CN108126634B - Hollow polymer brittle microsphere with micro-channels on surface and preparation method and application thereof - Google Patents

Hollow polymer brittle microsphere with micro-channels on surface and preparation method and application thereof Download PDF

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CN108126634B
CN108126634B CN201611091127.4A CN201611091127A CN108126634B CN 108126634 B CN108126634 B CN 108126634B CN 201611091127 A CN201611091127 A CN 201611091127A CN 108126634 B CN108126634 B CN 108126634B
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microspheres
microsphere
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hollow
temperature
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CN108126634A (en
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蒋赞
郑翔龙
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Guangzhou Blue Moon Industrial Co ltd
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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
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
    • C08F212/36—Divinylbenzene
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • 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
    • C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
    • C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
    • C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a hollow polymer microsphere with micro-channels on the surface, a preparation method and application thereof, wherein the method comprises the following steps: 1) preparing an oil-in-water type micro-droplet suspension; 2) preparing a mixed solution containing a polymerization monomer, a cross-linking agent and an initiator; 3) dripping the mixed solution obtained in the step 2) into the suspension obtained in the step 1) at a certain temperature, reacting, and forming a cross-linked polymer shell layer on the surface of the micro-droplet; 4) regulating and controlling the temperature of the reaction system and reacting for a certain time at the temperature to obtain the hollow polymer microsphere with the micro-channels on the surface. The microsphere belongs to a high molecular polymer material, has the performances of low density, good thermal insulation, sound insulation, light scattering and the like, and can be widely applied to the fields of medical treatment, cosmetics, cleaning/nursing products, sewage treatment, catalyst loading and the like.

Description

Hollow polymer brittle microsphere with micro-channels on surface and preparation method and application thereof
Technical Field
The invention relates to a hollow polymer brittle microsphere with a microchannel on the surface, a preparation method and application thereof, belonging to the field of polymer functional materials.
Background
The hollow polymer microsphere is a microsphere with a polymer shell layer and a cavity structure in the interior, has the performances of low density, thermal insulation, sound insulation, good light scattering and the like, and is widely applied to the fields of catalyst loading, drug slow release, cosmetic coating, sewage treatment and the like.
At present, the main methods for preparing hollow polymer microspheres include a suspension polymerization method, a self-assembly method and a solvent volatilization method, and meanwhile, an acid-base swelling method, an emulsion polymerization method, a template method and the like. For the suspension polymerization method, firstly, a Pickering emulsification method is utilized to prepare W/O type droplets, then the droplets are dispersed in a water phase to form a W/O/W type suspension system, the temperature is raised to enable an initiator in an oil phase to initiate polymerization to obtain microspheres with a water phase core and a polymer shell, and the water phase core is removed by methods such as high temperature and etching to obtain the hollow polymer microspheres. The self-assembly method is characterized in that a polymerizable functional group is introduced into the copolymer to initiate polymerization by utilizing the principle that an amphiphilic block copolymer can be agglomerated into a closed spherical micelle with an inner-outer double-layer structure in an aqueous solution near the critical micelle concentration, so that the hollow polymer microspheres combined by covalent bonds can be obtained. The solvent volatilization method comprises the steps of dispersing prepared polymer microspheres in water, adding a benign solvent into the system to swell the microspheres, freezing the system by using liquid nitrogen after swelling is finished, solidifying the solvent swelled inside the microspheres into a solid, slowly heating the system to slowly volatilize the solvent inside the microspheres, and finally obtaining the hollow polymer microspheres with single holes on the surfaces.
In addition, chinese patents CN102585279A, CN201410785640.8 and CN201510197352.5 respectively report methods for preparing low-density polymer microspheres with impermeable surfaces by using a gas suspension method, an oligomer pre-coating method and a suspension polymerization in-situ blocking method. The gas suspension method (CN102585279A) covers the holes on the surface of the porous or hollow microsphere with water on the surface by using the water-fast drying monomer to seal the holes, and prepares the polymer microsphere with no surface permeability. The oligomer pre-coating method (CN201410785640.8) utilizes the characteristics of high viscosity and poor fluidity of oligomers in good organic solvents to dissolve the oligomers in volatile organic solvents to prepare polymer solution with proper viscosity, and then porous or hollow microspheres are added to volatilize the organic solvents while stirring, so as to obtain the polymer porous or hollow microspheres with closed surface pore channels. The suspension polymerization in-situ sealing method (CN201510197352.5) takes permeable microspheres with micro-channels on the surface as seeds, utilizes the characteristic that monomers and polymers have good affinity to enable the monomers to diffuse to the surfaces of the seed microspheres to form a monomer liquid layer, and then carries out in-situ polymerization reaction to form polymer coating layers to seal the micro-channel on the surfaces of the microspheres, so as to obtain the low-density sealed hollow or porous microspheres with non-permeable surfaces.
