbonates, cyanates, thiocyanates, isocyanates, isothiocyanates, carboxylates, oxalates, and nitrates or an anion containing the same, and the sum of a, b, and c may be an integer selected to balance the charge of M'. Although not particularly limited, a and b may be integers greater than 1, specifically a may be 1 to 4, b may be 4 to 6, and c may be 0.

[0041] Although not specifically limited, the metal cyanide salt used to form the above-mentioned double metal cyanide compound may include potassium hexacyanocobaltate(III), potassium hexacyanoferrate(II), potassium hexacyanoferrate(III), or calcium hexacyanocobaltate(II).

[0042] In one example, the above (A) bimetallic cyanide compound can be represented by the following chemical formula 3.

[0043] [Chemical Formula 3]

[0044] M x [M' x' (CN) y ] z

[0045] In the above chemical formula 3, M is the same as defined in relation to chemical formula 1, M' is the same as defined in relation to chemical formula 2, and x, x', y and z may be values ​​(e.g., integers) selected to satisfy the electronic neutrality of the bimetallic cyanide compound.

[0046] Although not specifically limited, according to specific embodiments of the present application, M may be Zn(II), Fe(II), Co(II), or Ni(II), and M' may be Co(III), Fe(III), Cr(III), or Ir(III). Also, x may be 3, x' may be 1, y may be 6, and z may be 2. For example, as the bimetallic cyanide compound of Formula 3, zinc hexacyanocobalt(III), zinc hexacyanoiridium(III), zinc hexacyanoferrate(III), and cobalt(II) hexacyanocobalt(III) may be used.

[0047] In one example, the catalyst may contain 35 to 90 weight percent of the (A) bimetallic cyanide compound based on 100 weight percent of the total catalyst amount. Specifically, the lower limit of the content of the (A) bimetallic cyanide compound may be, for example, 40 weight percent or more, 45 weight percent or more, 50 weight percent or more, 55 weight percent or more, 60 weight percent or more, 65 weight percent or more, 70 weight percent or more, 75 weight percent or more, 80 weight percent or more, or 85 weight percent or more. The upper limit may be, for example, 85 weight percent or less, 80 weight percent or less, 75 weight percent or less, 70 weight percent or less, 65 weight percent or less, 60 weight percent or less, 55 weight percent or less, 50 weight percent or less, 45 weight percent or less, or 40 weight percent or less. When the above content range is satisfied, it is advantageous for achieving structural stability of the catalyst and the desired effect.

[0048] The above (B) organic complex ligand is a complexing agent (CA). Specifically, the above organic complex ligand is a water-soluble organic compound having atoms such as oxygen, nitrogen, phosphorus, or sulfur, and is a component capable of forming a complex with the above (A) bimetallic cyanide compound. The type of organic complex ligand is not particularly limited.

[0049] In one example, the organic complex ligand may include one or more selected from alcohols, aldehydes, ketones, ethers, esters, amides, ureas, nitriles, and sulfides.

[0050] According to a specific embodiment of the present application, the organic complex ligand may be an alcohol complexing agent or may include the same. For example, as the organic complex ligand, one or more alcohol complexing agents selected from tert-butanol, n-butanol, iso-butanol, and sec-butanol may be used, but the types are not limited to the alcohols listed above.

[0051] In one example, the catalyst may contain 5 to 35 weight percent of the organic complex ligand (B) based on 100 weight percent of the total catalyst amount. Specifically, the lower limit of the content of the organic complex ligand (B) may be, for example, 10 weight percent or more, 15 weight percent or more, 20 weight percent or more, 25 weight percent or more, or 30 weight percent or more. And, the upper limit of the content may be, for example, 30 weight percent or less, 25 weight percent or less, 20 weight percent or less, 15 weight percent or less, or 10 weight percent or less. Satisfying the above content range is advantageous for achieving structural stability of the catalyst and the desired effect.

[0052] The catalyst of the present application comprises a (C) co-complexing agent (Co-CA) having a structure different from the (B) organic complex ligand. As the co-complexing agent, the catalyst of the present application comprises a polysiloxane-containing polyol. As confirmed by the experimental examples below, the catalyst of the present application containing a polysiloxane-containing polyol exhibits a faster reaction rate than the catalyst of the prior art containing known complexing agents, thereby increasing productivity.

