CN114805817A - Bimetallic catalyst, preparation method thereof and application thereof in preparation of polyether polyol - Google Patents
Bimetallic catalyst, preparation method thereof and application thereof in preparation of polyether polyol Download PDFInfo
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
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- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
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- 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
- C08G65/2603—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 the other compounds containing oxygen
- C08G65/2606—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 the other compounds containing oxygen containing hydroxyl groups
- C08G65/2609—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 the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
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- 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
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- 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
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/395—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing phosphorus
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- C—CHEMISTRY; METALLURGY
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- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- Y02P20/584—Recycling of catalysts
Abstract
A high-efficiency bimetallic catalyst, its preparation method and application in preparing polyether polyol are disclosed. The novel 3OP four-tooth ligand with 1P and 3O is coordinated with metal to form a four-tooth chelate, and the chelate is loaded on silica gel to obtain the bimetallic catalyst. The capture property, the water absorption property and the special space structure of the novel ligand of the silica gel matrix act together, so that the induction period of the catalyst is short in the process of preparing polyether polyol and is not influenced by the moisture content of the monomer, and the final product has low unsaturation degree and narrow molecular weight distribution.
Description
Technical Field
The application relates to the field of catalysts and polyether polyols, in particular to a high-efficiency bimetallic catalyst, a preparation method thereof and application thereof in preparation of polyether polyols.
Background
The universal tire rubber company in the United states in the sixties of the last century discovers for the first time that double metal cyanide complex (DMC) is used as a catalyst to prepare long-chain polyether polyol, the catalytic efficiency is far higher than that of other traditional alkali metal systems, and the prepared polyether polyol has the advantages of low unsaturation degree and narrow distribution. Most of the double metal cyanide complex catalysts on the market at present adopt zinc cobaltcyanide as a main structure, namely double metal cyanide salt, and are coordinated with a plurality of small molecules or polymers with oxygen atoms to obtain the final catalyst. The catalyst has the advantages of high activity and no need of post treatment under normal conditions. But is greatly affected by the moisture content of the monomer during the activation stage, even to the point of being non-activatable. In addition, in some cases (e.g., for maternal and infant products), post-treatment is required to remove metal ions. In this case, the disadvantage that such catalysts are not easily removed by post-treatment increases the production cost and also limits their application to the mother-and-baby or cosmetic markets.
Therefore, it is necessary to develop a highly efficient bimetallic catalyst which is water-absorbent and easily recycled.
Disclosure of Invention
The following is a summary of the subject matter described in detail herein. This summary is not intended to limit the scope of the claims.
To solve the problems of the prior art, it is an object of the present application to provide a bimetallic catalyst. When the catalyst is used for preparing polyether polyol, the catalyst has the characteristics of water absorption, easy recovery and high efficiency.
The novel 3OP four-tooth ligand with 1P and 3O is coordinated with metal to form a four-tooth chelate, and the chelate is loaded on silica gel to obtain the bimetallic catalyst. The capture property, the water absorption property and the special space structure of the novel ligand of the silica gel matrix act together, so that the induction period of the catalyst is short in the process of preparing polyether polyol and is not influenced by the moisture content of the monomer, and the final product has low unsaturation degree and narrow molecular weight distribution.
In order to achieve the above purpose, the following technical scheme is adopted in the application:
a method of making a bimetallic catalyst, the method comprising the steps of:
s1: reacting biphenyl with hydroxyl and benzyl bromide with acetyl chloride to obtain a product A;
illustratively, the reaction of S1 is as follows:
s2: the product A reacts with diphenyl phosphorus chloride to obtain a catalyst ligand B;
illustratively, the reaction of S2 is as follows:
s3: carrying anilino siloxane on silica gel through reaction to obtain a product C;
illustratively, the reaction of S3 is as follows:
s4: carrying out substitution reaction on the product C and the ligand B, and loading the ligand B on silica gel to obtain a product D;
illustratively, the reaction of S4 is as follows:
s5: dipping the product D in a metal salt solution to obtain a bimetallic catalyst;
illustratively, the reaction of S5 is as follows:
the silica gel matrix has a water absorption effect, can absorb trace moisture in the monomer, and reduces the poisoning effect of the moisture on the catalyst; in addition, the silica gel matrix can form hydrogen bonds with epoxide, so that raw materials are stably gathered near the active metal center, and the activity of polymer reaction is improved. In addition, since phosphorus is less electronegative than oxygen, the novel ligand (ligand B) in the present application employs 3 oxygen atoms and 1 phosphorus atom, and the resulting catalyst has improved activity compared to a catalyst containing 4O atoms and more stable properties compared to a catalyst containing a plurality of P atoms. Meanwhile, the ligand has a special spatial structure, diphenyl phosphorus and tert-butyl biphenol construct larger steric hindrance around an active metal center, and only one corner without steric hindrance hydroxyl is left for coordination polymerization of epoxide, so that a polyether polyol product with high molecular weight and narrow distribution is obtained.
