CN107254163B - 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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Abstract
The present invention discloses a kind of nylon/SiO 2 composite microsphere and its preparation method and application.The spherical and/or subsphaeroidal particle that the complex microsphere is 0.5~300 μm of partial size, is made 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 to hydrolyze to obtain by carrying out silica in situ in apertures nylon micro-sphere dispersion liquid.The water absorption rate of apertures nylon complex microsphere can be effectively reduced in the addition of silica, improve thermal stability, crystal property and mechanical strength.The complex microsphere can be used as SLS Selective Laser Sintering consumptive material, widen SLS technology in the application in the fields such as aviation, automobile, medical instrument, electronic instrument, machine die, the art work.
Description
Technical field
The present invention relates to technical field of polymer materials.More particularly, to a kind of nylon/SiO 2 composite microsphere and
Preparation method and application.
Background technique
Nylon is the crystalline polymer as made from amino acid or corresponding lactams.As one of five large-engineering plastics,
Because of melting temperature with higher and glass transition temperature, good mechanical property, wearability, impact flexibility and it is excellent from
Lubricity and formability, and it is widely used in the fields such as automobile, machinery, space flight and aviation, military affairs, medical treatment, electronics.But it is many
Nylon products are because of fragile under low temperatureization, the disadvantages of water absorption rate is big, poor dimensional stability, greatly limit its application.It is industrial normal
Nylon material is modified using inorganic particle to improve above-mentioned unfavorable factor.The nylon composite wood enhanced by inorganic nanometer powder
The preparation of material and performance study are by wide coverage.The preparation method of conventional composite materials will mainly in a manner of melt blending
Inorganic particle introduces nylon matrix.Since nano inoganic particle surface free energy height is easy to reunite, it will lead to powder and be difficult to poly-
It is evenly dispersed in conjunction object matrix, reduce the mechanical property of composite material.Recently, nylon 6/nanometer is prepared using in situ synthesis
Extensive concern of the composite material by domestic and foreign scholars.One is also mentioned in the Chinese invention patent of Publication No. CN101570590A
Kind in-situ polymerization mode prepares nylon66 fiber/SiO2The method of composite material.Minami et al. is with sol-gel method in nylon-6 matrix
Growth in situ SiO on bottom2Film (J.Sol-Gel Sci.Technol.1996,6,107-111.).Publication No.
The Chinese invention patent of CN101348609A is prepared for nylon 6/SiO with similar mode2Sheet material.The study found that passing through nanometer
Water absorption rate can be significantly reduced in silica modified obtained nylon composite materials, and nano silica crystallizes power in nylon 6
Play an important role in, the relatively pure nylon 6 of composite material have better thermal stability, stretch modulus, yield strength,
Hardening modulus and tensile strength are all significantly improved.But the composite material that above-mentioned in-situ polymerization generates is mainly nylon film
Material or sheet material, Nano-meter SiO_22It is mainly distributed on nylon matrix surface, load capacity is low.With high degree of dispersion, high load amount
Nylon/SiO2The preparation of complex microsphere does not have been reported that also so far.
Nylon micro mist with nylon 12 and nylon 6 for representative is that current 3D printing-selective laser sintering (SLS) technology makes
With widest raw material.But simple nylon powder is applied to 3D printing and has certain defect.Such as: 12 preparation cost of nylon
Height, expensive, glass transition temperature is low；6 water absorption rate of nylon is high, poor dimensional stability etc..This strongly limits SLS technologies
Using and development.It is mentioned in the Chinese invention patent of Publication No. CN104910614A nylon 12, micro inorganic fillers are white
Carbon black, coupling agent, antioxidant and other auxiliary agents, which first dissolve, to be spray-dried to obtain nylon composite powder again.Publication No.
The Chinese invention patent of CN102337021A inhales 12 resin of nylon, glass microballoon, coupling agent, flow promortor, antioxidant and light
It receives agent progress mechanical mixture and obtains composite powder, modified material effectively prevents the warpage of selective laser sintering and moulding part
Problem on deformation.It but is all that filler and nylon are passed through mechanical mixture, this method by the method blended by physics in above-mentioned patent
Matrix and filler is set to be difficult to be uniformly mixed, material mechanical performance promotion is limited, especially for 6 dusty material of nylon, water absorption rate
High problem still is difficult to overcome.
