CN114940752A - Catalyst for ring-opening polymerization of epoxy and preparation method and application thereof - Google Patents

Catalyst for ring-opening polymerization of epoxy and preparation method and application thereof Download PDF

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CN114940752A
CN114940752A CN202210735169.6A CN202210735169A CN114940752A CN 114940752 A CN114940752 A CN 114940752A CN 202210735169 A CN202210735169 A CN 202210735169A CN 114940752 A CN114940752 A CN 114940752A
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boron nitride
catalyst
ring
opening polymerization
epoxy
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CN114940752B (en
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王利国
曾宪强
李会泉
曹妍
贺鹏
陈家强
郑征
徐爽
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Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
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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
    • C08G65/2603—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2642—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds characterised by the catalyst used
    • C08G65/2645—Metals or compounds thereof, e.g. salts
    • C08G65/2663—Metal cyanide catalysts, i.e. DMC's
    • 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
    • C08G65/2693—Supported catalysts
    • 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

Abstract

The invention provides a catalyst for ring-opening polymerization of epoxy and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a carrier, an active component and a solvent, drying after mixing, and grinding to obtain the catalyst for epoxy ring-opening polymerization, wherein the carrier comprises boron nitride and/or modified boron nitride. The carrier is matched with the active component, so that the reaction activity of the ring-opening polymerization reaction of the epoxy compound can be improved, and the polymerization rate is improved.

Description

Catalyst for ring-opening polymerization of epoxy and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a catalyst for ring-opening polymerization of epoxy, a preparation method and application thereof.
Background
Polyethers are a class of polymeric materials widely used in the field of synthesis of polyurethanes, electrolytes for lithium batteries, paper making, paints, elastomers, foams, cosmetics, etc., and are prepared by ring-opening polymerization of epoxide monomers, for example, ethylene oxide and propylene oxide are the most commonly used monomers.
The most used catalysts in the industry for the synthesis of polyethers are alkali metal hydroxides or Zn-Co Double Metal Cyanide (DMC). Potassium hydroxide is the most commonly used catalyst because of its relatively low cost and moderate catalytic activity. However, since strong basicity easily causes isomerization reaction of monomers, high quality polyether products cannot be prepared. In addition, when potassium hydroxide is used as a catalyst, the polyether product needs to be refined to remove potassium ions, which increases the production cost. The double metal cyanide is used as a substitute catalyst of potassium hydroxide, does not need further purification operation in the using process, has high catalytic activity, and can realize the polymerization conversion of the monomer into polyether in a short reaction time.
The catalytic activity of double metal cyanide catalysts is mainly affected by metal active sites, but the metal active sites can not completely participate in the reaction process, so that the utilization rate of active metals is low. Researchers have successfully improved the activity of double metal cyanide catalysts by immobilizing the double metal cyanide on a support, while reducing the amount of active metal required. The commonly used carrier is silicon oxide and titanium dioxide, boron nitride is a crystal formed by nitrogen atoms and boron atoms, has the advantages of high thermal conductivity, high specific surface area, strong chemical stability and the like, and can be applied to catalytic systems such as ammonia synthesis, CO oxidation, Fischer-Tropsch synthesis and the like as the carrier.
The invention adopts boron nitride or modified boron nitride as a double metal cyanide catalyst carrier, and double metal cyanide as an active component, and prepares a high-activity catalyst for epoxy ring-opening polymerization by a simple impregnation loading method, and a preparation method and application thereof.
Disclosure of Invention
The invention aims to provide a catalyst for epoxy ring-opening polymerization, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst for ring-opening polymerization of epoxy, the method comprising the steps of:
mixing a carrier, an active component and a solvent, drying after mixing, and grinding to obtain the catalyst for epoxy ring-opening polymerization.
The support comprises boron nitride and/or modified boron nitride.
Preferably, the mixing comprises ultrasound and/or stirring.