In the present application, the biphenyl having a hydroxyl group and benzyl bromide described in S1 is preferably 5, 5-dibromo-3, 3-di-t-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl; preferably, the molar ratio of the biphenyl to the acetyl chloride is 1 (1-5), preferably 1 (1.1-1.5).
In the present application, the reaction of S1 is carried out in a solvent which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran.
In the present application, the reaction of S1 is performed in an alkaline environment using one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate, preferably triethylamine.
In the application, the reaction temperature of S1 is-10-5 ℃, the reaction time is 10-24 h, the preferable reaction temperature is-5-0 ℃, and the reaction time is 11-13 h.
In one embodiment, when the product is separated by S1, a chromatographic column is used, and the eluent used comprises ethyl acetate and petroleum ether in a volume ratio of 5: 1.
In the application, the molar ratio of the diphenyl phosphorus chloride to the product A in S2 is 1 (1-5), preferably 1 (1.1-1.5).
In the present application, the reaction of S2 is carried out in a solvent which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran.
In the present application, the reaction of S2 is performed in an alkaline environment using one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate, preferably triethylamine.
In the application, the reaction temperature of S2 is-10 ℃, the reaction time is 10-24 h, preferably-5-0 ℃, and the reaction time is 10-12 h.
In one embodiment, when the product is separated by S2, a chromatographic column is used, and the eluent comprises ethyl acetate and petroleum ether at a volume ratio of 10: 1.
In the application, the mass ratio of the silica gel to the THF to the anilino siloxane in S3 is 1 (30-50): (3-10), preferably 1 (30-40): (3-5).
In the application, the raw material silica gel of S3 is silica gel after being soaked and cleaned by acetone.
In the present application, the reaction of S3 is carried out in a solvent, preferably the solvent is one or more of toluene, xylene, tetrahydrofuran and acetone, more preferably tetrahydrofuran.
In the application, the reaction temperature of S3 is 60-100 ℃, the reaction time is 4-30 h, the preferable reaction temperature is 70-80 ℃, and the reaction time is 6-8 h.
In the application, the mass ratio of the product C to the ligand B in S4 is 1 (1-15), preferably 1 (6-10).
In the present application, the reaction of S4 is carried out in a solvent which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably acetone.
In the application, the reaction temperature of S4 is 20-100 ℃, the reaction time is 12-50 h, the preferable reaction temperature is 50-70 ℃, and the reaction time is 40-50 h.
In the present application, the reaction of S4 is performed in a basic environment using one or more of potassium carbonate, triethylamine and cesium carbonate, preferably potassium carbonate.
In the present application, the metal salt in S5 is any two of zinc chloride, aluminum chloride, tin chloride, cobalt chloride, ferric chloride, and magnesium chloride, and preferably aluminum chloride and zinc chloride; preferably, the metal salt solution is a THF solution of aluminum chloride and zinc chloride, and the concentration of the solution is preferably 20-50%, and further preferably 25-40%; preferably, the mass ratio of the product D to the metal salt is 1 (0.2-20): 0.25-20), preferably 1 (1-2.5): 1-2.5.
In the application, the dipping temperature is 70-100 ℃, the dipping time is 2-12 h, and the dipping temperature is preferably 70-80 ℃, and the dipping time is 2-4 h.
It is another object of the present application to provide a bimetallic catalyst.
A bimetallic catalyst is prepared by the preparation method. The catalyst has the excellent performance of preparing polyether polyol with narrow distribution and low viscosity.
It is a further object of the present application to provide a use of the bimetallic catalyst.
The use of a bimetallic catalyst prepared by the preparation method for the catalytic preparation of polyether polyols, preferably for the preparation of narrow-distribution polyether polyols having a molecular weight of 500-.