In summary, the suspension polymerization method, the template method and the self-assembly method require high temperature, calcination, swelling with organic solvent or etching treatment in the preparation process, are inconvenient in operation method, and are not suitable for industrial production. The preparation process of the hollow or porous microsphere with the surface without permeability is to prepare the microsphere after plugging the pore canal on the surface of the microsphere, the pore canal before plugging is larger and reaches micron order, and if the pore canal is not plugged, the permeability is very obvious, but the plugging step increases the operation difficulty and the uniformity of the preparation method.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a preparation method of hollow polymer microspheres with micro channels on the surface, and the hollow polymer microspheres with micro channels on the surface, which have special mechanical properties, organic solvent resistance and temperature resistance, can be prepared by the method.
It is another object of the present invention to provide hollow polymeric microspheres having micro channels on the surface prepared by the above method, which have specific mechanical properties, organic solvent resistance and temperature resistance.
It is still another object of the present invention to provide applications of the hollow polymer microspheres having micro-channels on the surface, which are used in the fields of medical treatment, cosmetics, cleaning/caring products (such as cleaning agents, caring agents, etc.), sewage treatment, catalyst loading, etc.
In order to achieve the above purpose, the invention provides the following technical scheme: a preparation method of hollow polymer microspheres with micro-channels on the surface comprises the following steps:
1) preparing an oil-in-water type micro-droplet suspension;
2) preparing a mixed solution containing a polymerization monomer, a cross-linking agent and an initiator;
3) dripping the mixed solution obtained in the step 2) into the suspension obtained in the step 1) at a certain temperature, reacting, and forming a cross-linked polymer shell layer on the surface of the micro-droplet;
4) regulating and controlling the temperature of the reaction system and reacting for a certain time at the temperature to prepare the hollow polymer microsphere with the micro-channels on the surface.
The method further comprises the steps of:
5) the product of step 4) is further processed as follows: and (4) flotation and drying.
According to the invention, step 1) is specifically: firstly, adding an organic solvent into an aqueous phase system, dispersing the organic solvent in the aqueous phase system under stirring, gradually heating to prepare an oil-in-water type micro-droplet suspension;
wherein the aqueous phase system is an aqueous solution dissolved with a colloid protective agent.
Wherein the colloid protective agent is polyvinyl alcohol, such as polyvinyl alcohol 1788. Still preferably, in the aqueous phase system, the mass percentage of the colloid protective agent is 0.5-5.0 wt%.
Wherein the temperature is gradually increased and the system temperature (T) is enabled1) Stabilized below the boiling point (T) of the organic solvent0) A temperature of 12 to 40 ℃ i.e. T0(℃)-T1(DEG C) 12-40 ℃. Preferably, T0(℃)-T1(DEG C) 15-35 (DEG C); also preferably, T0(℃)-T1(℃)＝15～30(℃)。
Wherein the organic solvent is one of n-hexane, cyclohexane, n-heptane, isooctane and methylcyclohexane. Preferably, the amount of the organic solvent is 1 to 30 wt%, preferably 5 to 25 wt%, and further preferably 5 to 20 wt% of the mass of water.
According to the invention, in step 2), the hollow polymer microspheres can be rendered brittle by selecting appropriate polymerized monomers. The polymerization monomer is one or more of styrene and alkyl (meth) acrylate, and the amount of the polymerization monomer is 30-100 wt% of the mass of the organic solvent. Preferably, the alkyl (meth) acrylate is selected from C (meth) acrylic acid1-4One or more alkyl esters, and more preferably one or more alkyl esters selected from methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Also preferably, the polymerized monomer is one or two of styrene, methyl acrylate and methyl methacrylate, or a mixture of one or two of styrene, methyl acrylate and methyl methacrylate and one or two of ethyl acrylate and ethyl methacrylate respectively.
Wherein the crosslinking agent is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene and methylcyclopentadiene, and the amount of the crosslinking agent is 50-100 wt% of the mass of the polymerized monomer.
Wherein the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide, and the amount of the initiator is 1-3 wt% of the total mass of the polymerization monomer and the cross-linking agent.
According to the invention, the reaction temperature (T) in step 3)2) Controlled below the boiling point (T) of the organic solvent0) A temperature of 12 to 40 ℃ i.e. T0(℃)-T2(DEG C) 12 to 40 (DEG C), preferably T0(℃)-T2(DEG C) 15 to 35 (DEG C), and further preferably T0(℃)-T2(DEG C) 15-30 (DEG C); the reaction time is 0.5 to 4 hours, preferably 0.5 to 2 hours.
