CN114249885A - Bimetallic catalyst and preparation method and application thereof - Google Patents

Bimetallic catalyst and preparation method and application thereof Download PDF

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CN114249885A
CN114249885A CN202210019698.6A CN202210019698A CN114249885A CN 114249885 A CN114249885 A CN 114249885A CN 202210019698 A CN202210019698 A CN 202210019698A CN 114249885 A CN114249885 A CN 114249885A
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CN114249885B (en
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殷玲
李兴伟
丁志勇
崔焱朝
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Wanhua Chemical Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G65/269—Mixed catalyst systems, i.e. containing more than one reactive component or catalysts formed in-situ
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/16—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • 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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
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Abstract

The invention discloses a bimetallic catalyst and a preparation method and application thereof. The bimetallic catalyst contains more than two metal complexes

Description

Bimetallic catalyst and preparation method and application thereof
Technical Field
The invention relates to the field of catalysts, and particularly relates to a bimetallic catalyst, and a preparation method and application thereof.
Background
The traditional bimetallic catalyst taking zinc cobaltate cyanide as a center and coordinating various ligands is widely applied to the field of polyether, and the produced polyether polyol has the advantages of low unsaturation degree (0.005-0.008 mol/kg), narrow distribution (Mw/Mn <1.2) and the like. However, the catalyst is sensitive to alkaline environment, so sulfuric acid or phosphoric acid and the like are usually added to adjust the acidic environment in the use process, which easily causes the decomposition of the zinc cobalt cyanide to generate hydrocyanic acid, and has potential risk. Therefore, it is necessary to develop a high activity catalyst without cyano group.
Polyether polyol is generally used for preparing polyurethane products, along with the rapid development of economy in China, the demand of polyurethane is gradually increased, the application field is wider and wider, and because of different use environments, a plurality of products have a mildew phenomenon in the use process. How to create a preparation method of the mildew-resistant polyurethane without influencing the performance of products has a very positive significance in the industry.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a novel bimetallic catalyst which does not contain cyano groups and has high catalytic activity.
The invention also aims to provide a preparation method and application of the bimetallic catalyst.
In order to achieve the above objects and achieve the above technical effects, the present invention adopts the following technical scheme:
a bimetallic catalyst comprising two or more metal complexes having the structure:
Figure BDA0003461962790000021
wherein M is one of zinc, aluminum, tin, cobalt, iron and magnesium.
Preferably, the bimetallic catalyst comprises two of the above metal complexes, preferably, the molar ratio of the two metals is 1: 2-2: 1.
another object of the present invention is to provide a method for preparing a bimetallic catalyst.
A method for preparing a bimetallic catalyst, the method comprising the steps of:
s1, reacting 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene with bromine to generate a product C1;
Figure BDA0003461962790000022
s2: c1 was coupled with potassium vinyltrifluoroborate via SUZUKI to give product C2;
Figure BDA0003461962790000023
s3: c2 reacts with 2,2, 2-trifluoroethanethiol to generate the novel fluorine-containing organic ligand.
Figure BDA0003461962790000024
S4: and (3) reacting the product of S3 with a salt solution of metal M to obtain a crude metal complex.
Figure BDA0003461962790000031
S5 the bimetallic catalyst can be obtained by mixing more than two metal complexes or simultaneously adding more than two salts of the metal M into S4.
In the invention, the molar ratio of the 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene to bromine in S1 is 1 (2-3), preferably 1 (2-2.4).
In the present invention, the reaction of S1 is carried out in a solvent, which is any organic solvent capable of dissolving 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene, preferably dichloromethane and/or tetrahydrofuran, more preferably tetrahydrofuran.
In the invention, the reaction temperature of S1 is 5-25 ℃, the reaction time is 10-24 h, and the preferable reaction temperature is 5-15 ℃ and the reaction time is 11-13 h.
