CN114805817B - 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 PDF

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CN114805817B
CN114805817B CN202110116798.6A CN202110116798A CN114805817B CN 114805817 B CN114805817 B CN 114805817B CN 202110116798 A CN202110116798 A CN 202110116798A CN 114805817 B CN114805817 B CN 114805817B
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殷玲
吕树卫
李传亮
刘斌
石正阳
秦承群
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Wanhua Chemical Group Co Ltd
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    • 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
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Abstract

Disclosed herein are a high-efficiency bimetallic catalyst, a method for preparing the same, and applications in preparing polyether polyols. The novel 3OP tetradentate ligand with 1P and 3O is coordinated with metal to form tetradentate chelate, and the tetradentate chelate is loaded on silica gel to obtain the bimetallic catalyst. The combination of the trapping property and the water absorption property of the silica gel matrix and the special spatial structure of the novel ligand ensures that the induction period of the catalyst is short and is not influenced by the moisture content of monomers in the process of preparing polyether polyol, and the final product has low unsaturation degree and narrow molecular weight distribution.

Description

Bimetallic catalyst, preparation method thereof and application thereof in preparation of polyether polyol
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 preparing polyether polyols.
Background
The universal tire rubber company in the United states in the last sixties discovered for the first time that double metal cyanide complexes (DMC) were used as catalysts to prepare long-chain polyether polyols, which were far more efficient than other conventional alkali metal systems and produced polyether polyols with low unsaturation and narrow distribution. Most of the double metal cyanide complex catalysts on the market at present adopt cobalt zinc cyanide as a main structure, namely double metal cyanide salt, and are coordinated with various 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 general conditions. But is greatly affected by the moisture content of the monomer during the activation phase, even to the point where activation is not possible. In addition, in some cases (for example, in the case of mother and infant products), a post-treatment is required to remove metal ions. At this time, the disadvantage that the catalyst is not easy to remove by post-treatment is that the application of the catalyst in the mother and infant or cosmetic market is limited while the production cost is increased.
Therefore, it is highly desirable to develop a highly effective bimetallic catalyst that is water-absorptive and easily recoverable.
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 existing in 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 tetradentate ligand with 1P and 3O is coordinated with metal to form tetradentate chelate, and the tetradentate chelate is loaded on silica gel to obtain the bimetallic catalyst. The combination of the trapping property and the water absorption property of the silica gel matrix and the special spatial structure of the novel ligand ensures that the induction period of the catalyst is short and is not influenced by the moisture content of monomers in the process of preparing polyether polyol, and the final product has low unsaturation degree and narrow molecular weight distribution.
In order to achieve the above object, the present application adopts the following technical scheme:
a method of preparing a bimetallic catalyst, the method comprising the steps of:
s1: the biphenyl with hydroxyl and benzyl bromide reacts with acetyl chloride to obtain a product A;
illustratively, the reaction of S1 is as follows:
Figure BDA0002921013700000021
s2: the product A reacts with diphenyl phosphorus chloride to obtain a catalyst ligand B;
illustratively, the reaction of S2 is as follows:
Figure BDA0002921013700000022
s3: carrying out reaction and immobilization on anilino siloxane to obtain a product C;
illustratively, the reaction of S3 is as follows:
Figure BDA0002921013700000031
s4: the product C and the ligand B undergo substitution reaction, and the ligand B is loaded on silica gel to obtain a product D;
illustratively, the reaction of S4 is as follows:
Figure BDA0002921013700000032
s5: immersing the product D in a metal salt solution to obtain a bimetallic catalyst;
illustratively, the reaction of S5 is as follows:
Figure BDA0002921013700000033
the silica gel matrix has the function of absorbing water, 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 bond with epoxide, so that raw materials are stably gathered near the center of active metal, and the activity of polymer reaction is improved. In addition, since phosphorus has weaker electronegativity than oxygen, the novel ligand (ligand B) in the present application adopts 3 oxygen atoms and 1 phosphorus atom, and the final catalyst has improved activity compared with a catalyst containing 4O atoms and more stable properties compared with a catalyst containing a plurality of P atoms. Meanwhile, the ligand has a special space structure, diphenyl phosphorus and tert-butyl biphenol construct larger steric hindrance around the active metal center, and only one corner of the unhindered hydroxyl is vacated for epoxide coordination polymerization, so that a polyether polyol product with high molecular weight and narrow distribution is obtained.
