CN107254163A - A kind of nylon/SiO 2 composite microsphere, preparation method and application - Google Patents
A kind of nylon/SiO 2 composite microsphere, preparation method and application Download PDFInfo
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- CN107254163A CN107254163A CN201610178084.7A CN201610178084A CN107254163A CN 107254163 A CN107254163 A CN 107254163A CN 201610178084 A CN201610178084 A CN 201610178084A CN 107254163 A CN107254163 A CN 107254163A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/1605—Excipients; Inactive ingredients
- A61K9/1611—Inorganic compounds
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/14—Particulate form, e.g. powders, Processes for size reducing of pure drugs or the resulting products, Pure drug nanoparticles
- A61K9/16—Agglomerates; Granulates; Microbeadlets ; Microspheres; Pellets; Solid products obtained by spray drying, spray freeze drying, spray congealing,(multiple) emulsion solvent evaporation or extraction
- A61K9/1605—Excipients; Inactive ingredients
- A61K9/1629—Organic macromolecular compounds
- A61K9/1641—Organic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, poloxamers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/286—Phases chemically bonded to a substrate, e.g. to silica or to polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/14—Powdering or granulating by precipitation from solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/03—Powdery paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The present invention discloses a kind of nylon/SiO 2 composite microsphere and its preparation method and application.The complex microsphere is the spherical and/or subsphaeroidal particle of 0.5~300 μm of particle diameter, is made up of apertures nylon micro-sphere matrix and the silica for being dispersed in apertures nylon micro-sphere hole and/or surface.Wherein the content of apertures nylon micro-sphere is 10~99.9wt%, and dioxide-containing silica is 0.1~90wt%.The complex microsphere is obtained by carrying out silica in situ hydrolysis in apertures nylon micro-sphere dispersion liquid.The addition of silica can effectively reduce the water absorption rate of apertures nylon complex microsphere, improve heat endurance, crystal property and mechanical strength.The complex microsphere can widen application of the SLS technologies in fields such as aviation, automobile, medicine equipment, electronic instrument, machine die, the arts work as SLS Selective Laser Sintering consumptive materials.
Description
Technical field
The present invention relates to technical field of polymer materials.It is multiple more particularly, to a kind of nylon/silica
Close microballoon and its preparation method and application.
Background technology
Nylon is the crystalline polymer as made from amino acid or corresponding lactams.Moulded as five large-engineerings
One of material, because having higher a melting temperature and glass transition temperature, good mechanical property, wearability,
Impact flexibility, and excellent self lubricity and formability, and be widely used in automobile, machinery,
The fields such as space flight and aviation, military affairs, medical treatment, electronics.But many nylon products are because fragile under low temperatureization, inhale
Water rate is big, the shortcomings of poor dimensional stability, greatly limit its application.Industrially frequently with inorganic particle
Improve above-mentioned unfavorable factor to nylon material modification.Pass through the enhanced nylon composite wood of inorganic nanometer powder
The preparation of material and performance study are by wide coverage.The preparation method of conventional composite materials is mainly with molten
Melt blending method and inorganic particle is introduced into nylon matrix.Because nano inoganic particle surface free energy is high easily
Reunite, powder can be caused to be difficult to dispersed in polymeric matrix, reduce the mechanical property of composite
Energy.Recently, nylon 6 nano-composite is prepared by the extensive of domestic and foreign scholars using in situ synthesis
Concern.Also a kind of in-situ polymerization mode is mentioned in Publication No. CN101570590A Chinese invention patent
Prepare nylon66 fiber/SiO2The method of composite.Minami et al. is with sol-gel process at nylon-6 matrix bottom
Upper growth in situ SiO2Film (J.Sol-Gel Sci.Technol.1996,6,107-111.).Publication No.
CN101348609A Chinese invention patent is prepared for nylon 6/SiO with similar mode2Sheet material.Research
It was found that, water absorption rate can be significantly reduced by nano-silicon dioxide modified obtained nylon composite materials, is received
Rice silica plays an important role in the crystallization kinetics of nylon 6, the relatively pure nylon 6 of composite
With more preferable heat endurance, its stretch modulus, yield strength, hardening modulus and tensile strength have bright
It is aobvious to improve.But, the composite that above-mentioned in-situ polymerization is produced is mainly nylon film material or sheet material,
Nano-meter SiO_22Nylon matrix surface is mainly distributed on, load capacity is low.With high degree of dispersion, high capacity amount
Nylon/SiO2The preparation of complex microsphere does not have been reported that also so far.