Summary of the invention
The first purpose of this invention is to provide a kind of nylon/SiO 2 composite microsphere, in the complex microsphere, dioxy
The uniform and stable hole for being dispersed in apertures nylon micro-sphere of SiClx and/or surface, and the complex microsphere has excellent heat steady
Qualitative, physical mechanical property, 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, and use is molten
Glue-gel method in-situ polymerization silica in the polyamide skeleton of apertures, the preparation method is simple easily controllable, has both solved a large amount of
The silica problem evenly dispersed in apertures nylon micro-sphere matrix, and can introducing by hydrophobic silica, polyamide skeleton
The raising collaboration of structure crystalline degree solves the problems, such as nylon material water absorption rate；Simultaneously effectively improve nylon composite granule heap density,
Thermal stability, crystal property and mechanical strength.
Third object of the present invention is to provide a kind of application of nylon/nano silica complex microsphere.
In order to achieve the above first purpose, the present invention adopts the following technical solutions:
A kind of nylon/SiO 2 composite microsphere, the complex microsphere are spherical or subsphaeroidal particle, partial size is 0.5~
300μm；The complex microsphere is made of apertures nylon micro-sphere and silica；Silica is dispersed in nano particle to be contained
The hole of hole nylon micro-sphere and/or surface, and/or be filled in apertures nylon micro-sphere hole in micron order continuous state；It is described multiple
It closes in microballoon, the content of apertures nylon micro-sphere is 10~99.9wt%, and dioxide-containing silica is 0.1~90wt%.
Preferably, it is micro- to can be selected from 6 microballoon of nylon, nylon66 fiber microballoon, 12 microballoon of nylon, nylon 11 for the apertures nylon micro-sphere
One or more of ball, nylon 1212 microballoon, nylon 612 microballoon, nylon 610 microballoon or nylon 1010 microballoon.
Preferably, the partial size of the nanometer silicon dioxide particle is 10~500nm.
Preferably, before nonloaded silica, apertures nylon micro-sphere is apparent spherical or subsphaeroidal porous structure, apertures
The partial size of nylon micro-sphere is 0.5~300 μm, 0.01~150m of specific surface area2/ g, porosity 1%~95%, aperture be 0.01~
10μm。
Preferably, the complex microsphere is using apertures nylon micro-sphere as template, and silica precursor is micro- in apertures nylon
What the hole and/or surface in situ of ball hydrolyzed.
Preferably, the apertures nylon micro-sphere can be commercially available or by document " Mater.Des.2015,87,656-662 "
" J.Appl.Polym.Sci.1994,54,1363-1369 " or the Chinese invention of Publication No. " 102140246 A of CN " it is special
Reaction method in benefit is prepared；
It further, include mechanical crushing method, dissolution spray-on process, chemical precipitation method, lotion by the method for reaction preparation
Polymerization, suspension polymerisation, seeding polymerization, dispersin polymerization, emulsifier-free emulsion polymerization, microemulsion or thin cream polymerization.
In the present invention, on apertures nylon micro-sphere after nonloaded silica, the pore structure part of apertures nylon micro-sphere matrix or
All silica-filled, the complex microsphere particle size of formation remains unchanged substantially, and porosity, Kong Rong, aperture obviously subtract
It is small.
To reach above-mentioned second purpose, the present invention is adopted the following technical solutions:
A kind of preparation method of nylon/SiO 2 composite microsphere is to carry out two in apertures nylon micro-sphere dispersion liquid
Silica in-situ hydrolysis obtains, and specifically 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 apertures Buddhist nun
Imperial microballoon dispersion liquid；
2) silica precursor is added in Xiang Shangshu dispersion liquid, is vigorously stirred, 0~100 DEG C of 0.5~48h of reaction takes out
Filter, washing, drying, obtain nylon/SiO 2 composite microsphere.
Preferably, in step 1), the catalyst in amines catalyst, acid catalyst or alkali catalyst one
Kind；The amines catalyst is selected from one of ethylenediamine, hexamethylene diamine, tetramethylammonium, polyvinylamine, ammonium hydroxide and its derivative or several
Kind；The acid catalyst is selected from one or more of hydrochloric acid, sulfuric acid, formic acid or glacial acetic acid；The alkali catalyst is selected from
The one or two of NaOH solution or KOH solution；It is highly preferred that the catalyst is selected from amines catalyst, it is most preferably, described
Catalyst is selected from ammonium hydroxide.
