CN111375359A - Monodisperse core-shell structure organic-inorganic composite nano rubber particle and preparation method and application thereof - Google Patents
Monodisperse core-shell structure organic-inorganic composite nano rubber particle and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a monodisperse core-shell structure organic-inorganic composite nano rubber particle, a preparation method and application thereof. Compared with the prior art, the monodisperse core-shell structure organic-inorganic composite nano rubber particle and the preparation process thereof have the advantages of simple operation, strong controllability, easy realization of industrial production and low cost, the monodisperse core-shell structure organic-inorganic composite nano rubber particle has smaller controllable diameter size, nano-scale distribution, spherical shape, good dispersibility and uniform granularity, and when the monodisperse core-shell structure organic-inorganic composite nano rubber particle is used as an organic functional resin toughening and reinforcing material, the toughness and the strength of various prepared resin products can be obviously improved, the impact resistance of the products is improved, and the products can better meet the requirements of practical application. The low dielectric constant materials have wide application prospects in the technical fields of wind power blades, high-toughness resin accessory products and the like.
Description
Technical Field
The invention relates to the technical field of preparation and application of functional composite materials, in particular to a monodisperse core-shell structure organic-inorganic composite nano rubber particle material, a preparation method and application thereof.
Background
The polymer resin has excellent processing performance and bonding characteristic, the cured product of the polymer resin has good dimensional stability, high strength and good chemical resistance, can meet the requirements of different use and processing performance, is an important component of an adhesive, a composite material and an electronic packaging material, is widely applied to the fields of mechatronics, aerospace, daily necessities and the like, and becomes a material with the largest use amount and the widest application. However, when the common polymer resin is cured, the crosslinking density is high, the molecular chain rigidity is high, and the problems of large internal stress, poor toughness, easy cracking, insufficient strength and the like of a cured product are caused, so that liquid rubber and thermoplastic resin are often introduced to toughen and modify the thermosetting polymer resin so as to be applied to more high and new technical fields. Although the mechanical property of the liquid rubber toughening is obviously improved, a small part of the liquid rubber toughening is dissolved in a matrix to cause incomplete phase separation, so that the elastic modulus and the glass transition temperature (Tg) of a resin system are greatly reduced. The introduction of thermoplastic resin into the thermosetting polymer resin matrix is not ideal in toughening effect, and the viscosity of the system is greatly increased, thereby affecting the processability. The novel core-shell structure latex particle takes a nano-scale polymeric sphere as a core to prepare a core-shell structure compound. The latex particles are filled into a rubber substrate, so that the double bonds on the surfaces of the core-shell nano latex particles and the substrate are subjected to chemical reaction. The rubber latex core in the filler material with the core-shell structure can play a role in reinforcing and toughening resin, good compatibility with a resin matrix can be realized through the structure of the shell and the selection of the composition of the shell, and an excellent dispersion state can be kept in the matrix. The design of the structure essentially effectively adjusts the interface action between the filling particles and the polymer resin matrix, effectively reduces the size of a disperse phase, and obviously improves the processing rheological property, the dynamic viscoelastic property, the mechanical property and the like of the polymer resin; especially, the performance of the resin under dynamic working conditions is improved, and the aims of reducing the self-mass, reducing the internal consumption, improving various performances of resin materials, improving the use efficiency and reducing the environmental pollution are fulfilled.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide organic-inorganic composite nano rubber particles with a monodisperse core-shell structure, a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: the organic-inorganic composite nano rubber particles with the monodisperse core-shell structure are characterized in that the core part of the composite nano rubber particles is made of organic rubber particle materials, and porous organic-inorganic coating materials are used as the shell part of the outer layer.
Further, the diameter of the composite nanometer rubber particle is 70nm-300 nm; preferably, 70nm to 150 nm;
and/or the diameter of the core part is 60nm-250 nm; preferably 80nm to 150 nm;
and/or the thickness of the shell part is 0nm-100 nm; preferably 15nm to 70 nm;
further, the cladding rate of the shell part of the composite nano-particle is not less than 90%;
and/or the shell part material is a mesoporous coating material, and the mesoporous coating material is selected from one or any combination of organic molecule modified inorganic oxide, inorganic simple substance, inorganic salt, high molecular polymer and organic-inorganic hybrid molecular polymer.
Further, the organic molecule-modified inorganic oxide may be a non-metal oxide and/or a metal oxide, including SiO2、TiO2、ZrO2、CeO2、SnO2、Al2O3One or any combination thereof;
the inorganic simple substance modified by the organic molecules can be one of carbon, silicon, gold and titanium or any combination thereof;
the inorganic salt modified by organic molecules can be one of carbonate, phosphate, sulfite, silicate, aluminosilicate and the like or any combination thereof;
the high molecular polymer can be a carbon chain polymer or a hybrid chain polymer, and comprises one or any combination of polystyrene, phenolic resin, polyacrylic acid, polybarbituric acid, polyurethane and the like;
the organic-inorganic hybrid molecular polymer can be one of organic silicon polymer, organic sulfur polymer, organic fluorine polymer, organic aluminum polymer and organic titanium polymer or any combination thereof.
