CN114940752B - Catalyst for epoxy ring-opening polymerization and preparation method and application thereof - Google Patents

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

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CN114940752B
CN114940752B CN202210735169.6A CN202210735169A CN114940752B CN 114940752 B CN114940752 B CN 114940752B CN 202210735169 A CN202210735169 A CN 202210735169A CN 114940752 B CN114940752 B CN 114940752B
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boron nitride
catalyst
opening polymerization
ring
preparation
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CN114940752A (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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    • 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

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

The invention provides a catalyst for epoxy ring-opening polymerization, a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing a carrier, an active component and a solvent, mixing, drying, and grinding to obtain the catalyst for ring-opening polymerization of epoxy, 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 epoxy ring-opening polymerization and preparation method and application thereof
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a catalyst for epoxy ring-opening polymerization, a preparation method and application thereof.
Background
Polyethers are a type of polymer material widely used in the fields of synthetic polyurethane, lithium battery electrolyte, paper making, coating, elastomer, foam plastic, cosmetics and the like, and are formed by ring-opening polymerization of epoxide monomers, for example, ethylene oxide and propylene oxide are the most commonly used polymerization monomers.
The catalysts most used in the industry for the synthesis of polyethers are alkali metal hydroxides or Zn-Co Double Metal Cyanides (DMC). The most commonly used catalyst for potassium hydroxide is the one with moderate catalytic activity due to its low cost. However, since the strong alkali easily causes isomerization reaction of the monomer, a high quality polyether product cannot be prepared. In addition, when potassium hydroxide is used as a catalyst, the polyether product needs to be refined to remove potassium ions, and the production cost is increased. Double metal cyanide is used as a substitute catalyst of potassium hydroxide, no further purification operation is needed in the use process, and the double metal cyanide has high catalytic activity and can realize the polymerization and conversion of monomers into polyether in a shorter reaction time.
The catalytic activity of double metal cyanide catalysts is mainly affected by the metal active sites, but the metal active sites cannot all participate in the reaction during the reaction, resulting in lower utilization of the active metal. Researchers have successfully improved the activity of double metal cyanide catalysts by immobilizing double metal cyanide on a support, while reducing the amount of active metal required. The commonly used carrier is silicon oxide and titanium dioxide, and boron nitride is a crystal formed by nitrogen atoms and boron atoms, has the advantages of high heat conductivity, high specific surface area, strong chemical stability and the like, and can be used as a carrier for catalytic systems such as ammonia synthesis, CO oxidation, fischer-Tropsch synthesis and the like.
The invention adopts boron nitride or modified boron nitride as a double metal cyanide catalyst carrier, 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, and a preparation method and application thereof.
In order to achieve the aim of the invention, 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 the carrier, the active component and the 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, for example, 300r/min, 400r/min, 500r/min, 600r/min, 700r/min or 800r/min, but the stirring speed is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the stirring time is 12-20h, for example, 12h, 13h, 14h, 15h, 16h, 18h or 20h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the drying method includes vacuum drying, the temperature of the vacuum drying is 90-110 ℃, for example, 90 ℃, 95 ℃,100 ℃, 105 ℃ or 110 ℃, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the solvent comprises water.
Preferably, the mass ratio of carrier, active ingredient to 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, as are other non-recited values within the range of values.
The particle diameter D50 of the catalyst for ring-opening polymerization for epoxy resin obtained after the above-mentioned grinding is preferably 0.5 to 1. Mu.m, 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. Mu.m, but is not limited to the values recited, and other values not recited in the numerical range are equally 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, drying and crystallizing to obtain a crystallization precursor;
(2) Pyrolyzing the crystal precursor obtained in the step (1) in 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): 1-4): 20-50.
The mass ratio of boric acid to nitrogen source in step (1) is 1 (20-40), for example, it may be 1:20, 1:25, 1:30, 1:35 or 1:40, but not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
The mass ratio of boric acid to dispersant in step (1) is 1 (1-4), for example, 1:1, 1:2, 1:3 or 1:4, but is not limited to the recited values, and other non-recited values in the range of values are equally applicable.
The mass ratio of boric acid to water in the step (1) is 1 (20-50), for example, 1:20, 1:25, 1:30, 1:35, 1:40, 1:45 or 1:50, but is not limited to the recited values, and other non-recited values in the numerical range are equally applicable.
Preferably, the nitrogen source of step (1) comprises urea and/or melamine.