Preferably, the stirring speed is 300-800r/min, such as 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, but not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the stirring time is 12-20h, for example 12h, 13h, 14h, 15h, 16h, 18h or 20h, but is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
Preferably, the drying method comprises vacuum drying at a temperature of 90-110 deg.C, such as 90 deg.C, 95 deg.C, 100 deg.C, 105 deg.C or 110 deg.C, but not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the solvent comprises water.
Preferably, the mass ratio of the carrier, active ingredient and solvent is 1 (0.1-0.4):10, which may be, for example, 1:0.1:10, 1:0.15:10, 1:0.2:10, 1:0.25:10, 1:0.3:10, 1:0.35:10 or 1:0.4:10, but is not limited to the recited values, and other values not recited within the range of values are equally applicable.
Preferably, the particle size D50 of the catalyst for ring-opening polymerization of epoxy obtained after grinding is 0.5 to 1 μm, and may be, for example, 0.5. mu.m, 0.6. mu.m, 0.7. mu.m, 0.8. mu.m, 0.9. mu.m or 1 μm, but is not limited to the values listed, and other values not listed in the numerical ranges are also applicable.
Preferably, the preparation method of the boron nitride comprises the following steps:
(1) mixing boric acid, a nitrogen source, a dispersing agent and water, uniformly dispersing, and drying and crystallizing to obtain a crystal precursor;
(2) pyrolyzing the crystal precursor obtained in the step (1) under a protective atmosphere to obtain the boron nitride;
preferably, the mass ratio of the boric acid, the nitrogen source, the dispersing agent and the water in the step (1) is 1 (20-40) to (1-4) to (20-50).
The ratio of the boric acid to the nitrogen source in step (1) is 1:20 to 40 by mass, and may be, for example, 1:20, 1:25, 1:30, 1:35 or 1:40, but is not limited to the values recited, and other values not recited in the range of values are also applicable.
The ratio of boric acid to dispersant in step (1) is 1 (1-4) by mass, and may be, for example, 1:1, 1:2, 1:3 or 1:4, but is not limited to the values recited, and other values not recited within the range of values are also applicable.
The ratio of boric acid to water in step (1) is 1 (20-50) by mass, and may be, for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
Preferably, the nitrogen source of step (1) comprises urea and/or melamine.
Preferably, the dispersing agent in step (1) comprises any one or a combination of at least two of PEG-200, PEG-400 or PEG-1000, and typical but non-limiting combinations include a combination of PEG-200 and PEG-400, a combination of PEG-400 and PEG-1000, a combination of PEG-200 and PEG-1000, or a combination of PEG-200, PEG-400 and PEG-1000.
Preferably, the method of uniformly dispersing in step (1) includes ultrasonic dispersion, and the time of ultrasonic dispersion is 5-15min, such as 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but is not limited to the enumerated values, and other unrecited values in the numerical range are also applicable.
Preferably, the drying temperature in step (1) is 90-100 ℃, for example 90 ℃, 92 ℃, 95 ℃, 96 ℃, 98 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the range of values are equally applicable; the time is 8-12h, for example 8h, 9h, 10h, 11h or 12h, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the gas used in the protective atmosphere in step (2) comprises nitrogen and/or an inert gas.
Preferably, the pyrolysis temperature in step (2) is 900-; the time is 6-9h, for example 6h, 7h, 8h or 9h, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the preparation method of the modified boron nitride comprises the following steps:
(a) mixing nitrate, boron nitride and water, uniformly dispersing, and drying to obtain a precursor;
(b) and (b) pyrolyzing the precursor obtained in the step (a) in a protective atmosphere to obtain the modified boron nitride.
After the modified boron nitride is doped with metal, the dispersed metal sites can be used as Lewis acid sites to activate epoxide, thereby accelerating the ring opening step.
Preferably, the mass ratio of the nitrate, the boron nitride and the water in the step (a) is (0.1-0.5): (1-3): (20-30).