In the present application, the biphenyl with hydroxyl and benzyl bromide in S1 is preferably 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl; preferably, the molar ratio of biphenyl to 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 ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran.
In this application, 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.
In the present application, the reaction temperature of S1 is-10 to 5 ℃, the reaction time is 10 to 24 hours, preferably the reaction temperature is-5 to 0 ℃, and the reaction time is 11 to 13 hours.
In one embodiment, when the product is separated by S1, the product is separated by a chromatographic column, and the eluent used includes ethyl acetate and petroleum ether in a volume ratio of 5:1.
In the present application, the molar ratio of diphenyl phosphorus chloride to the product A in S2 is 1 (1-5), preferably 1 (1.1-1.5).
In this application, the reaction of S2 is carried out in a solvent which is an ether and/or ketone, preferably tetrahydrofuran and/or acetone, more preferably tetrahydrofuran.
In this application, 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.
In the present application, the reaction temperature of S2 is-10 to 10 ℃, the reaction time is 10 to 24 hours, preferably the reaction temperature is-5 to 0 ℃, and the reaction time is 10 to 12 hours.
In one embodiment, when the product is separated by S2, the product is separated by a chromatographic column, and the eluent used includes ethyl acetate and petroleum ether in a volume ratio of 10:1.
In the application, the mass ratio of the silica gel to the THF to the anilino siloxane in the S3 is 1 (30-50): (3-10), preferably 1 (30-40): (3-5).
In the application, the raw material silica gel of S3 is the silica gel soaked and cleaned by acetone.
In this application, the reaction of S3 is performed in a solvent, preferably the solvent is one or more of toluene, xylene, tetrahydrofuran and acetone, more preferably tetrahydrofuran.
In the present application, the reaction temperature of S3 is 60 to 100 ℃, the reaction time is 4 to 30 hours, preferably the reaction temperature is 70 to 80 ℃, and the reaction time is 6 to 8 hours.
In the present application, the mass ratio of the product C to the ligand B in S4 is 1 (1-15), preferably 1 (6-10).
In this application, the reaction of S4 is carried out in a solvent which is an ether and/or ketone, preferably tetrahydrofuran and/or acetone, more preferably acetone.
In the present application, the reaction temperature of S4 is 20 to 100 ℃, the reaction time is 12 to 50 hours, preferably 50 to 70 ℃, and the reaction time is 40 to 50 hours.
In this application, the reaction of S4 is carried out in an alkaline environment, using one or more of potassium carbonate, triethylamine and cesium carbonate, preferably potassium carbonate.
In the application, 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 metal salt solution is a THF solution of aluminum chloride and zinc chloride, preferably at a solution concentration of 20% to 50%, further preferably 25% to 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 present application, the dipping temperature is 70 to 100℃and the dipping time is 2 to 12 hours, preferably 70 to 80℃and the dipping time is 2 to 4 hours.
It is another object of the present application to provide a bimetallic catalyst.
The bimetallic catalyst is prepared by adopting 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 500-20000 g/mol.
In the present application, the method for preparing the polyether polyol comprises the following steps: in the presence of an initiator and a catalyst, controlling the temperature and pressure conditions, adding epoxide monomers into a reactor, and carrying out polymerization reaction to obtain a final product; preferably, difunctional or trifunctional polyethers having a molecular weight of more than 400g/mol are used as starter; preferably, the reaction temperature is controlled to be 100-180 ℃, preferably 130-140 ℃, and the pressure is controlled to be 0.1-0.6 MPa, preferably 0.1-0.2 MPa; preferably, a portion of the epoxide monomer is added first, the catalyst is activated when the pressure drops to half of the initial pressure, the monomer addition is started to continue, and the final product is obtained when the pressure is no longer reduced.
The beneficial effects of the application are as follows:
the silica gel with the water absorption function is used as a carrier, so that the catalyst poisoning phenomenon caused by high monomer water content can be reduced;
the catalyst is loaded on the 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 further illustrate the technical solutions provided by the present application, but the present application is not limited to the listed examples, but includes any other known modifications within the scope of the claims of the present application.