[0053] In one example, the polysiloxane-containing polyol may be a polysiloxane compound having at least two hydroxyl groups (-OH) at both ends.

[0054] According to a specific embodiment of the present application, the polysiloxane-containing polyol, which is the co-forming agent (C), is a compound having at least two hydroxyl groups at both ends and may have a structure comprising a polysiloxane-containing unit represented by the following chemical formula 4.

[0055] [Chemical Formula 4]

[0056]

[0057] In the above chemical formula 4,

[0058] R is each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and

[0059] l is a number between 1 and 300, and

[0060] Organic groups having hydroxyl groups are attached to both ends of the unit indicated by *.

[0061] In a specific embodiment of the present application, l of Formula 4 can be adjusted considering the size of the catalyst, degree of hydrophobicity, dispersibility, or ease of coordination bonding. For example, if the value of I is too small, there are limitations in dispersing the catalyst or controlling the particle size of the catalyst, and if the value of I is too large, hydrophobicity increases, which causes a problem in that it cannot effectively coordinate to the catalyst during catalyst synthesis. Considering these points, the lower limit of the value of l may be, for example, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more. And the upper limit may be, for example, 250 or less, 200 or less, 150 or less, or 100 or less.

[0062] In a specific embodiment of the present application, the organic group that can be bonded to * of Formula 4 may be, for example, an aromatic ring having at least one hydroxyl group or may include the same.

[0063] In one example, the weight-average molecular weight (Mw) of the compound represented by Chemical Formula 4 above may be 300 or more. Specifically, the weight-average molecular weight may be 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, or 8000 or more. And the upper limit may be, for example, 10,000 or less. Specifically, the upper limit of the weight-average molecular weight may be, for example, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less. Considering the size, dispersibility, ease of coordination, and catalytic performance of the catalyst, the molecular weight of the compound represented by Chemical Formula 4 can be appropriately controlled within the molecular weight range described above.

[0064] Unless otherwise specifically defined, molecular weight in this specification may be the weight-average molecular weight of polystyrene equivalent measured by the GPC method (e.g., g / mol).

[0065] According to a specific embodiment of the present application, the polysiloxane-containing polyol that is the cohesive agent may be a polysiloxane compound having an organic group comprising an aromatic ring having at least one hydroxyl group bonded to both ends.

[0066] In one example, the polysiloxane-containing polyol may be a compound represented by the chemical formula 5 below.

[0067] [Chemical Formula 5]

[0068]

[0069] In the above chemical formula 5,

[0070] R1 and R8 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and

[0071] m1 and n1 are each independently integers from 1 to 4, and

[0072] R2 and R7 are, identically or differently, alkylene groups, heteroalkylene groups, cycloalkylene groups, arylene groups, or heteroarylene groups, and

[0073] R3, R4, R5 and R6 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and

[0074] l1 is a number between 1 and 300.

[0075] In a specific embodiment of the present application, m1 and n1 of the formula 5 may each independently be 1, 2, 3 or 4, and if m1 or n1 is less than 4, 1 to 3 hydrogens may be located at a position where R1 or R8 can be located in the aromatic ring.

[0076] In a specific embodiment of the present application, l1 of Formula 5 can be adjusted by considering the size of the catalyst, the degree of hydrophobicity, dispersibility, or ease of coordination bonding. For example, if the value of I1 is too small, there are limitations in dispersing the catalyst or controlling the particle size of the catalyst, and if the value of I1 is too large, hydrophobicity increases, which causes a problem in that it cannot effectively coordinate to the catalyst during catalyst synthesis. In this regard, the lower limit of l1 of Formula 5 may be, for example, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more. And the upper limit may be, for example, 250 or less, 200 or less, 150 or less, 100 or less, or 50 or less.

[0077] In one example, the weight-average molecular weight (Mw) of the compound represented by Chemical Formula 5 above may be 300 or more. Specifically, the weight-average molecular weight may be 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, or 8000 or more. And the upper limit may be, for example, 10,000 or less. Specifically, the upper limit of the weight-average molecular weight may be, for example, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less. Considering the size, dispersibility, ease of coordination, and catalytic performance of the catalyst, the molecular weight of the compound represented by Chemical Formula 5 can be appropriately controlled within the molecular weight range described above.