In the invention, the SUZUKI coupling in S2 is carried out in an organic solvent and an alkaline environment by adopting a palladium catalyst; preferably, the palladium catalyst is selected from one or more of palladium acetate, tetrakis (triphenylphosphine) palladium, diphenylphosphine palladium dichloride and 1, 1-diphenylphosphine ferrocene palladium dichloride; preferably, the organic solvent is ether and/or toluene, wherein the ether is selected from one or more of 1, 4-dioxane, THF and diethyl ether; preferably, the alkaline environment is obtained by adding a base to the system, preferably, the added base is one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate.
In the invention, the reaction conditions in S2 are that the temperature is 90-120 ℃, the reaction time is 24-72 h, preferably the reaction temperature is 100-110 ℃, and the reaction time is 60-72 h; preferably, the molar ratio of the C1, the potassium vinyltrifluoroborate, the palladium catalyst and the alkali is 1: 1-6: 0.001-0.008: 0.1-0.5, preferably 1: 2-4: 0.002-0.006: 0.2-0.4.
In the invention, the reaction conditions in S3 are that the temperature is 90-150 ℃, the reaction time is 5-24 h, preferably the reaction temperature is 110-120 ℃, and the reaction time is 6-8 h; preferably, the molar ratio of the C2 to the 2,2, 2-trifluoroethanethiol is 1 (2-3), preferably 1 (2-2.4).
In the invention, an initiator can be added into the S3, the initiator can be selected from azo initiators, and the addition amount of the initiator can be 0.01-0.06 of the molar amount of the product C2.
In the present invention, the salt of the metal M described in S4 belongs to lewis acids, preferably zinc chloride, aluminum chloride, tin chloride, cobalt chloride, ferric chloride and magnesium chloride; preferably, the salt of the metal M needs to be dissolved in THF at high temperature in advance; more preferably, the THF is anhydrous THF at a temperature of 50-70 deg.C.
In the invention, the reaction conditions in S4 are that the temperature is 70-100 ℃, the reaction time is 2-12 h, preferably the reaction temperature is 70-80 ℃, and the reaction time is 2-4 h; the molar ratio of the fluorine-containing organic ligand prepared in S3 to the salt of the metal M is 1: 1-1: 20, preferably 1: 10-1: 15.
In the invention, more than two kinds of metal M salts can be simultaneously added into S4 to react with the product in S3 to prepare more than two kinds of metal complexes, or one kind of metal M complex can be independently prepared and more than two kinds of metal complexes are mixed.
It is a further object of the present invention to provide the use of said bimetallic catalyst.
Use of the bimetallic catalyst of the invention for the catalytic preparation of polyether polyols, preferably for the preparation of narrow-distribution polyether polyols having a molecular weight of 500-.
In the invention, 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 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; the catalyst is the bimetallic catalyst or the bimetallic catalyst prepared by the preparation method.
Preferably, the adding amount of the catalyst is 30-120ppm of the mass of the product polyether polyol; 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 catalyst of the invention can be used for preparing polyether polyol with excellent performances of narrow distribution, low unsaturation degree, bacteriostasis and the like.
A polyurethane foam is prepared from the polyether polyol disclosed by the invention.
In the present invention, the pressures are gauge pressures.
Compared with the prior art, the invention has the following beneficial effects:
1) the catalyst does not contain cyano, and free cyano or complex cyano releases hydrocyanic acid when meeting acid, so the catalyst reduces the synthetic process and the risk of using the catalyst;
2) the catalyst of the invention introduces fluorine element, and the catalyst does not need to be separated, so that the prepared polyether polyol has the bacteriostatic effect, and the anti-mildew performance of the polyurethane product can be improved.
3) The traditional bimetallic catalyst taking zinc cobaltate cyanide as a center and coordinating with various ligands is easy to combine with oxygen atoms in water due to the electron supply characteristic of active center zinc ions, so that the activity is reduced. The invention takes a novel ligand as a center and coordinates with active center metal ions, thereby avoiding oxygen atoms in water molecules from occupying active points, improving the activity of the catalyst and shortening the activation time. The obtained polyether polyol has the advantages of narrow distribution (1.02-1.03) and low unsaturation degree (0.002-0.003).
