CN114621494B - Preparation method of microcapsule with core-shell structure and microcapsule thereof - Google Patents
Preparation method of microcapsule with core-shell structure and microcapsule thereof Download PDFInfo
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- CN114621494B CN114621494B CN202111121709.3A CN202111121709A CN114621494B CN 114621494 B CN114621494 B CN 114621494B CN 202111121709 A CN202111121709 A CN 202111121709A CN 114621494 B CN114621494 B CN 114621494B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/18—In situ polymerisation with all reactants being present in the same phase
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
- C08F220/46—Acrylonitrile with carboxylic acids, sulfonic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/22—Expandable microspheres, e.g. Expancel®
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/14—Thermal energy storage
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- Manufacturing Of Micro-Capsules (AREA)
Abstract
The invention relates to C08J9/32, in particular to a preparation method of a microcapsule with a core-shell structure and the microcapsule thereof. The method comprises the following steps: 1) Placing the oil phase and the water phase into an emulsifying kettle for ultrasonic irradiation, and simultaneously shearing, dispersing and premixing to form a suspension; 2) Transferring the suspension into a reaction kettle, and carrying out ultrasonic irradiation suspension polymerization reaction under the nitrogen atmosphere; 3) And after the reaction is finished, drying and filtering to obtain the microcapsule with the core-shell structure. The core-shell structure microcapsule obtained by the preparation method has the advantages of good surface morphology, uniform particle size distribution, excellent foaming performance, excellent storage stability and the like.
Description
Technical Field
The invention relates to C08J9/32, in particular to a preparation method of a microcapsule with a core-shell structure and the microcapsule thereof.
Background
The core-shell structure microcapsule takes the foaming agent as a core and the polymer as a shell, has excellent mechanical properties and high temperature resistance, and is widely used in the technical fields of paint, construction, aerospace and the like, but the particle size, the foaming property and the like of the core-shell structure microcapsule are easily influenced by a preparation method, so that the prepared core-shell structure microcapsule cannot fully meet the requirements of customers.
According to the preparation method of the thermally expandable microsphere with controllable particle size disclosed in the patent CN201811551809.8, a reaction material is emulsified in a membrane emulsification mode to obtain a microemulsion with controllable and uniform particle size, so that the thermally expandable microsphere prepared by in-situ polymerization has a microsphere emulsion with narrow particle size distribution and controllable and uniform particle size.
The patent CN201910976930.3 is a polymethacrylimide thermal expansion microsphere and a preparation method thereof, adopts a Pickering emulsion suspension polymerization method, and is prepared from acrylonitrile, methacrylic acid and acrylamide compound monomers, and has the advantages of good foaming performance, difficult agglomeration and the like.
However, the preparation method is complex in operation, and the surface quality of the prepared thermal expansion microsphere is serious due to the fact that the formation of the foam holes is too dependent on the diffusion of gas, so that the surface quality of the prepared thermal expansion microsphere is easy to cause rough capsule wall, concave and the like, the application of the thermal expansion microsphere is severely restricted, and the production cost is increased.
Disclosure of Invention
In order to solve the technical problem, a first aspect of the present invention provides a method for preparing a microcapsule with a core-shell structure, comprising the following steps: 1) Placing the oil phase and the water phase into an emulsifying kettle for ultrasonic irradiation, and simultaneously shearing, dispersing and premixing to form a suspension; 2) Transferring the suspension into a reaction kettle, and carrying out ultrasonic irradiation suspension polymerization reaction under the nitrogen atmosphere; 3) And after the reaction is finished, drying and filtering to obtain the microcapsule with the core-shell structure.
Preferably, the mass ratio of the oil phase to the water phase is (1-4): (6-9).
Preferably, the ultrasonic dispersion frequency of the step 1) is 4500-5500W; the rotation speed of ultrasonic dispersion is 4500-5500rpm.
Preferably, the pre-mixing time of the step 1) is 3-8min.
Further preferably, the frequency of the ultrasonic dispersion in the step 1) is 4700-5000W; the rotation speed of ultrasonic dispersion is 5100-5300rpm.
Oil phase
Preferably, the oil phase comprises acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof, a cross-linking agent, an oil-soluble initiator, branched paraffins.
Preferably, the mass ratio of the acrylonitrile, the methacrylonitrile, the acrylic acid and the derivatives thereof is (9-12): (3-7): (2-4).