[0078] In one example, considering the structure and function of the catalyst, l1 in the compound represented by the chemical formula 5 above may be 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, or 60 or more, and the upper limit may be, for example, 100 or less, 90 or less, 80 or less, 70 or less, 60 or less, 50 or less, or 40 or less. In addition, the weight-average molecular weight of the compound of Formula 5 may be 1000 or more, 1500 or more, 2000 or more, 2500 or more, 3000 or more, 3500 or more, 4000 or more, 4500 or more, or 5000 or more, and the upper limit of the molecular weight may be, for example, 7000 or less, 6500 or less, 6000 or less, 5500 or less, 5000 or less, 4500 or less, 4000 or less, or 3500 or less.

[0079] In another example, the polysiloxane-containing polyol may be a compound represented by the chemical formula 6 below.

[0080] [Chemical Formula 6]

[0081]

[0082] In the above chemical formula 6,

[0083] R9 and R18 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and

[0084] m2 and n2 are each independently integers from 1 to 4, and

[0085] R10 and R17 are each independently, directly bonded, or identically or differently, an alkylene group, a heteroalkylene group, a cycloalkylene group, an arylene group, or a heteroarylene group, and

[0086] R11 and R16 are, identically or differently, alkylene groups, heteroalkylene groups, cycloalkylene groups, arylene groups, or heteroarylene groups, and

[0087] R12, R13, R14, and R15 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure, or alkylthio group or arylthio group, and

[0088] l2 is a number between 1 and 300.

[0089] In a specific embodiment of the present application, m2 and n2 of the formula 6 may be 1, 2, 3 or 4, and if m2 or n2 is less than 4, 1 to 3 hydrogens may be located at the positions where R9 or R18 can be located in the aromatic ring.

[0090] In a specific embodiment of the present application, with respect to R10 and R17 of the above formula 6, direct bonding means that there is no atom at the position indicated by R10 or R17.

[0091] In a specific embodiment of the present application, l2 of Formula 6 can be adjusted by considering the size of the catalyst, the degree of hydrophobicity, dispersibility, or ease of coordination bonding. For example, if the value of I2 is too small, there are limitations in dispersing the catalyst or controlling the particle size of the catalyst, and if the value of I2 is too large, hydrophobicity increases, which causes a problem in that it cannot effectively coordinate to the catalyst during catalyst synthesis. In this regard, the lower limit of l2 of Formula 6 may be, for example, 10 or more, 20 or more, 30 or more, 40 or more, 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, or 100 or more. And the upper limit may be, for example, 250 or less, 200 or less, 150 or less, 100 or less, or 50 or less.

[0092] In one example, the weight-average molecular weight (Mw) of the compound represented by Chemical Formula 6 above may be 300 or more. Specifically, the weight-average molecular weight may be 400 or more, 500 or more, 600 or more, 700 or more, 800 or more, 900 or more, 1000 or more, 2000 or more, 3000 or more, 4000 or more, 5000 or more, 6000 or more, 7000 or more, or 8000 or more. And the upper limit may be, for example, 10,000 or less. Specifically, the upper limit of the weight-average molecular weight may be, for example, 9,000 or less, 8,000 or less, 7,000 or less, 6,000 or less, 5,000 or less, 4,000 or less, 3,000 or less, 2,000 or less, or 1,000 or less. Considering the size, dispersibility, ease of coordination, and catalytic performance of the catalyst, the molecular weight of the compound represented by Chemical Formula 6 can be appropriately controlled within the molecular weight range described above.

[0093] In one example, considering the structure and function of the catalyst, etc., l2 in the compound represented by the chemical formula 6 above may be 50 or more, 60 or more, 70 or more, 80 or more, 90 or more, 100 or more, or 110 or more, and the upper limit may be, for example, 150 or less, 140 or less, 130 or less, 120 or less, 110 or less, 100 or less, or 90 or less. In addition, the weight-average molecular weight of the compound of Formula 6 may be 4000 or more, 4500 or more, 5000 or more, 5500 or more, 6000 or more, 6500 or more, 7000 or more, 7500 or more, 8000 or more, or 8500 or more, and the upper limit of the molecular weight may be, for example, 13000 or less, 12500 or less, 12000 or less, 11500 or less, 11000 or less, 10500 or less, 10000 or less, 9500 or less, 9000 or less, 8500 or less, 8000 or less, or 7500 or less.