Detailed Description
The present invention is further described below with reference to examples.
The test methods and characterization procedures involved in the examples are as follows: 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; NMR: and adding a small amount of dried sample into a nuclear magnetic tube, adding deuterated dimethyl sulfoxide (DMSO-d6) to dissolve, and performing test characterization after uniform ultrasonic dispersion. Test range: 0 to 16 ppm.
The raw material sources are as follows:
4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene CAS: 83016-16-4 from Shanghai Nafu Biotechnology, Inc.; the bromine water is from Beijing Datian Fengtu chemical technology, Inc.; THF was obtained from chemical reagents of Mimi Europe, Inc., Tianjin; sodium carbonate was from Hebei Yangxi chemical Co., Ltd; the ethyl acetate is from Henan Tianfu chemical Co., Ltd; the potassium carbonate is from chemical reagent of Mimi Europe, Inc. of Tianjin; tetrabutylammonium bromide is from Zhengzhou alpha chemical industry Co., Ltd; the potassium vinyltrifluoroborate is from Zhengzhou alpha chemical industry Co., Ltd; the 2,2, 2-trifluoroethanethiol is obtained from Shanghai Jinle Kogyo Co.
Example 1
1. Synthesizing a bimetallic catalyst:
s1, slowly dripping 4mol of bromine into 400ml of THF solution dissolved with 2mol of 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene under the conditions of inert gas atmosphere, 5 ℃ and magnetic stirring, reacting for 12h, adding saturated sodium carbonate aqueous solution prepared by 2mol of sodium carbonate, extracting the reaction solution by 400ml of ethyl acetate and 600ml of water respectively, and performing rotary evaporation to obtain 1.80mol of a product C1.
S2: a30% potassium carbonate aqueous solution containing 0.36mol of potassium carbonate, 1.8mol of product C1, 3.6mol of potassium vinyltrifluoroborate and 2000ml of THF were sequentially added to a three-necked flask with a magneton stirrer, nitrogen was substituted three times, 0.0036mol of tetrakis (triphenylphosphine) palladium was added under a nitrogen atmosphere, the temperature was raised to 110 ℃ for reaction, the reaction was terminated after 72 hours, and the mixture was cooled to room temperature. Filter through funnel and use 1000ml CH2Cl2Washing, and respectively using 2000ml of CH for filtrate2Cl2And 400ml of brine, drying the obtained liquid by using anhydrous MgSO4, filtering, and carrying out rotary evaporation on the filtrate to obtain a crude product; separation by column chromatography using dichloromethane/petroleum ether (1:5 by volume) gave 1.50mol of product C2.
S3: mixing 1mol of the product C2, 2.2mol of 2,2, 2-trifluoroethanethiol and 0.02mol of azobisisobutyronitrile, carrying out reflux reaction for 6h at 110 ℃ by using 2000ml of toluene as a solvent, cleaning by using 3000ml of ethanol after the reaction is finished, and removing volatile components by reduced pressure distillation to obtain 0.86mol of the product C3.
S4: at 70 ℃, 0.5mol of aluminum chloride and 0.5mol of zinc chloride are dissolved in THF, the temperature is kept, 0.1mol of product C3 is added into the THF for reaction for 2 hours, 1000ml of ethanol is adopted for washing after rotary evaporation to obtain a crude catalyst, 500ml of deionized water is used for washing, and the crude catalyst is placed in a vacuum oven at 50 ℃ for 4 hours to obtain 0.092mol of catalyst product.