In the present application, the method for preparing the polyether polyol is as follows: in the presence of an initiator and a catalyst, controlling the temperature and pressure conditions, adding an epoxide monomer into a reactor, and carrying out polymerization reaction to obtain a final product; preferably, a di-or trifunctional polyether having a molecular weight of greater than 400g/mol is used as starter; preferably, the reaction temperature is controlled to be 100-180 ℃, preferably 130-140 ℃, and the pressure is 0.1-0.6 MPa, preferably 0.1-0.2 MPa; preferably, a portion of the epoxide monomer is added, the catalyst is activated when the reaction pressure drops to half the initial pressure, and the addition of monomer is continued until the reaction pressure no longer drops, yielding the final product.
The beneficial effect of this application is as follows:
according to the method, silica gel with a water absorption effect is used as a carrier, so that the catalyst poisoning phenomenon caused by high monomer moisture content can be reduced;
the application loads the catalyst on silica gel, so that the catalyst has the advantage of being recyclable;
the catalyst prepared by using the novel ligand has high activity, and the obtained polyether polyol has the advantages of narrow distribution (1.02-1.03) and low unsaturation degree (0.002-0.003).
Still other aspects will be apparent upon reading and understanding the detailed description.
Detailed Description
The following examples are provided to further illustrate the technical solutions provided in the present application, but the present application is not limited to the listed examples, and may include any other known modifications within the scope of the claims of the present application.
Information of main raw materials: triethylamine purchased from Zibo Xuyin chemical Co., Ltd; THF, purchased from new materials, denafil, usa ltd; 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl, purchased from Jiangsu Ming chemical Sancheng Biotech limited; acetyl chloride, ethyl acetate and petroleum ether, purchased from Shandong Weiming chemical Co., Ltd; diphenylphosphoryl chloride, purchased from Shanghai Jinjinle industries, Ltd; silica gel purchased from Qingdao Ponkayai high and new technology materials, Inc.; 4- (2-triethoxysilylethyl) aniline, purchased from golden mosaic, inc, shanghai; ethanol, K 2 CO 3 Acetone, aluminum chloride, and zinc chloride, available from Kemiou Chemicals, Inc.
The main characterization method comprises the following steps: the molecular weight of the prepared product is tested by using a high-resolution mass spectrum (Waters Xevo G2 QTof), and the sample preparation method comprises the steps of dissolving a small amount of samples in methanol or acetonitrile for testing; testing the molecular weight distribution (PDI) of the prepared product by using a BOEN326985 gel permeation chromatograph; testing the viscosity of the prepared product by using an NDJ-79 rotary viscometer; determining the hydroxyl value of the product by using an MB3600-CH20 hydroxyl value analysis tester; the unsaturation of the product was tested using a KEM-Autopotentiometric titrator AT-510, Kyoto electronics, Japan.
Main device information: the chromatographic column is a silica gel column (coarse pore, 200-300 meshes).
Example 1
1. Synthesizing a bimetallic catalyst:
s1: in ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.1moL of 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl is added and stirred for 10min, 0.11moL of acetyl chloride is slowly added into the flask, ice bath conditions are kept, reaction is carried out for 12h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: the petroleum ether with the volume ratio of 5:1 is used as eluent to be separated and rotationally distilled by a chromatographic column to obtain 0.092mol (50.968g) of solid product.
S2: under ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.092mol of S1 product is added, stirred for 10min, 0.1045mol of diphenyl phosphorus chloride is slowly added into the flask, the ice bath condition is kept, the reaction is carried out for 12h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: the petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and evaporated by a chromatographic column to obtain 0.087mol (62.25g) of solid product.
S3: 30g of silica gel, 900ml of THF and 90g of 4- (2-triethoxysilylethyl) aniline (mass ratio is 1:30:3) are sequentially added into a 2L three-neck flask, the mixture is heated, stirred, condensed and refluxed for 6h at 70 ℃, then cooled to normal temperature and filtered, a filter cake is washed by 100ml of ethanol solution and then washed by 100ml of distilled water until the pH value of the filtrate is 7, and the filter cake is dried for 2h at 100 ℃ to obtain 100g of activated silica gel.