The mass ratio of nitrate to boron nitride in step (a) is (0.1-0.5): (1-3), and may be, for example, 0.1:1, 0.3:1, 0.5:1, 0.3:2, 0.5:1, 0.5:2 or 0.5:3, but is not limited to the values recited, and other values not recited within the range of values are equally applicable.
The ratio of boron nitride to water in step (a) is (1-3) to (20-30), and may be, for example, 1:20, 1:25, 1:30, 2:20, 2:25, 2:30, 3:20, or 3:25, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the nitrate in step (a) comprises any one of lanthanum nitrate, cerium nitrate, zinc nitrate, copper nitrate or cobalt nitrate or a combination of at least two of them, typical but non-limiting combinations include a combination of lanthanum nitrate and cerium nitrate, a combination of cerium nitrate and zinc nitrate, a combination of zinc nitrate and copper nitrate, a combination of copper nitrate and cobalt nitrate, a combination of lanthanum nitrate, cerium nitrate and zinc nitrate, a combination of zinc nitrate, copper nitrate and cobalt nitrate, or a combination of lanthanum nitrate, cerium nitrate, zinc nitrate, copper nitrate and copper nitrate.
Preferably, the method for uniformly dispersing in step (a) comprises post-ultrasonic stirring.
Preferably, the stirring time is 10 to 20 hours, for example 10 hours, 12 hours, 15 hours, 16 hours, 18 hours or 20 hours, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the drying temperature in step (a) is from 90 ℃ to 100 ℃, for example 90 ℃, 92 ℃, 95 ℃, 96 ℃, 98 ℃ or 100 ℃, but not limited to the recited values, and other values not recited in the numerical ranges are equally applicable; the time is 10-20h, for example 10h, 12h, 15h, 16h, 18h or 20h, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the gas used in the protective atmosphere of step (b) comprises nitrogen and/or an inert gas.
Preferably, the pyrolysis temperature in step (b) is 600-700 ℃, for example 600 ℃, 620 ℃, 640 ℃, 650 ℃, 680 ℃ or 700 ℃, but not limited to the recited values, and other unrecited values within the numerical range are equally applicable; the time is 5-8h, for example 5h, 6h, 7h or 8h, but is not limited to the values listed, and other values not listed in the numerical range are equally applicable.
Preferably, the active component comprises a double metal cyanide.
The double metal cyanide of the present invention is a double metal cyanide that is conventional in the art, and the present invention is not particularly limited, and for example, the preparation method of the double metal cyanide of the present invention comprises the following steps:
(I) mixing zinc acetate dihydrate solution with acetic acid, then mixing the obtained mixed solution with a molecular sieve, heating and stirring to obtain dispersion liquid;
and (II) dropwise adding a potassium cobalt cyanide aqueous solution to the dispersion liquid obtained in the step (I), and then sequentially carrying out centrifugation, washing, ultrasound treatment and drying to obtain the double metal cyanide.
In a second aspect, the present invention provides a catalyst for ring-opening polymerization of epoxy, which is prepared by the preparation method of the first aspect.