Preferably, in step 1), the solvent be selected from deionized water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol,
One or more of formic acid, glacial acetic acid or hydrochloric acid；It is highly preferred that the solvent is selected from ethyl alcohol.
Preferably, in step 2), the silica precursor is in ethyl orthosilicate or dimethylethoxysilane
One or two.
Preferably, in step 2), the additional amount of silica precursor be apertures nylon micro-sphere weight 0.1%~
8000%, addition speed is 1mL/h~1000mL/h.
Preferably, the additional amount of the catalyst is 0.1wt%~1000wt% of silica precursor；The solvent
Additional amount be 0.001~5000 times of apertures nylon micro-sphere weight.
To reach above-mentioned third purpose, the present invention is adopted the following technical solutions:
The present invention also protects above-mentioned nylon/SiO 2 composite microsphere to apply in chromatographic isolation, drug delivery and sustained release, function
Expect, the application of the new material in 3D printing field.
Preferably, the present invention protects the nylon/SiO 2 composite microsphere in 3D printing-Selective Laser Sintering
In application.
It is highly preferred that it is 20~90 μm of nylon/SiO 2 composite microspheres in 3D printing-choosing that the present invention, which protects the partial size,
Application in selecting property laser sintering technology.
Preferably, the present invention also protect the nylon/SiO 2 composite microsphere aerospace, automobile, medical instrument,
The application in the fields such as electronic instrument, machine die, the art work.
New approaches are used in nylon of the present invention/nano silica complex microsphere preparation method, silica is uniform
It is dispersed in nylon micro-sphere, has not only solved the problems, such as that a large amount of silica are evenly dispersed in nylon matrix, but also hydrophobic two can be passed through
The introducing of silica, the raising collaboration of polyamide skeleton structure crystalline degree solve the problems, such as nylon material water absorption rate；It effectively improves simultaneously
Heap density, thermal stability, crystal property and the mechanical strength of nylon composite granule.
Beneficial effects of the present invention are as follows:
The present invention use new thinking, with sol-gel method in nylon micro-sphere stephanoporate framework growth in situ silica,
Novel nylon/silica composite granules are prepared, preparation method is simply easy to implement, and has both solved a large amount of silica in nylon
The evenly dispersed problem of matrix, and can be assisted by the introducing of nanometer silicon dioxide particle, the raising of polyamide skeleton structure crystalline degree
It is same to solve the problems, such as nylon material water absorption rate；Effectively improve simultaneously the heap density of nylon composite granule, thermal stability, crystal property with
And mechanical strength.The composite granule has the characteristics that heap density is high, porosity is low, good fluidity, can be used as chromatographic isolation, drug
The new material application of transmission and sustained release, field of functional coatings is 20~90 μm compound micro- by further preferable particle size
Ball powder, the complex microsphere powder can be used as the consumptive material in 3D printing-Selective Laser Sintering.To widen SLS technology
Application in more areas such as aerospace, automobile, medical instrument, electronic instrument, machine die, the art work, personalized customization.
Detailed description of the invention
Specific embodiments of the present invention will be described in further detail with reference to the accompanying drawing.
Fig. 1 shows the scanning electron microscopic picture for 6 microballoon of apertures nylon that the present invention uses.
Fig. 2 shows the scanning electron microscopic picture for 12 microballoon of apertures nylon that the present invention uses.
Fig. 3 shows the scanning electron microscopic picture for 6/ SiO 2 composite microsphere of nylon that embodiment 1 is prepared.
Fig. 4 shows the scanning electron microscopic picture for 12/ SiO 2 composite microsphere of nylon that embodiment 2 is prepared.
Fig. 5 shows the scanning electron microscopic picture for 6/ SiO 2 composite microsphere of nylon that embodiment 3 is prepared.
Fig. 6 shows the scanning electron microscopic picture for 6/ SiO 2 composite microsphere of nylon that embodiment 4 is prepared.
Fig. 7 shows the scanning electron microscopic picture for 6/ SiO 2 composite microsphere of nylon that embodiment 5 is prepared.