2. And (3) synthesis of polyether polyol:
1) mixing 500g of polyglycerol with molecular weight of 500g/mol as an initiator with 0.030g of 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 vacuum-pumping environment;
2) heating to 130 ℃, adding 50g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) the time for the pressure to drop to half of the initial pressure was 5min, 450g of propylene oxide was added to the reaction vessel, and the reaction temperature was controlled at 135 ℃ and the pressure at 0.1MPa (in terms of gauge pressure) during the reaction. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 2
1. Synthesizing a bimetallic catalyst:
s1, slowly and dropwise adding 4.2mol of bromine into 400ml of THF solution dissolved with 2mol of 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene under the conditions of inert gas atmosphere, 5 ℃ and magnetic stirring, reacting for 12 hours, adding saturated sodium carbonate aqueous solution prepared by 2.2mol of sodium carbonate, extracting reaction liquid by 400ml of ethyl acetate and 600ml of water respectively, and performing rotary evaporation to obtain 1.82mol of product C1.
S2: a30% potassium carbonate aqueous solution prepared from 0.54mol of potassium carbonate, 1.8mol of a product C1, 5.4mol of potassium vinyltrifluoroborate and 2000ml of THF are sequentially added into a three-neck flask with a magneton stirring, nitrogen is replaced for three times, 0.0072mol of tetrakis (triphenylphosphine) palladium is added under nitrogen atmosphere, the temperature is raised to 110 ℃ for reaction, the reaction is stopped after 72 hours, and the mixture is cooled to room temperature. Filter through funnel and use 1000ml CH2Cl2Washing, and respectively using 2000ml of CH for filtrate2Cl2And 400ml of brine, drying the obtained liquid by using anhydrous MgSO4, filtering, and carrying out rotary evaporation on the filtrate to obtain a crude product; separation by column chromatography using dichloromethane/petroleum ether (1:5 by volume) gave 1.6mol of product C2.
S3: mixing 1mol of the product C2, 2.3mol of 2,2, 2-trifluoroethanethiol and 0.03mol of azobisisobutyronitrile, carrying out reflux reaction for 6h at 110 ℃ by using 2000ml of toluene as a solvent, cleaning by using 3000ml of ethanol after the reaction is finished, and removing volatile components by reduced pressure distillation to obtain 0.86mol of the product C3.
S4: at 70 ℃, 0.6mol of cobalt chloride and 0.9mol of zinc chloride are dissolved in THF, the temperature is kept, 0.1mol of product C3 is added into the THF for reaction for 2 hours, 1000ml of ethanol is adopted for washing after rotary evaporation to obtain a crude catalyst, 500ml of deionized water is used for washing, and the crude catalyst is placed in a vacuum oven at 50 ℃ for 4 hours to obtain 0.094mol of catalyst product.
2. And (3) synthesis of polyether polyol:
1) mixing 500g of polyglycerol with molecular weight of 500g/mol as an initiator with 0.030g of 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 vacuum-pumping environment;
2) heating to 130 ℃, adding 50g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) the time for the pressure to drop to half of the initial pressure was 4min, 450g of propylene oxide was added to the reaction vessel, and the reaction temperature was controlled at 135 ℃ and the pressure at 0.1MPa (in terms of gauge pressure) during the reaction. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 3
1. Synthesizing a bimetallic catalyst:
s1, slowly and dropwise adding 4.4mol of bromine into 400ml of THF solution dissolved with 2mol of 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene under the conditions of inert gas atmosphere, 5 ℃ and magnetic stirring, reacting for 12h, adding saturated sodium carbonate aqueous solution prepared by 2.4mol of sodium carbonate, extracting the reaction solution by 400ml of ethyl acetate and 600ml of water respectively, and performing rotary evaporation to obtain 1.84mol of product C1.
S2: a30% potassium carbonate aqueous solution prepared by 0.72mol of potassium carbonate, 1.8mol of a product C1, 7.2mol of potassium vinyltrifluoroborate and 2000ml of THF are sequentially added into a three-neck flask with a magneton stirring, nitrogen is replaced for three times, 0.0108mol of tetrakis (triphenylphosphine) palladium is added under the nitrogen atmosphere, the temperature is raised to 110 ℃ for reaction, the reaction is stopped after 72 hours, and the reaction is cooled to room temperature. Filter through funnel and use 1000ml CH2Cl2Washing, and respectively using 2000ml of CH for filtrate2Cl2And 400ml of brine, drying the obtained liquid by using anhydrous MgSO4, filtering, and carrying out rotary evaporation on the filtrate to obtain a crude product; separation by column chromatography using dichloromethane/petroleum ether (1:5 by volume) gave 1.6mol of product C2.