In a third aspect, the present invention provides a use of the catalyst for ring-opening polymerization of epoxy according to the second aspect for ring-opening polymerization of epoxy compounds;
the epoxy compound includes any one of ethylene oxide, propylene oxide or butylene oxide or a combination of at least two thereof.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention can prepare a high-activity and stable double metal cyanide catalyst loaded with boron nitride or modified boron nitride by a simple impregnation loading method. In the catalytic polymerization of epoxy compounds, the activity of double metal cyanide compounds is enhanced by dispersion on a carrier, and the availability and number of metal active sites are increased;
(2) the boron nitride is used as a carrier, so that the boron nitride has a dispersing effect, boron atoms in the boron nitride have electron-deficient characteristics, have Lewis acidity and have an epoxy monomer activating effect, and the boron nitride and double metal cyanide cooperate to activate the epoxy monomer, so that the catalytic activity is further improved;
(3) according to the invention, after boron nitride is modified, Lewis acidity is enhanced, and the effect of activating an epoxy monomer by cooperating with double metal cyanide is enhanced, so that the catalytic activity is further improved;
(4) the invention adopts boron nitride or modified load double metal cyanide, reduces the consumption of active metal in the catalytic process, and can further reduce the cost of industrial production of polyether.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The double metal cyanide compounds used in the examples of the present invention and the comparative examples were prepared by the following method comprising the steps of:
(1) adding zinc acetate dihydrate (3mmol, 657mg) into 15mL of deionized water, mixing and stirring until the zinc acetate dihydrate is dissolved, and then adding 5mL of acetic acid and mixing uniformly;
(2) adding 2g of molecular sieve into the solution in the step (1), raising the temperature to 80 ℃, and continuing stirring;
(3) and (3) preparing 10mL of aqueous solution from potassium cobalt cyanide (1.5mmol, 498mg), dripping the aqueous solution into the dispersion liquid obtained in the step (2) at the speed of 5 seconds per drop, immediately taking out the reaction liquid after the dripping is finished, centrifuging the reaction liquid at the speed of 3500r/min for 3min, washing the reaction liquid with deionized water for three times, using 30mL of water each time, carrying out ultrasonic treatment for 30min, and carrying out vacuum drying at 80 ℃ for 10h to obtain 0.62g of double metal cyanide.
In the specific embodiment, the sources of the raw materials are as follows:
1, 2-butylene oxide: CAS number; 106-88-7, which is steamed after being refluxed in calcium hydride for 8 hours and purchased from Shanghai Aladdin Biotechnology GmbH.
Polyethylene glycol-400 (PEG-400): CAS number; 25322-68-3, molecular weight 400, available from Shanghai Aladdin Biotechnology Ltd.
Zinc acetate dihydrate: CAS number; 25322-68-3, available from Shanghai Allantin Biotechnology, Inc.
Potassium cobalt cyanide: CAS number; 13963-58-1, available from Shanghai Aladdin Biotechnology Ltd.
Acetic acid: CAS number; 64-19-7, available from Shanghai Allantin Biotechnology Ltd.
PEG-1000: 25322-68-3, average molecular weight 1000, available from Shanghai Aladdin Biotechnology Ltd.
The formula for the double metal cyanide loading is: (total mass of solid-mass of boron nitride)/total mass of solid X100%
Example 1
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of boron nitride and 0.2g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring at 500r/min for 16h, performing vacuum drying at 100 ℃ for 10h, and grinding to obtain the catalyst with the particle size D50 of 0.8 mu m for epoxy ring-opening polymerization.
The preparation method of the boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 2
This example provides a process for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 1 in that the mass of double metal cyanide in this example is 0.4g, and the rest is the same as example 1.
Example 3
This example provides a process for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 1 in that the mass of double metal cyanide in this example is 0.5g, and the rest is the same as example 1.
Example 4
This example provides a process for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 1 in that the mass of double metal cyanide in this example is 0.6g, and the rest is the same as example 1.
Example 5
This example provides a process for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 1 in that the mass of double metal cyanide in this example is 0.8g, and the rest is the same as example 1.
Example 6
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of modified boron nitride and 0.5g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring at 500r/min for 16h, performing vacuum drying at 100 ℃ for 10h, and grinding to obtain the catalyst with the particle size D50 of 0.8 mu m for the epoxy ring-opening polymerization.
The preparation method of the modified boron nitride comprises the following steps: adding 0.1g of cerium nitrate and 2g of boron nitride into 20mL of deionized water, performing ultrasonic treatment for 10min to obtain a dispersion, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, pyrolyzing the precursor at 650 ℃ for 6h under a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
the preparation method of the used boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 7
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 6 in that the mass of cerium nitrate in this example is 0.3g, and the rest is the same as example 6.
Example 8
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 6 in that the mass of cerium nitrate in this example is 0.5g, and the rest is the same as example 6.