Main raw material information: triethylamine purchased from the company Zibo silver chemical Co., ltd; THF, purchased from shandong fil new materials limited; 5, 5-dibromo-3, 3-di-tert-butyl-6, 6-dimethyl-2, 2-dihydroxy-1, 1-biphenyl, purchased from Jiangsu Ming chemical Chemie biotechnology Co., ltd; acetyl chloride, ethyl acetate and petroleum ether, purchased from Shandong Weiming chemical industry Co., ltd; diphenyl phosphorus chloride purchased from Shanghai Jin Jinle industries, inc.; silica gel purchased from Qingdao bang KagaoMaterials limited; 4- (2-triethoxysilylethyl) aniline, purchased from Shanghai Jin Jinle industries, inc.; ethanol, K 2 CO 3 Acetone, aluminum chloride, zinc chloride, purchased from kemi chemical reagent limited.
The main characterization method comprises the following steps: the molecular weight of the prepared product is tested by utilizing a high-resolution mass spectrum (Waters Xevo G2 QTof), and the sample preparation method is to take a small amount of sample to be dissolved in methanol or acetonitrile for testing; molecular weight distribution (PDI) of the prepared product was tested 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 product was tested for unsaturation using a Kyoto electronics, inc. KEM-automatic potentiometric titrator AT-510, japan.
Main device information: the chromatographic column is silica gel column (coarse pore, 200-300 mesh).
Example 1
1. Synthesis of bimetallic catalyst:
s1: under 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, after stirring for 10min, 0.11moL of acetyl chloride is slowly added into the flask, ice bath conditions are maintained, reaction is carried out for 12h, and a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with a volume ratio of 5:1 is used as eluent to separate and rotationally distill through a chromatographic column to obtain 0.092mol (50.968 g) 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 and stirred for 10min, 0.1045mol of diphenyl phosphorus chloride is slowly added into the flask, ice bath conditions are kept, and the reaction is carried out for 12h, so that a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and distilled by a chromatographic column to obtain 0.087mol (62.25 g) solid product.
S3: 30g of silica gel, 900ml of THF and 90g of 4- (2-triethoxysilylethyl) aniline (mass ratio of 1:30:3) are sequentially added into a 2L three-neck flask, heated, stirred, condensed and refluxed for 6 hours at 70 ℃, cooled to normal temperature, filtered by suction, a filter cake is washed with 100ml of ethanol solution, then washed with 100ml of distilled water until the pH=7 of the filtrate, and the filter cake is dried for 2 hours at 100 ℃ to obtain 100g of activated silica gel.
S4: a250 mL two-necked flask was taken and 6g K was successively put into a flask 2 CO 3 30mL of acetone and 10g of S3 are added into a flask to be stirred, the flask is evacuated and replaced by nitrogen three times, then the flask is placed in an oil bath to be heated to 60 ℃, the mixture is stirred for 10min, 60g of S2 is dissolved in 100mL of acetone, and then the mixture is slowly added into the flask to react for 48h. After the reaction was completed, after the system was cooled to room temperature, it was filtered, and the filter cake was washed with 50ml of water and 50ml of ethanol, respectively, and then dried in vacuo at 50℃for 2 hours to obtain 56g of a catalyst precursor.
S5: 56g of the S4 product was added to 224g of 25% strength aluminum chloride THF and 560g of 25% strength zinc chloride THF at 70℃and reacted for 2 hours, and after filtration, it was washed with 50ml of ethanol, 50ml of deionized water and 50ml of ethanol and placed in a vacuum oven at 50℃for 2 hours to give 110g of a catalyst product.
The test element results of the EDX3600K total element analyzer of the catalyst using Tianrui are as follows: c,46.55; h,5.86; al,0.82; n,1.70; o,24.22; p,1.88; si,17.01; zn,1.98.
2. Synthesis of polyether polyol:
1) 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, maintaining the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuum environment;
2) Heating to 130 ℃, adding 60g of propylene oxide accounting for about 10% of the mass of the initiator, and then observing pressure change;
3) And (3) adding propylene oxide into the reaction vessel after the pressure is reduced to half of the initial pressure, and controlling the reaction temperature to 130 ℃ and the pressure to 0.1MPa (in terms of gauge pressure) in the reaction process. The reaction is carried out until the pressure is not reduced, and the polyether polyol product is obtained.