Fig. 8 shows the scanning electron microscopic picture for 6/ SiO 2 composite microsphere of nylon that embodiment 6 is prepared.
Specific embodiment
In order to illustrate more clearly of the present invention, the present invention is done further below with reference to preferred embodiments and drawings
It is bright.Similar component is indicated in attached drawing with identical appended drawing reference.It will be appreciated by those skilled in the art that institute is specific below
The content of description is illustrative and be not restrictive, and should not be limited the scope of the invention with this.
The apertures nylon micro-sphere selected in the embodiment of the present application is dissolution-intermediate processing preparation, specific as follows:
6 microballoon of apertures nylon the preparation method comprises the following steps:
Dissolution-precipitation method prepare 6 microballoon of apertures nylon: by 6 pellet of 40g nylon, 240ml formic acid, being added in reaction kettle and rise
For temperature to 80 DEG C, stirring 2h dissolves material sufficiently, and it is 10%g/ml polyvinylpyrrolidone (PVP- that 400ml concentration, which is then added,
K30 ethanol solution) is stood after being vigorously stirred, and powder is precipitated.It filters, ethanol washing, it is porous to obtain polyamide for vacuum drying
Microballoon；The scanning electron microscopic picture of 6 microballoon of nylon of gained apertures is as shown in Figure 1；The average grain diameter of 6 microballoon of gained nylon is 60 μ
M, specific surface area 23m2/ g, porosity 77%, aperture are 0.1~2 μm, heap density 0.2g/mL.
12 microballoon of apertures nylon the preparation method comprises the following steps:
Dissolution-precipitation method prepare 12 microballoon of apertures nylon: 12 pellet of 40g nylon, 240ml acetic acid are added in reaction kettle
100 DEG C are warming up to, stirring 2h dissolves material sufficiently, and it is 20%g/ml polyvinylpyrrolidone that 400ml concentration, which is then added,
(PVP-K30) ethanol solution is stood after being vigorously stirred, and powder is precipitated.It filters, ethanol washing, vacuum drying obtains polyamide
Porous microsphere；The scanning electron microscopic picture of 12 microballoon of nylon of gained apertures is as shown in Figure 2；12 microspherulite diameter of gained nylon is 60 μ
M, specific surface area 1.1m2/ g, porosity 62%, aperture are 0.1~4 μm, heap density 0.36g/mL.
Likewise, other apertures nylon 11 microballoons, nylon 1212 microballoon, nylon 612 microballoon, nylon in the embodiment of the present invention
610 microballoons or nylon 1010 microballoon are prepared using above-mentioned similar dissolution-precipitation method.Gained apertures nylon micro-sphere
The properties such as partial size, specific surface area, porosity aperture it is different with preparation method and preparation condition and be varied.
Embodiment 1
Take 6 microballoon of 0.5g apertures nylon, the ammonium hydroxide that 3mL concentration is 25%, 10mL deionized water are added the three of 150mL together
In mouth flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；3mL ethyl orthosilicate is dissolved in 30mL ethyl alcohol by 5mL/h
Rate of addition be added in above-mentioned dispersion liquid, 30 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, washed, is done
It is dry, obtain nylon/SiO 2 composite microsphere of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 3；The partial size of complex microsphere is 40~60 μm, and surface only has
Least a portion of micropore exists, and nano silica partial size is 200~300nm in complex microsphere, and is uniformly dispersed in porous Buddhist nun
In imperial 6 microballoons.The specific surface area of complex microsphere is 11m2/ g, porosity 30%.Nano silica in gained complex microsphere
Content is 55wt%.
Embodiment 2
Take 12 microballoon of 0.5g apertures nylon, three mouthfuls of 150mL burnings are added in the ammonium hydroxide that 1mL concentration is 25%, 5mL ethyl alcohol together
In bottle, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；1mL ethyl orthosilicate is dissolved in the drop in 10mL ethyl alcohol by 5mL/h
Acceleration is added in above-mentioned dispersion liquid, and 30 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, washed, it is dry, it obtains
To 12/ SiO 2 composite microsphere of nylon of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 4；The partial size of complex microsphere is 60 μm, and surface is only seldom
Partial micropore exists, and nano silica partial size is 200~300nm in complex microsphere, and is uniformly dispersed in porous nylon
In 12 microballoons.Complex microsphere specific surface area is 5m2/ g, porosity 20%.The content of nano silica in gained complex microsphere
For 40wt%.
