CN114805781B - Poly (carbonate-ether) polyol and preparation method thereof - Google Patents

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

Info

Publication number
CN114805781B
CN114805781B CN202210548812.4A CN202210548812A CN114805781B CN 114805781 B CN114805781 B CN 114805781B CN 202210548812 A CN202210548812 A CN 202210548812A CN 114805781 B CN114805781 B CN 114805781B
Authority
CN
China
Prior art keywords
carbonate
polyol
ether
zinc
carbon dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202210548812.4A
Other languages
Chinese (zh)
Other versions
CN114805781A (en
Inventor
秦玉升
古雅楠
索泓一
曲瑞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yantai University
Original Assignee
Yantai University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yantai University filed Critical Yantai University
Priority to CN202210548812.4A priority Critical patent/CN114805781B/en
Publication of CN114805781A publication Critical patent/CN114805781A/en
Application granted granted Critical
Publication of CN114805781B publication Critical patent/CN114805781B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Toxicology (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The application discloses poly (carbonate-ether) polyol and a preparation method thereof, and belongs to the technical field of polymer preparation. According to the preparation method, through design synthesis of the bimetallic catalyst, under the condition of carbon dioxide pressure, the bimetallic catalyst is used for catalyzing the polymerization reaction of the epoxy compound and the chain transfer agent to obtain the poly (carbonate-ether) polyol, so that efficient preparation of the carbon dioxide-based polyol with different molecular weights is realized, the content of carbonate units in the prepared polyol is controllable, and the content of cyclic carbonate byproducts is extremely low.