S4: a250 mL two-neck flask was taken, and 6g K was added in order 2 CO 3 30mL of acetone and 10g S3 were added to the flask and stirred, evacuated and replaced with nitrogen three times, then the flask was placed in an oil bath to raise the temperature to 60 ℃ and stirred for 10min, then the 60g S2 product was dissolved in 100mL of acetone and slowly added to the flask to react for 48 h. After the reaction is finished, the system is cooled to room temperature and then filtered, filter cakes are respectively washed by 50ml of water and 50ml of ethanol, and then the filter cakes are dried in vacuum for 2 hours at the temperature of 50 ℃ to obtain 56g of catalyst precursor.
S5: 56g of the S4 product is added into 224g of a THF solution of aluminum chloride with the concentration of 25 percent and 560g of a THF solution of zinc chloride with the concentration of 25 percent at the temperature of 70 ℃, reacted for 2 hours, filtered, washed by 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and placed in a vacuum oven at the temperature of 50 ℃ for 2 hours to obtain 110g of a catalyst product.
The catalyst uses an EDX3600K full-element analyzer of Tianrui to test the element results as follows: c, 46.55; h, 5.86; 0.82 parts of Al; n, 1.70; o, 24.22; p, 1.88; si, 17.01; zn, 1.98.
2. And (3) synthesis of polyether polyol:
1) respectively mixing 600g of polyglycerol with the molecular weight of 600g/mol as an initiator with the bimetallic catalyst, heating to 100 ℃, stirring until the materials are uniformly dispersed, keeping the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuumizing environment;
2) heating to 130 ℃, adding 60g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) when the pressure is reduced to half of the initial pressure, propylene oxide is added into the reaction vessel, and the reaction temperature is controlled at 130 ℃ and the pressure is controlled at 0.1MPa (according to gauge pressure) in the reaction process. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 2
1. Synthesizing a bimetallic catalyst:
s1: in ice bath, 5g of triethylamine is dissolved in a 100m L single-neck flask containing 30mL of THF, 0.1mol of 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl is added and stirred for 10min, then 0.12mol of acetyl chloride is slowly added into the flask, ice bath conditions are kept, reaction is carried out for 11h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: petroleum ether with the volume ratio of 5:1 is used as eluent to be separated and rotary evaporated by a chromatographic column to obtain 0.093mol (51.52g) of solid product.
S2: under ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.093mol of S1 product is added, stirred for 10min, 0.1116mol of diphenyl phosphorus chloride is slowly added into the flask, the ice bath condition is kept, the reaction is carried out for 10h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: the petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and evaporated by a chromatographic column to obtain 0.088mol (64.988g) of solid product.
S3: 10g of silica gel, 300ml of THF and 50g of 4- (2-triethoxysilylethyl) aniline (mass ratio is 1:30:5) are sequentially added into a 1L three-neck flask, the mixture is heated, stirred, condensed and refluxed for 8h at 70 ℃, then cooled to normal temperature and filtered, a filter cake is washed by 100ml of ethanol solution and then by 100ml of distilled water until the pH value of the filtrate is 7, and the filter cake is dried for 2h at 100 ℃ to obtain 40g of activated silica gel.
S4: a250 mL two-neck flask was taken, and 6g K was added in order 2 CO 3 30ml of acetone, 6g S3 were added to the flask and stirred, evacuated and replaced with nitrogen three times, after which the flask was filledThe mixture is put in an oil bath kettle to be heated to 50 ℃, stirred for 10min, and then the product of 60g S2 is dissolved in 100ml of acetone and slowly added into the flask to react for 50 h. After the reaction is finished, the system is cooled to room temperature and then filtered, filter cakes are respectively washed by 50ml of water and 50ml of ethanol, and then the filter cakes are dried in vacuum for 2 hours at the temperature of 50 ℃, so that 52g of catalyst precursor is obtained.
S5: at 70 ℃, 52g of the S4 product is added into 208g of a 25% aluminum chloride THF solution and 130g of a 40% zinc chloride THF solution, reacted for 2 hours, filtered, washed by 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and placed in a vacuum oven at 50 ℃ for 2 hours, so as to obtain 86g of a catalyst product.
2. And (3) synthesis of polyether polyol:
1) respectively mixing 600g of polyglycerol with the molecular weight of 600g/mol as an initiator with the bimetallic catalyst, heating to 100 ℃, stirring until the materials are uniformly dispersed, keeping the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuumizing environment;
2) heating to 130 ℃, adding 60g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) when the pressure is reduced to half of the initial pressure, propylene oxide is added into the reaction vessel, and the reaction temperature is controlled at 100 ℃ and the pressure is controlled at 0.6MPa (according to gauge pressure) in the reaction process. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 3
1. Synthesizing a bimetallic catalyst:
s1: in ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.1mol of 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl is added and stirred for 10min, then 0.15mol of acetyl chloride is slowly added into the flask, ice bath conditions are kept, reaction is carried out for 12h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: the petroleum ether with the volume ratio of 5:1 is used as eluent to be separated and rotationally distilled by a chromatographic column to obtain 0.096mol (53.18g) of solid product.