Preferably, the dispersant of 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 uniform dispersion in step (1) includes ultrasonic dispersion for 5-15min, for example, 5min, 6min, 7min, 8min, 9min, 10min, 11min, 12min, 13min, 14min or 15min, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Preferably, the drying temperature in step (1) is 90-100deg.C, for example, 90 ℃, 92 ℃, 95 ℃, 96 ℃, 98 ℃ or 100deg.C, but not limited to the values recited, and other values not recited in the range are equally applicable; the time is 8-12h, for example, 8h, 9h, 10h, 11h or 12h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the gas used in the protective atmosphere in step (2) comprises nitrogen and/or inert gas.
Preferably, the pyrolysis temperature in step (2) is 900-950 ℃, such as 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, or 950 ℃, but not limited to the recited values, and other non-recited values within the range of values are equally applicable; the time is 6-9h, and may be, for example, 6h, 7h, 8h or 9h, but is not limited to the recited values, and other non-recited values within the range of values 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 (3) 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 the 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 the 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 recited values, and other non-recited values in the numerical range are equally applicable.
The mass ratio of boron nitride to water in the step (a) is (1-3): (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 non-recited values in the range of values are equally applicable.
Preferably, the nitrate of step (a) comprises any one or a combination of at least two of lanthanum nitrate, cerium nitrate, zinc nitrate, copper nitrate or cobalt nitrate, typically but not limited to 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 of uniform dispersion of step (a) comprises post-ultrasound agitation.
Preferably, the stirring time is 10-20h, for example, 10h, 12h, 15h, 16h, 18h or 20h, but not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the temperature of the drying in step (a) is 90-100 ℃, for example, 90 ℃, 92 ℃, 95 ℃, 96 ℃, 98 ℃ or 100 ℃, but not limited to the recited values, other non-recited values within the range of values are equally applicable; the time is 10-20h, for example, 10h, 12h, 15h, 16h, 18h or 20h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the gas used in the protective atmosphere in step (b) comprises nitrogen and/or an inert gas.
Preferably, the pyrolysis in step (b) has a temperature of 600-700 ℃, such as 600 ℃, 620 ℃, 640 ℃, 650 ℃, 680 ℃, or 700 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable; the time is 5-8h, for example, 5h, 6h, 7h or 8h, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the active component comprises double metal cyanide.
The double metal cyanide is conventional in the art, the invention is not particularly limited, and the preparation method of the double metal cyanide comprises the following steps:
(I) Mixing zinc acetate dihydrate solution with acetic acid, then mixing the obtained mixed solution with a molecular sieve, and heating and stirring to obtain a dispersion liquid;
and (II) dropwise adding the aqueous solution of cobalt potassium cyanide into the dispersion liquid obtained in the step (I), and sequentially centrifuging, washing, ultrasonic treatment and drying to obtain the double metal cyanide.
In a second aspect, the present invention provides a catalyst for epoxy ring-opening polymerization, which is prepared by the preparation method in the first aspect.
In a third aspect, the present invention provides the use of the catalyst for ring-opening polymerization of epoxy compound according to the second aspect;
the epoxy compound includes any one or a combination of at least two of ethylene oxide, propylene oxide, or butylene oxide.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention can prepare a double metal cyanide catalyst loaded by high-activity and stable boron nitride or modified boron nitride through a simple impregnation loading method. In the catalytic epoxy compound polymerization reaction, double metal cyanide activity is enhanced by being dispersed on a carrier, and the availability and the number of metal active centers are improved;
(2) The boron nitride serving as a carrier has dispersing effect, boron atoms in the boron nitride have electron-deficient characteristics and Lewis acidity, have the effect of activating an epoxy monomer, and synergistically activate the epoxy monomer with double metal cyanide, so that the catalytic activity is further improved;
(3) After the boron nitride is modified, lewis acidity is enhanced, and the effect of the boron nitride and double metal cyanide synergistic activated epoxy monomer is enhanced, so that the catalytic activity is further improved;
(4) The invention adopts boron nitride or modified supported double metal cyanide, reduces the consumption of active metal in the catalytic process, and can further reduce the cost of industrialized production of polyether.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
The double metal cyanide compounds used in the examples and comparative examples of the present invention were prepared by the following method comprising the steps of:
(1) Zinc acetate dihydrate (3 mmol,657 mg) is added into 15mL deionized water, mixed and stirred until dissolved, and then 5mL acetic acid is added for even mixing;
(2) Adding 2g of molecular sieve into the solution in the step (1), raising the temperature to 80 ℃, and continuing stirring;
(3) Taking cobalt potassium cyanide (1.5 mmol,498 mg) to prepare 10mL of aqueous solution, dripping the aqueous solution into the dispersion liquid in the step (2) at a speed of 5 seconds/drop, immediately taking out the reaction liquid after the dripping, centrifuging at a speed of 3500r/min for 3min, washing with deionized water 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.