Description

Poly (carbonate-ether) polyol and preparation method thereof
Technical Field
The application 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 with a carbonate bond and an ether bond structure, which is synthesized by taking carbon dioxide as a raw material, is mainly used as a raw material for polyurethane synthesis, and has the advantages of environment friendliness, environmental protection, low cost and the like due to the fact that the carbon dioxide is taken as an inexpensive waste gas resource, and is a novel polyol material with the most development potential, and is concerned by scientific research and industry.
The most critical problem in the preparation of polyols from carbon dioxide and epoxy compounds is the design of the catalyst. Since carbon dioxide copolymerization reaction was found, catalyst research has been attracting attention as a factor limiting the most central development of this field, for which many studies have been conducted by multi-national scientists, thereby developing a series of catalyst systems. However, the preparation of carbon dioxide based polyols requires the molecular weight control achieved by the addition of chain transfer agents, and therefore, the catalyst activity requirements are higher, and only high molecular weight carbon dioxide based polymer synthesis can be achieved, due to the lower catalyst activity in the early stages.
Until about 90 s of the last century, double Metal Cyanide (DMC) catalysts applied in the field of olefin oxide homopolymerization were applied to catalyze copolymerization of carbon dioxide and olefin oxide, successfully realizing preparation of carbon dioxide-based polyol and promoting rapid development of the field of synthesizing high polymer from carbon dioxide as a raw material. Up to now, catalysts used in this field have been mainly Double Metal Cyanide (DMC). Although DMC systems have the advantage of high activity compared to other catalyst systems, they suffer from the problems of difficult control of carbonate unit content (typically less than 30 mole percent), higher levels of by-product cyclic carbonates, and the like when catalyzing low molecular weight carbon dioxide-based polyols prepared by copolymerizing carbon dioxide with epoxides. Chinese patent application publication No. CN1060299a discloses the preparation of aliphatic poly (carbonate-ether) polyols, which are prepared by using a high polymer supported bimetallic catalyst to catalyze the reaction of carbon dioxide with epoxide, but the obtained polymer has a high ether segment content and a carbonate content of less than 30%. Chinese patent application publication No. CN102206333a discloses a low molecular weight poly (carbonate-ether) polyol, a preparation method and use thereof, wherein a bimetallic complex catalyst is used to catalyze copolymerization of carbon dioxide and propylene oxide to prepare poly (carbonate-ether) polyol, the carbonate content is increased to 45% -60%, the ether segment content is still higher, and the cyclic carbonate byproduct in the product reaches 3%.
The presence of cyclic by-products in the polyol product affects the properties of the further prepared polyurethane material and must therefore be removed during production, whereas the energy consumption of the purification stage is greatly increased due to the higher boiling point of the cyclic carbonate. Therefore, if an improved catalyst can be prepared, the control of the content of polyol carbonate is realized, and the cyclic byproducts are controlled at a lower level, the performance and quality of the carbon dioxide-based polyol can be improved, and the large-scale application of the carbon dioxide-based polyol is promoted.
Disclosure of Invention
In order to solve the technical problems, the application provides a poly (carbonate-ether) polyol and a preparation method thereof, and the high-efficiency preparation of the carbon dioxide-based polyol with different molecular weights can be realized through the design and synthesis of a catalyst, wherein the content of carbonate units in the prepared polyol is controllable, and the content of cyclic carbonate byproducts is extremely low.
In order to achieve the above object, the present application provides the following solutions:
the application provides a preparation method of a bimetallic catalyst, which comprises the following steps:
(1) Dissolving metal cyanide complex with solvent, stirring to obtain metal cyanide complex solution S1;
(2) Dissolving zinc metal 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, and pulping to obtain a precipitate;
(4) And drying the precipitate in vacuum to constant weight to obtain the bimetallic catalyst.
Further, the slurrying is to stir the centrifuged precipitate into paste by using a poor solvent for the precipitate, and aims to wash off 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 hexacyanoferrite and potassium hexacyanoruthenium (II) carboxylate, more preferably one or more of potassium cobalt cyanide and potassium hexacyanoferrite.
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, 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, zirconium ammonium carbonate, zirconium trifluoroacetylacetonate, cerium (III) nitrate hexahydrate, cerium bromide, cerium sulfate, cerium ammonium 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 activity of the catalyst, and the insoluble or poorly soluble metal salt can also realize improvement of the performance of the bimetallic catalyst on the premise of providing defective sites.
Further, the solvent in the step (1) and the step (2) is deionized water or a mixed solvent consisting of deionized water and alcohol and ether solvents in any proportion, wherein the alcohol is one or more of n-butanol, isobutanol, tertiary butanol, 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, in the step (1), the mass ratio of the metal cyanide complex to the solvent 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 h, the temperature is 20-120 ℃, the stirring time in the step (2) is 0.5-24 h, 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 the step (3) is 1mL/min to 500mL/min.
The application also provides a bimetallic catalyst prepared by the preparation method.
The application also provides a preparation method of the poly (carbonate-ether) polyol, which comprises the following steps: under the condition of carbon dioxide pressure, catalyzing the epoxy compound and the chain transfer agent to carry out polymerization reaction by using the bimetallic catalyst to obtain the poly (carbonate-ether) polyol.