S2: in ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.096mol of S1 product is added, stirred for 10min, 0.1248mol of diphenyl phosphorus chloride is slowly added into the flask, ice bath condition is kept, reaction is carried out for 12h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: the petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and rotationally distilled by a chromatographic column to obtain 0.091mol (67.2g) of solid product.
S3: 20g of silica gel, 800ml of THF and 60g of 4- (2-triethoxysilylethyl) aniline (mass ratio is 1:40:3) are sequentially added into a 2L three-neck flask, the mixture is heated, stirred, condensed and refluxed for 7h at 80 ℃, then cooled to room temperature and filtered, a filter cake is washed by 100ml of ethanol solution and then washed by 100ml of distilled water until the pH value of the filtrate is 7, and the filter cake is dried for 2h at 100 ℃ to obtain 60g of activated silica gel.
S4: a250 ml two-neck flask was taken, and 6g K was sequentially placed 2 CO 3 The product of 30ml of acetone and 8g S3 is added into a flask and stirred, evacuated and replaced by nitrogen for three times, then the flask is placed in an oil bath kettle and heated to 70 ℃, after stirring for 10min, the product of 64g S2 is dissolved in 30ml of acetone and slowly added into the flask to react for 40 h. After the reaction is finished, the system is cooled to room temperature and then filtered, filter cakes are respectively washed by 50ml of water and 50ml of ethanol, and then the filter cakes are dried in vacuum for 2 hours at the temperature of 50 ℃ to obtain 60g of catalyst precursor.
S5: 30g of S4 product is taken and added into 187.5g of aluminum chloride THF solution with the concentration of 40 percent and 250g of zinc chloride THF solution with the concentration of 30 percent at the temperature of 80 ℃, reaction is carried out for 2h, after filtration, the mixture is washed by 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and the mixture is placed in a vacuum oven at the temperature of 50 ℃ for 2h, so that 63g of catalyst product is obtained.
2. And (3) synthesis of polyether polyol:
1) respectively mixing 600g of polyglycerol with the molecular weight of 600g/mol as an initiator with the bimetallic catalyst, heating to 100 ℃, stirring until the materials are uniformly dispersed, keeping the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuumizing environment;
2) heating to 130 ℃, adding 60g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) when the pressure is reduced to half of the initial pressure, propylene oxide is added into the reaction vessel, and the reaction temperature is controlled at 140 ℃ and the pressure is controlled at 0.2MPa (according to gauge pressure) in the reaction process. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 4
1. Synthesizing a bimetallic catalyst:
s1: in ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.1mol of 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl is added and stirred for 10min, then 0.12mol of acetyl chloride is slowly added into the flask, ice bath conditions are kept, reaction is carried out for 11h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: petroleum ether with the volume ratio of 5:1 is used as eluent to be separated and rotary evaporated by a chromatographic column to obtain 0.093mol (51.52g) of solid product.
S2: under ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30ml of THF, 0.093mol of S1 product is added, stirred for 10min, 0.1302mol of diphenyl phosphorus chloride is slowly added into the flask, the ice bath condition is kept, the reaction is carried out for 12h, and rotary evaporation is carried out to obtain a crude product; using ethyl acetate: petroleum ether with the volume ratio of 10:1 is used as eluent to obtain 0.088mol (64.99g) of solid product by separation and rotary evaporation through a chromatographic column.
S3: 10g of silica gel, 350ml of THF and 40g of 4- (2-triethoxysilylethyl) aniline (mass ratio is 1:35:4) are sequentially added into a 2L three-neck flask, the mixture is heated, stirred, condensed and refluxed for 8h at 80 ℃, then cooled to normal temperature and filtered, a filter cake is washed by 100ml of ethanol solution and then by 100ml of distilled water until the pH value of the filtrate is 7, and the filter cake is dried for 2h at 100 ℃ to obtain 37g of activated silica gel.