Embodiment 3
Take 6 microballoon of 0.5g apertures nylon, the ammonium hydroxide that 5mL concentration is 25%, 18mL deionized water are added the three of 150mL together
In mouth flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；6mL ethyl orthosilicate is dissolved in 30mL ethyl alcohol by 5mL/h
Rate of addition be added in above-mentioned dispersion liquid, 30 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, washed, is done
It is dry, obtain nylon/SiO 2 composite microsphere of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 5；Complex microsphere partial size is 60 μm, and surface only has seldom portion
The micropore divided exists, and nano silica partial size is 200~300nm in complex microsphere, is uniformly dispersed in 6 microballoon of porous nylon
In.Complex microsphere specific surface area 2m2/ g, porosity 30%.Nano silica contains in complex microsphere on gained complex microsphere
Amount is 65wt%.
Embodiment 4
Take 6 microballoon of 0.5g apertures nylon, three mouthfuls of 150mL burnings are added in the ammonium hydroxide that 5mL concentration is 25%, 18mL ethyl alcohol together
In bottle, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 7mL dimethylethoxysilane be dissolved in 30mL ethyl alcohol by
The rate of addition of 5mL/h is added in above-mentioned dispersion liquid, and 80 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, is washed
It washs, it is dry, obtain nylon/SiO 2 composite microsphere of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 6；Complex microsphere partial size is 60 μm, and surface only has seldom portion
The micropore divided exists, and silica is dispersed in 6 microballoon of porous nylon in micron order non-individual body.The specific surface area of microballoon is
1.5m2/ g, porosity 28%.The content of nano silica is 70wt% in gained complex microsphere.
Embodiment 5
Take 6 microballoon of 0.5g apertures nylon, the hydrochloric acid that 5mL concentration is 17%, 18mL deionized water are added the three of 150mL together
In mouth flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；7mL ethyl orthosilicate is dissolved in 30mL ethyl alcohol by 5mL/h
Rate of addition be added in above-mentioned dispersion liquid, 30 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, washed, is done
It is dry, obtain nylon/SiO 2 composite microsphere of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 7；Complex microsphere partial size is 60 μm, and surface only has seldom portion
The micropore divided exists, and nano silica partial size is 200~300nm in complex microsphere, is uniformly dispersed in 6 microballoon of porous nylon
In.Complex microsphere specific surface area 4m2/ g, porosity 28%.The content of nano silica is 72wt% in gained complex microsphere.
Embodiment 6
Take 6 microballoon of 0.5g apertures nylon, the hydrochloric acid that 5mL concentration is 17%, 18mL deionized water are added the three of 150mL together
In mouth flask, ultrasonic 0.5h obtains apertures nylon micro-sphere dispersion liquid；By 0.5mL ethyl orthosilicate be dissolved in 30mL ethyl alcohol by
The rate of addition of 20mL/h is added in above-mentioned dispersion liquid, and 30 DEG C are quickly stirred to react 10h；Acquired solution after reaction is filtered, is washed
It washs, it is dry, obtain nylon/SiO 2 composite microsphere of good dispersion.
The scanning electron microscopic picture of gained complex microsphere is as shown in Figure 8；Complex microsphere partial size is 60 μm, and surface has still and has very much
Micropore exists, and nano silica partial size is 200~300nm in complex microsphere, is uniformly dispersed in 6 microballoon of porous nylon.
Complex microsphere specific surface area 14m2/ g, porosity 28%.The content of nano silica is 5wt% in gained complex microsphere.
Embodiment 7-10
Embodiment 3 is repeated, difference is only that, reaction temperature is changed to 0 DEG C, 50 DEG C, 60 DEG C, 100 DEG C from 30 DEG C respectively, remaining
Condition is constant, the nylon/SiO 2 composite microsphere being prepared.
Embodiment 11-16
Embodiment 3 is repeated, difference is only that, it is micro- that 6 microballoon of apertures nylon is changed to apertures nylon66 fiber microballoon, nylon 11 respectively
Ball, nylon 1010 microballoon, nylon 1212 microballoon, nylon 612 microballoon, nylon 610 microballoon, remaining condition is constant, and Buddhist nun is prepared
Dragon/SiO 2 composite microsphere performance is close in embodiment 3.