[0094] Although not specifically limited, compounds such as those of the above chemical formula 5 or 6 can be obtained, for example, by reacting a bis(hydrogen) polysiloxane with a hydroxyl-containing aromatic ring compound having an unsaturated bond.

[0095] If the content of the above (C) co-forming agent is excessively small, the dispersibility of the catalyst is poor, and if it is excessively large, it blocks the active sites of the catalyst; therefore, if an appropriate content is not used, there is a problem of reduced catalyst activity. Taking these points into consideration, the above-mentioned bimetallic cyanide (DMC) catalyst may contain 3 to 50 weight% of the above-mentioned (C) co-forming agent based on a content of 100 weight%. Specifically, the lower limit of the above-mentioned (C) co-forming agent may be, for example, 5 weight% or more, 10 weight% or more, 15 weight% or more, 20 weight% or more, 25 weight% or more, 30 weight% or more, 35 weight% or more, 40 weight% or more, or 45 weight% or more. And, the upper limit may be, for example, 45 weight% or less, 40 weight% or less, 35 weight% or less, 30 weight% or less, 25 weight% or less, 20 weight% or less, 15 weight% or less, 10 weight% or less, or 5 weight% or less.

[0096] The use of the above catalyst is not particularly limited. For example, the above catalyst can be used as a catalyst for producing polyols or polymer copolymers by copolymerizing alkylene oxides with carbon dioxide. In addition, for example, the above catalyst can be used as a catalyst in the production of polyether polyols, specifically in a method of producing polyether polyols by adding alkylene oxides to a starting material containing active hydrogen atoms.

[0098] In another example relating to the present application, the present application relates to a method for preparing a double metal cyanide (DMC) catalyst. According to a specific embodiment of the present application, a double metal cyanide catalyst can be prepared through a reaction between (A) a double metal cyanide compound, (B) an organic complex ligand, and (C) a co-complexing agent.

[0099] The description of (A) the double metal cyanide compound, (B) the organic complex ligand, and (C) the polysiloxane-containing polyol that is a co-complexing agent is the same as described above.

[0100] In one example, the method may include the steps of: (a1) mixing and reacting a metal salt, (a2) a metal cyanide salt, and (B) an organic complex ligand in a solvent (e.g., water); and after the reaction, (C) adding a polysiloxane polyol, which is a co-complexing agent, to further react.

[0101] In another example, the method may include the step of (a1) reacting a metal salt and (a2) a metal cyanide salt to produce (A) a bimetallic cyanide compound; and the step of reacting (A) the bimetallic cyanide compound, (B) an organic complex ligand, and (C) a co-complexing agent.

[0102] In the above-described method, the reaction for catalyst preparation may be carried out simultaneously with stirring or mixing, or after stirring and mixing.

[0103] In addition, the stirring, mixing, and / or reaction may be carried out in an aqueous solution. The aqueous solution may contain water and, in some cases, may additionally contain alcohol.

[0104] According to a specific embodiment of the present application, milling using a device such as a ball grinder may be performed together when stirring or mixing is performed.

[0105] In one example, the method may further include the step of separating a solid catalyst by filtration or centrifugation. The method or conditions for performing filtration or centrifugation may be appropriately controlled by a person skilled in the art. Although not particularly limited, the centrifugation may be performed, for example, using an aqueous washing solution, and the aqueous washing solution may include water and an alcohol (e.g., t-butanol belonging to the category of organic complex ligands). Such centrifugation may be repeated one or more times.

[0106] In one example, the method may further include a step of washing the separated solid catalyst. Although not particularly limited, the washing may be performed, for example, using an aqueous washing solution, and the aqueous washing solution may include an alcohol (e.g., t-butanol belonging to the category of organic complex ligands). The washing may be repeated one or more times.

[0107] In one example, the method may further include a step of grinding the catalyst. Such grinding may be performed before, after, or simultaneously with the washing described above. When grinding the catalyst, known grinding methods or equipment (e.g., ball milling) may be used.