Example 2
1. Synthesis of bimetallic catalyst:
s1: under 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, after stirring for 10min, 0.12mol of acetyl chloride is slowly added into the flask, ice bath conditions are maintained, reaction is carried out for 11h, and a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with a volume ratio of 5:1 is used as eluent to separate and rotationally distill through a chromatographic column to obtain 0.093mol (51.52 g) 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 and stirred for 10min, 0.1116mol of diphenyl phosphorus chloride is slowly added into the flask, ice bath conditions are kept, and the reaction is carried out for 10h, so that a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and distilled by a chromatographic column to obtain 0.088mol (64.988 g) solid product.
S3: 10g of silica gel, 300ml of THF and 50g of 4- (2-triethoxysilylethyl) aniline (mass ratio of 1:30:5) are sequentially added into a 1L three-neck flask, heated, stirred, condensed and refluxed for 8 hours at 70 ℃, cooled to normal temperature, filtered by suction, a filter cake is washed with 100ml of ethanol solution, then washed with 100ml of distilled water until the pH value of the filtrate is=7, and the filter cake is dried for 2 hours at 100 ℃ to obtain 40g of activated silica gel.
S4: a250 mL two-necked flask was taken and 6g K was successively put into a flask 2 CO 3 30ml of acetone and 6g of S3 are added into a flask to be stirred, the nitrogen is pumped out and replaced three times, then the flask is placed in an oil bath to be heated to 50 ℃, the mixture is stirred for 10 minutes, 60g of S2 is dissolved in 100ml of acetone, and then the mixture is slowly added into the flask to react for 50 hours. After the reaction was completed, after the system was cooled to room temperature, it was filtered, and the filter cake was washed with 50ml of water and 50ml of ethanol, respectively, and then dried in vacuo at 50℃for 2 hours to obtain 52g of a catalyst precursor.
S5: 52g of the S4 product was added to 208g of 25% strength aluminum chloride THF and 130g of 40% strength zinc chloride THF at 70℃and reacted for 2 hours, and after filtration, washed with 50ml of ethanol, 50ml of deionized water and 50ml of ethanol and placed in a vacuum oven at 50℃for 2 hours to give 86g of a catalyst product.
2. Synthesis of polyether polyol:
1) 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, maintaining the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuum environment;
2) Heating to 130 ℃, adding 60g of propylene oxide accounting for about 10% of the mass of the initiator, and then observing pressure change;
3) And (3) adding propylene oxide into the reaction vessel after the pressure is reduced to half of the initial pressure, and controlling the reaction temperature to 100 ℃ and the pressure to 0.6MPa (in terms of gauge pressure) in the reaction process. The reaction is carried out until the pressure is not reduced, and the polyether polyol product is obtained.
Example 3
1. Synthesis of bimetallic catalyst:
s1: under 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, after stirring for 10min, 0.15mol of acetyl chloride is slowly added into the flask, ice bath conditions are maintained, reaction is carried out for 12h, and a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with a volume ratio of 5:1 is used as eluent to separate and rotationally distill through a chromatographic column to obtain 0.096mol (53.18 g) solid product.
S2: under ice bath, 5g of triethylamine is dissolved in a 100ml single-neck flask containing 30m of THF, 0.096mol of S1 product is added and stirred for 10min, 0.1248mol of diphenyl phosphorus chloride is slowly added into the flask, ice bath conditions are kept, and the reaction is carried out for 12h, so that a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether is separated by a chromatographic column in a volume ratio of 10:1 as eluent to obtain 0.091mol (67.2 g) solid product.
S3: 20g of silica gel, 800ml of THF and 60g of 4- (2-triethoxysilylethyl) aniline (the mass ratio is 1:40:3) are sequentially added into a 2L three-neck flask, the mixture is heated, stirred, condensed and refluxed for 7 hours at 80 ℃, then cooled to normal temperature, filtered by suction, a filter cake is washed by 100ml of ethanol solution, then 100ml of distilled water is used for washing until the pH=7 of the filtrate, and the filter cake is dried for 2 hours at 100 ℃ to obtain 60g of activated silica gel.
