CN114805781A - Poly (carbonate-ether) polyol and preparation method thereof - Google Patents

Poly (carbonate-ether) polyol and preparation method thereof Download PDF

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CN114805781A
CN114805781A CN202210548812.4A CN202210548812A CN114805781A CN 114805781 A CN114805781 A CN 114805781A CN 202210548812 A CN202210548812 A CN 202210548812A CN 114805781 A CN114805781 A CN 114805781A
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carbonate
polyol
ether
zinc
preparation
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CN114805781B (en
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秦玉升
古雅楠
索泓一
曲瑞
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Yantai University
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/32—General preparatory processes using carbon dioxide
    • C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's

Abstract

The invention discloses poly (carbonate-ether) polyol and a preparation method thereof, belonging to the technical field of polymer preparation. According to the preparation method, the bi-metal catalyst is designed and synthesized, and the bi-metal catalyst is used for catalyzing the epoxy compound and the chain transfer agent to perform polymerization reaction under the condition of carbon dioxide pressure to obtain the poly (carbonate-ether) polyol, so that the high-efficiency preparation of carbon dioxide-based polyols with different molecular weights is realized, the content of carbonate units in the prepared polyol is controllable, and the content of cyclic carbonate by-products is extremely low.

Description

Poly (carbonate-ether) polyol and preparation method thereof
Technical Field
The invention relates to poly (carbonate-ether) polyol and a preparation method thereof, belonging to the technical field of polymer preparation.
Background
The carbon dioxide-based polyol is a novel polyol which is synthesized by taking carbon dioxide as a raw material and has a carbonate bond and an ether bond structure, is mainly used as a raw material for polyurethane synthesis, has the advantages of greenness, environmental protection, low cost and the like due to the fact that the novel polyol is synthesized by taking cheap waste gas resource carbon dioxide as a raw material, is a novel polyol material with the most development potential, and is concerned by scientific research and industrial circles.
The most critical problem in the preparation of polyols from carbon dioxide and epoxy compounds is the design of the catalyst. Since the discovery of carbon dioxide copolymerization, catalyst research has been spotlighted as the most central factor limiting the development of this field, and many scientists have conducted a great deal of research to develop a series of catalyst systems. However, the preparation of carbon dioxide-based polyols requires the control of molecular weight by adding a chain transfer agent, so that the catalyst activity is more demanding, and the synthesis of high molecular weight carbon dioxide-based polymers was only possible at an early stage due to the low catalyst activity.
Until about 90 years in the last century, Double Metal Cyanide (DMC) catalysts applied in the field of alkylene oxide homopolymerization were applied to catalyze the copolymerization of carbon dioxide and alkylene oxide, so that the preparation of carbon dioxide-based polyols was successfully realized, and the rapid development of the field of synthesizing polymers by using carbon dioxide as a raw material was promoted. To date, the catalysts used in this field have been predominantly Double Metal Cyanide (DMC). Although the DMC system has the advantage of high activity compared with other catalyst systems, when the DMC system is used for catalyzing low-molecular-weight carbon dioxide-based polyol prepared by copolymerizing carbon dioxide and epoxide, the problems of difficult control of carbonate unit content (generally lower than 30 mol%), high content of cyclic carbonate serving as a byproduct and the like exist. Chinese patent application publication No. CN1060299A discloses preparation of aliphatic poly (carbonate-ether) polyol, which is prepared by using a high polymer supported bimetallic catalyst to catalyze the reaction of carbon dioxide and epoxide, but the obtained polymer has high ether segment content, and the carbonate content is lower than 30%. The Chinese patent with application publication number CN102206333A discloses a low molecular weight poly (carbonate-ether) polyol, a preparation method and application thereof, wherein a bimetallic complex catalyst is used for catalyzing carbon dioxide and propylene oxide to copolymerize to prepare the poly (carbonate-ether) polyol, the content of carbonate is increased to 45-60%, the content of ether segments is still higher, and the cyclic carbonate byproduct in the product reaches 3%.