Preferably, the acrylic acid and its derivatives include acrylic acid: methyl methacrylate, N-methylolacrylamide. The acrylic acid: methyl methacrylate and N-methylolacrylamide with the mass ratio of (12-17): (3-5): (3-5).
Because acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof and other monomers can be directly polymerized to form the shell of the microcapsule with the core-shell structure, the morphological stability of the shell raw material must be ensured, and the effects of good foaming effect and good storage performance are also achieved. The unexpected study of the present invention found that by acrylic acid: the third monomer formed by combining methyl methacrylate, N-methylolacrylamide composite acrylic acid and derivatives thereof can remarkably improve the morphological stability and foaming performance of the microcapsule with the core-shell structure. It is presumed that because the active groups contained in the acrylic acid and N-methylol acrylamide can form hydrogen bond action with substances in the system, the compactness of the polymer formed by the reaction with substances such as acrylonitrile, methacrylonitrile and the like on the surface of gaseous alkane is improved, and meanwhile, the polymer and methyl methacrylate form a stable structure, so that retraction during cooling is prevented, and the storage stability and foaming performance of the polymer are prolonged.
Preferably, the cross-linking agent comprises at least one of DPGDA, EGDMA, HDDMA, NPGDA, TMPTA, TPGDA.
Further preferably, the cross-linking agent is DPGDA.
Preferably, the cross-linking agent is used in an amount of 0.3 to 0.5wt% based on the total mass of acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof.
Preferably, the oil-soluble initiator comprises dibenzoyl peroxide and tributylamine. The mass ratio of the dibenzoyl peroxide to the tributylamine is 1: (0.5-1).
Preferably, the oil-soluble initiator accounts for 0.9-1.2wt% of the total mass of the oil phase.
Preferably, the branched alkane comprises at least one of isopentane, isohexane, isoheptane, isooctane.
Further preferably, the branched alkane comprises isopentane and isohexane. The mass ratio of isopentane to isohexane is (1.5-2): (0.7-1).
The branched alkane accounts for 16-19wt% of the total mass of the oil phase.
Aqueous phase
Preferably, the aqueous phase comprises silica, polyvinylpyrrolidone, a polymerization inhibitor and sodium chloride.
Preferably, the silica has a BET specific surface area of 200m 2 And/g, the primary particle size is 12nm. The silica is colloidal silica.
Preferably, the average molecular weight of the polyvinylpyrrolidone is 35000-40000.
Preferably, the mass ratio of the silicon dioxide to the polyvinylpyrrolidone is (3-5): (0.2-0.5).
Preferably, the polymerization inhibitor comprises potassium dichromate and/or sodium nitrite.
Preferably, the polymerization inhibitor accounts for 0.05-0.07% of the total mass of the water phase.
Further preferably, the sodium chloride comprises 20-23wt% of the total mass of the aqueous phase.
Preferably, the reaction pressure in the step 2) is 0.4-0.5MPa, the reaction temperature is 25-45 ℃ and the reaction time is 8-12h.
Further preferably, the reaction pressure in the step 2) is 0.45-0.48MPa, the reaction temperature is 30-38 ℃ and the reaction time is 10-11h.
According to the invention, unexpected researches show that the prepared core-shell structure microcapsule has better morphology, stability and other performances when the reaction pressure is controlled to be 0.45-0.48MPa, the reaction temperature is 30-38 ℃ and the reaction time is 10-11 hours. Presumably, because the gas-liquid interface is constantly changed in an oscillating way due to higher ultrasonic frequency and rotating speed in the preparation process, substances such as acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof in the system are mutually bonded and crosslinked into a stable network structure, so that the collision between the core-shell structure microcapsules is prevented from becoming large due to overhigh temperature, the formed shell is uneven, and the foaming performance and stability of the core-shell structure microcapsules are influenced.
Preferably, the ultrasonic dispersion frequency in the step 2) is 4500-5500W, and the ultrasonic dispersion rotating speed is 4500-5500rpm.
Further preferably, the frequency of the ultrasonic dispersion in the step 2) is 5000-5200W, and the rotating speed of the ultrasonic dispersion is 4700-5000rpm.
The second aspect of the invention provides a microcapsule prepared by the preparation method of the microcapsule with the core-shell structure.