S4: a250 ml two-necked flask was taken and 6g K was successively put into a flask 2 CO 3 30ml of acetone and 8g of S3 are added into a flask to be stirred, the nitrogen is pumped out and replaced three times, then the flask is placed in an oil bath to be heated to 70 ℃, the mixture is stirred for 10 minutes, 64g of S2 is dissolved in 30ml of acetone, and then the mixture is slowly added into the flask to react for 40 hours. Reverse-rotationAfter the reaction was completed, the reaction mixture was cooled to room temperature and then filtered, and the filter cake was washed with 50ml of water and 50ml of ethanol, respectively, and then dried in vacuo at 50℃for 2 hours to obtain 60g of a catalyst precursor.
S5: at 80℃30g of the S4 product was taken and added to 187.5g of 40% strength aluminum chloride THF solution and 250g of 30% strength zinc chloride THF solution, reacted for 2h, filtered and washed with 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and placed in a vacuum oven at 50℃for 2h to give 63g of catalyst product.
2. Synthesis of polyether polyol:
1) 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, maintaining the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuum environment;
2) Heating to 130 ℃, adding 60g of propylene oxide accounting for about 10% of the mass of the initiator, and then observing pressure change;
3) And (3) adding propylene oxide into the reaction vessel after the pressure is reduced to half of the initial pressure, and controlling the reaction temperature to 140 ℃ and the pressure to 0.2MPa (in terms of gauge pressure) in the reaction process. The reaction is carried out until the pressure is not reduced, and the polyether polyol product is obtained.
Example 4
1. Synthesis of bimetallic catalyst:
s1: under 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, after stirring for 10min, 0.12mol of acetyl chloride is slowly added into the flask, ice bath conditions are maintained, reaction is carried out for 11h, and a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with a volume ratio of 5:1 is used as eluent to separate and rotationally distill through a chromatographic column to obtain 0.093mol (51.52 g) 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 and stirred for 10min, 0.1302mol of diphenyl phosphorus chloride is slowly added into the flask, ice bath conditions are kept, and the reaction is carried out for 12h, so that a crude product is obtained by rotary evaporation; ethyl acetate: petroleum ether with the volume ratio of 10:1 is used as eluent to be separated and distilled by a chromatographic column to obtain 0.088mol (64.99 g) solid product.
S3: 10g of silica gel, 350ml of THF and 40g of 4- (2-triethoxysilylethyl) aniline (mass ratio of 1:35:4) are sequentially added into a 2L three-neck flask, heated, stirred, condensed and refluxed for 8 hours at 80 ℃, cooled to normal temperature, filtered by suction, a filter cake is washed with 100ml of ethanol solution, then washed with 100ml of distilled water until the pH=7 of the filtrate, and the filter cake is dried for 2 hours at 100 ℃ to obtain 37g of activated silica gel.
S4: a250 mL two-necked flask was taken and 6g K was successively put into a flask 2 CO 3 30ml of acetone and 8g of S3 are added into a flask to be stirred, the nitrogen is pumped out and replaced three times, then the flask is placed in an oil bath to be heated to 70 ℃, the mixture is stirred for 10min, 72g of S2 is dissolved in 100ml of acetone, and then the mixture is slowly added into the flask to react for 50h. After the reaction was completed, after the system was cooled to room temperature, it was filtered, and the filter cake was washed with 50ml of water and 50ml of ethanol, respectively, and then dried in vacuo at 50℃for 2 hours to obtain 66g of a catalyst precursor.
S5: at 80℃33g of the S4 product were added to 165g of 25% strength aluminum chloride in THF and 206g of 40% strength magnesium chloride in THF, reacted for 2h, filtered and washed with 50ml of ethanol, 50ml of deionized water and 50ml of ethanol, and placed in a vacuum oven at 50℃for 2h to give 60g of catalyst product.
2. Synthesis of polyether polyol:
1) 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, maintaining the temperature at 100 ℃, and stirring and dehydrating for 2 hours in a vacuum environment;
2) Heating to 130 ℃, adding 60g of propylene oxide accounting for about 10% of the mass of the initiator, and then observing pressure change;
3) And (3) adding propylene oxide into the reaction vessel after the pressure is reduced to half of the initial pressure, and controlling the reaction temperature to 180 ℃ and the pressure to 0.6MPa (in terms of gauge pressure) in the reaction process. The reaction is carried out until the pressure is not reduced, and the polyether polyol product is obtained.