The sources of the raw materials in the specific embodiment are as follows:
1, 2-epoxybutane: CAS number; 106-88-7, reflux in calcium hydride for 8h, re-steaming for use, purchased from Shanghai Ala Biochemical technologies Co., ltd.
Polyethylene glycol-400 (PEG-400): CAS number; 25322-68-3, molecular weight 400, available from Shanghai Ala Biotechnology Co., ltd.
Zinc acetate dihydrate: CAS number; 25322-68-3, available from Shanghai Ala Biotechnology Co., ltd.
Potassium cobalt cyanide: CAS number; 13963-58-1, available from Shanghai Ala Biotechnology Co., ltd.
Acetic acid: CAS number; 64-19-7 available from Shanghai Ala Biochemical technologies Co., ltd.
PEG-1000:25322-68-3, average molecular weight 1000, available from Shanghai Ala Biotechnology Co., ltd.
The formula for calculating the load of double metal cyanide is as follows: (total mass of solid-mass of boron nitride)/total mass of solid ×100%
Example 1
The embodiment provides a preparation method of a catalyst for epoxy ring-opening polymerization, which comprises the following steps:
2g of boron nitride and 0.2g of double metal cyanide are added into 20mL of deionized water, the mixture is stirred for 16h by ultrasonic treatment for 10min and 500r/min, the mixture is dried for 10h at 100 ℃ in vacuum, and the mixture is ground to obtain the catalyst for ring-opening polymerization of epoxy with the particle size D50 of 0.8 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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Example 2
This example provides a method for producing a catalyst for ring-opening polymerization of epoxy, which differs from example 1 in that the mass of double metal cyanide compound in this example is 0.4g, and the remainder is the same as in example 1.
Example 3
This example provides a method for producing a catalyst for ring-opening polymerization of epoxy, which differs from example 1 in that the mass of double metal cyanide compound in this example is 0.5g, and the remainder is the same as in example 1.
Example 4
This example provides a method for producing a catalyst for ring-opening polymerization of epoxy, which differs from example 1 in that the mass of double metal cyanide compound in this example is 0.6g, and the remainder is the same as in example 1.
Example 5
This example provides a method for producing a catalyst for ring-opening polymerization of epoxy, which differs from example 1 in that the mass of double metal cyanide compound in this example is 0.8g, and the remainder is the same as in example 1.
Example 6
The embodiment provides a preparation method of a catalyst for epoxy ring-opening polymerization, which comprises the following steps:
2g of modified boron nitride and 0.5g of double metal cyanide are added into 20mL of deionized water, the mixture is stirred for 16h by ultrasonic treatment for 10min and 500r/min, the mixture is dried for 10h at 100 ℃ in vacuum, and the mixture is ground to obtain the catalyst for ring-opening polymerization of epoxy with the particle size D50 of 0.8 mu m.
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 liquid, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, performing pyrolysis on the precursor at 650 ℃ for 6h under nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Example 7
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy, 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, 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 producing a catalyst for ring-opening polymerization of epoxy, which differs from example 6 in that cerium nitrate is replaced by copper nitrate in the same mass as in example 6, and the remainder is the same as in example 6.
Example 10
This example provides a method for preparing a catalyst for ring-opening polymerization of epoxy, which differs 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 epoxy ring-opening polymerization, which comprises the following steps:
2g of boron nitride and 0.2g of double metal cyanide are added into 20mL of deionized water, ultrasonic treatment is carried out for 10min, stirring is carried out for 16h at 300r/min, vacuum drying is carried out for 10h at 100 ℃, and grinding is carried out to obtain the catalyst for epoxy ring-opening polymerization with the particle size D50 of 1 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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Example 12
The embodiment provides a preparation method of a catalyst for epoxy ring-opening polymerization, which comprises the following steps:
2g of boron nitride and 0.2g of double metal cyanide are added into 20mL of deionized water, the mixture is stirred for 16h by ultrasonic treatment for 10min,800r/min, vacuum dried for 10h at 100 ℃, and ground to obtain the catalyst for ring-opening polymerization of epoxy 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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Example 13
The embodiment provides a preparation method of a catalyst for epoxy ring-opening polymerization, which comprises the following steps:
2g of modified boron nitride and 0.5g of double metal cyanide are added into 20mL of deionized water, ultrasonic treatment is carried out for 10min, stirring is carried out for 16h at 300r/min, vacuum drying is carried out for 10h at 100 ℃, and grinding is carried out to obtain the catalyst for epoxy ring-opening polymerization with the particle size D50 of 1 mu m.