S4: a250 mL two-neck flask was taken, and 6g K was added in order 2 CO 3 30ml of acetone and 8g S3 are added into a flask and stirred, the flask is evacuated and replaced by nitrogen for three times, then the flask is placed in an oil bath kettle and heated to 70 ℃, after stirring for 10min, the product of 72g S2 is dissolved in 100ml of acetone and slowly added into the flask for reaction for 50 h. After the reaction is finished, the system is cooled to room temperature and then filtered, filter cakes are respectively washed by 50ml of water and 50ml of ethanol, and then the filter cakes are dried in vacuum for 2 hours at the temperature of 50 ℃, so that 66g of catalyst precursor is obtained.
S5: adding 33g of S4 product into 165g of aluminum chloride THF solution with the concentration of 25% and 206g of magnesium chloride THF solution with the concentration of 40% at 80 ℃, reacting for 2h, filtering, washing with 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and placing in a vacuum oven at 50 ℃ for 2h to obtain 60g of catalyst product.
2. And (3) synthesis of polyether polyol:
1) respectively mixing 600g of polyglycerol with the molecular weight of 600g/mol as an initiator with the bimetallic catalyst, heating to 100 ℃, stirring until the materials are uniformly dispersed, keeping the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuumizing environment;
2) heating to 130 ℃, adding 60g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) when the pressure is reduced to half of the initial pressure, propylene oxide is added into the reaction vessel, and the reaction temperature is controlled at 180 ℃ and the pressure is controlled at 0.6MPa (according to gauge pressure) in the reaction process. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Comparative example 1
This comparative example differs from examples 1, 2, 3 and 4 described above in that the bimetallic catalyst used in the preparation of the polyether polyol of this comparative example is a commercially available bimetallic catalyst, and the remaining conditions are the same as in example 3. Wherein, the commercial bimetallic catalyst is purchased from Shanghai Qike fluorosilicone materials Co., Ltd, and the name is: a DMC bimetallic catalyst. The bimetallic elements are zinc and cobalt.
The test results are shown in table 1:
TABLE 1 test results
Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
PO consumption | 652g | 643g | 860g | 626g | 560g |
Hydroxyl number | 140 | 141 | 117 | 143 | 145 |
Degree of unsaturation | 0.003 | 0.004 | 0.002 | 0.003 | 0.07 |
PDI | 1.03 | 1.03 | 1.02 | 1.03 | 1.04 |
Activation time | 3min | 3min | 2min | 3min | 4min |
Catalyst recovery | 99% | 99% | 98% | 98% | 1% |
Note: the time when the pressure is reduced by half is the activation time; catalyst recovery was achieved by positive pressure filter, 5 micron filter cloth.
As can be seen from the test results of examples 1, 2, 3, 4 and comparative example 1 in table 1, the bimetallic catalysts synthesized in examples 1, 2, 3, 4 of the present application consume larger amount of PO (propylene oxide) in the process of preparing polyether polyol than comparative example 1, i.e., lower hydroxyl value, larger molecular weight, and shorter activation time under the same conditions, indicating that the bimetallic catalysts synthesized in examples 1, 2, 3, 4 of the present application have higher catalytic ability and activity than the commercial catalysts of comparative example 1; the sequences of the amounts of PO (propylene oxide) consumed by the bimetallic catalysts synthesized in examples 1, 2, 3 and 4 in the process for preparing polyether polyol are example 3 > example 1 > example 2 > example 4, namely, the sequences of the molecular weights of the prepared polyether polyols are example 3 > example 1 > example 2 > example 4, and the sequences of the activation speeds (short activation time indicates high activation speed) are example 3 > example 1 > example 2 > example 4, which indicate that the catalytic capacities and the activity sequences of the bimetallic catalysts synthesized in examples 1, 2, 3 and 4 in the process are example 3 > example 1 > example 2 > example 4. Compared with the recovery indexes of the synthesized bimetallic catalyst and the commercially available catalyst, the recovery rate of the bimetallic catalyst is higher. Comparing the indexes of the polyether polyol prepared by the bimetallic catalyst synthesized in the embodiment of the application and the commercial catalyst, the unsaturation degree and PDI of the polyether polyol prepared by the bimetallic catalyst of the application are superior to those of the polyether polyol prepared by the commercial catalyst.