Furthermore, the core material is nano organic rubber particles and/or other organic rubber particles with modified surfaces.
Further, the core material is one of styrene butadiene rubber nanoparticles, isoprene rubber nanoparticles, nitrile rubber nanoparticles, ethylene propylene rubber nanoparticles, butyl rubber nanoparticles, organofluorine rubber nanoparticles, organosulfur rubber nanoparticles, organosilicon rubber nanoparticles, organoaluminum rubber nanoparticles, organotitanium rubber nanoparticles, or any combination thereof.
A preparation method of monodisperse core-shell structure organic-inorganic composite nano rubber particles is characterized in that the surface of a nano organic rubber particle serving as a core part is coated with a shell part material.
The coating method includes a chemical precipitation method, which is a method of performing precipitation polymerization on the surface of the core material by a precursor of the shell material under certain conditions through chemical and/or physical action.
The application of the monodisperse core-shell structure organic-inorganic composite nano rubber particles is characterized in that the monodisperse core-shell structure organic-inorganic composite nano rubber particles are used in toughening and strengthening of organic resin or in preparation of resin related materials with high toughness and high strength requirements;
or, the monodisperse core-shell structure organic-inorganic composite nano rubber particles and the organic polymer resin are compounded and used in resin related materials with high toughness and high strength requirements.
Further, the resin related material with high toughness and high strength requirement is a wind power generation fan blade or a high-strength resin impeller blade.
Compared with the prior art, the monodisperse core-shell structure organic-inorganic composite nano rubber particle and the preparation process thereof have the advantages of simple operation, strong controllability, easy realization of industrial production and low cost, the monodisperse core-shell structure organic-inorganic composite nano rubber particle has smaller controllable diameter size, nano-scale distribution, spherical shape, good dispersibility and uniform granularity, and when the monodisperse core-shell structure organic-inorganic composite nano rubber particle is used as an organic functional resin toughening and reinforcing material, the toughness and the strength of various prepared resin products can be obviously improved, the impact resistance of the products is improved, and the products can better meet the requirements of practical application. The low dielectric constant materials have wide application prospects in the technical fields of wind power blades, high-toughness resin accessory products and the like.
The invention coats the uniform and compact organic-inorganic composite shell material on the outer layer of the nanometer rubber particle as the core part, thereby providing the monodisperse core-shell structure organic-inorganic composite nanometer rubber particle material with the characteristics of lower cost, simple preparation, controllable size, uniform structure and the like.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the characteristics of the monodisperse core-shell structure organic-inorganic composite nano rubber particle material.
Detailed Description
The inventor of the invention coats the uniform and compact organic-inorganic composite shell material on the outer layer of the nano rubber particle serving as the core part, thereby providing the monodisperse core-shell structure organic-inorganic composite nano rubber particle material with the characteristics of lower cost, simple preparation, controllable size, uniform structure and the like, and completing the invention on the basis.
In the present application, "core-shell structure" generally refers to a composite structure formed by one material encapsulating another material.
In the present application, "nano-rubber particles" generally refer to organic high molecular polymer particles having a size of 70 to 150 nm.
In the present application, the "nano-rubber coating material" generally means a material that can be used to coat a nano-rubber material as a core portion and can form a shell portion on the surface of the nano-rubber material as the core portion.
Monodisperse core-shell structure organic-inorganic composite nano rubber particle
The invention provides a monodisperse core-shell structure organic-inorganic composite nano rubber particle material, wherein the core part of the composite nano rubber particle is an organic polymer rubber nano particle material, the shell part of the composite nano rubber particle is an organic-inorganic composite coating material, the surface of the organic polymer rubber material as the core part in the core-shell structure composite nano rubber particle can be coated and/or sealed by the coating material as the shell part material, so as to form a core-shell structure, the coating and/or sealing can be compact and/or uniform, and the coating of the core part by the shell part can be formed by mechanisms such as chemical bond action, electrostatic action, adsorption layer medium action and the like.
In the monodisperse core-shell structure organic-inorganic composite nano rubber particle provided by the invention, the shape of the monodisperse core-shell structure organic-inorganic composite nano rubber particle is usually regular or irregular spherical, the diameter of the microsphere can be usually 30-50nm, 50-70nm, 70-90nm, 90-120nm, 120-plus-150 nm, 150-plus-200 nm or 200-plus-300 nm, and a person skilled in the art can adjust the diameter of the core part and/or the thickness of the shell part of the monodisperse core-shell structure organic-inorganic composite nano rubber particle, so that the overall diameter of the composite nano rubber particle can be adjusted.