According to the invention, in step 4), the temperature (T) of the reaction system is controlled3) To below the boiling point (T) of the organic solvent0) A temperature of 0 to 10 ℃ i.e. T0(℃)-T3(DEG C) 0 to 10 (DEG C), preferably T0(℃)-T3(DEG C) 5-10 (DEG C). And reacting at the temperature for 1 to 6 hours, preferably 2 to 4 hours.
According to the invention, in the step 4), after the reaction is finished, the system is cooled and cooled to room temperature, and the hollow polymer microspheres are obtained after filtration, washing, air drying and vacuum drying.
According to the invention, the flotation of step 5) is lower alcohol soaking and sedimentation.
According to the invention, step 5) is specifically: dispersing the hollow polymer microspheres obtained in the step 4) in lower alcohol, stirring the mixture for indefinite time, precipitating a part of the microspheres floating on the liquid level of the lower alcohol to the bottom of the container, filtering the mixture after the precipitation is completed, and air-drying and vacuum-drying the floating microspheres at the upper part to obtain the final hollow polymer microspheres.
According to the invention, in the step 5), the stirring at random time is specifically performed by stirring at a rotation speed of 300-400 rpm for 5-20 minutes (e.g., 10 minutes) every 1-2 hours, continuously operating for 10-15 times (e.g., 12 times), and then standing for 12-36 hours (e.g., 24 hours).
Wherein the lower alcohol is C1-6Alkyl alcohol, preferably C1-4Alkyl alcohols, e.g. methanol, ethanol, propanol or butanol, and the likeEthanol is preferred.
The invention also provides the following technical scheme:
a hollow polymer microsphere with micro channels on the surface is a hollow microsphere, a shell layer is a cross-linked polymer, the particle size of the microsphere is 1-300 micrometers, and the thickness of the shell layer is 0.01-100 micrometers; wherein the surface of the microsphere is provided with micro channels, and the pore diameter of the micro channels is less than or equal to 0.05 micron.
According to the invention, the particle size of the microsphere is 100-250 micrometers, 100-200 micrometers, 30-150 micrometers, 50-150 micrometers or 5-50 micrometers. The thickness of the shell layer is preferably 0.1-50 micrometers, such as 5-30 micrometers, 1-15 micrometers, 3-20 micrometers, 10-20 micrometers or 0.5-6 micrometers. The pore diameter of the microchannel is preferably 0.03 μm or less, and more preferably 0.02 μm or less.
According to the invention, the micro-channels on the surface of the hollow polymer microsphere are communicated with the cavity inside the hollow polymer microsphere.
According to the invention, the polymerization monomer of the cross-linked polymer is one or more of styrene and alkyl (meth) acrylate. Preferably, the alkyl (meth) acrylate is selected from C (meth) acrylic acid1-4One or more alkyl esters, and more preferably one or more alkyl esters selected from methyl methacrylate, ethyl methacrylate, methyl acrylate and ethyl acrylate. Also preferably, the polymerized monomer is one or two of styrene, methyl acrylate and methyl methacrylate, or a mixture of one or two of styrene, methyl acrylate and methyl methacrylate and one or two of ethyl acrylate and ethyl methacrylate respectively. The crosslinking agent of the crosslinked polymer is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene, and methylcyclopentadiene.
According to the invention, the hollow polymeric microspheres are hollow polymeric brittle microspheres.
The term "brittle" as used herein means: the property of the microspheres that the microspheres break and break under the action of external force; in particular, the property of the microspheres that only a small deformation, i.e., fracture failure, occurs under a certain external force is called brittleness. The brittleness is also a particular mechanical property of the microspheres of the invention.
According to the invention, the hollow polymer microsphere is prepared by the preparation method of the hollow polymer microsphere with the micro-channels on the surface.
The invention further provides the following technical scheme:
the hollow polymer microsphere with the micro-channels on the surface has good light scattering property, thermal insulation and sound insulation, also has the characteristics of special mechanical property, organic solvent resistance, temperature resistance and the like, and can be widely applied to the fields of medical treatment, cosmetics, cleaning/nursing products (such as cleaning agents, nursing agents and the like), sewage treatment, catalyst loading and the like.
According to the invention, the microspheres are used as reservoirs, for example, for storing raw materials of medicines, cleaning products, care products, cosmetics, sewage treatment agents, catalysts and the like.