S3: mixing 1mol of the product C2, 2mol of 2,2, 2-trifluoroethanethiol and 0.04mol of azobisisobutyronitrile, carrying out reflux reaction for 6h at 110 ℃ by using 2000ml of toluene as a solvent, cleaning by using 3000ml of ethanol after the reaction is finished, and removing volatile components by reduced pressure distillation to obtain the product C3 of 0.8 mol.
S4: at 70 ℃, 0.4mol of ferric chloride and 0.8mol of magnesium chloride are dissolved in THF, the temperature is kept, 0.1mol of product C3 is added into the THF for reaction for 2 hours, 1000ml of ethanol is adopted for washing after rotary evaporation to obtain a crude catalyst, 500ml of deionized water is used for washing, and the crude catalyst is placed in a vacuum oven at 50 ℃ for 4 hours to obtain 0.094mol of catalyst product.
2. And (3) synthesis of polyether polyol:
1) mixing 500g of polyglycerol with molecular weight of 500g/mol as an initiator with 0.030g of 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 vacuum-pumping environment;
2) heating to 130 ℃, adding 50g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) the time for the pressure to drop to half of the initial pressure was 7min, 450g of propylene oxide was added to the reaction vessel, and the reaction temperature was controlled at 135 ℃ and the pressure at 0.1MPa (in terms of gauge pressure) during the reaction. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Example 4
1. Synthesizing a bimetallic catalyst:
s1, slowly and dropwise adding 4.8mol of bromine into 400ml of THF solution dissolved with 2mol of 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene under the conditions of inert gas atmosphere, 5 ℃ and magnetic stirring, reacting for 12h, adding saturated sodium carbonate aqueous solution prepared by 2mol of sodium carbonate, extracting the reaction solution by 400ml of ethyl acetate and 600ml of water respectively, and performing rotary evaporation to obtain 1.84mol of product C1.
S2: a30% potassium carbonate aqueous solution prepared by 0.72mol of potassium carbonate, 1.8mol of a product C1, 3.6mol of potassium vinyltrifluoroborate and 2000ml of THF are sequentially added into a three-neck flask with a magneton stirring, nitrogen is replaced for three times, 0.0108mol of tetrakis (triphenylphosphine) palladium is added under the nitrogen atmosphere, the temperature is raised to 110 ℃ for reaction, the reaction is stopped after 72 hours, and the reaction is cooled to room temperature. Filter through funnel and use 1000ml CH2Cl2Washing, and respectively using 2000ml of CH for filtrate2Cl2And 400ml of brine, drying the obtained liquid by using anhydrous MgSO4, filtering, and carrying out rotary evaporation on the filtrate to obtain a crude product; separation by column chromatography using dichloromethane/petroleum ether (1:5 by volume) gave 1.54mol of product C2.
S3: mixing 1mol of the product C2, 2.4mol of 2,2, 2-trifluoroethanethiol and 0.03mol of azobisisobutyronitrile, carrying out reflux reaction for 6h at 110 ℃ by using 2000ml of toluene as a solvent, cleaning by using 3000ml of ethanol after the reaction is finished, and removing volatile components by reduced pressure distillation to obtain 0.86mol of the product C3.
S4: at 70 ℃, 0.6mol of cobalt chloride and 0.8mol of magnesium chloride are dissolved in THF, the temperature is kept, 0.1mol of product C3 is added into the THF for reaction for 2 hours, 1000ml of ethanol is adopted for washing after rotary evaporation to obtain a crude catalyst, 500ml of deionized water is used for washing, and the crude catalyst is placed in a vacuum oven at 50 ℃ for 4 hours to obtain 0.094mol of catalyst product.