The presence of cyclic by-products in the polyol product can affect the performance of the further prepared polyurethane material, so that the cyclic by-products must be removed in the production process, and the energy consumption in the purification process is greatly increased due to the high boiling point of the cyclic carbonate. Therefore, if an improved catalyst can be prepared, the content of the polycarbonate of the polyol can be controlled, and the cyclic by-products can be controlled to a lower level, the performance and the quality of the carbon dioxide-based polyol can be improved, and the scale application of the carbon dioxide-based polyol can be promoted.
Disclosure of Invention
In order to solve the technical problems, the invention provides a poly (carbonate-ether) polyol and a preparation method thereof, which can realize the high-efficiency preparation of carbon dioxide-based polyols with different molecular weights by the design and synthesis of a catalyst, and the prepared polyol has controllable carbonate unit content and extremely low content of cyclic carbonate by-products.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a bimetallic catalyst, which comprises the following steps:
(1) dissolving a metal cyanide complex compound by using a solvent, and stirring to obtain a metal cyanide complex compound solution S1;
(2) dissolving metal zinc salt and trace metal salt by using a solvent, and stirring to obtain a solution S2;
(3) placing the solution S2 in a carbon dioxide atmosphere, pressurizing, injecting the metal cyanide complex solution S1, stirring, centrifuging, pulping and washing to obtain a precipitate;
(4) and drying the precipitate in vacuum to constant weight to obtain the bimetallic catalyst.
Further, the pulping is to use poor solvent of the precipitate to stir the centrifuged precipitate into paste, and aims to wash away the solvent used in the reaction process and unreacted raw materials.
Further, the molar ratio of the metal cyanide complex to the metal zinc salt is 1: 1.5-10, and the molar ratio of the metal cyanide complex to the trace metal salt is 50-5000: 1.
Further, the metal cyanide complex is a water-soluble metal hydride, preferably one or more of potassium cobalt cyanide, potassium hexacyanoferrate and potassium hexacyanoruthenium (II), more preferably one or more of potassium cobalt cyanide and potassium hexacyanoferrate.
Further, the metal zinc salt is one or more of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate and zinc sulfate, preferably one or more of zinc chloride, zinc benzoate, zinc nitrate and zinc sulfate, and more preferably one or more of zinc chloride, zinc nitrate and zinc sulfate.
Further, the trace metal salt is one or more of zirconium chloride, zirconium acetylacetonate, ammonium zirconium carbonate, zirconium trifluoroacetylacetonate, cerium (III) nitrate hexahydrate, cerium bromide, cerium sulfate, cerous sulfate, ammonium cerium nitrate, cerium chloride, ruthenium trichloride, ruthenium acetylacetonate, indium trichloride, indium acetate, indium chloride, indium (III) nitrate hydrate, indium sulfate, cesium chloride, cesium oxalate, cesium nitrate, and cesium sulfate, and the trace metal salt can provide oxygen defects or metal defects, but the solubility of the trace metal salt is not a necessary factor for influencing the catalyst activity, and the insoluble or poorly soluble metal salt can also improve the performance of the bimetallic catalyst on the premise of providing defect sites.
Further, the solvent in the step (1) and the step (2) is deionized water or a mixed solvent composed of deionized water and alcohols and ether solvents in any proportion, wherein the alcohols are one or more of n-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, ethylene glycol and butanediol; the ethers are one or more of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, glycerol, dimethyl ether, tetrahydrofuran and 1, 4-epoxy hexacyclic ring.
Further, the mass ratio of the metal cyanide complex to the solvent in the step (1) is 0.01-20: 1, the mass ratio of the metal zinc salt to the solvent in the step (2) is 0.01-10: 1.
further, the stirring time in the step (1) is 0.5-24 hours, the temperature is 20-120 ℃, the stirring time in the step (2) is 0.5-24 hours, the temperature is 0-120 ℃, the pressurizing pressure in the step (3) is 0.1-15 MPa, and the temperature is 20-150 ℃.
Further, the injection rate of the metal cyanide complex solution S1 in step (3) is 1mL/min to 500 mL/min.