Further, the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-epoxybutane, epoxycyclohexane, epoxycyclopentane, epoxychloropropane, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide and 4-vinyl-1, 2-epoxycyclohexane; the chain transfer agent is one or more of water, small molecular alcohols, phenols, thiols, carboxylic acids, hydroxy acids and oligomers containing hydroxy groups.
Further, the small molecule alcohol is ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 2-butanediol, 1, 3-butanediol, 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, polyester triol or pentaerythritol; the phenol is preferably catechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 4 '-ethylenebisphenol, 4' - (2-methylpropylene) bisphenol, 4- (2-ethylhexyl) bisphenol, 2 '-methylenebisphenol, or 2,2' - (1, 2-cyclohexanediyl-dinitroso ethylene) bisphenol; the thiol is preferably methyl mercaptan, dithiol or 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.
Further, 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 to 12MPa, preferably 1 to 6MPa, more preferably 3 to 5MPa; the polymerization reaction temperature is 20 to 150 ℃, preferably 50 to 120 ℃, more preferably 60 to 100 ℃, and the polymerization reaction time is 0.5 to 48 hours, preferably 2 to 12 hours, more preferably 3 to 8 hours.
The application also provides the poly (carbonate-ether) polyol prepared by the preparation method.
The preparation of the poly (carbonate-ether) polyols of the present application may be carried out in high pressure polymerization reactors of various sizes, preferably under constant pressure and continuous stirring, such as stirring at a speed of 500 rpm. After the polymerization reaction is finished, cooling the polymerization kettle to room temperature, discharging residual carbon dioxide, washing a polymer obtained by the polymerization reaction with water or an alcohol solvent, and drying to obtain a crude product of the carbon dioxide-based polyol.
The application discloses the following technical effects:
1) The cyclic carbonate in the poly (carbonate-ether) polyol prepared by the application has lower weight content, higher carbonate unit content and adjustable content of 42-86 percent. Therefore, the catalyst provided by the application has higher catalytic activity and better product selectivity, and the content of carbonate units is controllable.
2) According to the preparation method of the poly (carbonate-ether) polyol, according to the different types and the different amounts of chain transfer agents used in the preparation process, the catalyst activity can be regulated and controlled between 2.9 kg polyol and 15.9kg polyol/g catalyst, the catalyst activity is obviously improved, and the main reasons can be summarized as follows: firstly, the bimetallic catalyst is prepared in the carbon dioxide atmosphere, and carbon dioxide enables carboxyl carbonyl groups to be formed on the surface of the catalyst in the reaction, so that the activation and adsorption of carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like helps to introduce oxygen defects on the surface of the catalyst, carbon dioxide is easily adsorbed to the surface where the oxygen defects exist, and carbon atoms are connected with oxygen atoms near the oxygen defects or one oxygen atom of the carbon atoms is placed in the oxygen vacancies, thereby CO 2 The strong interaction of the oxygen atoms in (a) and the surface defects weakens the C=O bond so as to realize activation, so that the C=O bond is easier to break and the reaction is accelerated. The two reasons are most intuitively expressed as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the efficient catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
Detailed Description
Various exemplary embodiments of the application will now be described in detail, which should not be considered as limiting the application, but rather as more detailed descriptions of certain aspects, features and embodiments of the application.
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 application. In addition, for numerical ranges in this disclosure, it is understood that each intermediate value between the upper and lower limits of the ranges is also specifically disclosed. Every smaller range between any stated value or stated range, and any other stated value or intermediate value within the stated range, is also encompassed within the application. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless otherwise defined, 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 application 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 application. All documents mentioned in this specification are incorporated by reference 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 application described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those skilled in the art from consideration of the specification of the present application. The specification and examples of the present application are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are intended to be inclusive and mean an inclusion, but not limited to.
The raw materials used in the examples of the present application are commercially available.
In the embodiment of the application, "slurrying" refers to stirring the centrifuged precipitate into paste by using a poor solvent for the precipitate, and aims to wash off the solvent and unreacted raw materials used in the reaction process. The specific types of metal cyanide complexes, metal zinc salts, trace metal salts, epoxy compounds, and chain transfer agents used in the examples of the present application are all preferred.
The technical scheme of the application is further described by the following examples.
Example 1
(1) 332g of potassium cobalt cyanide is dissolved in 1000mL of deionized water, and stirred for 4 hours at 45 ℃ to prepare metal cyanide complex solution S1;
(2) 200g of zinc chloride and 0.0466g of zirconium chloride are dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 40 ℃ after pressurizing to 8MPa, injecting the solution S1 into the autoclave solution S2 at a speed of 50mL/min through a plunger pump, stirring for reaction for 0.5h after the injection is finished, decompressing the autoclave, and centrifuging the product and washing the product by using tert-butyl alcohol to obtain a precipitate product;
(4) The precipitated product was dried under vacuum at 45℃to a constant weight, and ground to obtain 472g of a bimetallic catalyst (DMC-Zr).
The elemental analysis results were: 21.8wt% of Zn; 11.2wt% of Co; 0.0091wt% of Zr; 28.9wt% of C; 3.1wt% of H; 15.9wt% of N.