The invention has the beneficial effects that:
the invention provides a method for simply and quickly preparing hollow polymer microspheres with microchannels on the surfaces, which has good universality. The shell layer of the polymer microsphere storage has good brittleness and has the functions of slow release and quick release. When in use, if no external force acts, the micromolecule substances in the cavity can be slowly released outwards through the micro-channels of the microspheres; when the micro-sphere is acted by external force, the micro-sphere can be broken instantly, and the substance in the cavity can be released rapidly. Moreover, by regulating and controlling the dosage and proportion of the polymerized monomer and the cross-linking agent, the hollow polymer microspheres with different shell thicknesses and strengths can be prepared, and the relationship between external force and microsphere crushing is further regulated and controlled. In addition, as the shell layer is a cross-linked polymer and has the insoluble and infusible properties, the prepared polymer microsphere also has good organic solvent resistance and temperature resistance. In addition, the polymer microsphere prepared by the method has the characteristics of good light scattering property, thermal insulation, sound insulation and the like, and can be widely applied to the fields of medical treatment, cosmetics, cleaning/nursing products (such as cleaning agents, nursing agents and the like), sewage treatment, catalyst loading and the like.
Detailed Description
As described above, the present invention discloses a method for preparing hollow polymer microspheres having microchannels on the surface, wherein the polymerization reaction is mainly performed on the surface of oil-in-water type micro-droplets by controlling the dosage ratio of water to organic solvent and the dosage ratio of organic solvent to polymeric monomer and cross-linking agent, thereby forming a cross-linked polymer shell layer on the surface of the micro-droplets; secondly, by regulating and controlling the temperature of a reaction system, slowly volatilizing part of the organic solvent wrapped in the polymer shell layer to form a micro-channel on the surface of the microsphere, wherein the micro-channel is communicated with an internal cavity, and screening out the microsphere with better connectivity between the micro-channel on the surface of the microsphere and the internal cavity based on further treatment; furthermore, a hollow microsphere shell layer with brittleness is prepared by selecting proper polymerization monomers; furthermore, the thickness and the strength of the shell layer of the hollow polymer microsphere can be regulated and controlled by regulating and controlling the dosage of the polymerization monomer and the cross-linking agent, and the relationship between external force and microsphere crushing can be further regulated and controlled.
In a preferred embodiment of the present invention, the preparation method comprises the steps of: firstly, adding an organic solvent into an aqueous solution dissolved with a colloid protective agent, stirring at room temperature to disperse the organic solvent, and gradually heating to prepare an oil-in-water type micro-droplet suspension; preparing a mixed solution containing a polymerization monomer, an initiator and a cross-linking agent; the mixed solution was added dropwise to the above suspension. And controlling the dosage of the organic solvent to ensure that the polymerization reaction is gradually carried out on the surface of the micro-droplet to form a crosslinked polymer shell layer. In the initial stage of forming the polymer shell layer, the organic solvent wrapped in the polymer shell layer is slowly volatilized by regulating and controlling the system temperature, and the hollow polymer microsphere with the micro-channels on the surface is formed. And filtering, washing, air-drying and vacuum-drying the product, and then carrying out a flotation-drying operation process on the product to screen out the microspheres with better connectivity between the micro-channels on the surfaces of the microspheres and the internal cavities. In the method, the hollow microspheres with fragile shell layers can be prepared by selecting proper polymeric monomers; meanwhile, the hollow polymer microspheres with different shell thicknesses and strengths can be prepared by regulating and controlling the dosage and proportion of the polymerized monomer and the cross-linking agent.
In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:
(1) placing a reactor provided with a stirrer and a reflux condensing device in a water bath, adding 0.5-5.0 wt% of distilled water solution of a colloid protective agent and 5-20 wt% of an organic solvent into the reactor in sequence, adjusting the stirring speed to 500-3000 rpm, stirring for 10 minutes at room temperature, starting to heat and keeping the system temperature (T)1) Stabilized below the boiling point (T) of the organic solvent0) A temperature of 15 to 30 ℃ i.e. T0(℃)-T1The temperature is 15-30℃, and a stable oil-in-water micro-droplet suspension is formed.
(2) Placing a polymerization monomer with the mass of 30-100 wt% of the organic solvent and a cross-linking agent with the mass of 50-100 wt% of the polymerization monomer into a beaker, adding an initiator with the mass of 1-3 wt% of the total mass of the polymerization monomer and the cross-linking agent, and stirring until the initiator is completely dissolved to form a uniform mixed solution.
(3) Dropwise adding the mixed solution obtained in the step (2) into the suspension obtained in the step (1) by using a syringe pump, and keeping the system temperature (T) after dropwise adding2) At a temperature below the boiling point (T) of the organic solvent0) A temperature of 15 to 30 ℃ i.e. T0(℃)-T2The reaction is continued at 15 to 30 ℃ for 0.5 to 2 hours.
(4) Temperature (T) of the system3) Up to below the boiling point (T) of the organic solvent0) A temperature of 5 to 10 ℃ i.e. T0(℃)-T3The reaction is carried out at 5 to 10 ℃ and the reaction is carried out for 2 to 4 hours. And then cooling the system to room temperature, filtering, washing with water and ethanol for 2 times respectively, and air-drying and vacuum-drying to obtain the hollow polymer microspheres with the micro-channels on the surfaces.