The beneficial effects are that:
in the prior art, the temperature required for preparing the core-shell structure microcapsule is high, and the prepared core-shell structure microcapsule has poor morphology and stability. The invention is prepared by the steps of (1) acrylic acid: methyl methacrylate, N-methylolacrylamide composite acrylic acid and derivatives thereof form a third monomer, and acrylonitrile in the system and methacrylonitrile are subjected to polymerization reaction, and are continuously deposited on the surface of the gaseous alkane to form a flat and smooth shell; meanwhile, other reaction conditions such as reaction temperature of 30-38 ℃ are limited to prevent interaction among the core-shell structure microcapsules and influence uniformity of particle size distribution, so that the prepared core-shell structure microcapsules have the advantages of good surface morphology, uniform particle size distribution, foaming property, excellent storage stability and the like.
Detailed Description
Examples
Example 1
The preparation method of the microcapsule with the core-shell structure comprises the following steps: 1) Placing the oil phase and the water phase into an emulsifying kettle for ultrasonic irradiation, and simultaneously shearing, dispersing and premixing to form a suspension; 2) Transferring the suspension into a reaction kettle, and carrying out ultrasonic irradiation suspension polymerization reaction under the nitrogen atmosphere; 3) And after the reaction is finished, drying and filtering to obtain the microcapsule with the core-shell structure.
The mass ratio of the oil phase to the water phase is 3:7.
the frequency of the ultrasonic dispersion in the step 1) is 4800W. The rotational speed of the ultrasonic dispersion in the step 1) is 5200rpm. The premixing time in the step 1) is 5min.
The oil phase comprises acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof, a cross-linking agent, an oil-soluble initiator, and branched paraffins.
The mass ratio of the acrylonitrile to the methacrylonitrile to the acrylic acid to the derivatives thereof is 10:5:3.
the acrylic acid and the derivatives thereof comprise acrylic acid: methyl methacrylate, N-methylolacrylamide. The acrylic acid: methyl methacrylate and N-methylolacrylamide with mass ratio of 15:4.5:3.5.
the cross-linking agent is DPGDA (dipropylene glycol diacrylate). The amount of the cross-linking agent is 0.4wt% of the total mass of the acrylonitrile, the methacrylonitrile, the acrylic acid and the derivatives thereof.
The acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof, and the crosslinking agent were all purchased from new materials limited in Guangzhou.
The oil-soluble initiator comprises dibenzoyl peroxide and tributylamine. The mass ratio of the dibenzoyl peroxide to the tributylamine is 1:0.8. the oil-soluble initiator accounts for 1 weight percent of the total mass of the oil phase.
The branched alkanes include isopentane and isohexane. The mass ratio of isopentane to isohexane is 1.8:0.8. the branched alkane represents 17.8wt% of the total mass of the oil phase.
The water phase comprises silicon dioxide, polyvinylpyrrolidone, polymerization inhibitor and sodium chloride. The BET specific surface area of the silica was 200m 2 And/g, the primary particle size is 12nm. The silica was colloidal silica, available from Luo Fu medicine.
The average molecular weight of the polyvinylpyrrolidone is 37900, and the viscosity at 25 ℃ is 2.1-2.7 mPa.s. The polyvinylpyrrolidone is purchased from Gobekie, model: PVPK30.
The mass ratio of the silicon dioxide to the polyvinylpyrrolidone is 4:0.3.
the polymerization inhibitor is potassium dichromate. The polymerization inhibitor accounts for 0.06% of the total mass of the water phase.
The sodium chloride accounted for 21.5wt% of the total mass of the aqueous phase.
The reaction pressure of the step 2) is 0.47MPa, the reaction temperature is 38 ℃, and the reaction time is 10.5h. The frequency of the ultrasonic dispersion in the step 2) is 5200W, and the rotating speed of the ultrasonic dispersion is 4800rpm.
The second aspect of the invention provides a microcapsule prepared by the preparation method of the microcapsule with the core-shell structure.
Example 2
The specific embodiment of the preparation method of the microcapsule with the core-shell structure is the same as that of example 1, wherein the ultrasonic dispersion frequency of the step 2) is 5000W, and the ultrasonic dispersion rotating speed is 5000rpm.
Example 3
A preparation method of a microcapsule with a core-shell structure is similar to example 1, and the specific implementation mode is different in that the cross-linking agent is used in an amount of 0.5wt% of the total mass of acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof.