Particle size was analyzed by a Markov laser particle sizer, with an average particle size of 26nm and a concentration PDI value of 0.125.
Example 2
(1) 332g of potassium cobalt cyanide is dissolved in 1000mL of deionized water, and stirred for 4 hours at 45 ℃ to prepare metal cyanide complex solution S1;
(2) 230g of zinc nitrate and 0.177g of indium acetate are dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 40 ℃ after the pressure is increased to 1MPa, injecting the solution S1 into the autoclave solution S2 at the speed of 50mL/min through a plunger pump, stirring for reaction for 2 hours after the injection is finished, decompressing the autoclave, and obtaining a precipitate product through centrifugation and tertiary butanol pulping washing of the product;
(4) The precipitated product was dried under vacuum at 45℃to a constant weight, and ground to obtain 456g of a bimetallic catalyst (DMC-In-1).
The elemental analysis results were: 22.3wt% of Zn; 11.5wt% of Co; 0.028wt% of In; 29.3wt% of C; 3.5wt% of H; 15.3wt% of N.
Particle size was analyzed by a Markov laser particle sizer, with an average particle size of 35nm and a concentration PDI of 0.159.
Example 3
(1) 329g of potassium hexacyanoferrate is dissolved in 1000mL of deionized water and stirred for 4 hours at 45 ℃ to prepare a metal cyanide complex solution S1;
(2) 220g of zinc bromide and 0.177g of indium acetate are dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 40 ℃ after the pressure is increased to 1MPa, injecting the solution S1 into the autoclave solution S2 at the speed of 50mL/min through a plunger pump, stirring for reaction for 2 hours after the injection is finished, decompressing the autoclave, and obtaining a precipitate product through centrifugation and tertiary butanol pulping washing of the product;
(4) The precipitated product was dried under vacuum at 45℃to a constant weight, and then ground to obtain 426g of a bimetallic catalyst (DMC-In-2).
The elemental analysis results were: 23.4wt% of Zn; 11.9wt% of Fe; 0.020% by weight of In; 27.8wt% of C; 3.6wt% of H; 17.2wt% of N.
Particle size was analyzed by a Markov laser particle sizer, which had an average particle size of 33nm and a concentration PDI value of 0.187.
Example 4
(1) 332g of potassium cobalt cyanide is dissolved in 1000mL of deionized water and stirred for 2 hours at 40 ℃ to prepare a metal cyanide complex solution S1;
(2) 200g of zinc chloride and 0.082g of cerium chloride are dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 60 ℃ after pressurizing to 0.5MPa, injecting the solution S1 into the autoclave solution S2 at the speed of 50mL/min through a plunger pump, stirring for reaction for 1h after the injection is finished, decompressing the autoclave, and centrifuging the productWashing the tertiary butanol slurry to obtain a precipitate;
(4) The precipitated product was dried under vacuum at 45℃to a constant weight, and was ground to obtain 469g of a bimetallic catalyst (DMC-Ce).
The elemental analysis results were: 22.7wt% of Zn; 11.8wt% of Co; 0.008 wt.% Ce; 28.1wt% of C; 3.8wt% of H; 15.0wt% of N.
Particle size was analyzed by a Markov laser particle sizer, with an average particle size of 27nm and a concentration PDI value of 0.102.
Example 5
(1) 332g of potassium cobalt cyanide is dissolved in 1000mL of deionized water, and stirred for 4 hours at 45 ℃ to prepare metal cyanide complex solution S1;
(2) 100g of zinc chloride, 100g of zinc acetylacetonate and 1.68g of cesium chloride are dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 40 ℃ after the pressure is increased to 1MPa, injecting the solution S1 into the autoclave solution S2 at the speed of 50mL/min through a plunger pump, stirring for reaction for 4 hours after the injection is finished, decompressing the autoclave, and obtaining a precipitate product through centrifugation and tertiary butanol pulping washing of the product;
(4) The precipitated product was dried under vacuum at 45℃to a constant weight, and ground to give 475g of a bimetallic catalyst (DMC-Cs).
The elemental analysis results were: 20.5wt% of Zn; 12.5wt% of Co; 0.22wt% of Cs; 26.3wt% of C; 3.5wt% of H; 16.8wt% of N.
Particle size was analyzed by a malvern laser particle sizer, with an average particle size of 34nm and a concentration PDI value of 0.156.
Example 1-1
5mg of the bimetallic catalyst DMC-Zr prepared in example 1, 50mmol of dipropylene glycol and 2mol of propylene oxide were charged into a 500ml autoclave which had been previously subjected to dehydration and deoxidation treatment, and CO was charged 2 The reaction was stirred at 80℃until the pressure was 2MPa for 4 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, and the dioxide is slowly dischargedThe resulting product was dried under vacuum to remove unreacted propylene oxide to give 38.5g of poly (carbonate-ether) polyol with a catalyst activity of 7.7kg polyol/g catalyst. The number average molecular weight of the polymer was 870g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.09; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.2%, the carbonate unit content in the polymer was about 58%, and the titrimetric hydroxyl number was 143.0.
Examples 1 to 2
5mg of DMC-Zr, 20mmol of 1, 4-cyclohexanediol and 2mol of propylene oxide, which were the bimetallic catalyst prepared in example 1, were introduced into a 500ml autoclave which had been previously dehydrated and deoxygenated, and CO was charged 2 The reaction was stirred at 70℃until the pressure was 4MPa for 30 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, the catalyst activity was 5.0kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1200g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.05; the 1H-NMR analysis showed that the cyclic carbonate by-product was 0.95%, the carbonate unit content in the polymer was about 65%, and the titer was 92.8.
Examples 1 to 3
5mg of DMC-Zr, 30mmol of 1, 2-cyclohexanedimethanol and 1mol of propylene oxide, which were the bimetallic catalyst prepared in example 1, were introduced into a 500ml autoclave which had been previously dehydrated and deoxygenated, and CO was charged 2 The reaction was stirred at 80℃until the pressure was 2MPa for 8 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 60g of poly (carbonate-ether) polyol, the catalyst activity was 12kg polyol/g catalyst. The number average molecular weight of the polymer was 1890g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.08; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.9%, the carbonate unit content in the polymer was about 47%, and the titrimetric hydroxyl number was 58.5.