2. And (3) synthesis of polyether polyol:
1) mixing 500g of polyglycerol with molecular weight of 500g/mol as an initiator with 0.060g of 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 50g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) the time for the pressure to drop to half of the initial pressure was 2.5min, 450g of propylene oxide was added to the reaction vessel, and the reaction temperature was controlled at 135 ℃ and the pressure at 0.1MPa (in terms of gauge pressure) during the reaction. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Comparative example 1
The catalyst of the comparative example adopts a commercial bimetallic catalyst, and is purchased from Changzhou Hongyu chemical industry Co., Ltd, and the product name of the company is as follows: henzhou DMC bimetallic catalyst. The bimetallic elements are zinc and cobalt.
The catalyst is used for synthesizing polyether glycol. The following were used:
1) mixing 500g of polyglycerol with molecular weight of 500g/mol as an initiator with 0.030g of 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 vacuum-pumping environment;
2) heating to 130 ℃, adding 50g of propylene oxide accounting for 10 percent of the mass of the initiator, and observing pressure change;
3) the time for the pressure to drop to half of the initial pressure was 8min, 450g of propylene oxide was added to the reaction vessel, and the reaction temperature was controlled at 135 ℃ and the pressure at 0.1MPa (in terms of gauge pressure) during the reaction. Reacting until the pressure is not reduced any more to obtain the polyether polyol product.
Performance test 1:
the polyether polyol prepared in examples 1-4 and the polyether polyol prepared in comparative example 1 are tested for molecular weight of prepared products by using a high resolution mass spectrum (Waters Xevo G2 QTof), and a sample preparation method is to take a small amount of sample to dissolve 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 unsaturation degree according to the determination of the unsaturation degree of the 6 th part of GB/T12008.6-2010 plastic polyether polyol; the results are shown in the table.
Figure BDA0003461962790000111
Comparing examples 1-3 and comparative example 1, in which the catalyst addition amount was the same, it was found that the reaction time and the total reaction time of example 2 were the shortest, indicating that the catalyst activity of example 2 was the highest, and the catalyst activities of examples 1-3 according to the present invention were all higher than the commercial catalyst of comparative example 1; the PDI and unsaturation indicators for comparative examples 1-4 and comparative example 1, examples 1-4, were superior to comparative example 1.
Performance test 2:
preparing polyurethane foam: 50 parts of polyether polyol, 50 parts of H45D50 parts, 2 parts of silicone oil, 2 parts of diethanol amine, 20 parts of calcium carbonate and 3 parts of water in the embodiment 1/2/3/4 and the comparative example 1 are respectively taken, stirred uniformly, then 50 parts of isocyanate is added under high-speed stirring, stirred at high speed and foamed, and a polyurethane foam product is prepared.
And (3) testing the anti-mildew performance: polyurethane foam samples were commissioned to the service of the detection technology of the Zhongkou Co., Ltd. The mildew resistance can be characterized by a mildew resistance rating of no mildew at level 0 (no mildew observed at 50 times magnification with a microscope), trace growth at level 1 (mildew observed with the naked eye but less than 10% of growth coverage), mild growth at level 2 (greater than 10% and less than 25% of mildew area observed with the naked eye), moderate growth at level 3 (30% -60% of mildew area observed with the naked eye), and severe growth at level 4 (greater than 60% of mildew area observed with the naked eye).
Performance of Example 1 Example 2 Example 3 Example 4 Comparative example 1
Anti-mildew grade Stage 2 Level 1 Stage 2 Stage 2 Grade 3
Comparing the anti-mildew ratings of the polyurethane foams of examples 1-4 and comparative example 1, it can be seen that the polyether polyols of the examples of the present invention have anti-mildew effect, which is superior to the polyols prepared by the commercial catalysts, wherein the anti-mildew effect of the polyether polyol prepared by the catalyst of example 2 is the most excellent.

Claims (10)

1. A bimetallic catalyst, characterized in that the catalyst comprises two or more metal complexes having the structure:
Figure FDA0003461962780000011
wherein M is one of zinc, aluminum, tin, cobalt, iron and magnesium.