Example 9
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 6 in that cerium nitrate and the like are replaced with copper nitrate in mass, and the rest is the same as example 6.
Example 10
This example provides a method for producing a catalyst for ring-opening polymerization of epoxy resin, which is different from example 6 in that cerium nitrate and the like are replaced by lanthanum nitrate in this example, and the rest is the same as example 6.
Example 11
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of boron nitride and 0.2g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring for 16h at 300r/min, performing vacuum drying for 10h at 100 ℃, and grinding to obtain the catalyst for epoxy ring-opening polymerization with the particle size D50 of 1 micron.
The preparation method of the boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6 hours at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 12
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of boron nitride and 0.2g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring for 16h at 800r/min, performing vacuum drying for 10h at 100 ℃, and grinding to obtain the catalyst for epoxy ring-opening polymerization with the particle size D50 of 0.5 mu m.
The preparation method of the boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 13
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of modified boron nitride and 0.5g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring for 16h at 300r/min, performing vacuum drying for 10h at 100 ℃, and grinding to obtain the catalyst with the particle size D50 of 1 mu m for the ring opening polymerization of the epoxy.
The preparation method of the modified boron nitride comprises the following steps: adding 0.1g of cerium nitrate and 2g of boron nitride into 20mL of deionized water, performing ultrasonic treatment for 10min to obtain a dispersion, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, pyrolyzing the precursor at 650 ℃ for 6h under a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
the preparation method of the used boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h for crystallization to obtain a precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 14
The embodiment provides a preparation method of a catalyst for ring-opening polymerization of epoxy, which comprises the following steps:
adding 2g of modified boron nitride and 0.5g of double metal cyanide into 20mL of deionized water, performing ultrasonic treatment for 10min, stirring for 16h at 800r/min, performing vacuum drying for 10h at 100 ℃, and grinding to obtain the catalyst with the particle size D50 of 0.5 mu m for epoxy ring-opening polymerization.
The preparation method of the modified boron nitride comprises the following steps: adding 0.1g of cerium nitrate and 2g of boron nitride into 20mL of deionized water, performing ultrasonic treatment for 10min to obtain a dispersion, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, pyrolyzing the precursor at 650 ℃ for 6h under a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
the preparation method of the used boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Example 15
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy, which is the same as example 7 except that the pyrolysis for preparing modified boron nitride is carried out at 600 ℃ for 8 hours in a nitrogen atmosphere.
Example 16
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy, which is the same as example 7 except that pyrolysis in preparing modified boron nitride is carried out at 700 ℃ for 5 hours in a nitrogen atmosphere.
Example 17
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy resin, which is the same as that of example 7 except that the pyrolysis temperature in preparing modified boron nitride is 580 ℃.
Example 18
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy resin, which is the same as that of example 7 except that the pyrolysis temperature for preparing modified boron nitride is 720 ℃.
Comparative example 1
This comparative example provides a double metal cyanide preparation method comprising the steps of:
(1) adding zinc acetate dihydrate (3mmol, 657mg) into 15mL of deionized water, mixing and stirring until the zinc acetate dihydrate is dissolved, and then adding 5mL of acetic acid and mixing uniformly;
(2) adding 2g of molecular sieve into the solution in the step (1), raising the temperature to 80 ℃, and continuing stirring;
(3) and (3) preparing 10mL of aqueous solution from potassium cobalt cyanide (1.5mmol, 498mg), dripping the aqueous solution into the dispersion liquid obtained in the step (2) at the speed of 5 seconds per drop, immediately taking out the reaction liquid after the dripping is finished, centrifuging the reaction liquid at the speed of 3500r/min for 3min, washing the reaction liquid with deionized water for three times, using 30mL of water each time, carrying out ultrasonic treatment for 30min, and carrying out vacuum drying at 80 ℃ for 10h to obtain 0.62g of double metal cyanide.