In the monodisperse core-shell structure organic-inorganic composite nano rubber particle material provided by the invention, the organic high molecular nano rubber particles serving as the core part can be high molecular polymers with various compositions, single-component organic polymer nano particles, or organic polymer nano particles with various components, or organic-inorganic hybrid high molecular polymer nano particles. For example, the rubber material may be one or any combination of styrene-butadiene rubber nanoparticles, isoprene rubber nanoparticles, nitrile rubber nanoparticles, ethylene-propylene rubber nanoparticles, butyl rubber nanoparticles, organofluorine rubber nanoparticles, organosulfur rubber nanoparticles, organosilicon rubber nanoparticles, organoaluminum rubber nanoparticles, organotitanium rubber nanoparticles, and the like.
In the monodisperse core-shell structure organic-inorganic composite nano rubber particle provided by the invention, the diameter of the core part of the composite nano rubber particle can be 20-40nm, 40-60nm, 60-80nm, 80-100nm, 100-120nm, 120-150nm or 150-200 nm. The person skilled in the art can adjust the content of the organic polymerization precursor, the composition of the solvent or the concentration of the catalyst. The aim of adjusting the diameter of the core part can be achieved by controlling the reaction process.
In the monodisperse core-shell-structured organic-inorganic composite nano rubber particle provided by the invention, the shell part of the monodisperse core-shell-structured organic-inorganic composite nano rubber particle can be an organic-inorganic composite coating material, and the monodisperse core-shell-structured organic-inorganic composite nano rubber particle coating material is generally a material which can be used for coating the organic nano rubber particle serving as the core part and can form the shell part on the surface of the organic nano rubber particle serving as the core part. For example, the mesoporous coating material may be one or any combination of inorganic oxides, inorganic simple substances, inorganic salts, organic-inorganic hybrid molecular polymers, organic high molecular polymers, and the like, including but not limited to organic molecule modification. The organic molecule-modified inorganic oxide may be a non-metal oxide and/or a metal oxide, and examples of the inorganic oxide include, but are not limited to, SiO2、TiO2、ZrO2、CeO2、SnO2、Al2O3Etc. or any combination thereof, and the organic molecule is modifiedThe inorganic simple substance of (a) may be, for example, one or any combination of carbon, silicon, gold, titanium, etc., and the organic molecule-modified inorganic salt may be, for example, one or any combination of carbonate, phosphate, sulfite, silicate, aluminosilicate, etc. The organic-inorganic hybrid molecular polymer can be one of organic silicon polymer, organic sulfur polymer, organic fluorine polymer, organic aluminum polymer and organic titanium polymer or any combination thereof, the high molecular polymer can be carbon chain polymer and hybrid chain polymer, such as but not limited to one of polystyrene, phenolic resin, polyacrylic acid, poly barbituric acid, polyurethane and the like or any combination thereof, and in the monodisperse core-shell structure organic-inorganic composite nano rubber particle provided by the invention, the shell part of the composite nano particle can have the thickness of 0-5nm, 5-10nm, 10-15nm, 15-20nm, 20-30nm, 30-50nm, 50-70nm, 70-90nm, 90-100nm or 100-150 nm. The adjustment of the shell thickness can be achieved by the skilled person by adjusting the solvent composition, the temperature, the catalyst concentration, the precursor concentration or controlling other reaction conditions.
In the monodisperse core-shell structure organic-inorganic composite nano rubber particle provided by the invention, the shell coating rate of the composite nano particle is usually not less than 90%, not less than 92%, not less than 94%, not less than 96%, not less than 98%, not less than 99%, not less than 99.5%, or not less than 99.9%, the coating rate usually refers to the area percentage of the part of the surface of the core material covered with the shell material, and in a preferred embodiment of the invention, the core part of the composite nano particle is completely coated with the shell material.
Monodisperse core-shell structure organic-inorganic composite nano rubber particle
The invention also provides a preparation method and application of the core-shell structure composite microsphere.
In the preparation method of the monodisperse core-shell structure organic-inorganic composite nano rubber particles, the shell part of the composite microsphere can be an organic-inorganic composite coating material, and the organic-inorganic composite coating materialThe coating material is generally a material that can be used to coat the organic polymer nano rubber particle material as the core portion and can form the shell portion on the surface of the nano rubber particle material as the core portion. For example, the organic-inorganic composite coating material may be one or any combination of inorganic oxides, inorganic simple substances, inorganic salts, organic-inorganic hybrid molecular polymers, organic high molecular polymers, and the like, including but not limited to organic molecular modification. The organic molecule-modified inorganic oxide may be a non-metal oxide and/or a metal oxide, and examples of the inorganic oxide include, but are not limited to, SiO2、TiO2、ZrO2、CeO2、SnO2、Al2O3And the like, which may be, for example, one or any combination thereof including, but not limited to, carbon, silicon, gold, titanium, and the like, and the organic molecule-modified inorganic salt may be, for example, one or any combination thereof including, but not limited to, carbonate, phosphate, sulfite, silicate, aluminosilicate, and the like. The organic-inorganic hybrid molecular polymer can be one of organic silicon polymer, organic sulfur polymer, organic fluorine polymer, organic aluminum polymer, organic titanium polymer or any combination thereof, and the high molecular polymer can be carbon chain polymer, hybrid chain polymer, such as one of polystyrene, phenolic resin, polyacrylic acid, poly barbituric acid, polyurethane, or any combination thereof. The organic polymer rubber particles as the core portion can be coated by a suitable coating method selected by those skilled in the art according to the kind of the shell portion material. The core portion can be coated, for example, by a chemical precipitation method, which generally refers to a method in which a precursor of the shell portion material is precipitation-polymerized on the surface of the core portion material by a chemical and/or physical action under certain conditions. In one embodiment of the present invention, the surface of the organic nitrile rubber nanoparticles as the core portion may be coated with a precursor of the shell material under the catalysis of a catalyst (e.g., ammonia water, etc.), the precursor of the shell material may be an organic silane coupling agent, and a solvent may be usedThe organic solvent can be water or the like, the organic solvent can be one or any combination of ethanol, isopropanol and the like, for example, but not limited to, the organic solvent can be used for coating the organic nitrile rubber nanoparticle material serving as the core part with the silicon oxide modified by organic molecules, and the organic-inorganic composite nanoparticle particles with the core monodisperse core-shell structure can be prepared after drying and crushing treatment. The solvent removal method can be centrifugal separation and subsequent drying heat treatment, and the heat treatment temperature can be 50-70 ℃, 70-90 ℃, 90-110 ℃, 110-. The time of the drying heat treatment can be adjusted by those skilled in the art according to the specific conditions of the heat treatment, and for example, whether the reaction is completed or not can be judged according to the form of the reaction product, and the reaction time can be 1 to 2 hours, 2 to 3 hours, 3 to 4 hours, 4 to 5 hours, 5 to 6 hours, 6 to 7 hours, 7 to 8 hours, 8 to 9 hours, 9 to 10 hours, 10 to 11 hours, 11 to 12 hours, 12 to 13 hours, 13 to 14 hours, 14 to 15 hours, 15 to 16 hours, or not less than 16 hours. The catalyst used in the coating process may be one of an acid catalyst such as one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, oxalic acid, acetic acid, hydrogen bromide, etc., or any combination thereof, a base catalyst such as one of ammonia, sodium hydroxide, potassium hydroxide, urea, ethanolamine, etc., or any combination thereof, and the like. The amount of the catalyst may be 0.1-3%, 0.1-2%, 0.1-1%, 0.1-0.8%, 0.1-0.7%, or 0.1-0.6% by mass of the precursor of the shell material, in terms of mole ratio.
Application of monodisperse core-shell structure organic-inorganic composite nano rubber particles
The invention also provides application of the monodisperse core-shell structure organic-inorganic composite nano rubber particles, in particular application in preparing high-strength and high-toughness resin application materials.
The monodisperse core-shell structure organic-inorganic composite nano rubber particle provided by the invention has a compact shell part, and has the characteristics of low cost, strong controllability and uniform overall structure.
The invention also provides application of the monodisperse core-shell structure organic-inorganic composite nano rubber particle material in high-toughness and high-strength resin related materials. The application is specifically that the high-toughness and high-strength resin related material is a high-strength and high-toughness resin device material such as a wind power generation fan blade, a high-strength resin impeller blade and the like. The monodisperse core-shell structure organic-inorganic composite nano rubber particles can be compounded with high polymer resin and used for preparing high-strength high-toughness resin application materials. The proportion of the two can be adjusted by those skilled in the art according to the needs, for example, in the preparation of the high-strength high-toughness resin application material, the monodisperse core-shell structure organic-inorganic composite nano rubber particles can be uniformly mixed with the polymer resin, and the volume ratio of the monodisperse core-shell structure organic-inorganic composite nano rubber particles to the polymer resin can be 1: 7-8, 1: 8-9, 1: 9-10, 1: 10-15, 1: 15-20, 1: 20-30, 1: 30-50, 1: 50-100. The polymeric resin may be any of various polymeric resins suitable for high-strength and high-toughness resin applications, and may be a thermosetting resin, which generally refers to a resin that has plasticity (e.g., can soften and/or flow) during molding, can be formed into a certain shape, and undergoes an irreversible chemical reaction to crosslink and cure, and which generally cannot be softened and/or flowed again after curing even when subjected to heat or the like. Further, the polymer resin may be one or any combination thereof including, but not limited to, a bifunctional epoxy resin, a polyfunctional epoxy resin, and the like, and more specifically, may include, but is not limited to, a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a naphthalene type epoxy resin, an alicyclic type epoxy resin, a phenol-novolac type epoxy resin, a resorcinol type epoxy resin, an ethylene glycol type epoxy resin, a trifunctional type epoxy resin, a glycidylamine type epoxy resin, a hydantoin type epoxy resin, a terpene-modified epoxy resin, a 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide-modified resin, a 10- (2, 5-dihydroxyphenyl-9, 10-dihydro-9-oxa-10-phosph, 10- (2, 5-dihydroxynaphthyl-9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide modified resin, or any combination thereof.
The invention provides a monodisperse core-shell structure organic-inorganic composite nano rubber particle material which is low in cost, adjustable in size, uniform in overall structure and excellent in dispersibility, and a preparation method and application thereof. The invention creatively uses the monodisperse core-shell structure organic-inorganic composite nano rubber particle material with the characteristics of uniform structure and excellent dispersion performance to prepare the high-strength and high-toughness resin material, and has very important significance for the development of related technologies. The organic-inorganic composite nano rubber particle material with the core-monodisperse core-shell structure provided by the invention has the advantages of strong controllability of the preparation process, simple process, convenience in operation and low cost, the organic-inorganic composite nano rubber particle material with the core-monodisperse core-shell structure has smaller controllable diameter size, spherical appearance, good dispersibility and uniform granularity, when the organic-inorganic composite nano rubber particle material is used for preparing a composite resin material, the prepared product has better strength and toughness, and the high-strength high-toughness material has good application prospects in various technical fields.
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the various method steps is merely a convenient tool for identifying the various method steps, and is not intended to limit the order in which the method steps are arranged or the scope of the invention in which the invention may be practiced, and changes or modifications in the relative relationship may be made without substantially changing the technical content.
Example 1 nitrile rubber-organosilane coupling agent KH-520 core-shell structure
Adding 600g of deionized water (mass, the same below), 120g of acrylonitrile, 10g of methacrylic acid, 12g of emulsifier sodium dodecyl benzene sulfonate, 2g of regulator, 2g of activator and the like which are prepared in accurate amount into a 2L polymerization kettle, vacuumizing, introducing nitrogen, blowing for 2-3 times, adding 350g of butadiene, adjusting the temperature in the kettle to 70 ℃, and adding an initiator under an ultrasonic condition to initiate polymerization. After the reaction is finished for 12 hours, adding a polymerization terminator to stop the reaction, waiting for the temperature to be reduced to room temperature, using a deionized water washing agent twice, and then dispersing in water again to obtain the nano nitrile rubber particle emulsion with the diameter size of 80 nm. The morphology and properties are shown in FIG. 1. And then taking 50g of the emulsion, adding the emulsion into 200g of absolute ethyl alcohol, simultaneously adding 3g of ammonia water, then carrying out ultrasonic dispersion for 30min, adding 2ml of silane coupling agent KH520 into the solution, continuously stirring for 5 hours, carrying out centrifugal separation, and washing twice with ethanol to obtain the composite nano rubber particles with the inner cores of nano nitrile-butadiene rubber particles and the outer coating shell layers of silicon oxide core-shell structures modified by organosilane coupling agents. The prepared monodisperse core-shell structure composite nano rubber particles are added into liquid Vast Epikote828 type bisphenol A type epoxy resin, and the adding amount of the seasoning is 5 wt% of the weight of the high molecular resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
| Tensile Strength (MPa) | Flexural modulus of elasticity (MPa) | |
| Example 1 samples obtained | 11.26 | 2704 |
| Resin alone | 8.23 | 1824 |
It can be seen that, when the strength and toughness values of the composite nano rubber particle are tested, compared with a sample of the composite nano rubber particle which is not added with a monodisperse core-shell structure, the bending strength can be improved by nearly 40%, and the toughness index bending elastic modulus can also be improved by nearly 50%. FIG. 1 shows the prepared monodisperse core-shell structure organic-inorganic composite nano rubber particles.
Example 2 styrene-butadiene rubber-organosilane coupling agent KH-520 core-shell structure
The method comprises the steps of determining the amount of 500g of deionized water (mass, the same below), 100g of styrene, 5g of prepared proper amount of sodium dodecyl sulfate emulsifier, 2g of regulator alkylphenol polyoxyethylene, 2g of activator and the like, adding the mixture into a 2L polymerization kettle, vacuumizing, introducing nitrogen, blowing for 2-3 times, adding 150g of butadiene, adjusting the temperature in the kettle to 60 ℃, and adding 0.1-0.5 g of initiator sodium persulfate under the ultrasonic condition to initiate polymerization. After the reaction is carried out for 10 hours, 1g of polymerization terminator sodium dimethyldithiocarbamate is added, the temperature is kept to be room temperature, deionized water is used for washing twice, and then the mixture is dispersed in water again, so that the nano styrene-butadiene rubber particle emulsion with the diameter size of 90nm is obtained. The morphology and properties are shown in FIG. 1. And then taking 50g of the emulsion, adding the emulsion into 200g of absolute ethyl alcohol, simultaneously adding 3g of ammonia water, then carrying out ultrasonic dispersion for 30min, adding 2ml of silane coupling agent KH520 into the solution, continuously stirring for 5 hours, carrying out centrifugal separation, and washing twice with ethanol to obtain the composite nano rubber particles with the inner cores of nano styrene-butadiene rubber particles and the outer coating shell layers of silicon oxide core-shell structures modified by the organosilane coupling agent. The prepared monodisperse core-shell structure composite nano rubber particles are added into liquid Vast Epikote828 type bisphenol A type organic high polymer resin, and the adding amount of the flavoring is 5 wt% of the weight of the high polymer resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
| Tensile Strength (MPa) | Flexural modulus of elasticity (MPa) | |
| Example 2 samples obtained | 11.09 | 2561 |
| Resin alone | 8.23 | 1824 |
The strength and toughness values of the composite nano rubber particle are tested, and compared with a sample which is not added with the composite nano rubber particle with the monodisperse core-shell structure, the strength can be improved by nearly 40%, and the toughness can also be improved by nearly 40%.
Example 3 nitrile rubber-organosilane coupling agent KH-560 core-shell structure
Adding 600g of deionized water (mass, the same below), 120g of acrylonitrile, 10g of methacrylic acid, 5g of prepared proper amount of emulsifier sodium dodecyl benzene sulfonate, 2g of regulator, 2g of activator and the like into a 2L polymerization kettle, vacuumizing, introducing nitrogen, blowing for 2-3 times, adding 350g of butadiene, adjusting the temperature in the kettle to 60 ℃, and adding 2g of initiator under an ultrasonic condition to initiate polymerization. After 10 hours of reaction, 2g of a polymerization terminator is added to stop the reaction, deionized water is used twice after the temperature is adjusted to room temperature, and then the mixture is re-dispersed in water, so that the nano nitrile rubber particle emulsion with the diameter size of 70nm is obtained. The morphology and properties are shown in FIG. 1. And then taking 50g of the emulsion, adding the emulsion into 200g of absolute ethyl alcohol, simultaneously adding 3g of ammonia water, then carrying out ultrasonic dispersion for 30min, adding 2ml of silane coupling agent KH560 into the solution, continuously stirring for 5 hours, carrying out centrifugal separation, and washing twice with ethanol to obtain the composite nano rubber particles with the inner cores of nano nitrile-butadiene rubber particles and the outer coating shell layers of silicon oxide core-shell structures modified by organosilane coupling agents. The prepared monodisperse core-shell structure composite nanometer rubber particles are added into liquid organic high polymer resin liquid Vast Epikote828 type bisphenol A, and the adding amount of the flavoring is 5 wt% of the weight of the high polymer resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
The strength and toughness values of the composite nano rubber particle are tested, and compared with a sample which is not added with the composite nano rubber particle with the monodisperse core-shell structure, the strength can be improved by more than 50%, and the toughness can also be improved by nearly 70%.
Example 4 styrene-butadiene rubber-organosilane coupling agent KH-560 core-shell structure
The method comprises the steps of determining the amount of 500g of deionized water (mass, the same below), 100g of styrene, 5g of prepared proper amount of sodium dodecyl sulfate emulsifier, 2g of regulator alkylphenol polyoxyethylene, 2g of activator and the like, adding the mixture into a 2L polymerization kettle, vacuumizing, introducing nitrogen, blowing for 2-3 times, adding 150g of butadiene, adjusting the temperature in the kettle to 60 ℃, and adding 2g of initiator sodium persulfate to initiate polymerization under the ultrasonic condition. After the reaction is carried out for 8 hours, 1g of polymerization terminator is added, the temperature is kept to be room temperature, deionized water is used for washing twice, and then the mixture is dispersed in water again, so that the nano styrene-butadiene rubber particle emulsion with the diameter size of 80nm is obtained. The morphology and properties are shown in FIG. 1. And then taking 50g of the emulsion, adding the emulsion into 200g of absolute ethyl alcohol, simultaneously adding 3g of ammonia water, then carrying out ultrasonic dispersion for 30min, adding 2ml of silane coupling agent KH560 into the solution, continuously stirring for 5 hours, carrying out centrifugal separation, and washing twice with ethanol to obtain the composite nano rubber particles with the inner cores of nano styrene-butadiene rubber particles and the outer coating shell layers of silicon oxide core-shell structures modified by organosilane coupling agents. The prepared monodisperse core-shell structure composite nanometer rubber particles are added into liquid organic high polymer resin liquid Vast Epikote828 type bisphenol A, and the adding amount of the flavoring is 5 wt% of the weight of the high polymer resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
| Tensile Strength (MPa) | Flexural modulus of elasticity (MPa) | |
| Example 4 samples obtained | 11.85 | 2857 |
| Resin alone | 8.23 | 1824 |
The strength and toughness values of the composite nano rubber particle are tested, and compared with a sample which is not added with the composite nano rubber particle with the monodisperse core-shell structure, the strength can be improved by nearly 50%, and the toughness can be improved by more than 60%.
Example 5 styrene-butadiene rubber-Oligophenolic resin core-Shell Structure
The method comprises the steps of determining the amount of 500g of deionized water (mass, the same below), 100g of styrene, 3g of prepared proper amount of sodium dodecyl sulfate emulsifier, 2g of regulator alkylphenol polyoxyethylene, 2g of activator and the like, adding the mixture into a 2L polymerization kettle, vacuumizing, introducing nitrogen, blowing for 2-3 times, adding 150g of butadiene, adjusting the temperature in the kettle to 60 ℃, and adding an initiator sodium persulfate to initiate polymerization under the ultrasonic condition. After the reaction is carried out for 8 hours, 1g of polymerization terminator is added, the temperature is kept to be room temperature, deionized water is used for washing twice, and then the mixture is dispersed in water again, so that the nano styrene-butadiene rubber particle emulsion with the diameter size of 80nm is obtained. The morphology and properties are shown in FIG. 1. And then adding 250g of the emulsion into 300g of absolute ethyl alcohol, simultaneously adding 3g of o-diphenol and 3g of ammonia water, then ultrasonically dispersing for 30min, adding 2ml of formaldehyde solution into the solution, continuously stirring for 6 hours, performing centrifugal separation, and cleaning twice by using ethanol to obtain the core-shell structure composite nano rubber particles with nano styrene-butadiene rubber particles as cores and oligomeric phenolic resin as outer coating shells. The prepared monodisperse core-shell structure composite nanometer rubber particles are added into liquid organic high polymer resin liquid Vast Epikote828 type bisphenol A, and the adding amount of the flavoring is 5 wt% of the weight of the high polymer resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
| Tensile Strength (MPa) | Flexural modulus of elasticity (MPa) | |
| Example 5 samples obtained | 10.21 | 2306 |
| Resin alone | 8.23 | 1824 |
The strength and toughness values of the composite nano rubber particle are tested, and compared with a sample which is not added with the composite nano rubber particle with the monodisperse core-shell structure, the strength can be improved by nearly 30%, and the toughness can also be improved by nearly 30%.
Example 6 Silicone rubber-organosilane coupling agent KH-560 core-shell Structure
600g of deionized water (mass, the same below), 300g D4 (octamethylcyclotetrasiloxane), 5g of prepared emulsifier sodium dodecyl benzene sulfonate and 20g of fatty alcohol-polyoxyethylene ether are added into a 2L polymerization kettle, after vacuumizing, nitrogen is introduced to blow for 2-3 times, then 100g of aqueous solution containing 6g of dodecylbenzene sulfonic acid is slowly dripped into the reaction kettle, the temperature in the kettle is adjusted to 80 ℃, and reaction is carried out under high-speed shearing and stirring. After 5 hours of reaction, the temperature is reduced to 50 ℃, sodium bicarbonate is added to adjust the pH of the solution to about 7.0, the solution is cooled to room temperature at the same temperature, deionized water is used for washing twice, and then the solution is re-dispersed in water, so that the nano organic silicon rubber particle emulsion with the diameter size of 100nm is obtained. And then taking 50g of the emulsion, adding the emulsion into 200g of absolute ethyl alcohol, simultaneously adding 3g of ammonia water, then carrying out ultrasonic dispersion for 30min, adding 2ml of silane coupling agent KH560 into the solution, continuously stirring for 5 hours, carrying out centrifugal separation, and washing twice with ethanol to obtain the composite nano rubber particles with the inner cores of nano organic silicon rubber particles and the outer coating shell layers of silicon oxide core-shell structures modified by organic silane coupling agents. The prepared monodisperse core-shell structure composite nanometer rubber particles are added into liquid organic high polymer resin liquid Vast Epikote828 type bisphenol A, and the adding amount of the flavoring is 5 wt% of the weight of the high polymer resin. And shearing at a high speed, stirring and dispersing to uniformly disperse the particles in the polymer resin, adding a certain amount of curing agent, uniformly stirring, removing bubbles, and curing at 150 ℃ for 90 minutes to obtain a resin material sample.
The strength and toughness values of the composite nano rubber particle are tested, and compared with a sample which is not added with the composite nano rubber particle with the monodisperse core-shell structure, the strength can be improved by more than 30%, and the toughness can also be improved by more than 80%.
In conclusion, the present invention effectively overcomes various disadvantages of the prior art and has high industrial utilization value.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.
Claims (10)
1. The organic-inorganic composite nano rubber particles with the monodisperse core-shell structure are characterized in that the core part of the composite nano rubber particles is made of organic rubber particle materials, and porous organic-inorganic coating materials are used as the shell part of the outer layer.
2. The organic-inorganic composite nano rubber particle with the monodisperse core-shell structure according to claim 1, wherein the diameter of the composite nano rubber particle is 70nm-300 nm;
and/or the diameter of the core part is 60nm-250 nm;
and/or the shell section has a thickness of 0nm to 100 nm.
3. The organic-inorganic composite nano rubber particle with the monodisperse core-shell structure according to claim 1, wherein the coating rate of the shell part of the composite nano particle is not less than 90%;
and/or the shell part material is a mesoporous coating material, and the mesoporous coating material is selected from one or any combination of organic molecule modified inorganic oxide, inorganic simple substance, inorganic salt, high molecular polymer and organic-inorganic hybrid molecular polymer.
4. The organic-inorganic composite nano rubber particles with monodisperse core-shell structure as claimed in claim 3, wherein the inorganic oxide modified by organic molecules can be non-metal oxide and/or metal oxide, including SiO2、TiO2、ZrO2、CeO2、SnO2、Al2O3One or any combination thereof;
the inorganic simple substance modified by the organic molecules can be one of carbon, silicon, gold and titanium or any combination thereof;
the inorganic salt modified by organic molecules can be one of carbonate, phosphate, sulfite, silicate, aluminosilicate and the like or any combination thereof;
the high molecular polymer can be a carbon chain polymer or a hybrid chain polymer, and comprises one or any combination of polystyrene, phenolic resin, polyacrylic acid, polybarbituric acid, polyurethane and the like;
the organic-inorganic hybrid molecular polymer can be one of organic silicon polymer, organic sulfur polymer, organic fluorine polymer, organic aluminum polymer and organic titanium polymer or any combination thereof.
5. The organic-inorganic composite nano rubber particle with the monodisperse core-shell structure according to claim 1, wherein the core material is nano organic rubber particles and/or other organic rubber particles with modified surfaces.
6. The organic-inorganic composite nano rubber particles with a monodisperse core-shell structure according to claim 1 or 5, wherein the core material is one of styrene-butadiene rubber nanoparticles, isoprene rubber nanoparticles, nitrile rubber nanoparticles, ethylene-propylene rubber nanoparticles, butyl rubber nanoparticles, organofluorine rubber nanoparticles, organosulfur rubber nanoparticles, silicone rubber nanoparticles, organoaluminum rubber nanoparticles, organotitanium rubber nanoparticles, or any combination thereof.
7. A method for preparing monodisperse core-shell structured organic-inorganic composite nano-rubber particles according to claim 1, characterized in that the surface of the nano-organic rubber particles as the core portion is coated with a shell material.
8. The method for preparing monodisperse core-shell structure organic-inorganic composite nano-rubber particles according to claim 7, wherein the coating method comprises a chemical precipitation method, and the chemical precipitation method is a method in which a precursor of the shell material is subjected to precipitation polymerization on the surface of the core material through chemical and/or physical action.
9. The application of the monodisperse core-shell structure organic-inorganic composite nano rubber particles as claimed in claim 1, wherein the monodisperse core-shell structure organic-inorganic composite nano rubber particles are used in toughening and reinforcing of organic resin or in preparing resin related materials with high toughness and high strength requirements;
or, the monodisperse core-shell structure organic-inorganic composite nano rubber particles and the organic polymer resin are compounded and used in resin related materials with high toughness and high strength requirements.
10. The application of the monodisperse core-shell structure organic-inorganic composite nano rubber particles as claimed in claim 9, wherein the high-toughness high-strength resin related material is a wind power generation fan blade or a high-strength resin impeller blade.
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