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 liquid, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, performing pyrolysis on the precursor at 650 ℃ for 6h under nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Example 14
The embodiment provides a preparation method of a catalyst for epoxy ring-opening polymerization, which comprises the following steps:
2g of modified boron nitride and 0.5g of double metal cyanide are added into 20mL of deionized water, ultrasonic treatment is carried out for 10min,800r/min stirring is carried out for 16h, vacuum drying is carried out for 10h at 100 ℃, and grinding is carried out to obtain the catalyst for epoxy ring-opening polymerization with the particle size D50 of 0.5 mu m.
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 liquid, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, performing pyrolysis on the precursor at 650 ℃ for 6h under nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample;
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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground 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 pyrolysis in preparing modified boron nitride is pyrolysis at 600 ℃ for 8 hours under 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 pyrolysis at 700 ℃ for 5 hours under nitrogen atmosphere.
Example 17
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 temperature at the time of preparing modified boron nitride is 580 ℃.
Example 18
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 temperature at the time of preparing modified boron nitride is 720 ℃.
Comparative example 1
The comparative example provides a double metal cyanide compound, the preparation method comprising the following steps:
(1) Zinc acetate dihydrate (3 mmol,657 mg) is added into 15mL deionized water, mixed and stirred until dissolved, and then 5mL acetic acid is added for even mixing;
(2) Adding 2g of molecular sieve into the solution in the step (1), raising the temperature to 80 ℃, and continuing stirring;
(3) Taking cobalt potassium cyanide (1.5 mmol,498 mg) to prepare 10mL of aqueous solution, dripping the aqueous solution into the dispersion liquid in the step (2) at a speed of 5 seconds/drop, immediately taking out the reaction liquid after the dripping, centrifuging at a speed of 3500r/min for 3min, washing with deionized water 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 comparative example provides a boron nitride, the preparation method of which 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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground 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, performing ultrasonic treatment for 10min to obtain a dispersion liquid, stirring for 15h, drying at 100 ℃ for 15h to obtain a precursor, pyrolyzing the precursor for 6h in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain a target sample.
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 precursor is obtained by drying at 100 ℃ for 10h for crystallization. Finally, the completely recrystallized precursor is pyrolyzed for 6 hours at 950 ℃ in nitrogen atmosphere, cooled to room temperature and ground to obtain a target sample.
Application example 1
The catalysts prepared in examples 1 to 18 and comparative examples 1 to 3 were used in ring-opening polymerization of epoxy compounds, and the specific procedure was as follows:
under the protection of nitrogen, adding 1.5mg of catalyst into a 50mL autoclave, adding 5g of polyethylene glycol and 18g of 1, 2-epoxybutane, starting stirring, heating to 110 ℃, reacting for 6 hours, cooling to room temperature, and removing unreacted 1, 2-epoxybutane in vacuum to obtain polyether.
The results are shown in Table 1.
Application example 2
Under the protection of nitrogen, 1.5mg of double metal cyanide provided in comparative example 1, 5g of polyethylene glycol and 18g of 1, 2-epoxybutane are added into a 50mL autoclave, stirring is started, the temperature is raised to 110 ℃, the reaction is carried out for 6 hours, the reaction is cooled to room temperature, and unreacted 1, 2-epoxybutane is removed in vacuum, so as to obtain polyether.
Results: 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 modified boron nitride provided in example 6 are 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 6 hours, the temperature is cooled to room temperature, and unreacted 1, 2-epoxybutane is removed in vacuum, so that polyether is obtained.
Results: the conversion of 1, 2-butylene oxide was 45.6%.
TABLE 1
Figure BDA0003715021970000151
Figure BDA0003715021970000161
By catalyzing epoxide ring-opening polymerization reaction with example 3 and comparative example 1, example 3 was a boron nitride supported double metal cyanide catalyst catalyzing ring-opening polymerization of 1, 2-epoxybutane, the conversion rate of the 1, 2-epoxybutane was as high as 91.1%, whereas comparative example 1 double metal cyanide catalyst was catalyzing ring-opening polymerization of 1, 2-epoxybutane, the conversion rate of the 1, 2-epoxybutane was 25.1%. The result shows that the boron nitride and the double metal cyanide catalyst have synergistic catalysis and can improve the ring-opening polymerization rate of the 1, 2-epoxybutane. Example 7 modified boron nitride with supported double metal cyanide as catalyst has a 6 hr conversion of 1, 2-butylene oxide as high as 99.8%, showing the enhanced Lewis acidity and catalytic activity of the modified boron nitride with anchored metal sites.