(5) Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres irregularly (specifically, stirring the hollow polymer microspheres for 10 minutes at a rotating speed of 300-400 r/min every 2 hours, continuously operating for 12 times, then standing for 24 hours), slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the microspheres after the microspheres are completely settled, and air-drying and vacuum-drying the floating microspheres on the upper part to obtain the hollow polymer microspheres with better connectivity between the surface micro-channels and the inner cavities.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Furthermore, it should be understood that various changes or modifications can be made by those skilled in the art after reading the description of the present invention, and such equivalents also fall within the scope of the invention.
1. Macroscopic mechanical property test of microspheres
The macroscopic mechanical properties of the microspheres were tested as follows: a3.0 cm by 2.5cm by 0.2cm slide S was takenLower partPouring microspheres with the stacking volume of 0.05-0.1 mL on the glass slide SLower partPushing the microspheres to a single layer by using weighing paper, wherein the occupied area of the single-layer microspheres is more than 1.0cm by 1.0 cm; selecting an area with the most dense and smooth stacks of 0.3cm by 0.3cm as an area to be detected, and slightly removing microspheres in the rest areas by using weighing paper; another 0.5cm by 0.2cm slide SOn the upper partCovering the surface of the microsphere to be detected, and placing the glass slide SLower partGlass slide SOn the upper partAnd the microspheres are integrally moved to a weighing platform of an electronic balance and placed on a glass slide SOn the upper partAdding weights or other weights to the microsphere area to be detected, or directly pressing the glass slide S with the index fingerOn the upper partKeeping the force application between 0.1N and 30N, keeping the force application time for each pressing for 30s, and pressing once from four directions of front, back, left and right; pressing, and placing the glass slide SLower partAnd moving the microspheres to an optical microscope for observation, and inspecting the rupture condition of the microspheres.
2. Testing of microsphere organic solvent resistance
Adding 0.1g of microspheres into a sample bottle with a plug, adding 10g of common organic solvent such as ethanol, acetone, isopropanol, dichloromethane, chloroform, toluene, ethyl acetate, tetrahydrofuran, N-dimethylformamide and the like into the sample bottle, observing the dissolving conditions of the microspheres in the organic solvent after 1h, 24h and 168h by naked eyes, separating the microspheres from the solvent, and observing whether the microspheres swell under an optical microscope. If the microspheres are not dissolved in the organic solvent and do not swell under an optical microscope, the microspheres are considered to have good organic solvent resistance.
The following will further illustrate the specific operation of preparing a hollow polymer microsphere with micro-channels on the surface, with reference to specific examples.
Example 1: a preparation method of crosslinked polystyrene hollow polymer brittle microspheres with micro-channels on the surface comprises the following specific operation steps:
(1) placing a reactor provided with a stirrer and a reflux condensing device in a water bath, adding 300.0g of 1.0 wt% polyvinyl alcohol 1788 (with the molecular weight of 1700 and the alcoholysis degree of 88%) aqueous solution and 25.0g of n-heptane (with the boiling point of 98.5 ℃) into the reactor in sequence, adjusting the stirring speed to be 500rpm, stirring for 10 minutes at room temperature, starting heating and stabilizing the temperature of the system at 70 ℃ to form a stable oil-in-water micro-droplet suspension.
(2) 12.5g of styrene and 6.3g of divinylbenzene were placed in a beaker, and 0.4g of azobisisobutyronitrile was added thereto and stirred until the azobisisobutyronitrile was completely dissolved to form a uniform mixed solution. The mixed solution was added dropwise to the reaction system at 70 ℃ using a syringe pump, and after completion of the addition, the reaction was continued at 70 ℃ for 0.5 hour. The temperature of the system was raised to 90 ℃ and the reaction was continued for 2 hours. And then cooling the system to room temperature, filtering, washing with water and ethanol for 2 times respectively, and air-drying and vacuum-drying to obtain the cross-linked polystyrene hollow polymer microspheres with the micro-channels on the surfaces.
(3) Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres irregularly (specifically, stirring the hollow polymer microspheres for 10 minutes at a rotating speed of 300-400 r/min every 2 hours, continuously operating for 12 times, then standing for 24 hours), slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the microspheres after the microspheres are completely settled, and air-drying and vacuum-drying the floating microspheres on the upper part of the filter to obtain the crosslinked polystyrene hollow polymer microspheres with better connectivity between the surface micro-channels and the inner cavity.
The microspheres prepared in example 1 have strong hydrophobicity, large shell hardness, and moderate thickness and strength.
Macroscopic mechanical property test of the microsphere shows that: applying force of about 20N, pressing for four times respectively at the front, the back, the left and the right, observing under an optical microscope, and cracking about 90% of microspheres; the particle size of the microsphere is between 100 and 250 micrometers, the shell thickness of the microsphere is between 5 and 30 micrometers, and the pore diameter of the micro-channel is 0.04 micrometer. The organic solvent resistance test of the microspheres shows that: the microspheres have good organic solvent resistance.