Embodiment 17-21
Repeat embodiment 3, difference is only that, by the amount of ethyl orthosilicate be changed to respectively 0.05mL, 0.5mL, 10mL,
20mL, 40mL, remaining condition is constant, and the nylon/SiO 2 composite microsphere performance being prepared is close in embodiment 3.
Embodiment 22-25
Embodiment 3 is repeated, difference is only that, the reaction time is changed to 0.5h, 15h, 36h, 48h from 10h respectively, remaining
Part is constant, and the nylon/SiO 2 composite microsphere performance being prepared is close in embodiment 3.
Embodiment 26-28
Repeating embodiment 3, difference is only that the processing time of apertures nylon 6 microballoon ultrasound or stirring is 1h, 2h, 5h,
Remaining condition is constant, and the nylon/SiO 2 composite microsphere performance being prepared is close in embodiment 3.
Embodiment 29-31
Embodiment 3 is repeated, difference is only that, amount of alcohol is changed to 10mL, 50mL, 100mL remaining condition from 30mL not respectively
Become, the nylon/SiO 2 composite microsphere performance being prepared is close in embodiment 3.
Embodiment 32-35
Repeat embodiment 3, difference is only that, the amount of deionized water is changed to from 10mL respectively 0.5mL, 100mL,
1000mL, 2500mL, remaining condition is constant, and the nylon/SiO 2 composite microsphere performance being prepared is the same as phase in embodiment 3
Closely.
Embodiment 36-45
Embodiment 3 is repeated, difference is only that, catalyst is respectively selected from ethylenediamine, hexamethylene diamine, tetramethylammonium, polyvinylamine, salt
One of acid, sulfuric acid, formic acid, glacial acetic acid, NaOH solution, KOH solution, remaining condition is constant, the nylon/dioxy being prepared
The performance of SiClx complex microsphere is close in embodiment 3.
Embodiment 46-48
Embodiment 3 is repeated, difference is only that, solvent is respectively selected from formic acid, glacial acetic acid or hydrochloric acid, remaining condition is constant, system
Standby obtained nylon/SiO 2 composite microsphere performance is close in embodiment 3.
Embodiment 49
By 2 gained nylon of embodiment, 12/ SiO 2 composite microsphere 50g, antioxidant 2,2'- di-2-ethylhexylphosphine oxide-(4- first is added
Base -6- tert-butyl phenol) 0.1g, the stirring and mixing 1h in vertical stirrer, 200 meshes excessively after material is mixed evenly can be direct
For 3D printing-Selective Laser Sintering.
Embodiment 50
By 3 gained nylon of embodiment, 6/ SiO 2 composite microsphere 50g, antioxidant 2,2'- di-2-ethylhexylphosphine oxide-(4- first is added
Base -6- tert-butyl phenol) 0.1g, the stirring and mixing 1h in vertical stirrer, 200 meshes excessively after material is mixed evenly can be direct
For 3D printing-Selective Laser Sintering.
Embodiment 51
5 gained nylon of embodiment, 6/ SiO 2 composite microsphere 50g is stirred continuously and is removed with the immersion of 90~95% ethyl alcohol
Fill column after removing bubble, with the ethanol elution of 3-4 times of volume, be washed till eluent it is transparent and after being evaporated without residue.2- is successively used again
2.5 times of volume 5%NaOH aqueous solution elutions, are finally eluted to pH neutrality with distilled water, for stationary phase in column chromatography, separate egg
White matter, flavone compound.
Embodiment 52
Embodiment 51 is repeated, difference is, changes 6/ SiO 2 composite microsphere of nylon into embodiment 2 resulting nylon
12/ SiO 2 composite microsphere, remaining condition is constant, for stationary phase in column chromatography, protein isolate matter, flavone compound.
Embodiment 53
Nylon/SiO 2 composite microsphere obtained by embodiment 1-48 is directly used as the powdery paints of electrostatic spraying respectively.
Embodiment 54
Nylon/SiO 2 composite microsphere obtained by embodiment 1-48 further passes through physically or chemically absorption carriage respectively
Drug molecule is used as medicament slow release and studies.
