CN104194007B - Polymer base micro-/ nano filling modifier compound premix preparation method of granules - Google Patents
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Abstract
A kind of polymer base micro-/ nano filling modifier compound premix preparation method of granules, its preparation process: non-soluble polymer matrix dissolution is obtained in the first water-soluble solvent homogeneous polymer solution；Micro-/ nano filler is scattered in the second water-soluble solvent, agitated, heating, ultrasonic, add solubilizer or coupling agent and obtain homogeneous micro-/ nano filler dispersion liquid；Homogeneous micro-/ nano filler dispersion liquid is added in homogeneous polymer solution, mixes to obtain homogeneous solution system solution；And by its be droplet-like instill dress deionized water container in；The drop instilled coagulates rapidly for uniform particle sizes's spheric granules；Collect spheric granules in container, repeatedly clean, then drying obtains polymer base micro-/ nano filling modifier compound premix particle；This method is simple, and low cost can effectively reduce Nano filling reunion in polymeric matrix, can improve the polymeric matrix infiltration suction-operated to inorganic filler, strengthens both interface binding powers, improves filling-modified effect.
Description
Technical field
The present invention relates to a kind of polymer base micro-/ nano filling modifier compound premix preparation method of granules, its uniform particle sizes is controlled, can be applicable to micro-/ nano filling modifier polymer matrix composite, the superior dispersibility and the preparation of uniform and stable property that utilize solution mix, stable performance, the former pellet of composite of no-arbitrary pricing reunion or premix particle.
Technical background
Filling-modified is the modified method that high molecular polymer is conventional, but due to micron or Nano filling surface energy height own, it is prone to reunite, and interface bonding strength is low between organic polymer matrix and inorganic filler, poor compatibility, it is hardly formed finely dispersed compound system in actual polymer-filled modifying process, not only causing filling-modified can not attaining the results expected, composite property can be made on the contrary to decline, filling-modified particularly with Nano filling is particularly acute.Owing to nanoparticle size is little, specific surface is bigger, surface can be high, easily reunite, when using nano particle that polymeric matrix is filled with modification, often due to the reunion of nano particle self makes its size reach micron order even more greatly, the advantage of nano particle itself can not effectively play, and even can reduce the premium properties that material is intrinsic.Utilize premix to dose inorganic filler in matrix and can reduce filler self reunion, strengthening filler and the boundary strength of matrix, improve the performance of filling-modified composite.The superior dispersibility and the preparation of uniform and stable property that utilize solution mix, stable performance, and the former pellet of composite or premix particle that no-arbitrary pricing is reunited will inject new vitality for composite.
Summary of the invention
It is an object of the invention to provide a kind of polymer base micro-/ nano filling modifier compound premix preparation method of granules, its uniform particle sizes is controlled, the reunion in the composite of micron or nano-sized filler, the interface bond strength between reinforcer and polymeric matrix can be avoided.The method is simple to operate, and energy consumption is low, can be effectively improved inorganic filler dispersiveness in polymeric matrix.
Technical scheme is as follows:
The polymer base micro-/ nano filling modifier compound premix preparation method of granules that the present invention provides, its uniform particle sizes is controlled, and preparation process is as follows:
1) the non-soluble polymer matrix dissolution being dissolved completely in water-soluble solvent is obtained homogeneous polymer solution in the first water-soluble solvent；Described homogeneous polymer solution concentration is 0.05～0.2g/ml；
2) micro-/ nano filler is scattered in the second water-soluble solvent, is stirred；And heated process, ultrasonic disperse process, add solubilizer or add coupling agent, obtaining homogeneous micro-/ nano filler dispersion liquid, described homogeneous micro-/ nano filler dispersion liquid concentration is 0.01～0.2g/ml；Described micro-/ nano filler is CNT, graphene oxide, alumina powder, calcium carbonate powder, powder carbon fiber, pulverized glass fibres or graphite powder；
Described first water-soluble solvent and the second water-soluble solvent are identical or the water-soluble solvent of similar nature；Described first water-soluble solvent and the second water-soluble solvent are DMF, DMA or acetone；
3) homogeneous micro-/ nano filler dispersion liquid is added step 1) in homogeneous polymer solution in, agitated make the two mix to obtain homogeneous solution system solution, the viscosity of described homogeneous solution system solution controls 25～35Pa.s；
4) homogeneous solution system solution is transferred in the liquid separatnig container with orifice or micropore of the bottom, continue stirring, immediately below liquid separatnig container, 1cm～20cm position is placed the pellet equipped with deionized water and is collected container, being slowly stirred pellet with magnetic stirring apparatus and collect the deionized water in container, the valve then opening liquid separatnig container makes homogeneous mixed solution system solution be that droplet-like instills equipped with in the pellet collection container of deionized water；The drop quick solidification instilling the homogeneous mixed solution system solution in deionized water becomes the spheric granules of uniform particle sizes；Described first water-soluble solvent and the second water-soluble solvent separate out from spheric granules；
5) after homogeneous mixed solution all drips off, the spheric granules collected by pellet in container leaches, and repeatedly cleans by deionized water 3 to 5 times, and drying obtains polymer base micro-/ nano filling modifier compound premix particle afterwards；The first described water-soluble solvent and the second water-soluble solvent are recovered by distillation.