Example 2: a preparation method of crosslinked polymethyl acrylate hollow polymer brittle microspheres with micro channels on the surfaces comprises the following specific operation steps:
(1) placing a reactor provided with a stirrer and a reflux condensing device in a water bath, adding 300.0g of polyvinyl alcohol 1788 aqueous solution with the mass percent of 2.0 wt% and 29.4g of cyclohexane (the boiling point is 80.7 ℃) into the reactor in sequence, adjusting the stirring speed to be 1000rpm, stirring for 10 minutes at room temperature, starting heating and stabilizing the system temperature to be 60 ℃ to form stable oil-in-water micro-droplet suspension.
(2) 11.8g of methyl acrylate and 11.8g of methylcyclopentadiene were placed in a beaker, and 0.3g of benzoyl peroxide was added and stirred until the benzoyl peroxide was completely dissolved to form a uniform mixed solution. The mixed solution was added dropwise to the reaction system at 60 ℃ using a syringe pump, and after completion of the addition, the reaction was continued for 2 hours while keeping the temperature at 60 ℃. The temperature of the system was raised to 75 ℃ and the reaction was continued for 4 hours. And then cooling the system to room temperature, filtering, washing with water and ethanol for 2 times respectively, and air-drying and vacuum-drying to obtain the crosslinked polymethyl acrylate hollow polymer microsphere with the micro-channels on the surface.
(3) Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres irregularly (specifically, stirring the hollow polymer microspheres for 10 minutes at a rotating speed of 300-400 r/min every 2 hours, continuously operating for 12 times, then standing for 24 hours), slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the microspheres after the microspheres are completely settled, and air-drying and vacuum-drying the floating microspheres on the upper part to obtain the crosslinked polymethyl acrylate hollow polymer microspheres with better connectivity between the surface micro-channels and the inner cavities.
The microspheres prepared in example 2 have hydrophobicity, and the shell layer has low hardness, is thin and is fragile.
Macroscopic mechanical property test of the microsphere shows that: applying force at about 10N, pressing for four times, and observing under optical microscope to crack about 95% of microsphere; the particle size of the microsphere is between 100 and 200 mu m, the shell thickness of the microsphere is between 1 and 15 mu m, and the pore diameter of the microchannel is 0.03 mu m. The organic solvent resistance test of the microspheres shows that: the microspheres have good organic solvent resistance.
Example 3: a preparation method of crosslinked polymethyl methacrylate hollow polymer brittle microspheres with micro channels on the surface comprises the following specific operation steps:
(1) placing a reactor provided with a stirrer and a reflux condensing device in a water bath, adding 300.0g of polyvinyl alcohol 1788 aqueous solution with the mass percent of 0.5 wt% and 16.3g of normal hexane (the boiling point is 68.7 ℃) into the reactor in sequence, adjusting the stirring speed to 2000rpm, stirring for 10 minutes at room temperature, starting heating and stabilizing the system temperature at 49 ℃ to form stable oil-in-water micro-droplet suspension.
(2) 5.7g of methyl methacrylate and 4.0g of methylcyclopentadiene were placed in a beaker, and 0.1g of azobisisoheptonitrile was added and stirred until the azobisisoheptonitrile was completely dissolved to form a uniform mixed solution. The mixed solution was added dropwise to the reaction system at 49 ℃ using a syringe pump, and after completion of the addition, the reaction was continued for 2 hours while keeping the temperature at 49 ℃. The temperature of the system was raised to 62 ℃ and the reaction was continued for 3 hours. And then cooling the system to room temperature, filtering, washing with water and ethanol for 2 times respectively, and air-drying and vacuum-drying to obtain the cross-linked polymethyl methacrylate hollow polymer microspheres with micro-channels on the surfaces.
(3) Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres irregularly (specifically, stirring the hollow polymer microspheres for 10 minutes at a rotating speed of 300-400 r/min every 2 hours, continuously operating for 12 times, then standing for 24 hours), slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the microspheres after the microspheres are completely settled, taking the floating microspheres on the upper part, and carrying out air drying and vacuum drying on the floating microspheres to obtain the crosslinked polymethyl methacrylate hollow polymer microspheres with better connectivity between the surface micro-channels and the inner cavities.
The microspheres prepared in example 3 have strong hydrophobicity, large shell hardness, and moderate thickness and strength.
Macroscopic mechanical property test of the microsphere shows that: applying force at about 15N, pressing for four times, and observing under optical microscope to break 95% of microsphere; the particle size of the microsphere is 30-150 mu m, the shell thickness of the microsphere is 3-20 mu m, and the pore diameter of the micro-channel is 0.02 mu m. The organic solvent resistance test of the microspheres shows that: the microspheres have good organic solvent resistance.