Comparative example 1
This comparative example differs from examples 1, 2, 3 and 4 above in that the bimetallic catalyst used in the preparation of polyether polyol is a commercially available bimetallic catalyst, and the other conditions are the same as in example 3. Wherein, the commercial bimetallic catalyst is purchased from Shanghai Qik fluorosilicone materials Co., ltd, and the name is: DMC bimetallic catalyst. The bimetal element is 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
Unsaturation degree 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 that: the time of half pressure drop is the activation time; catalyst recovery was achieved by a 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, under the same conditions, the bimetallic catalysts synthesized in examples 1, 2, 3, 4 of the present application consume lower amounts of PO (propylene oxide) than comparative example 1, i.e., have lower hydroxyl numbers and higher molecular weights, while having a shorter activation time, indicating that the bimetallic catalysts synthesized in examples 1, 2, 3, 4 of the present application have higher catalytic capacities and activities than the commercially available catalysts of comparative example 1; the amount of PO (propylene oxide) consumed in the preparation of polyether polyol by the bimetallic catalyst synthesized in examples 1, 2, 3 and 4 of the present application is in the order of example 3 > example 1 > example 2 > example 4, i.e., the prepared polyether polyol has a molecular weight in the order of example 3 > example 1 > example 2 > example 4, and the activation rate (short activation time indicates a fast activation rate) is in the order of example 3 > example 1 > example 2 > example 4, indicating that the bimetallic catalyst synthesized in examples 1, 2, 3 and 4 of the present application has a catalytic capacity and an activity in the order of example 3 > example 1 > example 2 > example 4. Compared with the recovery index of the bimetallic catalyst synthesized by the embodiment of the application and the commercial catalyst, the recovery rate of the bimetallic catalyst is higher. Comparing the index of the polyether polyol prepared by the bimetallic catalyst synthesized in the embodiment of the application with the index of the polyether polyol prepared by 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 examples and comparative examples was 120ppm, which was now replaced with a PO having a moisture content of 3000ppm, was used in the preparation of the polyether polyols of examples and comparative examples, and the experiment 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 the following table 2:
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, 4 and comparative example 1 in table 2, it is understood that the bimetallic catalyst synthesized in the present application has excellent characteristics of short induction period, i.e., the activation time is not affected by the content of monomer moisture.

Claims (22)

1. A method of preparing a bimetallic catalyst comprising the steps of:
s1: reacting 5,5' -dibromomethyl-3, 3' -di-tert-butyl-6, 6' -dimethyl- [1,1' -biphenyl ] -2,2' -diol 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 4-anilino triethoxysilane and/or 4- (2-triethoxysilylethyl) aniline on silica gel through reaction to obtain a product C;
s4: the product C and the ligand B undergo substitution reaction, and the ligand B is loaded on silica gel to obtain a product D;
s5: immersing the product D in a metal salt solution to obtain a bimetallic catalyst;
wherein the molar ratio of the 5,5' -dibromomethyl-3, 3' -di-tert-butyl-6, 6' -dimethyl- [1,1' -biphenyl ] -2,2' -diol to the acetyl chloride in the S1 is 1 (1.1-1.5).
2. The preparation method according to claim 1, wherein the reaction of S1 is performed in a solvent, the solvent being an ether and/or a ketone;
and/or, the reaction of S1 is carried out in an alkaline environment, and one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate are adopted;
and/or the reaction temperature of the S1 is-10-5 ℃ and the reaction time is 10-24 hours.
3. The preparation method according to claim 2, wherein the solvent of S1 is tetrahydrofuran and/or acetone;
and/or, the reaction of S1 is carried out in an alkaline environment, and triethylamine is adopted;
and/or the reaction temperature of the S1 is-5-0 ℃ and the reaction time is 11-13 h.
4. A production method according to claim 3, wherein the solvent of S1 is tetrahydrofuran.
5. The preparation method according to claim 1, wherein the molar ratio of diphenyl phosphorus chloride to the product A in S2 is 1 (1-5);
and/or, the reaction of S2 is performed in a solvent, which is an ether and/or a ketone;
and/or, the reaction of S2 is carried out in an alkaline environment, and one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate are adopted;
and/or the reaction temperature of the S2 is-10 ℃ and the reaction time is 10-24 hours.