Comparative example 2
The present comparative example provides a boron nitride, the preparation method of which comprises the steps of:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Comparative example 3
The comparative example provides a modified boron nitride, the preparation method of which comprises the following steps:
adding 0.1g of cerium nitrate and 2g of boron nitride into 20mL of deionized water, carrying out ultrasonic treatment for 10min to obtain a dispersion, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, pyrolyzing the precursor for 6h under a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
The preparation method of the used boron nitride comprises the following steps:
firstly, 1g of boric acid, 30g of urea and 3g of PEG-1000 are dissolved in 30mL of deionized water, ultrasonic treatment is carried out for 10min, then the solution is poured into a quartz boat, and the quartz boat is dried at 100 ℃ for 10h to be crystallized to obtain the precursor. And finally, pyrolyzing the completely recrystallized precursor for 6h at 950 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
Application example 1
The catalysts prepared in examples 1-18 and comparative examples 1-3 are applied to ring-opening polymerization of epoxy compounds, and the specific operation steps are as follows:
under the protection of nitrogen, 1.5mg of catalyst is added into a 50mL autoclave, then 5g of polyethylene glycol and 18g of 1, 2-epoxybutane are added, stirring is started, the temperature is increased to 110 ℃, the reaction is carried out for 6h, the temperature is cooled to room temperature, and the unreacted 1, 2-epoxybutane is removed in vacuum, so that the polyether is obtained.
The results are shown in Table 1.
Application example 2
Under the protection of nitrogen, 1.5mg of the double metal cyanide provided in comparative example 1 is added into a 50mL autoclave, 5g of polyethylene glycol and 18g of 1, 2-epoxybutane are added, stirring is started, the temperature is raised to 110 ℃, the reaction is carried out for 6h, the temperature is cooled to room temperature, and the unreacted 1, 2-epoxybutane is removed in vacuum, so that the polyether is obtained.
As a result: the conversion of 1, 2-butylene oxide was 5.3%.
Application example 3
Under the protection of nitrogen, 1.5mg of the double metal cyanide catalyst provided in comparative example 1 and 4.5mg of the modified boron nitride provided in example 6 were added to a 50mL autoclave, 5g of polyethylene glycol and 18g of 1, 2-epoxybutane were then added, stirring was started, the temperature was raised to 110 ℃, reaction was carried out for 6 hours, cooling was carried out to room temperature, and unreacted 1, 2-epoxybutane was removed in vacuo to obtain polyether.
As a result: the conversion of 1, 2-butylene oxide was 45.6%.
TABLE 1
Figure BDA0003715021970000151
Figure BDA0003715021970000161
By catalyzing the epoxide ring-opening polymerization reaction by example 3 and comparative example 1, example 3 is boron nitride supported double metal cyanide catalyst catalyzing 1, 2-butylene oxide ring-opening polymerization for 6h, the conversion of 1, 2-butylene oxide is as high as 91.1%, while comparative example 1 is double metal cyanide catalyst catalyzing 1, 2-butylene oxide ring-opening polymerization for 6h, the conversion of 1, 2-butylene oxide is 25.1%. The result shows that the boron nitride and the double metal cyanide catalyst have synergistic catalysis effect and can improve the ring-opening polymerization rate of the 1, 2-epoxybutane. Example 7 the conversion rate of 1, 2-butylene oxide in 6 hours is as high as 99.8% by using the boron nitride modified supported double metal cyanide as the catalyst, which shows that the Lewis acidity and the catalytic activity are enhanced after the modified boron nitride is anchored with a metal site.
Example 7 and application example 3 in comparison, it can be found that the catalytic activity of double metal cyanide by loading onto modified boron nitride is significantly higher than that of the double metal cyanide and modified boron nitride mixture. It is shown that the zinc sites of DMC are very close to the Lewis sites on the surface of boron nitride, and the synergistic catalytic effect can be better generated. When boron nitride or modified boron nitride is used alone as a catalyst, the ring opening of the epoxy compound is difficult to realize only by the Lewis acid sites of boron and metal, so that the catalyst has no catalytic activity.