Examples 1 to 4
5mg is applied toThe bimetallic catalyst DMC-In-1 prepared In example 2, 30mmol of hydroquinone and 2mol of propylene oxide are added into a 500ml high-pressure reaction kettle which is subjected to dehydration and deoxidation treatment In advance, and CO is filled In 2 The reaction was stirred at 60℃until the pressure was 5MPa for 8 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, the catalyst activity was 9.6kg of polyol/g of catalyst. The polymer has a number average molecular weight of 1500g/mol and a molecular weight distribution of 1.05 as determined by gel permeation chromatography; the 1H-NMR analysis showed that the cyclic carbonate by-product was 0.9%, the carbonate unit content in the polymer was about 72%, and the titrimetric hydroxyl number was 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 charged into a 500ml autoclave which had been previously subjected to dehydration and deoxidation treatment, and CO was charged 2 The reaction was stirred at 50℃until the pressure was 5MPa for 6 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 18g of poly (carbonate-ether) polyol, the catalyst activity was 3.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 5200g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.05; the 1H-NMR analysis showed that the cyclic carbonate by-product was 0.75%, the carbonate unit content in the polymer was about 55%, and the titrimetric hydroxyl number was 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 added to a 500ml autoclave previously subjected to dehydration and deoxidation treatment, and CO was charged 2 The reaction was stirred at 70℃until the pressure was 2MPa for 24 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 33g of poly (carbonate-ether) polyol, the catalyst activity was 6.6kg of polyol/g of catalyst. By gel permeation chromatographyThe number average molecular weight of the polymer is 3200g/mol, and the molecular weight distribution is 1.04; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.2%, the carbonate unit content in the polymer was about 64%, and the titrimetric hydroxyl number was 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 added to a 500ml autoclave previously subjected to dehydration and deoxidation treatment, and CO was charged 2 The reaction was stirred at 85℃until the pressure was 2MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 48g of poly (carbonate-ether) polyol, the catalyst activity was 9.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 2400g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.03; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.2%, the carbonate unit content in the polymer was about 86%, and the titer hydroxyl number was 146.5.
Examples 1 to 8
5mg of the bimetallic catalyst DMC-Cs prepared in example 5, 5mmol of dipropylene glycol and 1mol of propylene oxide are added to a 500ml autoclave which had been previously dehydrated and deoxygenated, and CO is charged 2 The reaction was stirred at 75℃until the pressure was 2MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 18g of poly (carbonate-ether) polyol, the catalyst activity was 3.6kg of polyol/g of catalyst. The number average molecular weight of the polymer was 3600g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.08; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 2.9%, the carbonate unit content in the polymer was about 42%, and the titrimetric hydroxyl number was 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 (0.5 mol) and cyclohexene oxide (0.5 mol) were charged into a 500ml autoclave which had been previously subjected to dehydration and deoxidation treatment, and CO was charged 2 The reaction was stirred at 60℃until the pressure was 4MPa for 10 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 32g of poly (carbonate-ether) polyol, the catalyst activity was 6.4kg of polyol/g of catalyst. The polymer has a number average molecular weight of 1600g/mol and a molecular weight distribution of 1.06 as measured by gel permeation chromatography; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.1%, the carbonate unit content in the polymer was about 82%, and the titrimetric hydroxyl number was 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 added to a 500ml autoclave which has been previously treated with water and oxygen removal, and CO is charged 2 The reaction was stirred at 70℃until the pressure was 2MPa for 3 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 27g of poly (carbonate-ether) polyol, the catalyst activity was 5.4kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1800g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.12; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 1.50%, the carbonate unit content in the polymer was about 79%, and the titrimetric hydroxyl number was 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 added to a 500ml autoclave which has been previously dehydrated and deoxygenated, and CO is charged 2 The reaction was stirred at 70℃until the pressure was 4MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 25g of poly (carbonate-ether) polyol, the catalyst activity was 5kg of polyol/g of catalyst. The polymer has a number average molecular weight of 1300g/mol and a molecular weight distribution of 1.03 as measured by gel permeation chromatography; as a result of 1H-NMR analysis, it was found that the cyclic carbonate by-product was 2.30%, and the carbonate unit content in the polymer was about 70%The titrimetric hydroxyl number was 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 added to a 500ml autoclave which has been previously treated with water and oxygen removal, and CO is charged 2 The reaction was stirred at 80℃until the pressure was 3MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 29g of poly (carbonate-ether) polyol, the catalyst activity was 5.8kg of polyol/g of catalyst. The polymer has a number average molecular weight of 1500g/mol and a molecular weight distribution of 1.08 as measured by gel permeation chromatography; the 1H-NMR analysis showed that the cyclic carbonate by-product was 2.60%, the carbonate unit content in the polymer was about 63%, and the titrimetric hydroxyl number was 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 to a 500ml autoclave which has been previously dehydrated and deoxygenated, and CO is charged 2 The reaction was stirred at 80℃until the pressure was 2MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 27g of poly (carbonate-ether) polyol, the catalyst activity was 5.4kg of polyol/g of catalyst. The