In comparison of example 7 and application example 3, it was found that the catalytic activity of double metal cyanide by loading to modified boron nitride was significantly higher than that of double metal cyanide and modified boron nitride mixture. Indicating that the zinc sites of DMC are very close to the Lewis sites on the surface of boron nitride, a better synergistic catalytic effect can be achieved. When boron nitride or modified boron nitride is used alone as a catalyst, the Lewis acid site alone by boron and metal is difficult to achieve ring opening of the epoxy compound, and thus has no catalytic activity.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.

Claims (23)

1. A method for preparing a catalyst for ring-opening polymerization of epoxy, which 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 carrier is modified boron nitride;
the active component is double metal cyanide;
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; the nitrate comprises any one or a combination of at least two of lanthanum nitrate, cerium nitrate, zinc nitrate, copper nitrate and cobalt nitrate;
(b) Pyrolyzing the precursor obtained in the step (a) in a protective atmosphere to obtain the modified boron nitride;
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, drying and crystallizing to obtain a crystallization precursor;
(2) Pyrolyzing the crystal precursor obtained in the step (1) in a protective atmosphere to obtain the boron nitride.
2. The method of preparation according to claim 1, wherein the mixing comprises ultrasound and/or stirring.
3. The method according to claim 2, wherein the stirring speed is 300-800r/min.
4. The method of claim 2, wherein the stirring is for a period of 12-20 hours.
5. The method according to claim 2, wherein in the drying after mixing, the drying method comprises vacuum drying at a temperature of 90 to 110 ℃.
6. The method of claim 1, wherein the solvent comprises water.
7. The preparation method according to claim 1, wherein the mass ratio of the carrier, the active ingredient and the solvent is 1 (0.1-0.4): 10.
8. The process according to claim 1, wherein the particle diameter D50 of the catalyst for ring-opening polymerization obtained after grinding is 0.5 to 1. Mu.m.
9. The preparation method according to claim 1, wherein the mass ratio of boric acid, nitrogen source, dispersant and water in the step (1) is 1 (20-40): 1-4): 20-50.
10. The method of claim 1, wherein the nitrogen source of step (1) comprises urea and/or melamine.
11. The method of claim 1, wherein the dispersant of step (1) comprises any one or a combination of at least two of PEG-200, PEG-400, or PEG-1000.
12. The method of claim 1, wherein the method of uniform dispersion in step (1) comprises ultrasonic dispersion for a period of 5 to 15 minutes.
13. The method according to claim 1, wherein the drying in step (1) is carried out at a temperature of 90 to 100 ℃ for a time of 8 to 12 hours.
14. The method according to claim 1, wherein the gas used in the protective atmosphere in the step (2) comprises nitrogen and/or inert gas.
15. The method of claim 1, wherein the pyrolysis in step (2) is performed at a temperature of 900 to 950 ℃ for a period of 6 to 9 hours.
16. The method according to claim 1, wherein the mass ratio of the nitrate, boron nitride and water in the step (a) is (0.1-0.5): 1-3): 20-30.
17. The method of claim 1, wherein the method of uniform dispersion of step (a) comprises post-ultrasonic agitation.
18. The method of claim 17, wherein the stirring is for a period of 10 to 20 hours.
19. The method of claim 1, wherein the drying in step (a) is performed at a temperature of 90-100 ℃ for a time of 10-20 hours.
20. The method according to claim 1, wherein the gas used in the protective atmosphere in the step (b) comprises nitrogen and/or inert gas.
21. The method of claim 1, wherein the pyrolysis in step (b) is performed at a temperature of 600-700 ℃ for a period of 5-8 hours.
22. A catalyst for ring-opening polymerization of epoxy, characterized in that it is prepared by the preparation method according to any one of claims 1 to 21.
23. The use of the catalyst for ring-opening polymerization of epoxy according to claim 22, wherein the catalyst for ring-opening polymerization of epoxy compound is used for ring-opening polymerization of epoxy compound;
the epoxy compound includes any one or a combination of at least two of ethylene oxide, propylene oxide, or butylene oxide.
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