[0108] In one example, the method may further include a drying step for the catalyst. The drying conditions are not particularly limited, for example, drying may be performed at 150°C or lower or 100°C or lower.

[0110] In another example relating to the present application, the present application relates to a bimetallic cyanide catalyst composition.

[0111] In one example, the catalyst composition may comprise at least (A) a bimetallic cyanide compound, (B) an organic complex ligand, and (C) a polysiloxane-containing polyol that is a co-complexing agent, or a reaction product thereof. Additionally, the catalyst composition may further comprise water.

[0112] In another example, the catalyst composition may comprise at least (a1) a metal salt, (a2) a metal cyanide salt, (B) an organic complex ligand, and (C) a polysiloxane-containing polyol that is a co-complexing agent, or a reaction product thereof. Additionally, the catalyst composition may further comprise water.

[0113] The description regarding the characteristics of metal salts, metal cyanide salts, dimetallic cyanide compounds, organic complex ligands, and polysiloxane-containing polyols is the same as described above.

[0115] In another example relating to the present application, the present application relates to a method for producing a polymer or polyol using a bimetallic cyanide catalyst. Examples of polymers include polyethers, polycarbonates, polyether carbonates, polyalkylene ether carbonates, etc.

[0116] Specifically, the above method relates to a method for producing a polymer or polyol from one or more alkylene oxides and carbon dioxide in the presence of a bimetallic cyanide (DMC) catalyst having the characteristics described above.

[0117] In one example, the alkylene oxide may be ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide, or a mixture thereof, but is not limited to these. Effects of the invention

[0118] According to a specific embodiment of the present application, a bimetallic cyanide catalyst having a fast reaction rate and a high conversion rate can be provided. In addition, the present application has the effect of an invention that provides high economic efficiency or productivity in the manufacture of polymers or polyols. Specific details for implementing the invention

[0119] The operation and effects of the invention will be explained in more detail below through specific embodiments. However, these are presented merely as examples of the invention and do not limit the scope of the claims of the present application in any way.

[0121] Preparation Example: Preparation of DMC Catalyst

[0122] Preparation Example 1

[0123] An aqueous solution was prepared by dissolving 4g of K3[Co(CN)6] in 100ml of water. Then, a solution was prepared by dissolving 12.5g of ZnCl2 in a mixture of 30ml of water and 50ml of t-BuOH. These were then mixed while stirring.

[0124] To the solution of the white solid product generated during the above mixing, a solution in which a co-forming agent (Co-CA) of the following chemical formula 5-1 (wherein l1 is about 40 to 50 and the weight-average molecular weight is about 4000) is dissolved is additionally added and stirred for 1 hour. At this time, the co-forming agent solution is a solution in which 5g of the co-forming agent of the following chemical formula 5-1 is dissolved in 30ml of t-BuOH.

[0125] Subsequently, the precipitate was separated using a centrifuge. The white precipitate was dispersed in a water:t-BuOH = 1:1 solution (volume ratio) and then centrifuged. This centrifugation process was carried out sequentially in water:t-BuOH = 1:3 and t-BuOH solutions.

[0126] Then, the separated white powder was dried in a vacuum oven at a temperature of 60°C, and 7.8g of white powder was obtained after drying.

[0127] [Chemical Formula 5-1]

[0128]

[0129] Preparation Example 2

[0130] A DMC catalyst was prepared in the same manner as in Preparation Example 1, except that Co-CA represented by the chemical formula 6-1 below (wherein l2 is about 90 to 100 and its weight-average molecular weight is about 8000) was used.

[0131] [Chemical Formula 6-1]

[0132]

[0133] Preparation Example 3

[0134] A DMC catalyst was prepared in the same manner as in Preparation Example 1, except that a polyether diol of the comparative formula below (weight-average molecular weight about 3,000) was used as Co-CA instead of the compound of Formula 5-1.

[0135] [Comparative Chemical Formula]

[0136]

[0138] Example: Preparation of polyalkylene ether carbonate using the prepared DMC catalyst

[0139] Example 1

[0140] A mixture of 20 g of propylene oxide (PO), 20 g of MC (methylene chloride), and 0.01 g of the DMC catalyst prepared in Preparation Example 1 was reacted for about 3 hours under conditions of 30 bar CO2 and 85 ℃ to obtain 27.7 g of polypropylene ether carbonate (PPC).