For the nylon micro mist of representative it is current 3D printing-selective laser sintering with nylon 12 and nylon 6
(SLS) the most popular raw material of technology.But simple nylon powder is applied to 3D printing and had necessarily
Defect.For example：Nylon 12 prepares cost height, and expensive, glass transition temperature is low；Nylon 6 absorbs water
Rate is high, poor dimensional stability etc..This strongly limits the application of SLS technologies and development.Publication No.
Mentioned in CN104910614A Chinese invention patent by nylon 12, micro inorganic fillers white carbon,
Coupling agent, antioxidant and other auxiliary agents, which first dissolve to be spray-dried again, obtains nylon composite powder.Publication No.
CN102337021A Chinese invention patent helps the resin of nylon 12, glass microballoon, coupling agent, flowing
Agent, antioxidant and light absorber carry out mechanical mixture and obtain composite powder, and modified material is prevented effectively from
The buckling deformation problem of selective laser sintering and moulding part.But all it is to be blended by physics in above-mentioned patent
Method by filler and nylon by mechanical mixture, this method makes matrix and filler be difficult to be well mixed,
Material mechanical performance lifting is limited, and especially for the dusty material of nylon 6, the problem of water absorption rate is high remains unchanged
It is difficult to overcome.
The content of the invention
First purpose of the present invention is to provide a kind of nylon/SiO 2 composite microsphere, the complex microsphere
In, silica uniform and the stable hole and/or the surface that are dispersed in apertures nylon micro-sphere, and this is compound
Microballoon has excellent heat endurance, physical and mechanical properties, low water absorption rate and high powder heap density.
Second object of the present invention is to provide a kind of preparation method of nylon/SiO 2 composite microsphere,
Using sol-gel process in the polyamide skeleton of apertures in-situ polymerization silica, the preparation method is simply easy
It is controllable, a large amount of silica had both been solved the problem of apertures nylon micro-sphere matrix is dispersed, and can be led to
Cross the introducing of hydrophobic silica, the raising collaboration of polyamide skeleton structure crystalline degree and solve nylon material water suction
Rate problem；Heap density, heat endurance, crystal property and the power of nylon composite granule are effectively improved simultaneously
Learn intensity.
Third object of the present invention is the application for providing a kind of nylon/nano silicon complex microsphere.
To reach above-mentioned first purpose, the present invention uses following technical proposals：
A kind of nylon/SiO 2 composite microsphere, the complex microsphere is spherical or subsphaeroidal particle, particle diameter
For 0.5~300 μm；The complex microsphere is made up of apertures nylon micro-sphere and silica；Silica is in
Nano particle is dispersed in hole and/or the surface of apertures nylon micro-sphere, and/or is filled out in micron order continuous state
Fill in apertures nylon micro-sphere hole；In the complex microsphere, the content of apertures nylon micro-sphere is
10~99.9wt%, dioxide-containing silica is 0.1~90wt%.
Preferably, the apertures nylon micro-sphere may be selected from the microballoon of nylon 6, nylon66 fiber microballoon, nylon 12
Microballoon, nylon 11 microballoon, nylon 1212 microballoon, nylon 612 microballoon, NYLON610 microballoon or nylon
One or more in 1010 microballoons.
Preferably, the particle diameter of the nanometer silicon dioxide particle is 10~500nm.
Preferably, before nonloaded silica, apertures nylon micro-sphere is obvious spherical or subsphaeroidal apertures
Structure, the particle diameter of apertures nylon micro-sphere is 0.5~300 μm, 0.01~150m of specific surface area2/ g, porosity
1%~95%, aperture is 0.01~10 μm.
Preferably, the complex microsphere be using apertures nylon micro-sphere as template, silica precursor containing
What hole and/or the surface in situ hydrolysis of hole nylon micro-sphere were obtained.
Preferably, the apertures nylon micro-sphere can for it is commercially available or by document " Mater.Des.2015,87,
656-662 " or " J.Appl.Polym.Sci.1994,54,1363-1369 " or Publication No. " CN
Reaction method in 102140246 A " Chinese invention patent is prepared；
Further, it is heavy that the method prepared by reacting includes mechanical crushing method, dissolving spray-on process, chemistry
Shallow lake method, emulsion polymerization, suspension polymerisation, seeding polymerization, dispersin polymerization, emulsifier-free emulsion polymerization, micro emulsion gather
Close or thin breast polymerization.
In the present invention, on apertures nylon micro-sphere after nonloaded silica, the hole knot of apertures nylon micro-sphere matrix
Structure is partly or entirely silica-filled, and the complex microsphere particle size of formation remains unchanged substantially, hole
Gap rate, pore volume, aperture are obviously reduced.
To reach above-mentioned second purpose, the present invention uses following technical proposals：
A kind of preparation method of nylon/SiO 2 composite microsphere, it is in apertures nylon micro-sphere dispersion liquid
Carry out what silica in situ hydrolysis was obtained, specifically include following steps：
1) by apertures nylon micro-sphere, catalyst and solvent mix after, ultrasound or 0.5~5h is stirred at room temperature, obtain
To apertures nylon micro-sphere dispersion liquid；
2) silica precursor is added into above-mentioned dispersion liquid, be stirred vigorously, 0~100 DEG C of 0.5~48h of reaction,
Suction filtration, washing, drying, obtain nylon/SiO 2 composite microsphere.
Preferably, step 1) in, the catalyst is urged selected from amines catalyst, acid catalyst or bases
One kind in agent；The amines catalyst is selected from ethylenediamine, hexamethylene diamine, tetramethylammonium, polyvinylamine, ammonia
One or more in water and its derivative；The acid catalyst is selected from hydrochloric acid, sulfuric acid, formic acid or ice vinegar
One or more in acid；The alkali catalyst is selected from NaOH solution or one kind of KOH solution or two
Kind；It is highly preferred that the catalyst is selected from amines catalyst, most preferably, the catalyst is selected from ammoniacal liquor.
Preferably, step 1) in, the solvent is selected from deionized water, methanol, ethanol, isopropanol, just
One or more in butanol, ethylene glycol, formic acid, glacial acetic acid or hydrochloric acid；It is highly preferred that the solvent choosing
From ethanol.
Preferably, step 2) in, the silica precursor is selected from tetraethyl orthosilicate or dimethylethoxy
One or both of base silane.
Preferably, step 2) in, the addition of silica precursor is apertures nylon micro-sphere weight
0.1%~8000%, addition speed is 1mL/h~1000mL/h.
Preferably, the addition of the catalyst is 0.1wt%~1000wt% of silica precursor；Institute
The addition for stating solvent is 0.001~5000 times of apertures nylon micro-sphere weight.
To reach above-mentioned 3rd purpose, the present invention uses following technical proposals：
The present invention also protect above-mentioned nylon/SiO 2 composite microsphere chromatographic isolation, drug delivery and sustained release,
The application of functional paint, the new material in 3D printing field.
Preferably, the present invention protection nylon/SiO 2 composite microsphere is in 3D printing-selective laser
Application in sintering technology.
It is highly preferred that the present invention protection particle diameter exists for 20~90 μm of nylon/SiO 2 composite microspheres
Application in 3D printing-Selective Laser Sintering.
Preferably, the present invention also protect the nylon/SiO 2 composite microsphere Aero-Space, automobile,
The application in the fields such as medicine equipment, electronic instrument, machine die, the art work.
New approaches are used in the preparation method of nylon of the present invention/nano silicon complex microsphere, by titanium dioxide
Silicon is dispersed in nylon micro-sphere, has both been solved a large amount of silica and has been asked nylon matrix is dispersed
Topic, can solve Buddhist nun by the introducing of hydrophobic silica, the raising collaboration of polyamide skeleton structure crystalline degree again
Imperial material water absorption rate problem；The heap density, heat endurance, crystallization of nylon composite granule are effectively improved simultaneously
Performance and mechanical strength.
Beneficial effects of the present invention are as follows：
The present invention uses new thinking, and two are grown in nylon micro-sphere stephanoporate framework situ with sol-gel process
Silica, prepares novel nylon/silica composite granules, and preparation method is simply easily implemented, both solved
A large amount of silica can pass through nanometer silicon dioxide particle nylon matrix is dispersed the problem of again
Introduce, the raising collaboration of polyamide skeleton structure crystalline degree solves the problems, such as nylon material water absorption rate；Effectively simultaneously
Improve heap density, heat endurance, crystal property and the mechanical strength of nylon composite granule.The composite powder
The characteristics of body has heap density height, low porosity, good fluidity, can as chromatographic isolation, drug delivery and
Sustained release, the new material application of field of functional coatings, are 20~90 μm by further preferable particle size
Complex microsphere powder, the complex microsphere powder can be as the consumption in 3D printing-Selective Laser Sintering
Material.So as to widen SLS technologies Aero-Space, automobile, medicine equipment, electronic instrument, machine die,
The application of the more areas such as the art work, personalized customization.
Brief description of the drawings
The embodiment to the present invention is described in further detail below in conjunction with the accompanying drawings.
Fig. 1 shows the scanning electron microscopic picture for the microballoon of apertures nylon 6 that the present invention is used.
Fig. 2 shows the scanning electron microscopic picture for the microballoon of apertures nylon 12 that the present invention is used.
Fig. 3 shows the scanning electron microscopic picture for the SiO 2 composite microsphere of nylon 6/ that embodiment 1 is prepared.
Fig. 4 shows the scanning electron microscope (SEM) photograph for the SiO 2 composite microsphere of nylon 12/ that embodiment 2 is prepared
Piece.
Fig. 5 shows the scanning electron microscopic picture for the SiO 2 composite microsphere of nylon 6/ that embodiment 3 is prepared.
Fig. 6 shows the scanning electron microscopic picture for the SiO 2 composite microsphere of nylon 6/ that embodiment 4 is prepared.
Fig. 7 shows the scanning electron microscopic picture for the SiO 2 composite microsphere of nylon 6/ that embodiment 5 is prepared.
Fig. 8 shows the scanning electron microscopic picture for the SiO 2 composite microsphere of nylon 6/ that embodiment 6 is prepared.
Embodiment
In order to illustrate more clearly of the present invention, the present invention is done into one with reference to preferred embodiments and drawings
The explanation of step.Similar part is indicated with identical reference in accompanying drawing.Those skilled in the art
It should be appreciated that following specifically described content is illustrative and be not restrictive, it should not be limited with this
Protection scope of the present invention.
The apertures nylon micro-sphere selected in the embodiment of the present application is prepared by dissolving-intermediate processing, specific as follows：
The preparation method of the microballoon of apertures nylon 6 is：
Dissolving-precipitation method prepare the microballoon of apertures nylon 6：By the pellet of 40g nylon 6,240ml formic acid, plus
Enter to be warming up to 80 DEG C in reactor, stirring 2h makes material fully dissolve, then adding 400ml concentration is
The ethanol solution of 10%g/ml polyvinylpyrrolidones (PVP-K30), stands after being stirred vigorously, and separates out
Powder.Suction filtration, ethanol washing, vacuum drying obtains polyamide porous microsphere；The nylon 6 of gained apertures
The scanning electron microscopic picture of microballoon is as shown in Figure 1；The average grain diameter of the microballoon of gained nylon 6 is 60 μm, compares table
Area 23m2/ g, porosity 77%, aperture is 0.1~2 μm, heap density 0.2g/mL.
The preparation method of the microballoon of apertures nylon 12 is：
Dissolving-precipitation method prepare the microballoon of apertures nylon 12：By the pellet of 40g nylon 12,240ml acetic acid,
Add and 100 DEG C are warming up in reactor, stirring 2h makes material fully dissolve, and then adds 400ml concentration
For 20%g/ml polyvinylpyrrolidones (PVP-K30) ethanol solution, stood after being stirred vigorously, analysis
Go out powder.Suction filtration, ethanol washing, vacuum drying obtains polyamide porous microsphere；The Buddhist nun of gained apertures
The scanning electron microscopic picture of imperial 12 microballoons is as shown in Figure 2；The microspherulite diameter of gained nylon 12 is 60 μm, compares table
Area 1.1m2/ g, porosity 62%, aperture is 0.1~4 μm, heap density 0.36g/mL.
Likewise, other apertures nylon 11 microballoons, nylon 1212 microballoon, nylon in the embodiment of the present invention
612 microballoons, NYLON610 microballoon or nylon 1010 microballoon are also to use above-mentioned similar dissolving-precipitation method
Prepare.The properties such as particle diameter, specific surface area, the porosity aperture of gained apertures nylon micro-sphere are with preparation
Method and preparation condition are different and are varied from.
Embodiment 1
Take the ammoniacal liquor, 10mL deionized waters that the microballoon of 0.5g apertures nylon 6,3mL concentration are 25% together
In the three-necked flask for adding 150mL, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 3mL
Tetraethyl orthosilicate is dissolved in 30mL ethanol to be added in above-mentioned dispersion liquid by 5mL/h rate of addition, 30 DEG C
Quick stirring reaction 10h；Resulting solution filtering, washing, dry, obtain the Buddhist nun of good dispersion after reacting
Dragon/SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 3；The particle diameter of complex microsphere is 40~60 μm,
Surface only has least a portion of micropore and existed, and nano silicon particle diameter is 200~300nm in complex microsphere,
And be uniformly dispersed in the microballoon of porous nylon 6.The specific surface area of complex microsphere is 11m2/ g, porosity
30%.The content of nano silicon is 55wt% in gained complex microsphere.
Embodiment 2
Ammoniacal liquor, 5mL ethanol that the microballoon of 0.5g apertures nylon 12,1mL concentration are 25% is taken to add together
In 150mL three-necked flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By the positive silicic acid of 1mL
Ethyl ester is dissolved in 10mL ethanol to be added in above-mentioned dispersion liquid by 5mL/h rate of addition, and 30 DEG C are quickly stirred
Mix reaction 10h；Resulting solution filtering, washing, dry, obtain the nylon 12/ of good dispersion after reacting
SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 4；The particle diameter of complex microsphere is 60 μm, table
Face only has very least a portion of micropore and existed, and nano silicon particle diameter is 200~300nm in complex microsphere,
And be uniformly dispersed in the microballoon of porous nylon 12.Complex microsphere specific surface area is 5m2/ g, porosity 20%.
The content of nano silicon is 40wt% in gained complex microsphere.
Embodiment 3
Take the ammoniacal liquor, 18mL deionized waters that the microballoon of 0.5g apertures nylon 6,5mL concentration are 25% together
In the three-necked flask for adding 150mL, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 6mL
Tetraethyl orthosilicate is dissolved in 30mL ethanol to be added in above-mentioned dispersion liquid by 5mL/h rate of addition, 30 DEG C
Quick stirring reaction 10h；Resulting solution filtering, washing, dry, obtain the Buddhist nun of good dispersion after reacting
Dragon/SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 5；Complex microsphere particle diameter is 60 μm, surface
Only very least a portion of micropore is present, and nano silicon particle diameter is 200~300nm in complex microsphere,
Even is dispersed in the microballoon of porous nylon 6.Complex microsphere specific surface area 2m2/ g, porosity 30%.Gained
The content of nano silicon is 65wt% in complex microsphere on complex microsphere.
Embodiment 4
Ammoniacal liquor, 18mL ethanol that the microballoon of 0.5g apertures nylon 6,5mL concentration are 25% is taken to add together
In 150mL three-necked flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 7mL dimethyl
Ethoxysilane is dissolved in 30mL ethanol to be added in above-mentioned dispersion liquid by 5mL/h rate of addition, 80 DEG C
Quick stirring reaction 10h；Resulting solution filtering, washing, dry, obtain the Buddhist nun of good dispersion after reacting
Dragon/SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 6；Complex microsphere particle diameter is 60 μm, surface
Only very least a portion of micropore is present, and silica is dispersed in the microballoon of porous nylon 6 in micron order non-individual body
In.The specific surface area of microballoon is 1.5m2/ g, porosity 28%.Nano silicon in gained complex microsphere
Content be 70wt%.
Embodiment 5
Take the hydrochloric acid, 18mL deionized waters that the microballoon of 0.5g apertures nylon 6,5mL concentration are 17% together
In the three-necked flask for adding 150mL, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 7mL
Tetraethyl orthosilicate is dissolved in 30mL ethanol to be added in above-mentioned dispersion liquid by 5mL/h rate of addition, 30 DEG C
Quick stirring reaction 10h；Resulting solution filtering, washing, dry, obtain the Buddhist nun of good dispersion after reacting
Dragon/SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 7；Complex microsphere particle diameter is 60 μm, surface
Only very least a portion of micropore is present, and nano silicon particle diameter is 200~300nm in complex microsphere,
Even is dispersed in the microballoon of porous nylon 6.Complex microsphere specific surface area 4m2/ g, porosity 28%.Gained
The content of nano silicon is 72wt% in complex microsphere.
Embodiment 6
Take the hydrochloric acid, 18mL deionized waters that the microballoon of 0.5g apertures nylon 6,5mL concentration are 17% together
In the three-necked flask for adding 150mL, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 0.5mL
Tetraethyl orthosilicate is dissolved in 30mL ethanol to be added in above-mentioned dispersion liquid by 20mL/h rate of addition, 30 DEG C
Quick stirring reaction 10h；Resulting solution filtering, washing, dry, obtain the Buddhist nun of good dispersion after reacting
Dragon/SiO 2 composite microsphere.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 8；Complex microsphere particle diameter is 60 μm, surface
With the presence of still there is nano silicon particle diameter in many micropores, complex microsphere to be 200~300nm, uniformly
It is dispersed in the microballoon of porous nylon 6.Complex microsphere specific surface area 14m2/ g, porosity 28%.Gained is answered
The content for closing nano silicon in microballoon is 5wt%.
Embodiment 7-10
Repeat embodiment 3, differ only in, reaction temperature be changed to respectively from 30 DEG C 0 DEG C, 50 DEG C, 60 DEG C,
100 DEG C, remaining condition is constant, the nylon/SiO 2 composite microsphere prepared.
Embodiment 11-16
Embodiment 3 is repeated, is differed only in, it is micro- to make the microballoon of apertures nylon 6 into apertures nylon66 fiber respectively
Ball, nylon 11 microballoon, nylon 1010 microballoon, nylon 1212 microballoon, nylon 612 microballoon, NYLON610
Microballoon, remaining condition is constant, in the performance be the same as Example 3 for preparing nylon/SiO 2 composite microsphere
It is close.
Embodiment 17-21
Repeat embodiment 3, differ only in, by the amount of tetraethyl orthosilicate be changed to respectively 0.05mL, 0.5mL,
10mL, 20mL, 40mL, remaining condition are constant, the nylon/SiO 2 composite microsphere prepared
It is close in performance be the same as Example 3.
Embodiment 22-25
Repeat embodiment 3, differ only in, the reaction time is changed to from 10h respectively 0.5h, 15h, 36h,
48h, remaining condition is constant, the performance be the same as Example 3 of the nylon/SiO 2 composite microsphere prepared
In it is close.
Embodiment 26-28
Repeat embodiment 3, differ only in the microballoon of apertures nylon 6 ultrasound or stirring processing time for 1h,
2h, 5h, remaining condition are constant, the performance be the same as Example of the nylon/SiO 2 composite microsphere prepared
It is close in 3.
Embodiment 29-31
Embodiment 3 is repeated, is differed only in, amount of alcohol is changed to 10mL, 50mL, 100mL respectively from 30mL
Remaining condition is constant, close in the performance be the same as Example 3 of the nylon/SiO 2 composite microsphere prepared.
Embodiment 32-35
Repeat embodiment 3, differ only in, the amount of deionized water is changed to from 10mL respectively 0.5mL,
100mL, 1000mL, 2500mL, remaining condition are constant, and the nylon/silica prepared is combined
It is close in the performance be the same as Example 3 of microballoon.
Embodiment 36-45
Repeat embodiment 3, differ only in, catalyst be respectively selected from ethylenediamine, hexamethylene diamine, tetramethylammonium,
One kind in polyvinylamine, hydrochloric acid, sulfuric acid, formic acid, glacial acetic acid, NaOH solution, KOH solution,
Remaining condition is constant, close in the performance be the same as Example 3 of the nylon/SiO 2 composite microsphere prepared.
Embodiment 46-48
Embodiment 3 is repeated, is differed only in, solvent is respectively selected from formic acid, glacial acetic acid or hydrochloric acid, remaining
Part is constant, close in the performance be the same as Example 3 of the nylon/SiO 2 composite microsphere prepared.
Embodiment 49
By the SiO 2 composite microsphere 50g of 2 gained nylon of embodiment 12/, antioxidant 2,2'- methylene are added
Double-(4- methyl-6-tert-butylphenols) 0.1g, stirring mixes 1h in vertical stirrer, after material is mixed evenly
200 mesh sieves are crossed, 3D printing-Selective Laser Sintering is can be directly used for.
Embodiment 50
By the SiO 2 composite microsphere 50g of 3 gained nylon of embodiment 6/, antioxidant 2,2'- di-2-ethylhexylphosphine oxides are added
- (4- methyl-6-tert-butylphenols) 0.1g, stirring mixes 1h, mistake after material is mixed evenly in vertical stirrer
200 mesh sieves, can be directly used for 3D printing-Selective Laser Sintering.
Embodiment 51
By the SiO 2 composite microsphere 50g of 5 gained nylon of embodiment 6/, soaked with 90~95% ethanol, no
Disconnected stirring fills post after removing bubble, with the ethanol elution of 3-4 times of volume, is washed till eluent transparent and be evaporated
Afterwards without residue.Eluted, be finally eluted to distilled water with the 2-2.5 times of volume 5%NaOH aqueous solution successively again
PH is neutral, for stationary phase in column chromatography, protein isolate matter, flavone compound.
Embodiment 52
Embodiment 51 is repeated, difference is, change the SiO 2 composite microsphere of nylon 6/ into embodiment 2 gained
The SiO 2 composite microsphere of nylon 12/, remaining condition is constant, for stationary phase in column chromatography, separates egg
White matter, flavone compound.
Embodiment 53
Nylon/SiO 2 composite microsphere obtained by embodiment 1-48 is respectively directly used as the powder of electrostatic spraying
Coating.
Embodiment 54
Nylon/SiO 2 composite microsphere is respectively further by physically or chemically inhaling obtained by embodiment 1-48
Attached carrying medicament molecule, as medicament slow release research.
The performance test of gained nylon/SiO 2 composite microsphere：
The microballoon of apertures nylon 6, the microballoon of apertures nylon 12 and the embodiment used respectively in testing example
The properties of the nylon/SiO 2 composite microsphere obtained in 1-6, as a result as shown in table 1.
The properties of 1 nylon of table/SiO 2 composite microsphere
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and
It is not the restriction to embodiments of the present invention, for those of ordinary skill in the field,
It can also be made other changes in different forms on the basis of described above, here can not be to all
Embodiment be exhaustive, it is every to belong to the obvious change that technical scheme is extended out
Change or change the row still in protection scope of the present invention.
Claims (10)
1. a kind of nylon/SiO 2 composite microsphere, it is characterised in that the complex microsphere is spherical or near
Spheric granules, particle diameter is 0.5~300 μm；The complex microsphere is made up of apertures nylon micro-sphere and silica；
Silica is dispersed in hole and/or the surface of apertures nylon micro-sphere in nano particle, and/or in micron
Level continuous state is filled in apertures nylon micro-sphere hole；In the complex microsphere, apertures nylon micro-spheres contains
Measure as 10~99.9wt%, dioxide-containing silica is 0.1~90wt%.
2. nylon/SiO 2 composite microsphere according to claim 1, it is characterised in that described to contain
Hole nylon micro-sphere is selected from the microballoon of nylon 6, nylon66 fiber microballoon, the microballoon of nylon 12, nylon 11 microballoon, Buddhist nun
Imperial 1212 microballoons, nylon 612 microballoon, NYLON610 microballoon or one kind or several in nylon 1010 microballoon
Kind.
3. nylon/SiO 2 composite microsphere according to claim 1, it is characterised in that described to receive
The particle diameter of rice silica dioxide granule is 10~500nm.
4. nylon/SiO 2 composite microsphere according to claim 1, it is characterised in that in load
Before silica, the apertures nylon micro-sphere is spherical or subsphaeroidal particle, and 0.5~300 μm of particle diameter compares table
0.01~150m of area2/ g, porosity 1%~95%, aperture is 0.01~10 μm.
5. the preparation method of nylon/SiO 2 composite microsphere as described in claim any one of 1-4, its
It is characterised by, comprises the following steps：
1) by apertures nylon micro-sphere, catalyst and solvent mix after, ultrasound or 0.5~5h is stirred at room temperature, obtain
To apertures nylon micro-sphere dispersion liquid；
2) silica precursor is added into above-mentioned dispersion liquid, stirred, 0~100 DEG C of 0.5~48h of reaction,
Suction filtration, washing, drying, obtain nylon/SiO 2 composite microsphere.
6. preparation method according to claim 5, it is characterised in that step 1) in, it is described to urge
The one kind of agent in amines catalyst, acid catalyst or alkali catalyst；The amines catalyst
One or more in ethylenediamine, hexamethylene diamine, tetramethylammonium, polyvinylamine, ammoniacal liquor and its derivative；
One or more of the acid catalyst in hydrochloric acid, sulfuric acid, formic acid or glacial acetic acid；The bases is urged
Agent is selected from the one or two of NaOH solution or KOH solution；Preferably, the catalyst is selected from amine
Class catalyst, it is highly preferred that the catalyst is selected from ammoniacal liquor；
The solvent be selected from deionized water, methanol, ethanol, isopropanol, n-butanol, ethylene glycol, formic acid,
One or more in glacial acetic acid or hydrochloric acid；Preferably, the solvent is selected from ethanol；
Step 2) in, the silica precursor is in tetraethyl orthosilicate or dimethylethoxysilane
One or two.
7. preparation method according to claim 5, it is characterised in that step 2) in, silica
The addition of presoma is the 0.1%~8000% of apertures nylon micro-sphere weight, and addition speed is 1mL/h
~1000mL/h.
8. preparation method according to claim 5, it is characterised in that the addition of the catalyst
For 0.1wt%~1000wt% of silica precursor；The addition of the solvent is apertures nylon micro-sphere weight
0.001~5000 times of amount.
9. nylon/SiO 2 composite microsphere as claimed in claim 1 chromatographic isolation, drug delivery and
Sustained release, functional paint, the application of the new material in 3D printing field.
10. application according to claim 9, it is characterised in that particle diameter for 20~90 μm nylon/
SiO 2 composite microsphere as the consumptive material in 3D printing-Selective Laser Sintering application.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409921A (en) * | 2017-10-23 | 2018-08-17 | 同济大学 | A kind of 3D printing ultraviolet light solidification high hardness material and preparation method thereof |
| CN110639440A (en) * | 2019-09-24 | 2020-01-03 | 中国海洋大学 | Preparation method of carbon/silicon dioxide composite microspheres |
| US20210070993A1 (en) * | 2019-09-09 | 2021-03-11 | Xerox Corporation | Thermoplastic Polymer Particles and Methods of Production and Uses Thereof |
| CN112500699A (en) * | 2020-11-19 | 2021-03-16 | 裕克施乐塑料制品（太仓）有限公司 | Composite heat conduction material and preparation method thereof |
| CN115572479A (en) * | 2022-11-03 | 2023-01-06 | 贵州省材料产业技术研究院 | Inorganic nanoparticle reinforced polyamide 12 powder and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108126A (en) * | 2009-12-24 | 2011-06-29 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of nylon-6 conductive microsphere |
| CN102558846A (en) * | 2010-12-28 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Nylon/titanium dioxide nanometer composite microsphere and preparation method thereof |
| CN105440663A (en) * | 2014-08-07 | 2016-03-30 | 中国科学院理化技术研究所 | Preparation method of nylon micro powder for selective laser sintering |
-
2016
- 2016-03-25 CN CN201610178084.7A patent/CN107254163B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108126A (en) * | 2009-12-24 | 2011-06-29 | 上海杰事杰新材料(集团)股份有限公司 | Preparation method of nylon-6 conductive microsphere |
| CN102558846A (en) * | 2010-12-28 | 2012-07-11 | 合肥杰事杰新材料股份有限公司 | Nylon/titanium dioxide nanometer composite microsphere and preparation method thereof |
| CN105440663A (en) * | 2014-08-07 | 2016-03-30 | 中国科学院理化技术研究所 | Preparation method of nylon micro powder for selective laser sintering |
Non-Patent Citations (1)
| Title |
|---|
| 《电气电子绝缘技术手册》编辑委员会: "《电气电子绝缘技术手册》", 31 January 2008, 机械工业出版社 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108409921A (en) * | 2017-10-23 | 2018-08-17 | 同济大学 | A kind of 3D printing ultraviolet light solidification high hardness material and preparation method thereof |
| CN108409921B (en) * | 2017-10-23 | 2020-11-27 | 同济大学 | Ultraviolet-curing high-hardness material for 3D printing and preparation method thereof |
| US20210070993A1 (en) * | 2019-09-09 | 2021-03-11 | Xerox Corporation | Thermoplastic Polymer Particles and Methods of Production and Uses Thereof |
| CN110639440A (en) * | 2019-09-24 | 2020-01-03 | 中国海洋大学 | Preparation method of carbon/silicon dioxide composite microspheres |
| CN112500699A (en) * | 2020-11-19 | 2021-03-16 | 裕克施乐塑料制品（太仓）有限公司 | Composite heat conduction material and preparation method thereof |
| CN115572479A (en) * | 2022-11-03 | 2023-01-06 | 贵州省材料产业技术研究院 | Inorganic nanoparticle reinforced polyamide 12 powder and preparation method thereof |
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