The PO moisture content in the preparation of the polyether polyols of the examples and comparative examples was 120ppm, which was now replaced with PO having a moisture content of 3000ppm for the preparation of the polyether polyols of the examples and comparative examples, and the test was stopped after the pressure had dropped to half the initial pressure, the time was recorded. The catalytic effect of the catalyst is shown in table 2 below:
TABLE 2 test results
Performance of | Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 |
Activation time | 3min | 3min | 2min | 3min | 15min |
Comparing the test results of examples 1, 2, 3 and 4 with comparative example 1 in table 2, it can be seen that the bimetallic catalyst synthesized by the present application has the excellent characteristics of short induction period, i.e., activation time is not affected by the moisture content of the monomer.
Claims (10)
1. A method of preparing a bimetallic catalyst comprising the steps of:
s1: reacting biphenyl with hydroxyl and benzyl bromide with acetyl chloride to obtain a product A;
s2: the product A reacts with diphenyl phosphorus chloride to obtain a catalyst ligand B;
s3: carrying anilino siloxane on silica gel through reaction to obtain a product C;
s4: carrying out substitution reaction on the product C and the ligand B, and loading the ligand B on silica gel to obtain a product D;
s5: and (3) dipping the product D in a metal salt solution to obtain the bimetallic catalyst.
2. The production method according to claim 1, wherein the biphenyl having a hydroxyl group and benzyl bromide in S1 is 5, 5-dibromo-3, 3-di-t-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl.
3. The preparation method according to claim 1, wherein the molar ratio of biphenyl to acetyl chloride is 1 (1-5), preferably 1 (1.1-1.5);
and/or, the reaction of S1 is carried out in a solvent, which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran;
and/or the reaction of S1 is carried out in an alkaline environment using one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate, preferably triethylamine;
and/or the reaction temperature of S1 is-10-5 ℃, the reaction time is 10-24 h, preferably the reaction temperature is-5-0 ℃, and the reaction time is 11-13 h.
4. The preparation method of claim 1, wherein the molar ratio of the diphenyl phosphorus chloride to the product A in S2 is 1 (1-5), preferably 1 (1.1-1.5);
and/or the reaction of S2 is carried out in a solvent which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran;
and/or the reaction of S2 is carried out in an alkaline environment using one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate, preferably triethylamine;
and/or the reaction temperature of S2 is-10 ℃, the reaction time is 10-24 h, preferably the reaction temperature is-5-0 ℃, and the reaction time is 10-12 h.
5. The preparation method according to claim 1, wherein the silica gel of S3 is a silica gel after acetone soaking and washing;
and/or, the reaction of S3 is carried out in a solvent, preferably the solvent is one or more of toluene, xylene, tetrahydrofuran and acetone, more preferably tetrahydrofuran;
and/or the mass ratio of the silica gel to the solvent to the anilino siloxane in the S3 is (30-50): (3-10), preferably 1 (30-40): (3-5); and/or the reaction temperature of S3 is 60-100 ℃, the reaction time is 4-30 h, the preferable reaction temperature is 70-80 ℃, and the reaction time is 6-8 h.
6. The preparation method of claim 1, wherein the mass ratio of the product C to the ligand B in S4 is 1 (1-15), preferably 1 (6-10);
and/or, the reaction of S4 is carried out in a solvent which is an ether and/or a ketone, preferably tetrahydrofuran and/or acetone, more preferably acetone;
and/or the reaction of S4 is carried out in a basic environment using one or more of potassium carbonate, triethylamine and cesium carbonate, preferably potassium carbonate;
and/or the reaction temperature of S4 is 20-100 ℃, the reaction time is 12-50 h, the preferable reaction temperature is 50-70 ℃, and the reaction time is 40-50 h.
7. The catalyst preparation method according to claim 1, wherein the metal salt in S5 is any two of zinc chloride, aluminum chloride, tin chloride, cobalt chloride, ferric chloride and magnesium chloride, preferably aluminum chloride and zinc chloride;
preferably, the mass ratio of the product D to the metal salt is 1 (0.2-20): 0.25-20), preferably 1 (1-2.5): 1-2.5;
preferably, the dipping temperature is 70-100 ℃, the dipping time is 2-12 h, preferably the dipping temperature is 70-80 ℃, and the dipping time is 2-4 h.
8. A bimetallic catalyst prepared by the process of any one of claims 1 to 7.
9. Use of a bimetallic catalyst prepared by the preparation process according to any one of claims 1 to 7 or the bimetallic catalyst according to claim 8 for the catalytic preparation of polyether polyols, preferably for the preparation of narrow-distribution polyether polyols.