[0141] Example 2

[0142] A mixture of 20 g of propylene oxide (PO), 20 g of MC (methylene chloride), and 0.01 g of the DMC catalyst prepared in Preparation Example 2 was reacted for about 3 hours under conditions of 30 bar CO2 and 85 ℃ to obtain 27.0 g of polypropylene ether carbonate (PPC).

[0143] Comparative Example 1

[0144] A mixture of 20 g of propylene oxide (PO), 20 g of MC (methylene chloride), and 0.01 g of the DMC catalyst prepared in Preparation Example 3 was reacted for about 3 hours under conditions of 30 bar CO2 and 85 ℃ to obtain 27.6 g of polypropylene ether carbonate (PPC).

[0146] Evaluation of catalysts

[0147] 1. Activation

[0148] The activity of the catalyst is calculated through the ratio of the weight of the final PPC produced to the weight of the catalyst added during the reaction. That is, the catalytic activity can be expressed as g-PPC / g-cat, which is the weight of the final product PPC that can be produced with 1 g of the catalyst added.

[0149] 2. Carbonate content (CO 2 Ratio of repeating units attributable to)

[0150] The carbonate content was confirmed via NMR. Assuming that the case where CO2 and PO are mixed in a 1:1 ratio is 100% (when converted to mass, the case where 43% of the total repeating unit mass is attributed to CO2 corresponds to a carbonate content of 100%), the ratio of repeating units that are CO2 groups within the actual polymerized polymer was calculated via NMR, and the resulting value was recorded as the carbonate content.

[0151] 3. Conversion rate (ratio of POs that responded to the initial PO input)

[0152] The conversion rate was calculated based on the weight of the obtained polymer material. The content of unreacted PO and the ratio of the reaction product excluding it were calculated using the ratios of PO, PPC, and the byproduct cPC (Cyclic Propylene Carbonate) identified by NMR, and the ratio of the reacted material (PO) to the initial input PO was recorded as the conversion rate.

[0153] The evaluation results regarding the examples and comparative examples are as follows.

[0154] Example 1 Example 2 Comparative Example 1 active 2,600 g / g-cat 2,520 g / g-cat 2,580 g / g-cat Carbonate content 68 % 66 % 83 % Conversion rate (earnings basis) 97 % 95 % 88 % Reaction time 2.5 hr 2.5 hr 3.0 hr

[0155] As a result of confirming the catalyst activity based on the weight of the polymer material obtained through the reaction, it can be seen that both the catalysts of the example and the comparative example possess similar levels of high activity. Furthermore, it was confirmed that the carbonate content of the catalyst in the comparative example is higher, which implies that the catalyst in the comparative example can convert more CO2 than the catalyst in the example.

[0156] However, it can be seen that the conversion rate of the catalysts used in Examples 1 and 2 is higher than that of the Comparative Example. The above conversion rate is the result confirmed by the weight of the actual obtained polymer. Although the weight of the obtained polymer is similar between 27 and 28 g for both the Comparative Example and the catalysts in the Examples, the carbonate content, i.e., the CO2 content, of the Comparative Example is about 15% higher, so it can be inferred that that amount of PO was not converted into polymer.

[0157] In addition, as a result of confirming the theoretical conversion rate over time using NMR, it was found that in the case of Examples 1 and 2, a conversion rate of nearly 100% was already achieved at 2.5 hours, whereas Comparative Example 1 had a slow reaction rate of about 92% even after 3 hours of reaction. The reason for the faster reaction rates of Examples 1 and 2 is thought to be that the catalysts in Preparation Examples 1 and 2 have long chains with hydrophobicity, which can more easily promote cracking between catalysts compared to the catalyst in Preparation Example 3. In other words, it is thought that the reaction rate of the catalyst can be increased because the surface area of ​​the active catalyst is increased at a faster rate by micronizing the catalyst.

[0158] Ultimately, utilizing the novel catalyst used in the preparation example allows for the rapid conversion of polymers, thereby improving productivity and minimizing the loss of the initially input reactant (PO), which can ensure higher economic efficiency.