The invention also provides the bimetallic catalyst prepared by the preparation method.
The invention also provides a preparation method of the poly (carbonate-ether) polyol, which comprises the following steps: and catalyzing the epoxy compound and the chain transfer agent to perform polymerization reaction by using the bimetallic catalyst under the condition of carbon dioxide pressure to obtain the poly (carbonate-ether) polyol.
Further, the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexene oxide, cyclopentane epoxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide and 4-vinyl-1, 2-cyclohexene oxide; the chain transfer agent is one or more of water, small molecular alcohol, phenol, mercaptan, carboxylic acid, hydroxy acid and oligomer containing hydroxyl.
Further, the small molecular alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 1, 5-pentanediol, 1, 5-hexanediol, 1, 6-hexanediol, octanediol, decanediol, 1, 3-cyclopentanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, 1, 2-cyclohexanedimethanol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, trimethylolethane, trimethylolpropane, glycerol, 1,2, 4-butanetriol, polyestertriol or pentaerythritol; the phenol is preferably catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylenebiphenol, 4' - (2-methylpropylene) biphenol, 4- (2-ethylhexylene) biphenol, 2 '-methylenebiphenol, or 2,2' - (1, 2-cyclohexanediyl-dinitrosopropylene) biphenol; the thiol is preferably methyl mercaptan, dithiol or an oligomeric polythiol; the carboxylic acid is preferably malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, terephthalic acid, phthalic acid, isophthalic acid, maleic acid or oleic acid; the hydroxy acid is preferably lactic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxysuccinic acid, tartaric acid, citric acid or salicylic acid.
The mass ratio of the bimetallic catalyst to the epoxide is 1 (5000-2000000), preferably 1 (50000-2000000), more preferably 1 (1000000-2000000), and the molar ratio of the epoxide to the chain transfer agent is 100: 1-12.
Further, the pressure is 0.1-12 MPa, preferably 1-6 MPa, and more preferably 3-5 MPa; the temperature of the polymerization reaction is 20-150 ℃, preferably 50-120 ℃, more preferably 60-100 ℃, and the time of the polymerization reaction is 0.5-48 h, preferably 2-12 h, more preferably 3-8 h.
The invention also provides the poly (carbonate-ether) polyol prepared by the preparation method.
The preparation of the poly (carbonate-ether) polyols of the present invention may be carried out in high pressure polymerization reactors of various sizes, preferably under constant pressure and continuous stirring, such as at a speed of 500 rpm. After the polymerization reaction is finished, cooling the polymerization kettle to room temperature, discharging residual carbon dioxide, washing the polymer obtained by the polymerization reaction with water or an alcohol solvent, and drying to obtain a carbon dioxide-based polyol crude product.
The invention discloses the following technical effects:
1) the poly (carbonate-ether) polyol prepared by the method has lower weight content of cyclic carbonate and higher content of carbonate units, and is adjustable between 42 and 86 percent. Therefore, the catalyst provided by the invention has higher catalytic activity and better product selectivity, and the content of the carbonate unit is controllable.
2) According to the preparation method of the poly (carbonate-ether) polyol, the activity of the catalyst can be regulated and controlled between 2.9-15.9 kg of polyol/g of catalyst according to different types and dosage of chain transfer agents used in the preparation process, the activity of the catalyst is obviously improved, and the main reasons can be summarized into two aspects: firstly, the bimetallic catalyst is prepared in the carbon dioxide atmosphere, and the carbon dioxide enables the surface of the catalyst to form a carboxyl carbonyl group in the reaction, so that the activation and the adsorption of the carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like contributes to the introduction of oxygen defects on the catalyst surface, and carbon dioxide is easily adsorbed to the surface having oxygen defects and passes through the carbon atomsThe atom is linked to an oxygen atom near the oxygen defect or one of its oxygen atoms is placed in an oxygen vacancy, whereby CO 2 The strong interaction between the oxygen atom in the (C) ═ O bond and the surface defect weakens to activate, so that the (C) ═ O bond is easier to break to accelerate the reaction. The two reasons are most intuitively shown as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the high-efficiency catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every intervening value, to the extent any stated or intervening value in a stated range, and every other stated or intervening value in that stated range, is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The raw materials used in the examples of the present invention were all commercially available.