Example 4: a preparation method of crosslinked polystyrene-ethyl methacrylate hollow copolymer brittle microspheres with micro channels on the surface comprises the following specific operation steps:
(1) placing a reactor provided with a stirrer and a reflux condensing device in a water bath, adding 300.0g of polyvinyl alcohol 1788 aqueous solution and 43.7g of methylcyclohexane with the mass percent of 5 wt% into the reactor in sequence, adjusting the stirring speed to 3000rpm, stirring for 10 minutes at room temperature, starting to heat and stabilizing the temperature of the system at 75 ℃ to form stable oil-in-water micro-droplet suspension.
(2) 21.7g of ethyl methacrylate, 22.0g of styrene and 24.0g of divinylbenzene were put in a beaker, and 0.9g of azobisisobutyronitrile was added and stirred until the azobisisobutyronitrile was completely dissolved to form a uniform mixed solution. The mixed solution was added dropwise to the reaction system at 75 ℃ using a syringe pump, and after completion of the addition, the reaction was continued for 2 hours while keeping the temperature at 75 ℃. The temperature of the system was raised to 93 ℃ and the reaction was continued for 3.5 hours. And then cooling the system to room temperature, filtering, washing with water and ethanol for 2 times respectively, and air-drying and vacuum-drying to obtain the crosslinked polystyrene-ethyl methacrylate hollow polymer microspheres with the microchannels on the surfaces.
(3) Dispersing the prepared hollow polymer microspheres in a beaker filled with ethanol, stirring the hollow polymer microspheres irregularly (specifically, stirring the hollow polymer microspheres for 10 minutes at a rotating speed of 300-400 r/min every 2 hours, continuously operating for 12 times, then standing for 24 hours), slowly settling a part of the microspheres floating on the liquid level of the ethanol to the bottom of the beaker, filtering the microspheres after the microspheres are completely settled, taking the floating microspheres on the upper part, and carrying out air drying and vacuum drying on the floating microspheres to obtain the crosslinked polystyrene-ethyl methacrylate hollow polymer microspheres with better connectivity between the surface micro-channels and the inner cavity.
The microspheres prepared in example 4 have hydrophobicity, and the shell layer has low hardness, is thin and is fragile.
Macroscopic mechanical property test of the microsphere shows that: applying force of about 28N, pressing for four times respectively at the front, the back, the left and the right, observing under an optical microscope, and cracking about 90% of microspheres; the particle size of the microsphere is between 5 and 50 micrometers, the shell thickness of the microsphere is between 0.5 and 6 micrometers, and the pore diameter of the microchannel is less than 0.02 micrometer. The organic solvent resistance test of the microspheres shows that: the microspheres have good organic solvent resistance.
Examples 5 to 10: preparation method of crosslinked polystyrene-ethyl methacrylate hollow copolymer brittle microspheres with micro-channels on surfaces
Otherwise, the same procedure as in example 4, examples 5-10 was carried out except that the amounts and proportions of the polymerizable monomers and the crosslinking agent were different from those of example 4, and the specific values are shown in Table 1.
The corresponding macroscopic mechanical properties of the products of examples 5 to 10 are also given in table 1.
TABLE 1 macroscopic mechanical Properties of examples 5 to 10
Figure BDA0001168460570000131
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. A method for preparing hollow polymer microspheres with microchannels on the surface, which is characterized by comprising the following steps:
1) preparing an oil-in-water type micro-droplet suspension;
2) preparing a mixed solution containing a polymerization monomer, a cross-linking agent and an initiator; the polymerization monomer is two of styrene, methyl acrylate and methyl methacrylate, or a mixture of one or two of styrene, methyl acrylate and methyl methacrylate and one or two of ethyl acrylate and ethyl methacrylate;
3) dripping the mixed solution obtained in the step 2) into the suspension obtained in the step 1) at a certain temperature, reacting, and forming a cross-linked polymer shell layer on the surface of the micro-droplet; reaction temperature T in step 3)2Controlled below the boiling point T of the organic solvent0A temperature of 12 to 40 ℃ i.e. T0-T2＝12～40℃；
4) Regulating and controlling the temperature of the reaction system and reacting for a certain time at the temperature to prepare hollow polymer microspheres with micro-channels on the surfaces; in step 4), the temperature T of the reaction system is regulated3To below the boiling point T of the organic solvent00 to 10 ℃ i.e. T0-T3＝0～10℃；
5) The product of step 4) is further processed as follows: soaking in lower alcohol, settling and drying;
wherein the organic solvent is one of n-hexane, cyclohexane, n-heptane, isooctane and methylcyclohexane.