Comparative example 1
The specific embodiment of the preparation method of the microcapsule with the core-shell structure is the same as example 1, wherein the reaction pressure in the step 2) is 0.45MPa, the reaction temperature is 28 ℃, and the reaction time is 10.5h.
Comparative example 2
A preparation method of a microcapsule with a core-shell structure, and a specific embodiment is the same as in example 1, wherein the acrylic acid is as follows: methyl methacrylate and N-methylolacrylamide with the mass ratio of 10:4.5:3.5.
performance testing
1. Morphology testing: and measuring the appearance of the microcapsule with the core-shell structure by using a scanning electron microscope, vacuumizing by using a jet instrument for 4min, and performing the metal spraying for 4min at 38 mA.
2. Particle size testing: 1.5g of sample is taken, added into 25mL of deionized water, stirred and mixed uniformly, and then subjected to ultrasonic treatment for 2min, and the particle size distribution of the modified thermoplastic hollow polymer microspheres is measured by a laser particle sizer, wherein the particle size distribution is (D90-D10)/D50.
3. Foaming property test: 0.5mg of a core-shell structure microcapsule sample was weighed, placed in an aluminum crucible having a diameter of 6.4mm and a depth of 4mm, and heated from 30℃to 300℃at a heating rate of 10℃per minute with a force of 0.06N applied. Measurement of particle size D before foaming by laser particle size analyzer pre And particle diameter D after foaming Heat Foaming ratio=dheat/Dpre.
4. Storage stability test: the foamed samples were stored for 7 days, 3 months, and 6 months of expansion ratio, respectively.
TABLE 1 Performance test results
Claims (3)
1. The preparation method of the microcapsule with the core-shell structure is characterized by comprising the following steps of: 1) Placing the oil phase and the water phase into an emulsifying kettle for ultrasonic irradiation, and simultaneously shearing, dispersing and premixing to form a suspension; 2) Transferring the suspension into a reaction kettle, and carrying out ultrasonic irradiation suspension polymerization reaction under the nitrogen atmosphere; 3) Drying and filtering after the reaction is finished to obtain the microcapsule with the core-shell structure;
the mass ratio of the oil phase to the water phase is (1-4): (6-9);
the oil phase comprises acrylonitrile, methacrylonitrile, acrylic acid and derivatives thereof, a cross-linking agent, an oil-soluble initiator, and branched alkanes; the mass ratio of the acrylonitrile to the methacrylonitrile to the acrylic acid to the derivatives thereof is (9-12): (3-7): (2-4);
the acrylic acid and the derivatives thereof comprise acrylic acid, methyl methacrylate and N-methylolacrylamide; the mass ratio of the acrylic acid to the methyl methacrylate to the N-methylol acrylamide is (12-17): (3-5): (3-5);
the cross-linking agent is DPGDA; the dosage of the cross-linking agent is 0.3-0.5wt% of the total mass of the acrylonitrile, the methacrylonitrile, the acrylic acid and the derivatives thereof;
the oil-soluble initiator accounts for 0.9-1.2wt% of the total mass of the oil phase;
the branched alkane accounts for 16-19wt% of the total mass of the oil phase;
the ultrasonic dispersion frequency of the step 1) is 4500-5500W, and the ultrasonic dispersion rotating speed is 4500-5500rpm;
the reaction pressure of the step 2) is 0.45-0.48MPa, the reaction temperature is 30-38 ℃, and the reaction time is 10-11h; the ultrasonic dispersion frequency of the step 2) is 4500-5500W, and the rotating speed is 4500-5500rpm; the water phase comprises silicon dioxide, polyvinylpyrrolidone, polymerization inhibitor and sodium chloride.
2. The method of preparing a core-shell structured microcapsule according to claim 1, wherein the silica is colloidal silica.
3. A core-shell structure microcapsule prepared by the preparation method according to any one of claims 1 to 2.
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| WO2019049881A1 (en) * | 2017-09-06 | 2019-03-14 | 日油株式会社 | Heat-expandable microcapsules, production method therefor, and foamed molded article |
| CN111111573A (en) * | 2019-12-09 | 2020-05-08 | 三明市锦浪新材料科技有限公司 | Ultrasonic thermal expansion microcapsule and preparation method thereof |
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