In the embodiment of the present invention, "slurrying" means that the centrifuged precipitate is stirred into a paste by using a poor solvent for the precipitate, and the solvent used in the reaction process and unreacted raw materials are washed away. The specific types of metal cyanide complex, metal zinc salt, trace metal salt, epoxy compound, and chain transfer agent used in the examples of the present invention are all preferable.
The technical solution of the present invention is further illustrated by the following examples.
Example 1
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 200g of zinc chloride and 0.0466g of zirconium chloride in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 8MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 0.5h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) the precipitated product was vacuum dried at 45 ℃ to constant weight and ground to obtain 472g of a bimetallic catalyst (DMC-Zr).
The elemental analysis results were: 21.8 wt% of Zn; 11.2 wt% of Co; 0.0091 wt% of Zr; 28.9 wt% of C; 3.1 wt% of H; 15.9 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 26nm and a concentration PDI value of 0.125.
Example 2
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 230g of zinc nitrate and 0.177g of indium acetate in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 2 hours after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitate;
(4) the precipitated product was dried In vacuo at 45 ℃ to constant weight and ground to obtain 456g of a bimetallic catalyst (DMC-In-1).
The elemental analysis results were: 22.3 wt% of Zn; 11.5 wt% of Co; 0.028 wt% of In; 29.3 wt% of C; 3.5 wt% of H; 15.3 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 35nm and a concentration PDI value of 0.159.
Example 3
(1) Dissolving 329g of potassium hexacyanoferrate in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 220g of zinc bromide and 0.177g of indium acetate in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 2 hours after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitate;
(4) and (3) drying the precipitate product at 45 ℃ In vacuum to constant weight, and grinding to obtain 426g of a bimetallic catalyst (DMC-In-2).
The elemental analysis results were: 23.4 wt% of Zn; 11.9 wt% of Fe; 0.020 wt% of In; 27.8 wt% of C; 3.6 wt% of H; 17.2 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 33nm and a concentration PDI value of 0.187.
Example 4
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 2 hours at 40 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 200g of zinc chloride and 0.082g of cerium chloride in 300ml of deionized water, and stirring for 1h at 40 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 0.5MPa, controlling the temperature in the kettle to be 60 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reaction for 1h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) the precipitated product was dried in vacuo at 45 ℃ to constant weight and ground to obtain 469g of a bimetallic catalyst (DMC-Ce).
The elemental analysis results were: 22.7 wt% of Zn; 11.8 wt% of Co; 0.008 wt% of Ce; 28.1 wt% of C; 3.8 wt% of H; 15.0 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 27nm and a concentration PDI value of 0.102.
Example 5
(1) Dissolving 332g of potassium cobalt cyanide in 1000mL of deionized water, and stirring for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) dissolving 100g of zinc chloride, 100g of zinc acetylacetonate and 1.68g of cesium chloride in 300ml of deionized water, and stirring for 2 hours at the temperature of 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the kettle is in carbon dioxide atmosphere, pressurizing to 1MPa, controlling the temperature in the kettle to be 40 ℃, and injecting the solution S1 into the kettle at high pressure of 50mL/min through a plunger pumpIn the kettle solution S2, stirring and reacting for 4 hours after the injection is finished, decompressing the high-pressure kettle, centrifuging the product, and washing the product by tert-butyl alcohol slurry to obtain a precipitate product;
(4) and (3) drying the precipitated product in vacuum at the temperature of 45 ℃ to constant weight, and grinding to obtain 475g of bimetallic catalyst (DMC-Cs).
The elemental analysis results were: 20.5 wt% of Zn; 12.5 wt% of Co; 0.22 wt% of Cs; 26.3 percent by weight of C; 3.5 wt% of H; 16.8 wt% of N.