2. The catalyst according to claim 1, characterized in that said bimetallic catalyst comprises two of the above metal complexes, preferably in a molar ratio of 1: 2-2: 1.
3. a method of preparing the bimetallic catalyst of claims 1 or 2, comprising the steps of:
s1, reacting 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene with bromine to generate a product C1;
s2: c1 was coupled with potassium vinyltrifluoroborate via SUZUKI to give product C2;
s3: c2 reacts with 2,2, 2-trifluoroethanethiol to generate a novel fluorine-containing organic ligand;
s4: reacting the product of S3 with a salt solution of metal M to obtain a crude metal complex;
s5 the bimetallic catalyst can be obtained by mixing more than two metal complexes or simultaneously adding more than two salts of the metal M into S4.
4. The preparation method according to claim 3, wherein the molar ratio of the 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene to bromine in S1 is 1 (2-3), preferably 1 (2-2.4);
preferably, the reaction of S1 is carried out in a solvent, which is any organic solvent capable of dissolving 4, 5-dihydroxy-2, 6-dimethoxy-9, 10-dihydrophenanthrene, preferably dichloromethane and/or tetrahydrofuran;
preferably, the reaction temperature of S1 is 5-25 ℃, the reaction time is 10-24 h, the reaction temperature is 5-15 ℃, and the reaction time is 11-13 h.
5. The method according to claim 3, wherein the SUZUKI coupling in S2 is performed in an organic solvent and an alkaline environment using a palladium catalyst;
preferably, the palladium catalyst is selected from one or more of palladium acetate, tetrakis (triphenylphosphine) palladium, diphenylphosphine palladium dichloride and 1, 1-diphenylphosphine ferrocene palladium dichloride;
preferably, the organic solvent is ether and/or toluene, wherein the ether is selected from one or more of 1, 4-dioxane, THF and diethyl ether;
preferably, the alkaline environment is obtained by adding a base to the system, preferably, the added base is one or more of sodium carbonate, potassium carbonate, triethylamine and cesium carbonate.
6. The method according to any one of claims 3 to 5, wherein the reaction conditions in S2 are a temperature of 90 to 120 ℃ and a reaction time of 24 to 72 hours, preferably a reaction temperature of 100 to 110 ℃ and a reaction time of 60 to 72 hours; preferably, the molar ratio of the C1, the potassium vinyltrifluoroborate, the palladium catalyst and the alkali is 1: 1-6: 0.001-0.008: 0.1-0.5, preferably 1: 2-4: 0.002-0.006: 0.2-0.4.
7. The method according to any one of claims 3 to 6, wherein the reaction conditions in S3 are a temperature of 90 to 150 ℃ and a reaction time of 5 to 24 hours, preferably a reaction temperature of 110 to 120 ℃ and a reaction time of 6 to 8 hours;
preferably, the molar ratio of the C2 to the 2,2, 2-trifluoroethanethiol is 1 (2-3), preferably 1 (2-2.4);
preferably, an initiator is further added into the S3, the initiator can be selected from azo initiators, and the addition amount of the initiator can be 0.01-0.06 of the molar amount of the product C2.
8. The process according to any one of claims 3 to 7, wherein the salt of the metal M in S4 belongs to Lewis acids, preferably zinc chloride, aluminum chloride, tin chloride, cobalt chloride, ferric chloride and magnesium chloride;
preferably, the reaction conditions in S4 are that the temperature is 70-100 ℃, the reaction time is 2-12 h, the reaction temperature is 70-80 ℃, and the reaction time is 2-4 h; the molar ratio of the fluorine-containing organic ligand prepared in S3 to the salt of the metal M is 1: 1-1: 20, preferably 1: 10-1: 15.
9. Use of a bimetallic catalyst as described in claim 1 or 2 or as prepared by a process as described in any one of claims 3 to 8 for the catalytic preparation of polyether polyols, preferably for the preparation of polyether polyols having a molecular weight of 500-.
10. Use according to claim 9, the catalyst being added in an amount of 30-120ppm by mass of the product polyether polyol.
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