The above description is only for the specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the protection scope and the disclosure of the present invention.

Claims (10)

1. A preparation method of a catalyst for ring-opening polymerization of epoxy is characterized by comprising the following steps:
mixing a carrier, an active component and a solvent, drying after mixing, and grinding to obtain the catalyst for epoxy ring-opening polymerization;
the support comprises boron nitride and/or modified boron nitride.
2. The method of claim 1, wherein the mixing comprises sonication and/or stirring.
3. The method as claimed in claim 2, wherein the rotation speed of the stirring is 300-800 r/min;
preferably, the stirring time is 12-20 h;
preferably, the drying method comprises vacuum drying, and the temperature of the vacuum drying is 90-110 ℃.
4. The production method according to any one of claims 1 to 3, wherein the solvent comprises water;
preferably, the mass ratio of the carrier, the active component and the solvent is 1 (0.1-0.4) to 10;
preferably, the particle diameter D50 of the catalyst for ring-opening polymerization of epoxy obtained after grinding is 0.5 to 1 μm.
5. The method according to claim 4, wherein the method for producing boron nitride comprises the steps of:
(1) mixing boric acid, a nitrogen source, a dispersing agent and water, uniformly dispersing, and drying and crystallizing to obtain a crystal precursor;
(2) pyrolyzing the crystal precursor obtained in the step (1) under a protective atmosphere to obtain the boron nitride;
preferably, the mass ratio of the boric acid, the nitrogen source, the dispersing agent and the water in the step (1) is 1 (20-40) to (1-4) to (20-50).
6. The process according to claim 5, wherein the nitrogen source of step (1) comprises urea and/or melamine;
preferably, the dispersing agent in the step (1) comprises any one of PEG-200, PEG-400 or PEG-1000 or the combination of at least two of the PEG-200, the PEG-400 and the PEG-1000;
preferably, the method for uniformly dispersing in the step (1) comprises ultrasonic dispersing, wherein the ultrasonic dispersing time is 5-15 min;
preferably, the drying temperature in the step (1) is 90-100 ℃, and the time is 8-12 h;
preferably, the gas used in the protective atmosphere in the step (2) comprises nitrogen and/or inert gas;
preferably, the temperature of the pyrolysis in the step (2) is 900-950 ℃, and the time is 6-9 h.
7. The method according to claim 5 or 6, wherein the method for producing modified boron nitride comprises the steps of:
(a) mixing nitrate, boron nitride and water, uniformly dispersing, and drying to obtain a precursor;
(b) pyrolyzing the precursor obtained in the step (a) in a protective atmosphere to obtain the modified boron nitride;
preferably, the mass ratio of the nitrate, the boron nitride and the water in the step (a) is (0.1-0.5): (1-3): (20-30);
preferably, the nitrate of step (a) comprises any one of lanthanum nitrate, cerium nitrate, zinc nitrate, copper nitrate or cobalt nitrate or a combination of at least two thereof;
preferably, the method for uniformly dispersing in step (a) comprises ultrasonic post-stirring;
preferably, the stirring time is 10-20 h;
preferably, the drying temperature of the step (a) is 90-100 ℃, and the time is 10-20 h;
preferably, the gas used in the protective atmosphere of step (b) comprises nitrogen and/or an inert gas;
preferably, the temperature of the pyrolysis in the step (b) is 600-700 ℃ and the time is 5-8 h.
8. The method as claimed in any one of claims 1 to 7, wherein said active component comprises a double metal cyanide.
9. A catalyst for ring-opening polymerization of epoxy, which is obtained by the production method according to any one of claims 1 to 8.
10. Use of the catalyst for ring-opening polymerization of epoxy according to claim 9 for ring-opening polymerization of epoxy compound;
the epoxy compound includes any one of ethylene oxide, propylene oxide or butylene oxide or a combination of at least two thereof.
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