Claims

Claim 1 A bimetallic cyanide (DMC) catalyst comprising (A) a bimetallic cyanide compound; (B) an organic complex ligand; and (C) a polysiloxane-containing polyol, wherein (C) the polysiloxane-containing polyol is represented by the following chemical formula 5 or 6: [Chemical Formula 5] (wherein in the above formula 5, R1 and R8 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, m1 and n1 are each independently integers from 1 to 4, R2 and R7 are the same or different alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, and R3, R4, R5 and R6 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or It is an alkylthio group or an arylthio group, where l1 is a number between 1 and 300. [Chemical Formula 6] (wherein in the above formula 6, R9 and R18 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, m2 and n2 are each independently integers from 1 to 4, R10 and R17 are each independently directly bonded or are identically or differently alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, R11 and R16 are identically or differently alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, and R12, R13, R14 and R15 are each independently It is hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and l2 is a number between 1 and 300.). Claim 2 delete Claim 3 In claim 1, the (C) polysiloxane-containing polyol is a bimetallic cyanide (DMC) catalyst having a weight-average molecular weight in the range of 300 to 10,000. Claim 4 delete Claim 5 delete Claim 6 A bimetallic cyanide (DMC) catalyst according to claim 1, comprising 3 to 50 weight% of the (C) polysiloxane-containing polyol based on 100 weight% of the bimetallic cyanide (DMC) catalyst. Claim 7 In claim 1, the (A) bimetallic cyanide compound is a bimetallic cyanide (DMC) catalyst that is a reaction product of a water-soluble metal salt and a water-soluble metal cyanide salt. Claim 8 A bimetallic cyanide (DMC) catalyst according to claim 1, comprising 35 to 90 weight% of the (A) bimetallic cyanide compound based on 100 weight% of the bimetallic cyanide (DMC) catalyst. Claim 9 In claim 1, the (B) organic complex ligand is an alcohol complexing agent or a bimetallic cyanide (DMC) catalyst comprising the same. Claim 10 A bimetallic cyanide (DMC) catalyst according to claim 1, comprising 5 to 35 weight% of the (B) organic complex ligand based on 100 weight% of the bimetallic cyanide (DMC) catalyst. Claim 11 A method for preparing a dimetallic cyanide (DMC) catalyst comprising: (a1) mixing and reacting a metal salt, (a2) a metal cyanide salt, and (B) an organic complex ligand in a solvent; and after the reaction, adding (C) a polysiloxane polyol to further react, wherein (C) the polysiloxane-containing polyol is represented by the following Chemical Formula 5 or the following Chemical Formula 6: [Chemical Formula 5] (wherein in the above formula 5, R1 and R8 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, m1 and n1 are each independently integers from 1 to 4, R2 and R7 are the same or different alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, and R3, R4, R5 and R6 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or It is an alkylthio group or an arylthio group, where l1 is a number between 1 and 300. [Chemical Formula 6] (wherein in the above formula 6, R9 and R18 are each independently hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, m2 and n2 are each independently integers from 1 to 4, R10 and R17 are each independently directly bonded or are identically or differently alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, R11 and R16 are identically or differently alkylene group, heteroalkylene group, cycloalkylene group, arylene group or heteroarylene group, and R12, R13, R14 and R15 are each independently It is hydrogen, halide, hydroxyl group, amino group, alkyl group, haloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aryloxy group, alkoxy group, alicyclic structure, heteroalicyclic structure or alkylthio group or arylthio group, and l2 is a number between 1 and 300.). Claim 12 delete Claim 13 A method for producing a bimetallic cyanide (DMC) catalyst according to claim 11, wherein the (C) polysiloxane-containing polyol has a weight-average molecular weight in the range of 300 to 10,000. Claim 14 delete Claim 15 delete Claim 16 A method for preparing a bimetallic cyanide (DMC) catalyst according to claim 11, wherein the organic complex ligand (B) is an alcohol complexing agent or comprises the same. Claim 17 A method for producing a polymer or polyol from one or more alkylene oxides and carbon dioxide in the presence of a bimetallic cyanide (DMC) catalyst according to claim 1.

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