2. The preparation method according to claim 1, wherein step 1) is specifically: firstly, adding an organic solvent into an aqueous phase system, dispersing the organic solvent in the aqueous phase system under stirring, gradually heating to prepare an oil-in-water type micro-droplet suspension; wherein the aqueous phase system is an aqueous solution dissolved with a colloid protective agent.
3. The preparation method according to claim 2, wherein the colloid protective agent is polyvinyl alcohol, and the mass percentage of the colloid protective agent in the aqueous phase system is 0.5-5.0 wt%.
4. The method of claim 2, wherein T is0(℃)-T1(DEG C) 15-35 (DEG C), wherein T is1The system temperature, T, of step 1)0Is the boiling point of the organic solvent.
5. The method of claim 4, wherein T is0(℃)-T1(℃)＝15～30(℃)。
6. The preparation method according to claim 1, wherein the amount of the organic solvent is 1 to 30 wt% based on the mass of water.
7. The preparation method of claim 1, wherein the crosslinking agent is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene and methylcyclopentadiene, and the amount of the crosslinking agent is 50 to 100 wt% of the mass of the polymerized monomers;
the initiator is one of azobisisobutyronitrile, azobisisoheptonitrile and benzoyl peroxide, and the amount of the initiator is 1-3 wt% of the total mass of the polymerization monomer and the cross-linking agent.
8. The method of claim 1, wherein T is0(℃)-T2(℃)＝15～35(℃)。
9. Preparation according to claim 8Method, characterized in that T0(℃)-T2(℃)＝15～30(℃)。
10. The method according to claim 1, wherein the reaction time in the step 3) is 0.5 to 4 hours.
11. The method of claim 1, wherein T is0(℃)-T3(DEG C) 5-10 (DEG C); and reacting for 1-6 hours at the temperature.
12. The preparation method according to claim 1, wherein in the step 4), after the reaction is completed, the system is cooled and cooled to room temperature, and the hollow polymer microspheres are obtained by filtering, washing, air drying and vacuum drying.
13. The preparation method according to claim 1, wherein the step 5) is specifically: dispersing the hollow polymer microspheres obtained in the step 4) in lower alcohol, stirring the mixture for indefinite time, precipitating a part of the microspheres floating on the liquid level of the lower alcohol to the bottom of the container, filtering the mixture after the precipitation is completed, and air-drying and vacuum-drying the floating microspheres at the upper part to obtain the final hollow polymer microspheres.
14. The method of claim 13, wherein the lower alcohol is C1-6An alkyl alcohol.
15. The method of claim 14, wherein the lower alcohol is methanol, ethanol, propanol, or butanol.
16. The hollow polymer microsphere with the micro-channels on the surface prepared by the method of any one of claims 1 to 15, which is characterized in that the hollow polymer microsphere is a hollow microsphere, the shell layer is a cross-linked polymer, the particle size of the microsphere is 5 to 300 microns, and the thickness of the shell layer is 0.5 to 100 microns; wherein the surface of the microsphere is provided with micro channels, and the pore diameter of the micro channels is less than or equal to 0.05 micron;
the polymerization monomer of the cross-linked polymer is two of styrene, methyl acrylate and methyl methacrylate, or a mixture of one or two of styrene, methyl acrylate and methyl methacrylate and one or two of ethyl acrylate and ethyl methacrylate.
17. The hollow polymeric microspheres of claim 16, wherein the microspheres have a particle size of 100-250 microns, 100-200 microns, 30-150 microns, 50-150 microns, or 5-50 microns.
18. The hollow polymeric microsphere of claim 16, wherein the shell layer has a thickness of 10 to 30 microns, 5 to 15 microns, 8 to 20 microns, 10 to 20 microns, or 0.5 to 6 microns.
19. The hollow polymeric microsphere of claim 16, wherein the pore size of the microchannels is 0.03 μm or less.
20. The hollow polymeric microsphere of claim 19, wherein the pore size of the microchannels is 0.02 μm or less.
21. The hollow polymeric microsphere of claim 16, wherein the surface microchannels are open to internal cavities.
22. The hollow polymeric microspheres of claim 16, wherein the cross-linking agent of the cross-linked polymer is one or more of divinylbenzene, cyclopentadiene, dicyclopentadiene, and methylcyclopentadiene.
23. The hollow polymeric microsphere of claim 16, wherein said hollow polymeric microsphere is a hollow polymeric friable microsphere.
24. Use of hollow polymeric microspheres according to any one of claims 16 to 23 in medical, cosmetic, cleaning/care applications, sewage treatment, catalyst loading applications; alternatively, the microspheres are used as reservoirs.
25. The use of claim 24, wherein the microspheres are used for storing raw materials for pharmaceuticals, cleaning products, care products, cosmetics, sewage treatment agents, or catalysts.
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