number average molecular weight of the polymer was 2500g/mol as determined by gel permeation chromatography, and the molecular weight distribution was 1.09; the 1H-NMR analysis showed that the cyclic carbonate by-product was 2.2%, and the carbonate unit content in the polymer was about 68%, and the titrimetric hydroxyl number was 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 to a 500ml autoclave which has been previously dehydrated and deoxygenated, and CO is charged 2 The reaction was stirred at 70℃until the pressure was 4MPa for 4 hours. After the polymerization reaction is finished, the reaction kettle is cooled to room temperature, carbon dioxide is slowly discharged, and the obtained product is dried in vacuum to remove unreacted epoxypropaneThe alkane gave 32g of poly (carbonate-ether) polyol with a catalyst activity of 6.4kg polyol/g catalyst. The polymer has a number average molecular weight of 3300g/mol and a molecular weight distribution of 1.08 as measured by gel permeation chromatography; the results of 1H-NMR analysis showed that the cyclic carbonate by-product was 2.15%, and the carbonate unit content in the polymer was about 64%, and the titrimetric hydroxyl number was 51.0.
Comparative example 1
Step (1) was the same as in preparation example 1;
(2) 200g of zinc chloride is dissolved in 300ml of deionized water and stirred 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 autoclave is in a carbon dioxide atmosphere, controlling the temperature in the autoclave to be 20 ℃ after the pressure is increased to 15MPa, injecting the solution S1 into the autoclave solution S2 at the speed of 50mL/min through a plunger pump, stirring and reacting for 0.5h after the injection is finished, decompressing the autoclave, and obtaining a precipitate product through centrifugation and tert-butanol pulping and washing;
(4) The precipitate is dried to constant weight in vacuum at 45 ℃ and grinded to obtain the bimetallic catalyst DMC-1 4635 g.
The elemental analysis results were: 22.5wt% of Zn; 10.8wt% of Co; 27.9wt% of C; 3.3wt% of H; 16.2wt% of N. Particle size was analyzed by a Markov laser particle sizer, with an average particle size of 29nm and a concentration PDI 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 which had been previously dehydrated and deoxygenated (polymerization conditions were the same as in example 1, only the catalyst was changed), and CO was charged 2 The reaction was stirred at 80℃until the pressure was 2MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 10.5g of poly (carbonate-ether) polyol, the catalyst activity was 2.1kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1050g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.12; as a result of 1H-NMR analysis, it was found that the cyclic carbonThe acid ester by-product was 3.6%, the carbonate unit content in the polymer was about 41%, and the titrimetric hydroxyl number 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 introduced into a 500ml autoclave which had been previously dehydrated and deoxygenated (polymerization conditions were the same as In example 4, only the catalyst was changed), and CO was charged 2 The reaction was stirred at 60℃until the pressure was 5MPa for 8 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 9.8g of poly (carbonate-ether) polyol, the catalyst activity was 1.96kg of polyol/g of catalyst. The number average molecular weight of the polymer was 950g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.09; the 1H-NMR analysis showed that the cyclic carbonate by-product was 3.9%, and the carbonate unit content in the polymer was about 39%, and the titrimetric hydroxyl number 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 propylene oxide were charged into a 500ml autoclave which had been previously dehydrated and deoxygenated (polymerization conditions were the same as in example 7, only the catalyst was changed), and CO was charged 2 The reaction was stirred at 85℃until the pressure was 2MPa for 4 hours. After the polymerization reaction was completed, the reaction vessel was cooled to room temperature, carbon dioxide was slowly released, and the obtained product was dried under vacuum to remove unreacted propylene oxide, to obtain 10.6g of poly (carbonate-ether) polyol, the catalyst activity was 2.12kg of polyol/g of catalyst. The number average molecular weight of the polymer was 1200g/mol as measured by gel permeation chromatography, and the molecular weight distribution was 1.15; the 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 titrimetric hydroxyl number was 93.5.
From the above, it can be seen that the catalyst activity can be controlled between 2.9 kg polyol and 15.9kg polyol/g catalyst according to the different types and amounts of chain transfer agents used in the preparation process, and the catalyst activity is obviously improved, and the main reasons can be summarized as follows: a first partThe bimetallic catalyst is prepared in the carbon dioxide atmosphere, and carbon dioxide enables carboxyl carbonyl groups to be formed on the surface of the catalyst in the reaction, so that the activation and adsorption of carbon dioxide are facilitated; on the other hand, the introduction of trace metal elements such as zirconium, ruthenium, cerium, indium, cesium and the like helps to introduce oxygen defects on the surface of the catalyst, carbon dioxide is easily adsorbed to the surface where the oxygen defects exist, and carbon atoms are connected with oxygen atoms near the oxygen defects or one oxygen atom of the carbon atoms is placed in the oxygen vacancies, thereby CO 2 The strong interaction of the oxygen atoms in (a) and the surface defects weakens the C=O bond so as to realize activation, so that the C=O bond is easier to break and the reaction is accelerated. The two reasons are most intuitively expressed as the improvement of the dissolving (adsorbing) capacity of the reaction system to the carbon dioxide, which provides possibility for realizing the efficient catalysis of the copolymerization of the carbon dioxide and the alkylene oxide by the bimetallic catalyst to prepare the polyol.
The above embodiments are only illustrative of the preferred embodiments of the present application and are not intended to limit the scope of the present application, and various modifications and improvements made by those skilled in the art to the technical solutions of the present application should fall within the protection scope defined by the claims of the present application without departing from the design spirit of the present application.