The particle size was analyzed by a Malvern laser particle sizer, which showed an average particle size of 34nm and a concentration PDI value of 0.156.
Examples 1 to 1
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 50mmol of dipropylene glycol and 2mol of propylene oxide were placed in a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 38.5g of poly (carbonate-ether) polyol, having a catalyst activity of 7.7kg of polyol/g of catalyst. The number average molecular weight of the polymer was 870g/mol as determined by gel permeation chromatography, and the molecular weight distribution was 1.09; 1H-NMR analysis showed 1.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 58%, and a titration hydroxyl value of 143.0.
Examples 1 to 2
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of 1, 4-cyclohexanediol and 2mol of propylene oxide are placed in a 500ml autoclave which has been freed from water and oxygen and is charged with CO 2 The reaction was stirred for 30h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, having a catalyst activity of 5.0kg polyol/g catalyst. The number average molecular weight of the polymer was 1200g/mol, molecular weight distribution was 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate produced as a by-product was 0.95%, and polyThe carbonate unit content of the compound was about 65% and the titration hydroxyl number was 92.8.
Examples 1 to 3
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 30mmol of 1, 2-cyclohexanedimethanol and 1mol of propylene oxide are placed in a 500ml autoclave previously subjected to a water and oxygen removal treatment, and CO is introduced 2 The reaction is stirred for 8 hours at the temperature of 80 ℃ until the pressure is 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 60g of poly (carbonate-ether) polyol, having a catalyst activity of 12kg polyol/g catalyst. The number average molecular weight of the polymer was 1890g/mol, the molecular weight distribution was 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 1.9% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 47%, and a titration hydroxyl value of 58.5.
Examples 1 to 4
5mg of the bimetallic catalyst DMC-In-1 prepared In example 2, 30mmol of hydroquinone and 2mol of propylene oxide are introduced into a 500ml autoclave previously freed from water and oxygen, and CO is introduced 2 The reaction was stirred for 8h at a pressure of 5MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, having a catalyst activity of 9.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1500g/mol, the molecular weight distribution was 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed 0.9% cyclic carbonate by-product, about 72% carbonate units in the polymer and a titration hydroxyl number of 77.4.
Examples 1 to 5
5mg of the bimetallic catalyst DMC-In-2 prepared In example 3, 50mmol of dipropylene glycol and 1mol of propylene oxide were placed In a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 6h at 50 ℃ until the pressure was 5 MPa. After the polymerization reaction is finished, cooling the reaction kettle to room temperature, slowly discharging carbon dioxide to obtainThe product of (2) was dried under vacuum to remove unreacted propylene oxide to give 18g of poly (carbonate-ether) polyol having a catalyst activity of 3.6kg polyol/g catalyst. The polymer had a number average molecular weight of 5200g/mol and a molecular weight distribution of 1.05 as determined by gel permeation chromatography; 1H-NMR analysis showed 0.75% cyclic carbonate by-product, about 55% carbonate units in the polymer and a titration hydroxyl number of 21.6.
Examples 1 to 6
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 10mmol of dipropylene glycol and 1mol of propylene oxide were placed in a 500ml autoclave previously subjected to a dehydration and deoxygenation treatment, and CO was charged 2 The reaction was stirred for 24h at a pressure of 2MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 33g of poly (carbonate-ether) polyol, having a catalyst activity of 6.6kg of polyol/g of catalyst. The number average molecular weight of the polymer is 3200g/mol and the molecular weight distribution is 1.04 by gel permeation chromatography; 1H-NMR analysis showed 1.2% cyclic carbonate by-product, a carbonate unit content in the polymer of about 64%, and a titration hydroxyl value of 34.0.
Examples 1 to 7
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 20mmol of dipropylene glycol and 1mol of propylene oxide were placed in a 500ml autoclave previously subjected to a dehydration and deoxygenation treatment, and CO was charged 2 The reaction was stirred for 4h at 85 ℃ until the pressure was 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, having a catalyst activity of 9.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 2400g/mol, as determined by gel permeation chromatography, and the molecular weight distribution was 1.03; 1H-NMR analysis showed 1.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 86%, and a titration hydroxyl value of 146.5.
Examples 1 to 8
5mg of the bimetallic catalyst prepared in example 5DMC-Cs, 5mmol dipropylene glycol and 1mol propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal in advance, and CO is charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 75 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 18g of poly (carbonate-ether) polyol, having a catalyst activity of 3.6kg polyol/g catalyst. The number average molecular weight of the polymer is 3600g/mol and the molecular weight distribution is 1.08 by gel permeation chromatography; 1H-NMR analysis showed 2.9% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 42%, and a titration hydroxyl value of 32.5.
Examples 1 to 9
5mg of the bimetallic catalyst DMC-Cs prepared in example 5, 20mmol of dipropylene glycol and 1mol of propylene oxide (0.5mol) and cyclohexene oxide (0.5mol) were placed in a 500ml autoclave previously subjected to a water-removing and oxygen-removing treatment, and CO was charged 2 The reaction was stirred for 10h at a pressure of 4MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 32g of poly (carbonate-ether) polyol, having a catalyst activity of 6.4kg polyol/g catalyst. The number average molecular weight of the polymer was 1600g/mol, the molecular weight distribution was 1.06, as determined by gel permeation chromatography; 1H-NMR analysis showed 1.1% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 82%, and a titration hydroxyl value of 70.2.
Examples 1 to 10
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of sebacic acid and 1mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 3h at a pressure of 2MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 27g of poly (carbonate-ether) polyol having a catalyst activity of 5.4kg polyol/g catalyst. The determination is carried out by gel permeation chromatographyThe number average molecular weight of the polymer is 1800g/mol, and the molecular weight distribution is 1.12; 1H-NMR analysis showed 1.50% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 79%, and a titration hydroxyl value of 62.
Examples 1 to 11
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of trimesic acid and 1mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 4h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, with a catalyst activity of 5kg polyol/g catalyst. The number average molecular weight of the polymer was 1300g/mol and the molecular weight distribution was 1.03 as determined by gel permeation chromatography; 1H-NMR analysis showed 2.30% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 70%, and a titration hydroxyl value of 126.0.
Examples 1 to 12
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 20mmol of pentaerythritol and 2mol of propylene oxide are placed in a 500ml autoclave which has been previously freed from water and oxygen and is charged with CO 2 The reaction was stirred for 4h at a pressure of 3MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 29g of poly (carbonate-ether) polyol having a catalyst activity of 5.8kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1500g/mol, the molecular weight distribution was 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 2.60% of cyclic carbonate by-product, about 63% of carbonate units in the polymer and a titration hydroxyl number of 145.5.
Examples 1 to 13
5mg of the bimetallic catalyst DMC-Ce prepared in example 4, 10mmol of citric acid and 1mol of propylene oxide are added into a 500ml autoclave which is previously subjected to water removal and oxygen removal treatment, and CO is charged 2 Controlling the temperature until the pressure is 2MPaThe reaction was stirred at 80 ℃ for 4 h. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, thereby obtaining 27g of poly (carbonate-ether) polyol having a catalyst activity of 5.4kg polyol/g catalyst. The number average molecular weight of the polymer was 2500g/mol, the molecular weight distribution was 1.09 by gel permeation chromatography; 1H-NMR analysis showed 2.2% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 68%, and a titration hydroxyl value of 89.9.
Examples 1 to 14
5mg of the bimetallic catalyst DMC-In-1 prepared In example 2, 10mmol of phloroglucinol and 1mol of propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to water removal and oxygen removal In advance, and CO is filled into the kettle 2 The reaction was stirred for 4h at a pressure of 4MPa and a temperature of 70 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 32g of poly (carbonate-ether) polyol, having a catalyst activity of 6.4kg polyol/g catalyst. The number average molecular weight of the polymer was 3300g/mol, molecular weight distribution 1.08, as determined by gel permeation chromatography; 1H-NMR analysis showed 2.15% of cyclic carbonate by-product, a carbonate unit content in the polymer of about 64%, and a titration hydroxyl value of 51.0.
Comparative example 1
Step (1) the same as in preparation example 1;
(2) dissolving 200g of zinc chloride in 300ml of deionized water, and stirring for 2 hours at 45 ℃ to prepare a solution S2;
(3) adding the solution S2 into a high-pressure reaction kettle, and replacing CO in the reaction kettle 2 Ensuring that the inside of the kettle is in a carbon dioxide atmosphere, pressurizing to 15MPa, controlling the temperature in the kettle to be 20 ℃, injecting the solution S1 into the solution S2 of the high-pressure kettle at the speed of 50mL/min through a plunger pump, stirring for reacting for 0.5h after the injection is finished, relieving the pressure of the high-pressure kettle, and centrifuging and washing a product by tert-butyl alcohol pulping to obtain a precipitated product;
(4) and (3) drying the precipitated product at 45 ℃ in vacuum to constant weight, and grinding to obtain 1465 g of the bimetallic catalyst DMC-DMC.
The elemental analysis results were: 22.5 wt% of Zn; 10.8 wt% of Co; 27.9 wt% of C; 3.3 wt% of H; 16.2 wt% of N. The particle size was analyzed by a Malvern laser particle sizer, having an average particle size of 29nm and a concentration PDI value of 0.106.
Comparative examples 1 to 1
5mg of the bimetallic catalyst DMC-1 prepared in comparative example 1, 50mmol of dipropylene glycol and 2mol of propylene oxide were charged into a 500ml autoclave previously subjected to water and oxygen removal treatment (polymerization conditions were the same as in example 1, only the catalyst was changed), and CO was charged 2 The reaction was stirred for 4h at a pressure of 2MPa and a temperature of 80 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 10.5g of poly (carbonate-ether) polyol, having a catalyst activity of 2.1kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1050g/mol and the molecular weight distribution was 1.12 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate by-product was 3.6%, the carbonate unit content in the polymer was about 41%, and the titration hydroxyl value was 107.5.
Comparative examples 1 to 2
5mg of the bimetallic catalyst DMC-In-1 prepared In preparation example 2, 30mmol of hydroquinone and 2mol of propylene oxide were charged into a 500ml autoclave which had been previously freed from water and oxygen (polymerization conditions were the same as In example 4, only the catalyst was changed), CO was charged 2 The reaction was stirred for 8h at a pressure of 5MPa and a temperature of 60 ℃. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 9.8g of poly (carbonate-ether) polyol, having a catalyst activity of 1.96kg of polyol/g of catalyst. The number average molecular weight of the polymer was 950g/mol, the molecular weight distribution was 1.09, as determined by gel permeation chromatography; the 1H-NMR analysis showed that the cyclic carbonate by-product was 3.9%, the carbonate unit content in the polymer was about 39%, and the titration hydroxyl value was 118.
Comparative examples 1 to 3
5mg of the bimetallic catalyst DMC-1 prepared in comparative example 1, 20mmol of dipropylene glycol and 1mol of epoxyPropane was charged into a 500ml autoclave previously subjected to water removal and oxygen removal (polymerization conditions were the same as in example 7, only the catalyst was changed), CO was introduced 2 The reaction was stirred for 4h at 85 ℃ until the pressure was 2 MPa. After the polymerization reaction was completed, the reaction kettle was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was vacuum-dried to remove unreacted propylene oxide, to obtain 10.6g of poly (carbonate-ether) polyol, having a catalyst activity of 2.12kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1200g/mol, molecular weight distribution was 1.15 as determined by gel permeation chromatography; 1H-NMR analysis showed that the cyclic carbonate by-product was 8.9%, the carbonate unit content in the polymer was about 32%, and the titration hydroxyl value was 93.5.
From the above, it can be seen that, according to the different types and amounts of the chain transfer agents used in the preparation process, the catalyst activity can be regulated and controlled between 2.9-15.9 kg of polyol/g of catalyst, and the catalyst activity is obviously improved, and the main reasons can be summarized into two aspects: firstly, the bimetallic catalyst is prepared in the carbon dioxide atmosphere, and the carbon dioxide enables the surface of the catalyst to form a carboxyl carbonyl group in the reaction, so that the activation and the adsorption of the carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like contributes to the introduction of oxygen defects on the catalyst surface, carbon dioxide is easily adsorbed to the presence of surface oxygen defects, and CO is bonded to an oxygen atom in the vicinity of the oxygen defects through a carbon atom or one of its oxygen atoms is placed in an oxygen vacancy, whereby CO 2 The strong interaction between the oxygen atom in the (C) ═ O bond and the surface defect weakens to activate, so that the (C) ═ O bond is easier to break to accelerate the reaction. The two reasons are most intuitively shown as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the high-efficiency catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (10)

1. A preparation method of a bimetallic catalyst is characterized by comprising the following steps:
(1) dissolving a metal cyanide complex compound by using a solvent, and stirring to obtain a metal cyanide complex compound solution S1;
(2) dissolving metal zinc salt and trace metal salt by using a solvent, and stirring to obtain a solution S2;
(3) placing the solution S2 in a carbon dioxide atmosphere, pressurizing, injecting the metal cyanide complex solution S1, stirring, centrifuging, pulping and washing to obtain a precipitate;
(4) and drying the precipitate in vacuum to constant weight to obtain the bimetallic catalyst.
2. The method according to claim 1, wherein the molar ratio of the metal cyanide complex to the metal zinc salt is 1:1.5 to 10, and the molar ratio of the metal cyanide complex to the trace metal salt is 50 to 5000: 1.
3. The production method according to claim 1, wherein the metal cyanide complex is a water-soluble metal cyanide complex; the metal zinc salt is one or more of zinc chloride, zinc bromide, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc nitrate and zinc sulfate; the trace metal salt is one or more of zirconium chloride, zirconium acetylacetonate, ammonium zirconium carbonate, zirconium trifluoroacetylacetonate, cerium (III) nitrate hexahydrate, cerium bromide, cerium sulfate, cerous sulfate, ammonium ceric nitrate, cerium chloride, ruthenium trichloride, ruthenium acetylacetonate, indium trichloride, indium acetate, indium chloride, indium (III) nitrate hydrate, indium sulfate, cesium chloride, cesium oxalate, cesium nitrate and cesium sulfate.
4. The method according to claim 1, wherein the stirring time in step (1) is 0.5 to 24 hours and the temperature is 20 to 120 ℃, the stirring time in step (2) is 0.5 to 24 hours and the temperature is 0 to 120 ℃, the pressure for pressurizing in step (3) is 0.1 to 15MPa and the temperature is 20 to 150 ℃.
5. A bimetallic catalyst prepared by the preparation method of any one of claims 1 to 4.
6. A method of preparing a poly (carbonate-ether) polyol, comprising the steps of: catalyzing the polymerization of an epoxy compound and a chain transfer agent with the bimetallic catalyst of claim 5 under carbon dioxide pressure conditions to provide the poly (carbonate-ether) polyol.
7. The preparation method according to claim 6, wherein the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-epoxybutane, cyclohexene oxide, cyclopentane epoxide, chloropropylene oxide, glycidyl methacrylate ether, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide, 4-vinyl-1, 2-epoxycyclohexane; the chain transfer agent is one or more of water, small molecular alcohol, phenol, mercaptan, carboxylic acid, hydroxy acid and oligomer containing hydroxyl.
8. The preparation method of claim 6, wherein the mass ratio of the bimetallic catalyst to the epoxide is 1 (5000-2000000), and the molar ratio of the epoxide to the chain transfer agent is 100: 1-12.
9. The preparation method according to claim 6, wherein the pressure is 0.1 to 12MPa, the temperature of the polymerization reaction is 20 to 150 ℃, and the time is 0.5 to 48 hours.
10. A poly (carbonate-ether) polyol prepared by the method of any one of claims 6 to 9.
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