6. The preparation method according to claim 5, wherein the molar ratio of diphenyl phosphorus chloride to the product A in S2 is 1 (1.1-1.5);
and/or, the solvent tetrahydrofuran and/or acetone of the S2;
and/or, the reaction of S2 is carried out in an alkaline environment, and triethylamine is adopted;
and/or the reaction temperature of the S2 is-5-0 ℃ and the reaction time is 10-12 h.
7. The process according to claim 6, wherein the solvent for S2 is tetrahydrofuran.
8. 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 performed in a solvent;
and/or, the mass ratio of the silica gel, the solvent and the raw materials 4-anilinetriethoxysilane and/or 4- (2-triethoxysilylethyl) aniline in the S3 is 1 (30-50): (3-10);
and/or the reaction temperature of the S3 is 60-100 ℃ and the reaction time is 4-30 h.
9. The preparation method according to claim 8, wherein the solvent of S3 is one or more of toluene, xylene, tetrahydrofuran and acetone;
and/or, the mass ratio of the silica gel, the solvent and the raw materials 4-anilinetriethoxysilane and/or 4- (2-triethoxysilylethyl) aniline in the S3 is 1 (30-40): (3-5);
and/or the reaction temperature of the S3 is 70-80 ℃ and the reaction time is 6-8 h.
10. The preparation method according to claim 9, wherein the solvent of S3 is tetrahydrofuran.
11. The preparation method of claim 1, wherein the mass ratio of the product C to the ligand B in the S4 is 1 (1-15);
and/or, the reaction of S4 is performed in a solvent, which is an ether and/or a ketone;
and/or, the reaction of S4 is carried out in an alkaline environment, and one or more of potassium carbonate, triethylamine and cesium carbonate are adopted;
and/or the reaction temperature of the S4 is 20-100 ℃ and the reaction time is 12-50 h.
12. The preparation method of claim 11, wherein the mass ratio of the product C to the ligand B in the S4 is 1 (6-10);
and/or the solvent of S4 is tetrahydrofuran and/or acetone;
and/or, the reaction of S4 is carried out in an alkaline environment, and potassium carbonate is adopted;
and/or the reaction temperature of the S4 is 50-70 ℃ and the reaction time is 40-50 h.
13. The method of claim 12, wherein the solvent for S4 is acetone.
14. The method for preparing a catalyst according to claim 1, wherein the metal salt in S5 is any two of zinc chloride, aluminum chloride, tin chloride, cobalt chloride, iron chloride and magnesium chloride.
15. The catalyst preparation method according to claim 14, wherein the metal salts in S5 are aluminum chloride and zinc chloride;
the mass ratio of the product D to the metal salt is 1 (0.2-20) (0.25-20);
the dipping temperature is 70-100 ℃ and the dipping time is 2-12 h.
16. The method for preparing a catalyst according to claim 15, wherein the mass ratio of the product D to the metal salt in the S5 is 1 (1-2.5): 1-2.5;
the dipping temperature is 70-80 ℃ and the dipping time is 2-4 hours.
17. A bimetallic catalyst prepared by the method of any one of claims 1-16.
18. Use of a bimetallic catalyst prepared by the method of any one of claims 1-16 for the catalytic preparation of a polyether polyol.
19. Use according to claim 18, the bimetallic catalyst for the preparation of narrow-distribution polyether polyols.
20. The use according to claim 18, the method of preparing the polyether polyol being: in the presence of initiator and catalyst, the temperature and pressure conditions are controlled, epoxide monomer is added into the reactor, and the final product is obtained through polymerization.
21. Use according to claim 20, in which method a di-or tri-functional polyether having a molecular weight of more than 400g/mol is used as initiator;
controlling the reaction temperature to be 100-180 ℃ and the pressure to be 0.1-0.6 MPa;
and adding part of epoxide monomer, activating the catalyst when the pressure is reduced to half of the initial pressure, starting to continuously add the monomer, and obtaining the final product when the pressure is not reduced any more.
22. Use according to claim 21, wherein the reaction temperature is controlled to be 130-140 ℃ and the pressure is controlled to be 0.1-0.2 MPa in the process.
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