Claims (10)

1. A method for preparing a bimetallic catalyst, comprising the steps of:
(1) Dissolving metal cyanide complex with solvent, stirring to obtain metal cyanide complex solution S1;
(2) Dissolving zinc metal 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, and pulping to obtain a precipitate;
(4) Vacuum drying the precipitate to constant weight to obtain the bimetallic catalyst;
the pressurizing pressure in the step (3) is 0.1-15 MPa, and the temperature is 20-150 ℃;
the molar ratio of the metal cyanide complex to the trace metal salt is 50-5000:1;
the bimetallic catalyst is applied to the preparation of poly (carbonate-ether) polyols.
2. The process according to claim 1, wherein the molar ratio of metal cyanide complex to metal zinc salt is 1:1.5-10.
3. The method of 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, 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.
4. The method according to claim 1, wherein the stirring time in the step (1) is 0.5 to 24 hours, the temperature is 20 to 120 ℃, the stirring time in the step (2) is 0.5 to 24 hours, and the temperature is 0 to 120 ℃.
5. A bimetallic catalyst prepared by the method of any one of claims 1 to 4.
6. A method for 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 obtain the poly (carbonate-ether) polyol;
the chain transfer agent is one or more of water, small molecular alcohol, phenol, mercaptan, hydroxy acid and oligomer containing hydroxy;
the mass ratio of the bimetallic catalyst to the epoxide is 1 (5000-2000000).
7. The method according to claim 6, wherein the epoxy compound is one or more of ethylene oxide, propylene oxide, 1, 2-butylene oxide, cyclohexane oxide, cyclopentane oxide, epichlorohydrin, glycidyl methacrylate, methyl glycidyl ether, phenyl glycidyl ether, styrene oxide, and 4-vinyl-1, 2-cyclohexane oxide.
8. The process of claim 6 wherein the molar ratio of epoxide to chain transfer agent is from 100:1 to 12.
9. The method according to claim 6, wherein the pressure is 0.1 to 12MPa, the polymerization reaction temperature is 20 to 150 ℃ and the polymerization reaction 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.
CN202210548812.4A 2022-05-20 2022-05-20 Poly (carbonate-ether) polyol and preparation method thereof Active CN114805781B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210548812.4A CN114805781B (en) 2022-05-20 2022-05-20 Poly (carbonate-ether) polyol and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210548812.4A CN114805781B (en) 2022-05-20 2022-05-20 Poly (carbonate-ether) polyol and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114805781A CN114805781A (en) 2022-07-29
CN114805781B true CN114805781B (en) 2023-10-27