10. Use according to claim 9, wherein the process for preparing the polyether polyol is: in the presence of an initiator and a catalyst, controlling the temperature and pressure conditions, adding an epoxide monomer into a reactor, and carrying out polymerization reaction to obtain a final product;
preferably, a di-or trifunctional polyether having a molecular weight of greater than 400g/mol is used as starter;
preferably, the reaction temperature is controlled to be 100-180 ℃, preferably 130-140 ℃, and the pressure is 0.1-0.6 MPa, preferably 0.1-0.2 MPa;
preferably, a portion of the epoxide monomer is added, the catalyst is activated when the reaction pressure drops to half the initial pressure, and the addition of monomer is continued until the reaction pressure no longer drops, yielding the final product.
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004030816A1 (en) * | 2002-10-04 | 2004-04-15 | Johnson Matthey Public Limited Company | Hydrosilation catalyst |
JP2004339085A (en) * | 2003-05-13 | 2004-12-02 | Asahi Kasei Pharma Kk | METHOD FOR PRODUCING alpha-SUBSTITUTED PHENYL-ALKANECARBOXYLIC ESTER DERIVATIVE |
US20120302667A1 (en) * | 2011-05-23 | 2012-11-29 | Cheil Industries, Inc. | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same |
CN103467524A (en) * | 2013-10-10 | 2013-12-25 | 中国海洋石油总公司 | Bis-phosphorous acid triphenyl (3,3',5,5'-tetra-tert-butyl-2,2'-xenol) ester microwave synthesis method |
WO2015078218A1 (en) * | 2013-11-29 | 2015-06-04 | 凯莱英医药集团(天津)股份有限公司 | Polymer containing carboxyl group, method for preparing same and use thereof, method for preparing supported catalyst and penem antibiotic intermediates |
CN104817700A (en) * | 2015-04-21 | 2015-08-05 | 广州天赐高新材料股份有限公司 | Method for preparing polyether-modified silicone oil in presence of MOFs (metal-organic frameworks) supported catalyst |
US20160194441A1 (en) * | 2013-08-12 | 2016-07-07 | Repsol, S.A | Process for preparing polyether carbonate polyols |
CN111848840A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Silica gel supported zirconium-vanadium bimetallic complex, and preparation method and application thereof |
-
2021
- 2021-01-28 CN CN202110116798.6A patent/CN114805817B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2004030816A1 (en) * | 2002-10-04 | 2004-04-15 | Johnson Matthey Public Limited Company | Hydrosilation catalyst |
JP2004339085A (en) * | 2003-05-13 | 2004-12-02 | Asahi Kasei Pharma Kk | METHOD FOR PRODUCING alpha-SUBSTITUTED PHENYL-ALKANECARBOXYLIC ESTER DERIVATIVE |
US20120302667A1 (en) * | 2011-05-23 | 2012-11-29 | Cheil Industries, Inc. | Epoxy resin composition for encapsulating semiconductor device and semiconductor device encapsulated with the same |
US20160194441A1 (en) * | 2013-08-12 | 2016-07-07 | Repsol, S.A | Process for preparing polyether carbonate polyols |
CN103467524A (en) * | 2013-10-10 | 2013-12-25 | 中国海洋石油总公司 | Bis-phosphorous acid triphenyl (3,3',5,5'-tetra-tert-butyl-2,2'-xenol) ester microwave synthesis method |
WO2015078218A1 (en) * | 2013-11-29 | 2015-06-04 | 凯莱英医药集团(天津)股份有限公司 | Polymer containing carboxyl group, method for preparing same and use thereof, method for preparing supported catalyst and penem antibiotic intermediates |
CN104817700A (en) * | 2015-04-21 | 2015-08-05 | 广州天赐高新材料股份有限公司 | Method for preparing polyether-modified silicone oil in presence of MOFs (metal-organic frameworks) supported catalyst |
CN111848840A (en) * | 2020-07-13 | 2020-10-30 | 万华化学集团股份有限公司 | Silica gel supported zirconium-vanadium bimetallic complex, and preparation method and application thereof |
Non-Patent Citations (1)
Title |
---|
林雯: ""双膦配体的合成及其催化性能研究"", 化学反应工程与工艺, vol. 34, no. 5, pages 473 - 480 * |
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