The performance test of gained nylon/SiO 2 composite microsphere:
It is obtained in 6 microballoon of apertures nylon, 12 microballoon of apertures nylon used in testing example and embodiment 1-6 respectively
Nylon/SiO 2 composite microsphere properties, the results are shown in Table 1.
1 nylon of table/SiO 2 composite microsphere properties
Obviously, the above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be pair
The restriction of embodiments of the present invention may be used also on the basis of the above description for those of ordinary skill in the art
To make other variations or changes in different ways, all embodiments can not be exhaustive here, it is all to belong to this hair
The obvious changes or variations that bright technical solution is extended out are still in the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of nylon/SiO 2 composite microsphere, which is characterized in that the complex microsphere is spherical or close ball
Shape particle, partial size are 0.5 ~ 300 μm；The complex microsphere is made of apertures nylon micro-sphere and silica；Silica is in receive
Rice grain is dispersed in hole and/or the surface of apertures nylon micro-sphere, and/or is filled in apertures nylon in micron order continuous state
In microballoon hole；In the complex microsphere, the content of apertures nylon micro-sphere is 10 ~ 99.9wt%, dioxide-containing silica is 0.1 ~
90wt%；
The preparation method includes 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 apertures nylon micro-sphere
Dispersion liquid；
2) silica precursor is added in Xiang Shangshu dispersion liquid, stirs, 0 ~ 100 DEG C of 0.5 ~ 48h of reaction, filter, washing, do
It is dry, obtain nylon/SiO 2 composite microsphere；
Wherein, in step 1), the catalyst is selected from one of amines catalyst, acid catalyst or alkali catalyst；Institute
It states amines catalyst and is selected from one or more of ethylenediamine, hexamethylene diamine, polyvinylamine and its derivative；The acid catalyst
Selected from one or more of hydrochloric acid, sulfuric acid, formic acid or glacial acetic acid；The alkali catalyst is selected from ammonium hydroxide, NaOH solution or KOH
Solution.
2. the preparation method of nylon/SiO 2 composite microsphere according to claim 1, which is characterized in that the apertures
It is micro- that nylon micro-sphere is selected from 6 microballoon of nylon, nylon66 fiber microballoon, 12 microballoon of nylon, nylon 11 microballoon, nylon 1212 microballoon, nylon 612
One or more of ball, nylon 610 microballoon or nylon 1010 microballoon.
3. the preparation method of nylon/SiO 2 composite microsphere according to claim 1, which is characterized in that the nanometer
The partial size of silica dioxide granule is 10 ~ 500nm.
4. the preparation method of nylon/SiO 2 composite microsphere according to claim 1, which is characterized in that in load two
Before silica, the apertures nylon micro-sphere is spherical or subsphaeroidal particle, 0.5 ~ 300 μm of partial size, 0.01 ~ 150m of specific surface area2/
G, porosity 1% ~ 95%, aperture are 0.01 ~ 10 μm.
5. preparation method according to claim 1, which is characterized in that in step 1),
The solvent is in deionized water, methanol, ethyl alcohol, isopropanol, n-butanol, ethylene glycol, formic acid, glacial acetic acid or hydrochloric acid
It is one or more of；
In step 2, the silica precursor is selected from one of ethyl orthosilicate or dimethylethoxysilane or two
Kind.
6. preparation method according to claim 1, which is characterized in that in step 2, the additional amount of silica precursor
It is the 0.1% ~ 8000% of apertures nylon micro-sphere weight, addition speed is 1mL/h ~ 1000mL/h.
7. preparation method according to claim 1, which is characterized in that the additional amount of the catalyst is silica forerunner
0.1wt% ~ 1000wt% of body；The additional amount of the solvent is 0.001 ~ 5000 times of apertures nylon micro-sphere weight.
8. nylon/SiO 2 composite microsphere that preparation method as described in claim 1 is prepared is in chromatographic isolation, drug
Transmission and sustained release, functional paint, 3D printing field material application.
9. application according to claim 8, which is characterized in that nylon/SiO 2 composite microsphere that partial size is 20 ~ 90 μm
Application as the consumptive material in 3D printing-Selective Laser Sintering.
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| CN110639440A (en) * | 2019-09-24 | 2020-01-03 | 中国海洋大学 | Preparation method of carbon/silicon dioxide composite microspheres |
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| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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