Family

ID=82516191

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210548812.4A Active CN114805781B (en) 2022-05-20 2022-05-20 Poly (carbonate-ether) polyol and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114805781B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115490843B (en) * 2022-11-07 2023-06-02 科丰兴泰(杭州)生物科技有限公司 Method for preparing particle slow release fertilizer

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304946A (en) * 2000-08-16 2001-07-25 中国科学院山西煤炭化学研究所 Composite catalyst bimetal cyanide and its preparing process and application
CN102617844A (en) * 2012-03-28 2012-08-01 中国科学院长春应用化学研究所 Preparing method of poly (carbonic ester-ether) polyalcohol
CN102731766A (en) * 2012-07-24 2012-10-17 中国科学院长春应用化学研究所 Preparation method of aliphatic polycarbonate polyol
CN103360589A (en) * 2012-04-05 2013-10-23 中国石油天然气股份有限公司 Multi-metal cyanide catalyst and preparation and application thereof
CN110603279A (en) * 2017-03-01 2019-12-20 伊克尼克技术有限公司 Method for producing polyether carbonates
CN112029083A (en) * 2020-08-26 2020-12-04 烟台大学 Polyether carbonate polyol and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1304946A (en) * 2000-08-16 2001-07-25 中国科学院山西煤炭化学研究所 Composite catalyst bimetal cyanide and its preparing process and application
CN102617844A (en) * 2012-03-28 2012-08-01 中国科学院长春应用化学研究所 Preparing method of poly (carbonic ester-ether) polyalcohol
CN103360589A (en) * 2012-04-05 2013-10-23 中国石油天然气股份有限公司 Multi-metal cyanide catalyst and preparation and application thereof
CN102731766A (en) * 2012-07-24 2012-10-17 中国科学院长春应用化学研究所 Preparation method of aliphatic polycarbonate polyol
CN110603279A (en) * 2017-03-01 2019-12-20 伊克尼克技术有限公司 Method for producing polyether carbonates
CN112029083A (en) * 2020-08-26 2020-12-04 烟台大学 Polyether carbonate polyol and preparation method thereof

Also Published As

Publication number Publication date
CN114805781A (en) 2022-07-29

Similar Documents

Publication Publication Date Title
US11149117B2 (en) Alkylene oxide polymerization using a double metal cyanide catalyst complex and a magnesium, group 3-group 15 metal or lanthanide series metal compound
EP2709757B1 (en) Process for preparing highly active double metal cyanide catalysts and their use in the synthesis of polyether polyols
CN114805781B (en) Poly (carbonate-ether) polyol and preparation method thereof
CN112126053B (en) Preparation method and application of double metal cyanide catalyst
US6093793A (en) Process for the production of polyether polyols
CN102040731A (en) Method for preparing polyether polyol
JP4361688B2 (en) Method for producing long-chain polyether polyol without post-treatment
US11219887B2 (en) Method for preparing organic zinc catalyst, organic zinc catalyst prepared by the method and method for preparing polyalkylene carbonate resin using the catalyst
EP3415234A2 (en) Organic zinc catalyst, preparation method thereof, and method for preparing polyalkylene carbonate resin using same catalyst
JP2004051996A (en) Activated starting mixture and method relating thereto
KR102008546B1 (en) Process for making hybrid polyester-polyether polyols
CN115073723B (en) Separable catalyst and preparation method of low-molecular-weight narrow-distribution colorless poly (carbonate-ether) polyol
WO2023217161A1 (en) Zinc coordination polymer catalyst, preparation method therefor, and use thereof
JP2001519467A (en) Improved double metal cyanide catalyst for producing polyether polyols
JP2002522567A (en) Double metal cyanide catalysts for producing polyether polyols
CN101302286B (en) Multi-metal cyanide complex catalyst
CN102036749A (en) Double metal cyanide catalyst having a controlled reactivity for preparing a polyol and preparation thereof
US20030211935A1 (en) Double-metal cyanide catalysts for preparing polyether polyols
EP4273183A1 (en) Method for manufacturing polyalkylene carbonate resin
CN114736365A (en) Preparation method, product and application of bimetallic catalyst
JP2023533031A (en) Polymerization method
KR20240123215A (en) Polyalkylene carbonate resin composition
KR20240136775A (en) Double metal cyanide catalyst, preparation method of the catalyst, and preparation method of polyalkylene carbonate using the catalyst
RU2248241C2 (en) Double metal cyanide catalysts for production of polyetherpolyols
CN114174381A (en) Method for purifying polyether polyols

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant