CN109679144A

CN109679144A - A kind of micro-nano compound particle and its more rotor physics continuous modification preparation processes

Info

Publication number: CN109679144A
Application number: CN201811604305.8A
Authority: CN
Inventors: 王友善
Original assignee: Harbin Technology Co Ltd
Current assignee: Harbin Taiming Technology Co.,Ltd.
Priority date: 2018-12-26
Filing date: 2018-12-26
Publication date: 2019-04-26
Anticipated expiration: 2038-12-26
Also published as: CN109679144B

Abstract

The invention discloses a kind of micro-nano compound particle and its preparation processes, the micro-nano compound particle is the nanometer and the following scale particle of nanometer that insertion is less than porous micro-nano particle micro-pore diameter in porous micro-nano particle, to form three-dimensional porous and/or thorn-like micro-nano compound particle；Three-dimensional porous and/or thorn-like micro-nano compound particle single hole embedded quantity is the 1~100% of pore volume.High-speed flow kinetic energy insertion preparation process of the invention is easy to operate, and micro-nano compound particle good dispersion obtained is not easy to reunite, can be applied in polymer and its product.There is preferable reinforcing effect in rubber and its product, and show excellent mechanical property, shown in rubber for tire reinforcement, low-heat-generation, wet-sliding resistant performance collaboration castering action.

Description

A kind of micro-nano compound particle and its more rotor physics continuous modification preparation processes

Technical field

The present invention relates to technical field of novel materials, and in particular to a kind of novel micro nanometer compound particle and its preparation process and Device.

Background technique

Currently, micro/nano-scale (10-1000nm) particle plays in the fields such as modern industry, medicine, bioengineering already Important function out.There are the interactions of apparent surface between particle and its between polymeric matrix, and therefore, selection is suitable Particle and polymer resin matrix can improve the performance of material using certain Material cladding technique to a certain extent.

The form of particle directly affects the properties such as caking property, mechanical strength, the transparency of material, and directly related therewith It is effective dispersion problem of the following scale particle of compatibility and nanometer and nanometer of filler and matrix in composite material.Cause This, most of researchs all concentrate on how to obtain homogeneous mixture, for example, carrying out chemically or physically modified to particle surface and changing Become its interaction with matrix.

The fine dispersion of monodisperse particle just necessarily require be by inorganic fine powder disaggregation it is the most original, it is the most primary most Otherwise small scale particle shape will show the particle distribution form of polydispersion, the material properties of monodisperse particle be not achieved.Its Real, monodisperse is micro-nano and the following scale particle of nanometer is in post synthesis just usually because the reasons generation such as drying process is highly stable The morphology of the aggregate.Interparticle tie point usually plays the part of " nucleating agent " of random powder again and forms extremely stable large scale Structure.This interparticle interaction in certain external force, such as the effects of stirring, grinding, ultrasound under, can part divide again It dissipates.But when to act on particle size be 500nm or less of grinding or external force, need longer milling time and higher Severity of grind is easily introduced introduced contaminants and unpredictable phase transition (material instability aggregation) in this way.For receiving Rice and the following scale particle of nanometer, because its surface can be low, the stability of small scale particle is high not as good as large scale particle, they hold very much Easily flock together again.But, in general, if regulating and controlling the chemical composition of dispersion liquid, for example surfactant is added, changes Become matrix pH value, ionic strength and the certain cosolvents of addition, it is final to change phase interaction between nanometer and the following scale particle of nanometer It firmly include Van der Waals force, electrostatic electric double layer and rigidity interaction, the effect of external force still can make particle well divide It dissipates.But this is but also the application of micro-nano particle is much limited.

Certain be associated with is presented with its concentration in the function of high dispersive micro-nano particle.Using the filler of lower content, can subtract The decline of its few caused cohesive force；Meanwhile filler disperse in the base it is more uniform.In general, the weight of filler point Number should be less than 10%.But the dosage of filler is very little, can not usually play its effect.Therefore, many researchers have studied inorganic The aggregation or multidimensional package assembly of filler, such as particle crystallite, glassy state aggregation, mix with high molecular material.The study found that These structures have more brilliant value to the property promotion of material.For example, the following scale grain of micro-nano and nanometer that surface is modified Sub- silica, glassy state aggregation is because of glass transition temperature T.In room temperature range, at a certain temperature material is had There is extremely strong adhesive property；This property, which has been used, develops many outstanding products and launch.Another kind research compared with More materials is pelletron structural fibrous materials；Or nanometer and the following scale particulate reinforcement fibrous material of nanometer, this kind of material can be with By self-assembly method, microcosmic phase inversion, the preparation of the methods of island template and Electrospun.Relative to monodisperse particle, this Even if substance in the lower situation of dosage, also has promotion by a larger margin for material mechanical performance.Researcher It was found that can make each high-strength, lightweight if the fibrous material containing nanometer and the following scale particle of nanometer is compiled into network, have Material of different nature has in the fields such as filter membrane, sensor, microelectronics and optical element, biomedicine, security protection Important application value.

Patent CN2016101110205 discloses a kind of for the composite graphite alkene gel of gum filler and its preparation side Method is distributed in graphene uniform in the hole of porous-starch by gained graphene dispersion in porous-starch solution, improves stone The stability of black alkene, prevents the reunion of graphene, is directly appended in rubber substrate as filler, and good dispersion is not easy to reunite； Patent CN2017110853377 discloses a kind of modified carbon black composite material and preparation method and application again, by inorganic nano Material tight fits in the rough surface in carbon black microcrystalline region and/or is embedded in the micropore and mesoporous of carbon black, improves and changes Reinforcing property of the property carbon black composite material in rubber material, above-mentioned two patent selected respectively porous-starch and carbon black as Base material, and the selection of base material has substantially played conclusive use for micro-nano compound particle dispersion performance superiority and inferiority, such as Performance in porosity, Incoercibility and chemical stability directly influences absorption property, the surface of final substrate particles Energy, and then rolled into a ball by the different function of insertion protrusion so that can be in farther away molecule apart from above between micro-nano compound particle There are certain repulsion, avoid interparticle distance from the exponential growth of reuniting effect is closely caused excessively, macro manifestations are polymolecularity, are not easy Reunite, using porous-starch as base material, there is porous-starch composite graphite alkene gel the enzyme of uncooked amylum enzyme activity to be lower than The porosity cellular products for acting on uncooked amylum under gelatinization point and being formed are steady in porosity, Incoercibility and chemistry It is qualitative it is upper show as it is general, especially in chemical stability；And carbon black showed in porosity and chemical stability it is excellent, But in carbon black, carbon atom is arranged similarly to graphite, forms hexagon plane, usual 3~5 such level groups Structural instability is shown as under external force since it is layer structure at a crystallite.In view of the foregoing, above-mentioned formation Two kinds of micro-nano compound particles there are also further improved spaces in polymolecularity and in performance not easy to reunite.

Summary of the invention

For deficiency present in existing above-mentioned background, micro-nano compound particle good dispersion of the invention is not easy to reunite, There is preferable reinforcing effect in rubber and its product, and show excellent mechanical property, show to mend in rubber for tire By force, the collaboration castering action of low-heat-generation, wet-sliding resistant performance.

Meanwhile the present invention also provides the preparation process of a variety of above-mentioned micro-nano compound particles, preparation method is easy to operate, passes through The micro-nano compound particle that every kind of method obtains includes three-dimensional porous micro-nano particle and three-dimensional porous thorn-like micro-nano particle.

To achieve the goals above, the present invention is to realize by the following technical solutions:

A kind of micro-nano compound particle, in porous micro-nano particle insertion be less than porous micro-nano particle micro-pore diameter nanometer and Nanometer or less scale particle, to form three-dimensional porous and/or thorn-like micro-nano compound particle.

Optionally, described three-dimensional porous and/or thorn-like micro-nano compound particle single hole embedded quantity be pore volume 5~ 100%, BET nitrogen adsorption specific surface area are 30m²/ g~350m²/ g, preferably 300m²/ g~340m²/g。

Optionally, described three-dimensional porous and/or thorn-like micro-nano compound particle single hole embedded quantity be pore volume 75~ 95%,

Optionally, the porous micro-nano particle is spherical in shape, elliposoidal, water chestnut are spherical or irregular shape.

Optionally, the porous micro-nano particle diameter is 100nm~100 μm, porous structure aperture 1nm~500nm, hole depth 2nm~500nm, hole number 5000~300,000,000/g, 0.3~300m of BET method specific surface area²/ g, pH value 6~8.

Optionally, the porous micro-nano particle is silica or calcium carbonate or silica and/or calcium carbonate and three oxygen Change the compound porous micro-nano particle of two aluminium.

Optionally, the porous micro-nano particle include weight percent be 20%~95% silica or calcium carbonate and 5%~80% aluminum oxide.

Optionally, it is 30%~80% silica and 20%~70% that the porous micro-nano particle, which includes weight percent, Aluminum oxide.

Optionally, it is 40%~70% silica and 30%~60% that the porous micro-nano particle, which includes weight percent, Aluminum oxide.

Optionally, the nanometer and the following scale particle of nanometer are nano zine oxide, nano cupric oxide, small molecule function material Material, natural rubber high molecular material, synthetic rubber high molecular material, carbon nanotube, graphene, carbon black, white carbon black, titanium dioxide One of titanium, ferroso-ferric oxide, metal simple-substance nanoparticle are a variety of.

The present invention also provides the first preparation processes of above-mentioned micro-nano compound particle, pass through more rotor physics continuous modifications The nanometer of preforming and the following scale particle of nanometer are embedded in the micropore of porous micro-nano particle.

Optionally, it handles the time 4~48 hours, the indoor vacuum degree -1000KPa of negative pressure of vacuum ball milling~0KPa, ball milling 0.5~5 revolutions per second of room revolving speed, temperature 50 C~300 DEG C, the indoor air velocity 300m/s~1200m/s of airflow milling, revolving speed 0.5 ~5 revolutions per seconds, 80 DEG C~200 DEG C of temperature, pressure 100KPa~1000KPa.

Optionally, more rotor physics continuous modification devices include mechanical ball mill, negative pressure of vacuum mixing and high speed gas Two or more mixed method in stream mixing.

Optionally, the porous micro-nano particle is that silica membrane layer replaces on core with aluminum oxide film layer Cladding forms after porous composite layer and obtains porous micro-nano particle by broken screening.

Optionally, silica or calcium carbonate derive from siliceous/calcium material, comprising: alunite, rice hull ash, straw ash, illiteracy De- stone, talcum, yellow clay, mica, wollastonite, bauxite, albumen shale, diatomite, diatomaceous shale, opal.

Moreover, it relates to a variety of preparation processes.

The present invention also provides second of preparation processes of above-mentioned micro-nano compound particle, under the effect of high-speed flow kinetic energy, Nanometer and the following scale particle of nanometer are embedded in porous micro-nano particle.

Optionally, by the following ruler of nanometer and nanometer of porous micro-nano particle and preforming that weight ratio is 20:1~1:1 Particle is spent, by the way of being pre-mixed and being blown into or disperse synchronous charging, air velocity is 300m/s~1200m/s, temperature 80 DEG C~200 DEG C, pressure 100KPa~1000KPa.

It further include the above-mentioned high-speed flow kinetic energy flush mounting for preparing micro-nano compound particle, high-speed flow kinetic energy flush mounting For horizontal circle ring type airflow milling, circulating tube type airflow milling, double injecting type airflow millings, hit board-like airflow milling or the reverse gas of fluidized bed One of stream mill.

The third preparation process of above-mentioned micro-nano compound particle provided by the invention, at a high temperature of 500 DEG C~3500 DEG C, Nanometer and the following scale particle of nanometer are embedded into the micropore of porous micro-nano particle.

Optionally, the nanometer and the following scale particle of nanometer are preforming or the in-situ preparation in pyroreaction.

Optionally, comprising the following steps:

Temperature reaction stage, end air velocity are 5m/s~15m/s, and temperature is 500 DEG C~2000 DEG C；

Air-flow boost phase, air velocity are 20m/s~100m/s, and temperature is 600 DEG C~3500 DEG C；

The stage of reaction, conversion zone outlet temperature are lower than 800 DEG C.

Optionally, reaction weight of the produced in situ reaction raw materials of the nanometer and the following scale particle of nanometer in the stage of reaction Structure time 0.05s~5s.

Optionally, high temperature reaction stove includes: warming-up section part, air-flow accelerating sections part, conversion zone part and collection section portion Point, one or more chargings point are equipped on the warming-up section part and/or air-flow accelerating sections part and/or conversion zone part It is in bulk to set.

The present invention provides the preparation facilities of the third preparation method of above-mentioned micro-nano compound particle, in warming-up section part Dispersal of feed device is loss in weight feeder；Charging in air-flow accelerating sections part, conversion zone part and collection section part Dispersal device is aerosol dispersion device.

Optionally, high temperature reaction stove center line 0~D/2, D described in the nozzle distance of the aerosol dispersion device are nozzle institute In cavity diameter, the distance set on aerosol dispersion device to the air-flow accelerating sections partial inlet of air-flow accelerating sections part is 0 ~L, the distance set on aerosol dispersion device to the conversion zone entrance of conversion zone part are 0~L, and L is cavity length where nozzle.

Optionally, the Nozzle diameter of the aerosol dispersion device is 0.5mm~5mm.

Optionally, the aerosol dispersion device nozzle is sprayed into 0~90 ° of angle against air-flow.

Optionally, the draw ratio of the warming-up section part is 1:1~5:1, and the draw ratio of air-flow accelerating sections part is 5:1~10:1, the draw ratio of the conversion zone part are 2:1~15:1.

4th kind of preparation process of above-mentioned micro-nano compound particle provided by the invention, by the nanometer of preforming and nanometer with Lower scale particle is embedded into the micropore of porous micro-nano particle by lapping mode.

Optionally, continuous using mechanical load flush mounting or multiple step format is fed, 50 DEG C~100 DEG C of grinding temperature, turn 0.5~5 revolutions per second of speed.

Optionally, mechanical load flush mounting discharging suck selection by winnowing grader, classifier rotor frequency 10Hz~ 50Hz, wind speed 10m/s~200m/s.

5th kind of preparation process of above-mentioned micro-nano compound particle provided by the invention, by the nanometer of preforming and nanometer with Lower scale particle is embedded in the micropore of porous micro-nano particle by negative pressure of vacuum active force.

Optionally, it is -1000KPa~0KPa in vacuum degree, handles 4h~48h in the environment of 100 DEG C~300 DEG C of temperature, 0.5 revolutions per second~5 revolutions per seconds of revolving speed.

It optionally, the use of negative pressure of vacuum flush mounting is ribbon formula vacuum mixer, double star vacuum mixer, planetary vacuum One of mixing machine, vacuum dispersion machine and full negative pressure mixer.

6th kind of preparation process of above-mentioned micro-nano compound particle provided by the invention by porous micro-nano particle and nanometer and receives Meter or less scale particle be placed in liquid phase polarity dispersion, pH value of solution is 6~8,50~80 DEG C of temperature, add 100~ The electric field of 8000V/m, mixing time 0.1~2 hour, 30~200 revs/min of speed of agitator.

Optionally, the porous micro-nano particle and nanometer and the investment weight ratio of the following scale particle of nanometer are 20:1~1: 1。

Optionally, the nanometer and the following scale particle of nanometer are in-situ preparation in pre-generated or liquid phase reactor.

Optionally, raw material when in-situ preparation is zinc chloride, zinc sulfate, zinc nitrate, copper chloride, copper sulphate, copper nitrate, silicon One of sour sodium, silicone, iron chloride, ferric nitrate, ferric sulfate are a variety of.

Optionally, the liquid phase polarity dispersion solvent for use is water, methanol, ethyl alcohol, glycerine, trifluoroethanol, first Acid, triethanolamine, acetic acid, acetone, acetic acid ethyl ester, tetrahydrofuran, N-methyl pyrrolidones, ether, propylene oxide, dichloromethane One of alkane, chloroform, triethanolamine are a variety of.

The invention also includes above-mentioned micro-nano compound particle is applied to the technical fields such as chemical rubber, medical manufacture sustained release agent In.

Technical solution of the present invention has the advantages that

The embodiment of the invention provides a kind of micro-nano compound particles to pass through physics or change using porous micro-nano particle as matrix (including in-situ synthesized) mode, nanometer and the following scale particle of nanometer is embedded in the micropore of porous micro-nano particle, shape At three-dimensional porous and/or thorn-like micro-nano compound particle；Above-mentioned three-dimensional porous and/or thorn-like micro-nano compound particle is by such as attached It is micro- that three kinds of micro-nanos compound particle state composition shown in FIG. 1, nanometer and the following scale particle of nanometer are inserted into porous micro-nano particle In hole, single hole embedded quantity is the 50~100% of pore volume, i.e. the following scale particle of nanometer and nanometer largely insertion or all slotting Enter and at thorn-like；When preparing above-mentioned micro-nano compound particle, the good dispersion of the monodisperse particle of micro-nano is fixed against single point again The elimination of interaction force between shot, such as Van der Waals force, interparticle tie point " nucleating agent " active force, and will not be because of length The external force of time stirs and makes nanometer and the following scale particle of nanometer that unpredictable phase transition occur, i.e., material is unstable Property aggregation, at this point, the selection of base material for be made micro-nano compound particle absorption insertion volume and dispersibility have important shadow Ring, Choice of substrate materials silica or calcium carbonate when prepared by micro-nano compound particle or its formed with aluminum oxide it is porous Micro-nano compound particle, and it is 100nm~100 μm that the further parameter of the porous micro-nano particle as base material, which is partial size, it is more Pore structure aperture 1nm~500nm, hole depth 2nm~500nm, hole number 5000~300,000,000/g, BET method specific surface area 0.3~ 300m²/ g, pH value 6~8 are substrate using the porous micro-nano compound particle that silica or calcium carbonate and aluminum oxide are formed Material, prepared substrate particles have porosity, Incoercibility and chemical stability, and porous micro-nano particle porosity is reachable 90% or more, it is 5000-6000 times of active carbon, exactly this molecular sieve structure outstanding determines it with extremely strong object Manage absorption property；Meanwhile obtained micro-nano compound particle have outstanding space mechanics characteristic, as Fig. 4 and Fig. 5 be it is shown, be The three-dimensional diagram of the micro-nano compound particle space mechanics characteristic, the micro-nano compound particle in the porous structure on surface due to being embedded in Other a large amount of type materials, are provided with a variety of surface polarities of different materials, can carry out polymer under numerous conditions The reinforcing of intermolecular force can be provided when as reinforcing agent for rubber polymer under different temperatures pressure different operating environment Reinforcing function, to improve wearability, intensity and anti-slippery characteristic simultaneously.It can be increased by the addition of aluminum oxide The surface energy of big script porous silica or calcium carbonate.By taking zinc-oxide nano column as an example: simple porous silica silicon base institute Can it is embedding live the amount of nano zine oxide column only have the 40% of modified substrate (be added aluminum oxide), and not aluminum oxide It is added, the space three-dimensional structure stability that micro-nano compound particle is formed can also decline to a great extent.Not with traditional reinforcing particles material Together, different function outstanding embedded by micro-nano compound particle surface roll into a ball so that between micro-nano compound particle farther away molecule away from May be present certain repulsion from upper, it is therefore prevented that hypotelorism leads to the exponential growth of reuniting effect between particle, macro manifestations and For polymolecularity, it is not easy to reunite.

Micro-nano compound particle of the invention can construct stable spacial framework in condensate, if the present invention passes through The test done time show that the good dispersion of novel micro nanometer compound particle in the polymer is not easy to reunite, especially in rubber and There is preferable reinforcing effect in its product, promoted and made with reinforcement, the collaboration of low-heat-generation, wet-sliding resistant performance in rubber for tire With.

Detailed description of the invention

It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor It puts, is also possible to obtain other drawings based on these drawings.

Fig. 1 is micro-nano particle fraction of the invention, is completely embedded into and is formed thorn-like micro-nano compound particle schematic diagram；

Fig. 2 three-dimensional porous/thorn-like micro-nano compound particle 10000x and 100000x stereoscan photograph produced by the present invention；

Fig. 3 is that the high temperature reaction stove process units that three-dimensional porous/thorn-like micro-nano compound particle uses for preparing of the invention shows It is intended to；

Wherein, 1-7 be high temperature reaction stove temperature reaction section, air-flow accelerating sections, conversion zone, 7 of collection section different location Feed inlet；

A- temperature reaction section；B- air-flow accelerating sections；C- conversion zone；The collection section D-；E- cooler.

Fig. 4 and Fig. 5 is that the space mechanics characteristic three-dimensional of micro-nano compound particle of the present invention illustrates.

Specific embodiment

Technical solution of the present invention is clearly and completely described below in conjunction with attached drawing, it is clear that described implementation Example is a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill Personnel's every other embodiment obtained without making creative work, shall fall within the protection scope of the present invention.

In the description of the present invention, it should be noted that term " center ", "upper", "lower", "left", "right", "vertical", The orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" be based on the orientation or positional relationship shown in the drawings, merely to Convenient for description the present invention and simplify description, rather than the device or element of indication or suggestion meaning must have a particular orientation, It is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.

As long as in addition, the non-structure each other of technical characteristic involved in invention described below different embodiments It can be combined with each other at conflict.

Embodiment 1

A kind of micro-nano compound particle provided in this embodiment, it is micro- to be less than porous micro-nano particle for insertion in porous micro-nano particle The following scale particle of the nanometer and nanometer of bore dia, it is three-dimensional porous to form three-dimensional porous and/or thorn-like micro-nano compound particle And/or the single hole embedded quantity of thorn-like micro-nano compound particle is for 5~100%, the BET nitrogen adsorption specific surface area of pore volume 30m²/ g~350m²/ g, shown in Figure 1, it is that nanometer and the following scale particle of nanometer may be not that micro-nano compound particle state, which is constituted, Insertion or partial insertion are entirely insertable and also adhere to a degree of nanometer and nanometer or less at thorn-like, or even in matrix surface Scale particle, Fig. 2 are three-dimensional porous/thorn-like micro-nano compound particle 10000x and 100000x stereoscan photograph.

Specifically, the matrix of above-mentioned micro-nano compound particle, i.e., porous micro-nano particle can be silica or calcium carbonate, or The mixture of person's silica and/or calcium carbonate and aluminum oxide；The partial size of porous micro-nano particle is 100nm~100 μm, more Pore structure aperture be 1nm~500nm, hole depth 2nm~500nm, hole number 5000~300,000,000/g, BET method specific surface area 0.3~ 300m²/ g, porous micro-nano particle is spherical in shape, elliposoidal, water chestnut are spherical or other irregular shapes.

Specifically, above-mentioned nanometer and the following scale particle of nanometer are nano zine oxide, nano cupric oxide, small molecule function material Material, natural rubber high molecular material, synthetic rubber high molecular material, carbon nanotube, graphene, carbon black, white carbon black, titanium dioxide One of titanium, ferroso-ferric oxide, metal simple-substance nanoparticle are a variety of, wherein small molecule functional material is less than for molecular weight The functional molecular of 1000 dalton, generally small-micelle water, aglycon, yellow trunk member, glucoside member, alkaloid etc..

Embodiment 2

Present embodiments provide a kind of preparation process of above-mentioned micro-nano compound particle, comprising the following steps:

S1. it takes zinc nitrate hexahydrate to be dissolved in the zinc nitrate solution for forming 10g/ml in deionized water, stirs standby in 2 minutes With；

S2. porous micro-nano particle is obtained after silica being mixed with the porous micro-nano composite substrate of aluminum oxide with methanol Solution, be placed in Ultrasound Instrument and carry out ultrasonic disperse, supersonic frequency 60Hz, temperature is 50 DEG C hereinafter, ultrasonic time is 0.1h, Obtaining concentration is the porous micro-nano particle suspension of 20g/ml；In the present embodiment, composite substrate is the dioxy for being 20% with parts by weight SiClx and 80% aluminum oxide be made；

S3. ammonium hydroxide is taken to be dissolved in deionized water, the ammonium hydroxide for being configured to 30% concentration is spare；

S4. by the zinc nitrate solution configured in the porous micro-nano particle suspension configured in S2 and S1 with mass ratio 1:1's Ratio mixing, is added the external fixation or rotating electric field of 100V/m, 10 revs/min of rotating electric field revolving speed, magnetic agitation 0.1 is small When, 200 revs/min of revolving speed；

S5. the S3 ammonia spirit configured is added drop-wise in mixed solution dropwise, pH control range 6 keeps 50 DEG C of thermostatted waters Bath heating, stir about 1h；

S6. after reaction, by filtering, distillation water washing 1 time, dehydrated alcohol washing 2 times；

S7. the powder object that finishes of washing is placed in 50 DEG C of baking ovens after dry 8h and obtains three-dimensional porous/thorn-like micro-nano and answers Close particle powder.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 331m²The specific surface area of/g, sem test photo are as shown in Figure 2.

Embodiment 3

S1. copper sulphate is taken to be dissolved in the copper-bath for forming 20g/ml in deionized water, it is spare after stirring 2 minutes；

S2. porous micro-nano particle is obtained after calcium carbonate being mixed with the porous micro-nano composite substrate of aluminum oxide with ethyl alcohol Solution is placed in Ultrasound Instrument and carries out ultrasonic disperse, supersonic frequency 30Hz, and temperature is 80 DEG C hereinafter, ultrasonic time is 2h, obtains Concentration is the porous micro-nano particle suspension of 1g/ml；In the present embodiment, composite substrate be with parts by weight be 95% calcium carbonate and 5% aluminum oxide is made；

S3. urea is taken to be dissolved in deionized water, being configured to the buffer of 50% concentration, spare (ammonium root can be generated with copper ion Complex compound can not precipitate so changing buffer as urea configuration)；

S4. by the copper-bath configured in the porous micro-nano particle suspension configured in S2 and S1 with mass ratio 20:1's Ratio mixing, is added the external fixation or rotating electric field of 8000V/m, 50 revs/min of rotating electric field revolving speed, magnetic agitation 2 is small When, 30 revs/min of revolving speed；

S5. the S3 buffer configured is added drop-wise in mixed solution dropwise, pH control range 8 keeps 80 DEG C of waters bath with thermostatic control Heating, stir about 1h；

S6. after reaction, by filtering, distillation water washing 5 times, dehydrated alcohol washing 1 time；

S7. the powder object that finishes of washing is placed in 70 DEG C of baking ovens after dry 4h and obtains three-dimensional porous/thorn-like micro-nano and answers Close particle powder.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 310m²The specific surface area of/g.

Embodiment 4

S1. zinc sulfate is taken to be dissolved in the solution of zinc sulfate for forming 15g/ml in deionized water, it is spare after stirring 1 minute；

S2. porous micro-nano particle is obtained after silica being mixed with the porous micro-nano composite substrate of aluminum oxide with ethyl alcohol Solution mixed with ethyl alcohol after obtain the solution of porous micro-nano particle, be placed in Ultrasound Instrument and carry out ultrasonic disperse, supersonic frequency is 50Hz, temperature is 60 DEG C hereinafter, ultrasonic time is 2h, and obtaining concentration is the porous micro-nano particle suspension of 12g/ml；The present embodiment In, it is that 30% silica and 70% aluminum oxide are made that composite substrate, which is with parts by weight,；

S3. ammonium hydroxide is taken to be dissolved in deionized water, the ammonium hydroxide for being configured to 40% concentration is spare；

S4. by the solution of zinc sulfate configured in the porous micro-nano particle suspension configured in S2 and S1 with mass ratio 13:1's Ratio mixing, is added the external fixation or rotating electric field of 5000V/m, and 30 revs/min of rotating electric field revolving speed, magnetic agitation 1.5 Hour, 100 revs/min of revolving speed；

S5. the S3 ammonia spirit configured is added drop-wise in mixed solution dropwise, pH control range 7 keeps 60 DEG C of thermostatted waters Bath heating, stir about 1.5h；

S6. after reaction, by filtering, distillation water washing 3 times, dehydrated alcohol washing 2 times；

S7. the powder object that finishes of washing is placed in 60 DEG C of baking ovens after dry 4h and obtains three-dimensional porous/thorn-like micro-nano and answers Close particle powder.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 325m²The specific surface area of/g.

Embodiment 5

S1. the porous micro-nano particle being mixed to get silica and the porous micro-nano composite substrate of aluminum oxide and ethyl alcohol It is mixed with acetone, is placed in Ultrasound Instrument and carries out ultrasonic disperse, supersonic frequency 40Hz, temperature are 50 DEG C hereinafter, ultrasonic time is 1h, obtaining concentration is the porous micro-nano particle suspension of 13g/ml；In the present embodiment, composite substrate is with two that parts by weight are 80% Silica and 20% aluminum oxide be made；

S2. nano cupric oxide is added with the ratio of quality 1:10 into dispersing agent kayexalate, it will be above-mentioned molten Liquid mixes at room temperature, magnetic agitation 1 hour, obtains evenly dispersed carbon black suspension；

S3. porous micro-nano particle suspension is mixed with nano cupric oxide suspension with the mass ratio of 18:1, is added The external fixation of 5000V/m or rotating electric field, stir 2h by 35 revs/min of rotating electric field revolving speed；

S4. by solution by filtering, distillation water washing 3 times, dehydrated alcohol washing 2 times.

S5. the powder object that finishes of washing is placed in 70 DEG C of baking ovens after dry 5h and obtains three-dimensional porous/thorn-like micro-nano and answers Close particle powder.

It should be noted that the following scale particle of the nanometer and nanometer of 2~embodiment of embodiment 4 is the primary legal system of liquid phase , the nanometer and the following scale particle of nanometer of preforming mixing can also be inserted into liquid phase method, such as embodiment 5；Wherein, it prepares Nanometer and the following scale particle solution of nanometer, in addition to zinc nitrate, copper sulphate and zinc sulfate may be zinc chloride, copper chloride, One of copper nitrate, sodium metasilicate and silicone are a variety of；Solvent can also be trifluoroethanol, formic acid, three in addition to methanol, ethyl alcohol Ethanol amine, acetic acid, acetone, acetic acid ethyl ester, tetrahydrofuran, N-methyl pyrrolidones, ether, propylene oxide, methylene chloride, trichlorine One of methane, triethanolamine are a variety of；Ammonium hydroxide may be urea, sodium bicarbonate, sodium carbonate, sodium dihydrogen phosphate, phosphoric acid One of disodium hydrogen, potassium dihydrogen phosphate, barbital sodium, borax are a variety of.

Using three-dimensional porous obtained by the above method/thorn-like micro-nano compound particle, there are three kinds of structures, due in hole Surface can be much larger than surface, so the following scale particle of the zinc-oxide nano and nanometer that generate in liquid phase reactor can expand due to polarity Effect is dissipated prior to accumulating in hole, is formed as shown in Figure 1, the single hole embedded quantity of porous micro-nano particle is the 5- of hole total volume 100%, 3 kinds of structures, as shown in No. 1 of Fig. 1, celled portion may be present in three-dimensional porous/thorn-like micro-nano compound particle generated It is embedded in micro-nano particle, or as shown in No. 2 of Fig. 1, micropore completely fills micro-nano particle, or 3, No. 4 structures such as Fig. 1 Shown, zinc oxide particles continued growth accumulation becomes thorn-like micro-nano compound particle.Test measures, the preparation method produced three Tieing up porous/thorn-like micro-nano compound particle has 345m through the test of BET nitrogen adsorption methods²The specific surface area of/g illustrates most Zinc oxide particles are partly or entirely embedded in porous micro-nano particle.

Embodiment 6

Second of preparation process of above-mentioned micro-nano compound particle, i.e. high-speed flow kinetic energy embedding inlay technique are present embodiments provided, Specifically includes the following steps:

S1. diatomite ore is added in hammer mill, is crushed to the ore in sand form of 100 mesh；

S2. ore in sand form is put into Raymond mill and is ground, carried out 4 hours vacuum machine ball millings, 80 DEG C of grinding temperature, turn 2 revolutions per seconds of speed, partial size is less than 150 μm after grinding；

S4. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 50% silica and 50% aluminum oxide be made；

S5. powder and carbon nanotube after grinding are sent into double injecting type airflow mills with the weight ratio of 1:1, and it is small to carry out 12 When 300m/s grinding, 200 DEG C of temperature, pressure 100KPa, 1 revolutions per second of revolving speed, be made 10~20 μm of partial size powder, gained powder End part includes three-dimensional porous/thorn-like micro-nano compound particle.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in table.Three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added in standard tread rubber can make original tread Tb characteristic at 151 DEG C of glue promotes 9%, and the tg δ performance optimization 38% under the conditions of 60 DEG C, compression temperature rise amount reduces by 19%, Acker Grand abrasion reduce the anti-slippery characteristic promotion 45% under the conditions of 4%, 1mm moisture film.

Table: tread rubber application test data

Embodiment 7

S1. yellow clay ore is added in hammer mill, is crushed to the ore in sand form of 200 mesh；

S2. ore in sand form is put into Raymond mill and is ground, carry out 24 hours vacuum machine ball millings, 80 DEG C of grinding temperature, 2 revolutions per seconds of revolving speed, partial size is less than 150 μm after grinding；

S3. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 450% silica and 55% aluminum oxide be made；

S4. porous micro-nano particle and carbon black or carbon nanotube are sent into double injecting type airflow mills with the weight ratio of 20:1, The grinding of 12 hours 1200m/s is carried out, 80 DEG C of temperature, pressure 1000KPa, 5 revolutions per seconds of revolving speed, the powder of 10~20 μm of partial size is made End, gained powder part include three-dimensional porous/thorn-like micro-nano compound particle.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in table.Three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added in standard tread rubber can make original tread Tb characteristic at 151 DEG C of glue promotes 10%, and the tg δ performance optimization 46% under the conditions of 60 DEG C, compression temperature rise amount reduces by 22%, Acker Grand abrasion reduce the anti-slippery characteristic promotion 48% under the conditions of 9%, 1mm moisture film.

Table: tread rubber application test data

Embodiment 8

S1. smectite is added in hammer mill, is crushed to the ore in sand form of 200 mesh；

S3. spray coating liquor is respectively prepared in core in silica dioxide granule, calcium carbonate and the aluminum oxide powder obtained after grinding Alternating spray from level to level on body forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to use Parts by weight are that 35% silica and 65% aluminum oxide are made；

S4. porous micro-nano particle and carbon black or carbon nanotube are sent into circulating tube type airflow mill with the weight ratio of 12:1, The grinding of 12 hours 1000m/s is carried out, 130 DEG C of temperature, pressure 600KPa, 3 revolutions per seconds of revolving speed, the powder of 10~20 μm of partial size is made End, gained powder part include three-dimensional porous/thorn-like micro-nano compound particle.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in table.Three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added in standard tread rubber can make original tread Tb characteristic at 151 DEG C of glue promotes 16%, and the tg δ performance optimization 23% under the conditions of 60 DEG C, compression temperature rise amount reduces by 23%, Acker Grand abrasion reduce the anti-slippery characteristic promotion 47% under the conditions of 6%, 1mm moisture film.

Table: tread rubber application test data

Embodiment 9

Present embodiments provide the third preparation process of above-mentioned micro-nano compound particle, i.e., high-temperature reconstruction method insertion nanometer and Nanometer or less scale particle.

High temperature reaction stove as shown in Figure 3, including temperature reaction section A, air-flow accelerating sections B, conversion zone C, collection section D and place In 7 feed inlets of different location.Wherein, temperature reaction section draw ratio 1:1, flow acceleration section draw ratio are 10:1, reaction Section draw ratio is 2:1.In the present embodiment, temperature reaction section cavity diameter 1m, the cavity diameter 0.6m of flow acceleration, conversion zone Cavity diameter 1.5m.

Nano zine oxide is added in No. 1 feed inlet, nano zine oxide is blown by temperature reaction by loss in weight feeder Section, while guaranteeing carrier gas excess, so that the natural gas completely burned that warming-up section inlet is passed through.By adjusting natural gas feed speed Rate, so that burning zone end air velocity reaches 5m/s, 500 DEG C of temperature；The fuel of air-flow accelerating sections is subsequently entered due to compression Effect air velocity is promoted to 20m/s, and temperature reaches 600 DEG C, under the action of this high-speed flow, enters via feed inlet 4 Composite substrate made from porous alum stone is reacted with the high-temperature reconstruction of nano zine oxide can only continue 1s or so；At the end of conversion zone End sprays into 100 DEG C or less cooling waters by cooler E and reaction product is cooled to 800 DEG C or less；Reaction product after cooling down Cyclone separator into collection section completes gas solid separation, and gained raw material is as porous/thorn-like micro-nano compound particle, micropore portion Divide or had fully embedded into nano zine oxide.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in following table, the three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added into standard tread rubber can make Tb characteristic at 151 DEG C of original tread glue promotes 5%, and the tg δ performance optimization 17% under the conditions of 60 DEG C, compression temperature rise amount reduces 15%, Akron abrasion reduces the anti-slippery characteristic promotion 32% under the conditions of 3%, 1mm moisture film.

Table: tread rubber application test data

Embodiment 10

High temperature reaction stove as shown in Figure 3, including temperature reaction section, air-flow accelerating sections, conversion zone, collection section and in not With 7 feed inlets of position.Wherein, temperature reaction section draw ratio 5:1, flow acceleration section draw ratio are 5:1, conversion zone major diameter Than for 15:1.In the present embodiment, temperature reaction section cavity diameter 1.1m, the cavity diameter 0.8m of flow acceleration, conversion zone Cavity diameter 2.0m.

Nano zine oxide is added in No. 1 feed inlet, nano zine oxide is blown by temperature reaction by loss in weight feeder Section, while guaranteeing carrier gas excess, so that the natural gas completely burned that warming-up section inlet is passed through.By adjusting natural gas feed speed Rate, so that burning zone end air velocity reaches 15m/s, 2000 DEG C of temperature；The fuel of air-flow accelerating sections is subsequently entered due to pressure Contracting effect air velocity is promoted to 100m/s, and temperature reaches 3500 DEG C, under the action of this high-speed flow, via feed inlet 4 into Composite substrate made from the porous alum stone entered is reacted with the high-temperature reconstruction of nano zine oxide can only continue 5s or so；In conversion zone End 100 DEG C or less cooling waters are sprayed by cooler reaction product are cooled to 800 DEG C or less；Reaction after cooling down produces The cyclone separator that object enters collection section completes gas solid separation, and gained raw material is as porous/thorn-like micro-nano compound particle, micropore Partly or entirely it is embedded in nano zine oxide.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in following table, the three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added into standard tread rubber can make Tb characteristic at 151 DEG C of original tread glue promotes 8%, and the tg δ performance optimization 13% under the conditions of 60 DEG C, compression temperature rise amount reduces 21%, Akron abrasion reduces the anti-slippery characteristic promotion 33% under the conditions of 3%, 1mm moisture film.

Table: tread rubber application test data

Embodiment 11

High temperature reaction stove as shown in Figure 3, including temperature reaction section, air-flow accelerating sections, conversion zone, collection section and in not With 7 feed inlets of position.Wherein, temperature reaction section draw ratio 2:1, flow acceleration section draw ratio are 6:1, conversion zone major diameter Than for 8:1.In the present embodiment, temperature reaction section cavity diameter 1.3m, the cavity diameter 1.0m of flow acceleration, the chamber of conversion zone Body diameter 1.8m.

Nano zine oxide is added in No. 1 feed inlet, nano zine oxide is blown by temperature reaction by loss in weight feeder Section, while guaranteeing carrier gas excess, so that the natural gas completely burned that warming-up section inlet is passed through.By adjusting natural gas feed speed Rate, so that burning zone end air velocity reaches 10m/s, 1500 DEG C of temperature；The fuel of air-flow accelerating sections is subsequently entered due to pressure Contracting effect air velocity is promoted to 70m/s, and temperature reaches 2000 DEG C, under the action of this high-speed flow, enters via feed inlet 4 Porous alum stone made from composite substrate reacted with the high-temperature reconstruction of nano zine oxide and can only continue 5s or so；In conversion zone End sprays into 100 DEG C or less cooling waters by cooler and reaction product is cooled to 800 DEG C or less；Reaction product after cooling down Cyclone separator into collection section completes gas solid separation, and gained raw material is as porous/thorn-like micro-nano compound particle, micropore portion Divide or had fully embedded into nano zine oxide.

By the preparation method three-dimensional porous/thorn-like micro-nano compound particle produced be applied to tread rubber when performance boost such as Shown in following table, the three-dimensional porous/thorn-like micro-nano compound particle that 20% mass fraction is added into standard tread rubber can make Tb characteristic at 151 DEG C of original tread glue promotes 11%, and the tg δ performance optimization 46% under the conditions of 60 DEG C, compression temperature rise amount reduces 8%, Akron abrasion reduces the anti-slippery characteristic promotion 42% under the conditions of 3%, 1mm moisture film.

Table: tread rubber application test data

It should be noted that the porous micro-nano particle and/or zinc chloride, sulphur launched during reaction via 1-5 feed inlet Sour zinc, zinc nitrate, copper chloride, copper sulphate, copper nitrate, iron chloride, ferric nitrate, ferric sulfate, sodium metasilicate, methane, acetylene, propine, One of butane, natural gas, liquid hydrocarbon, clarified oil, heavy oil, kerosene, coal tar, cracked oil, carbolineum, silicone, silane are more Kind mixture completes high-temperature reconstruction reaction, and high-temperature reconstruction duration of the reaction 0.05-5s, following reaction product is in conversion zone end The 0-50 DEG C of cooling water temperature that cooled device sprays into immediately is to 800 DEG C or less.

The dispensing of 1-5 feed inlet is silicon carbide, carbon nanotube, the oxygen of porous micro-nano particle and/or preforming One or more of graphite alkene, nano zine oxide, nano cupric oxide, carbon black, acetylene black, white carbon black.

Reaction product after cooling down enter collection section cyclone separator complete gas solid separation, collection section front end (into Material mouth 6) or end (feed inlet 7) all can further put into porous micro-nano particle and carry out nanometer and the following scale particle of nanometer It is simply embedded into.

This method charging is not limited to 7 feed inlets, in temperature reaction section, air-flow accelerating sections, conversion zone, collection section institute There is position to may comprise one or more porous micro-nano particle feed inlets；Each feed inlet can be such that porous micro-nano particle disperses Enter in furnace in liquid feed, in individual gaseous stream or in individual aqueous streams.

Warming-up section feeding manner uses existing Schenck Process, the Schenck of ChagrinFalls, OH manufacture The charging of AccuRate Mechatron MC Feeder loss in weight feeder, enters porous micro-nano particle in furnace with combustion gas；? Air-flow accelerating sections, conversion zone and the feeding manner of collection section are aerosol dispersion device, and the injection diameter of the aerosol dispersion device is Raw material is sprayed into air-flow accelerating sections or conversion zone, optimal, the spray of the present embodiment against air-flow with 0~90 ° of angle by 0.5~3mm Bore dia is 2mm, and raw material is sprayed into air-flow accelerating sections and conversion zone against air-flow with 90 ° of angles, can be by micro-nano particle and dispersing agent Uniformly mixing, the nozzle distance reacting furnace center line D/2 (D is place reaction cavity diameter) of all aerosol dispersion devices, and gas The aerosol dispersion device of accelerating sections is flowed apart from air-flow accelerating sections entrance 2m, and the aerosol dispersion device of conversion zone is apart from conversion zone entrance 1m。

Being atomized dispersing agent used is kayexalate, smelling of cetyl trimethyl hinge, dodecyl sodium sulfate, ten One or more of dialkyl benzene sulfonic acids sodium, one polypropylene oxide of polyethylene oxide, one polyethylene oxide triblock copolymer.

Embodiment 12

The 4th kind of preparation process for present embodiments providing micro-nano compound particle, by mechanical load in porous micro-nano particle Micropore in be embedded in micro-nano particle, specifically comprise the following steps:

S1. by opal ore and alunite raw material investment hammer mill, it is crushed to the ore in sand form of 75 mesh；

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 70% silica and 30% aluminum oxide be made；

S3. porous micro-nano particle and carbon black will be obtained to grind in the weight ratio feeding vertical grinder of 10:1, carried out 48 hours mechanical ball mills, 50 DEG C of grinding temperature, 0.5 revolutions per second of revolving speed, partial size is less than 100 μm after grinding；

S4. particle is sent into selection by winnowing grader, classifier rotor frequency 50Hz, wind speed 10m/s, gained powder portion after grinding Subpackage contains three-dimensional porous/thorn-like micro-nano compound particle.

Embodiment 13

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 40% silica and 60% aluminum oxide be made；

S3. porous micro-nano particle and carbon black are obtained to be ground in the weight ratio feeding vertical grinder of 20:1, carries out 48 The mechanical ball mill of hour, 100 DEG C of grinding temperature, 5 revolutions per seconds of revolving speed, partial size is less than 100 μm after grinding；

S4. particle is sent into selection by winnowing grader, classifier rotor frequency 10Hz, wind speed 200m/s, gained powder after grinding Part includes three-dimensional porous/thorn-like micro-nano compound particle.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 330m²The specific surface area of/g.

Embodiment 14

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 50% silica and 50% aluminum oxide be made；

S3. porous micro-nano particle and carbon black will be obtained to grind in the weight ratio feeding vertical grinder of 1:1, carry out 48 The mechanical ball mill of hour, 80 DEG C of grinding temperature, 3 revolutions per seconds of revolving speed, partial size is less than 100 μm after grinding；

S4. particle is sent into selection by winnowing grader, classifier rotor frequency 120Hz, wind speed 100m/s, gained powder after grinding Part includes three-dimensional porous/thorn-like micro-nano compound particle.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 350m²The specific surface area of/g.

Embodiment 15

The 5th kind of preparation process for present embodiments providing micro-nano compound particle, below the nanometer and nanometer of preforming Scale particle is embedded in the micropore of porous micro-nano particle by negative pressure of vacuum active force, and specific steps include:

S1. kaolinite ore raw materials is put into hammer mill, is crushed to the ore in sand form of 75 mesh；

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 30% silica and 70% aluminum oxide be made；

S3. obtained porous micro-nano particle and white carbon black are sent into ribbon formula vacuum mixer with the weight ratio of 1:1, institute It is -1000KPa with vacuum degree, 300 DEG C of temperature, 0.5 revolutions per second of revolving speed, handles the time 48 hours, gained powder part may include three Tie up porous/thorn-like micro-nano compound particle.

Embodiment 16

S3. obtained porous micro-nano particle and white carbon black are sent into double star vacuum mixer with the weight ratio of 20:1, institute Be 0KPa with vacuum degree, 100 DEG C of temperature, 5 revolutions per seconds of revolving speed, handle the time 4 hours, gained powder part may include it is three-dimensional porous/ Thorn-like micro-nano compound particle.

Embodiment 17

S3. porous micro-nano particle and white carbon black will be obtained to be sent into planetary vacuum mixing machine with the weight ratio of 10:1, it is used Vacuum degree is -800KPa, 200 DEG C of temperature, 3 revolutions per seconds of revolving speed, is handled the time 36 hours, gained powder part may include that three-dimensional is more Hole/thorn-like micro-nano compound particle.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 340m²The specific surface area of/g.

Embodiment 18

The 6th kind of preparation process for present embodiments providing micro-nano compound particle, will be pre- by more rotor physics continuous modifications First molding nanometer and the following scale particle of nanometer are embedded in the micropore of porous micro-nano particle, and specific steps include:

S1. Talc Ore and opal raw ore are crushed, are ground 8 hours using vertical ball mill until 40 μm of grains Diameter；

S3. kayexalate and carbon black are mixed with the ratio of quality 10:1, above-mentioned solution is mixed at room temperature Stirring, obtains evenly dispersed carbon black suspension；

S4. by the porous micro-nano particle of 300-2500 mesh partial size made from carbon black suspension and step 1 according to the weight of 1:20 Ratio is sent into more rotor physics continuous modification devices, and the vacuum machine ball milling of 4 hours -1000KPa vacuum degrees, ball milling temperature are carried out 300 DEG C of degree, 0.5 revolutions per second of ball milling room revolving speed；

S5. gained powder is sent into the airflow milling room in more rotor physics continuous modification devices, carries out 24 hours 1200m/s High pressure draught mill, 80 DEG C of temperature, pressure 100KPa, 5 revolutions per seconds of revolving speed.

The preparation method three-dimensional porous/thorn-like micro-nano compound particle produced has through the test of BET nitrogen adsorption methods 320m²The specific surface area of/g.

Embodiment 19

S4. by the porous micro-nano particle of 300-2500 mesh partial size made from carbon black suspension and step 1 according to the weight of 1:1 Ratio is sent into more rotor physics continuous modification devices, and the vacuum machine ball milling of 48 hours 0KPa vacuum degrees, ball milling temperature are carried out 50 DEG C, 5 revolutions per seconds of ball milling room revolving speed；

S5. gained powder is sent into the airflow milling room in more rotor physics continuous modification devices, carries out 24 hours 300m/s High pressure draught mill, 200 DEG C of temperature, pressure 1000KPa, 0.5 revolutions per second of revolving speed.

Embodiment 20

S1. Talc Ore and opal raw ore are crushed, are ground 9 hours using vertical ball mill until 40 μm of grains Diameter；

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening；Composite substrate is to be with parts by weight 80% silica and 20% aluminum oxide be made；

S4. by the porous micro-nano particle of 300-2500 mesh partial size made from carbon black suspension and step 1 according to the weight of 1:15 Ratio is sent into more rotor physics continuous modification devices, and the vacuum machine ball milling of 4 hours -500KPa vacuum degrees, ball milling temperature are carried out 80 DEG C of degree, 3 revolutions per seconds of ball milling room revolving speed；

S5. gained powder is sent into the airflow milling room in more rotor physics continuous modification devices, carries out 24 hours 800m/s High pressure draught mill, 135 DEG C of temperature, pressure 200KPa, 4 revolutions per seconds of revolving speed.

Comparative example 1

S2. the solution that porous micro-nano particle is obtained after silica being mixed with methanol is placed in Ultrasound Instrument and carries out ultrasound Dispersion, supersonic frequency 50Hz, temperature is 30 DEG C hereinafter, ultrasonic time is 2h, and obtaining concentration is the porous micro-nano particle of 20g/ml Suspension；

S4. by the zinc nitrate solution configured in the porous micro-nano particle suspension configured in S2 and S1 with mass ratio 30:1's Ratio mixing, is added the external fixation or rotating electric field of 80V/m, 10 revs/min of rotating electric field revolving speed, magnetic agitation 0.1 is small When, 200 revs/min of revolving speed；

S5. the S3 ammonia spirit configured is added drop-wise in mixed solution dropwise, pH control range 6 keeps 80 DEG C of thermostatted waters Bath heating, stir about 1h；

S6. after reaction, by filtering, distillation water washing 1 time, dehydrated alcohol washing 1 time；

S7. the powder object that washing finishes is placed in 50 DEG C of baking ovens after dry 8h and obtains micro-nano compound particle powder.

Preparation method micro-nano compound particle produced has 110m through the test of BET nitrogen adsorption methods²The specific surface of/g Product.

Preparation method micro-nano compound particle produced is applied to tread rubber, 20% mass is added in standard tread rubber Three-dimensional porous/thorn-like micro-nano compound particle of score can make the Tb characteristic at 151 DEG C of original tread glue promote 2%, 60 DEG C of items Tg δ performance optimization 9% under part, compression temperature rise amount reduce by 8%, and Akron abrasion reduces the moisture-resistant under the conditions of 1%, 1mm moisture film Sliding characteristic promotes 16%.

Comparative example 2

The preparation process of above-mentioned micro-nano compound particle, i.e. high-speed flow kinetic energy embedding inlay technique are present embodiments provided, it is specific to wrap Include following steps:

S2. spray coating liquor is respectively prepared one layer on core in the silica dioxide granule and aluminum oxide powder obtained after grinding Layer alternating spray forms after porous composite layer and obtains porous micro-nano particle by broken screening, wherein composite substrate is to use weight Part is that 5% silica and 95% aluminum oxide are made；

S3. ore in sand form is put into Raymond mill and is ground, carried out 1 hour vacuum machine ball milling, 60 DEG C of grinding temperature, turn 1 revolutions per second of speed；

S4. powder and carbon nanotube after grinding are sent into double injecting type airflow mills with the weight ratio of 25:1, carry out 12 The grinding of hour 100m/s, temperature 70 C, pressure 100KPa, 1 revolutions per second of revolving speed, micro-nano compound particle processed.

Preparation method micro-nano compound particle produced has 130m through the test of BET nitrogen adsorption methods²The specific surface of/g Product.

Preparation method micro-nano compound particle produced is applied to tread rubber, 20% mass is added in standard tread rubber Three-dimensional porous/thorn-like micro-nano compound particle of score can make the Tb characteristic at 151 DEG C of original tread glue promote 2%, 60 DEG C of items Tg δ performance optimization 11% under part, compression temperature rise amount reduce by 9%, and Akron abrasion reduces the moisture-resistant under the conditions of 1%, 1mm moisture film Sliding characteristic promotes 17%.

Comparative example 3

Present embodiments provide a kind of preparation process of micro-nano compound particle, i.e., high-temperature reconstruction method insertion nanometer and nanometer with Lower scale particle.

High temperature reaction stove as shown in Figure 3, including temperature reaction section A, air-flow accelerating sections B, conversion zone C, collection section D and place In 7 feed inlets of different location.Wherein, temperature reaction section draw ratio 7:1, flow acceleration section draw ratio are 2:1, conversion zone Draw ratio is 2:1.In the present embodiment, temperature reaction section cavity diameter 1m, the cavity diameter 0.6m of flow acceleration, conversion zone Cavity diameter 1.5m.

Nano zine oxide is added in No. 1 feed inlet, nano zine oxide is blown by temperature reaction by loss in weight feeder Section, while guaranteeing carrier gas excess, so that the natural gas completely burned that warming-up section inlet is passed through.By adjusting natural gas feed speed Rate, so that burning zone end air velocity reaches 5m/s, 300 DEG C of temperature；The fuel of air-flow accelerating sections is subsequently entered due to compression Effect air velocity is promoted to 10m/s, and temperature reaches 400 DEG C, under the action of this high-speed flow, enters via feed inlet 4 Porous alum stone powder is reacted with the high-temperature reconstruction of nano zine oxide can only continue 8s or so；Pass through cooling in the end of conversion zone Device E sprays into 100 DEG C or less cooling waters and reaction product is cooled to 800 DEG C or less；Reaction product after cooling down enters collection section Cyclone separator complete gas solid separation, gained raw material is as porous/thorn-like micro-nano compound particle, celled portion or all embedding Nano zine oxide is entered.

Preparation method micro-nano compound particle produced has 133m through the test of BET nitrogen adsorption methods²The specific surface of/g Product.

Preparation method micro-nano compound particle produced is applied to tread rubber, 20% mass is added in standard tread rubber Three-dimensional porous/thorn-like micro-nano compound particle of score can make the Tb characteristic at 151 DEG C of original tread glue promote 5%, 60 DEG C of items Tg δ performance optimization 118% under part, compression temperature rise amount reduce by 7%, resisting under the conditions of Akron abrasion reduction by 1%, 1mm moisture film Wet and slippery characteristic promotes 19%.

Comparative example 4

The preparation process for present embodiments providing a kind of micro-nano compound particle, by mechanical load in porous micro-nano particle It is embedded in micro-nano particle in micropore, specifically comprises the following steps:

S2. ore in sand form and carbon black are sent into vertical grinder with the weight ratio of 25:1 and are ground, carry out 48 hours machinery Ball milling, 30 DEG C of grinding temperature, 6 revolutions per seconds of revolving speed.

Preparation method micro-nano compound particle produced has 80m through the test of BET nitrogen adsorption methods²The specific surface of/g Product.

Comparative example 5

The preparation process for present embodiments providing a kind of micro-nano compound particle, by the nanometer of preforming and the following ruler of nanometer Degree particle is embedded in the micropore of porous micro-nano particle by negative pressure of vacuum active force, and specific steps include:

S2. ore in sand form and white carbon black to be sent into ribbon formula vacuum mixer with the weight ratio of 30:1, vacuum degree used is- 1500KPa, 0.5 revolutions per second of revolving speed, handles the time 48 hours, obtains micro-nano compound particle by 80 DEG C of temperature.

Preparation method micro-nano compound particle produced has 100m through the test of BET nitrogen adsorption methods²The specific surface of/g Product.

Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or It changes still within the protection scope of the invention.

Claims

1. a kind of micro-nano compound particle, which is characterized in that it is straight to be less than porous micro-nano particle micropore for insertion in porous micro-nano particle The following scale particle of the nanometer and nanometer of diameter, to form three-dimensional porous and/or thorn-like micro-nano compound particle.

2. micro-nano compound particle according to claim 1, which is characterized in that described three-dimensional porous and/or thorn-like micro-nano is multiple The single hole embedded quantity of conjunction particle is that 1~100%, the BET nitrogen adsorption specific surface area of pore volume is 30m²/ g~350m²/ g, preferably 300m²/ g~340m²/g。

3. micro-nano compound particle according to claim 1 or 2, which is characterized in that described three-dimensional porous and/or thorn-like micro-nano It is 75%~95% that the single hole embedded quantity of compound particle, which is pore volume,.

4. micro-nano compound particle according to claim 1 or 2, which is characterized in that the porous micro-nano particle is spherical in shape, ellipse Spherical, water chestnut spherical shape or irregular shape.

5. micro-nano compound particle according to claim 4, which is characterized in that the porous micro-nano particle diameter is 100nm ~100 μm, porous structure aperture 1nm~500nm, hole depth 2nm~500nm, hole number 5000~300,000,000/g, BET method specific surface 0.3~300m of product²/ g, pH value 6~8.

6. micro-nano compound particle according to claim 4 or 5, which is characterized in that the porous micro-nano particle is titanium dioxide The compound porous micro-nano particle of silicon or calcium carbonate or silica and/or calcium carbonate and aluminum oxide.

7. micro-nano compound particle according to claim 6, which is characterized in that the porous micro-nano particle includes weight percent Than the aluminum oxide for 30%~100% silica or calcium carbonate and 0%~70%.

8. micro-nano compound particle according to claim 1, which is characterized in that the nanometer and the following scale particle of nanometer are Nano zine oxide, nano cupric oxide, small molecule functional material, natural rubber high molecular material, synthetic rubber high molecular material, carbon One of nanotube, graphene, carbon black, white carbon black, titanium dioxide, ferroso-ferric oxide, metal simple-substance nanoparticle are a variety of.

9. a kind of described in any item preparation processes of micro-nano compound particle of claim 1-8, which is characterized in that pass through more rotors The nanometer of preforming and the following scale particle of nanometer are embedded in the micropore of porous micro-nano particle by physics continuous modification.

10. the preparation process of micro-nano compound particle according to claim 9, which is characterized in that more rotor physics connect Continuous reforming apparatus includes two or more mixing side in mechanical ball mill, negative pressure of vacuum mixing and high-speed flow mixing Method.

11. the preparation process of micro-nano compound particle according to claim 9 or 10, which is characterized in that negative pressure of vacuum ball milling Indoor vacuum degree -1000KPa~0KPa, 0.5~5 revolutions per second of ball milling room revolving speed, temperature 50 C~300 DEG C；Airflow milling is indoor Air velocity 300m/s~1200m/s, 0.5~5 revolutions per second of revolving speed, 80 DEG C~200 DEG C of temperature, pressure 100KPa~1000KPa, The processing time 4~48 hours.

12. the porous micro-nano particle according to claim 4~6, which is characterized in that the titanium dioxide of the porous micro-nano particle Silicon, calcium carbonate or aluminum oxide derive from siliceous/calcium material, comprising: alunite, rice hull ash, straw ash, montmorillonite, talcum, One of yellow clay, mica, wollastonite, bauxite, albumen shale, diatomite, diatomaceous shale, opal or multiple combinations.

13. a kind of micro-nano compound particle any according to claim 1~8 is in polymer, plastics, rubber, coating, catalysis Agent, water process, soil improvement, chemical fertilizer, chemical rubber energy storage, daily-use chemical industry, prevent it is heat-insulated, inhale wave, stealthy, adsorbent material or Medical manufacture is sustained the application in agent carrier.