Described non-soluble polymer is polysulfones, Merlon, polyimides, polyether sulfone or polystyrene.
Described solubilizer and coupling agent are surface conditioning agent；
Described surface conditioning agent is titanate coupling agent, silane coupler or surfactant, and described surface conditioning agent addition is the 0.2%～5wt% of micro-/ nano filer content.
Described silane coupler is KH550 or KH560.
Described step 2) ultrasonic disperse be processed as the ultrasonic disperse that carries out in ultrasonic cell disruptor or ultrasonic cleaner and process, ultrasonic disperse processes the time and controls within 2 hours.
Described step 2) heat treatment temperature less than high molecular polymer and the degradation temperature of micro-/ nano filler.
Described step 3) mixing time be 10～30 minutes.
Described step 5) deionized water repeatedly clean as by the deionized water soaking and washing repeatedly of 5 times of spheric granules material volumes, clean for the first time and need to first soak 30 minutes.
The polymeric matrix of the present invention must be non-soluble polymer, and can be dissolved completely in water-soluble solvent, and water-soluble solvent is polysulfones, polyimides, polyether sulfone or polystyrene etc.；Polymer solution concentration general control is 0.05～0.2g/ml, made solution to have good mobility, there is certain viscosity simultaneously, general solution viscosity controls 25～about 35Pa.s, it is easy to solution to form drop and ooze continuously, the particle condensing into size uniform in water of uniformly continuous；
First water-soluble solvent of the present invention and the second water-soluble solvent is identical or similar nature；Described first water-soluble solvent and the second water-soluble solvent are DMF, DMA or acetone etc.；
Surface conditioning agent inorganic filler the to be helped lend some impetus to dispersions in a solvent such as the solubilizer of the present invention or coupling agent, improve polymer and the compatibility of inorganic filler and interface binding power, inorganic filler is made to can be uniformly dispersed in polymeric matrix, and material property is had no adverse effects, adapt to subsequent machining technology；Surface conditioning agent used is generally titanate coupling agent, silane coupler or surfactant etc.；
The ultrasonic disperse of the present invention is processed as carrying out ultrasonic disperse process in ultrasonic cell disruptor or ultrasonic cleaner, time general control was at 30～120 minutes, specifically regarding micron or Nano filling depending on the deployment conditions in dispersion phase, such as dispersion itself preferably, then can not use this technique；Described heating, it is noted that on polymer or the impact of filler generation, control temperature range, makes temperature be less than depolymerization temperature, and ensures that heating will not destroy the proper property of filler and mixed solution；
The pellet particle cleaning that the present invention prepares is wanted fully, repeatedly cleaning, in order to avoid there being dissolvent residual, affect composite premix performance, general with being five times in the deionized water soaking and washing 3 repeatedly of premix volume～5 times, cleans first immersion 30 minutes for the first time.
Compared with prior art, the preparation method of the polymer base micro-/ nano filling modifier compound premix particle that the present invention provides, the uniform particle sizes of prepared polymer base micro-/ nano filling modifier compound premix particle is controlled；Have the advantage that
1, filler is contributed to the most dispersed, it is to avoid reunite；
2, contribute to uniformly dosing and effective process to filling surface of various surface conditioning agent, concurrently facilitate that aid dispersion technique is the most ultrasonic, stirring, the use of molecule pulverizing etc.；
3, solvent is easy to reclaim, and not only reduces cost but also avoid polluting；
4, gained composite premix pellet appearance and size uniform, controllable, it is simple to further apply some fields that composite particle diameter is had particular/special requirement；
5, polymer heating for multiple times is melted, degradation with aging to avoid using conventional extrusion method for pre mixing to make, and ultimately results in composite property and declines, and this technique filler dispersion effect is substantially better than conventional melt extrusion premixing process；
6, solvent has annealing effect, i.e. solvent anneal to composite, and material molecular structure regularity own can be made to improve, and produces crystallite, makes composite structure more they tend to ordering, makes the performance such as mechanics of material increase；
7, polymeric matrix can be improved to the effect of impregnation of filler and interface bond strength by the peptizaiton of solwution method, so that composite stress effectively can transmit between filler and matrix, improve the overall performance of composite.
Accompanying drawing illustrates:
Fig. 1 is the structural representation that the present invention prepares the device of polymer base micro-/ nano filling modifier compound premix particle；
Fig. 2 is that graphene oxide strengthens modified poly (ether-sulfone) (PES) based composites premix (small size particle) and contrasts photo with PES polymer raw material；
Fig. 3 is micron CaCO3Filling-modified polyether sulfone (PES) based composites premix (large-size particles) photo；
Fig. 4 is CNT (CNT) filling-modified polysulfones (PSF) based composites premix (small size particle) photo；
Fig. 5 is graphite and CNT (CNT) filling-modified polysulfones (PSF) based composites premix (large-size particles) photo.
Detailed description of the invention
Embodiment 1
1) weigh 60g polyether sulfone (PES) particle and dose in DMF, mechanical agitation so that it is fully dissolve, prepare the polyether sulfone homogeneous solution that 300ml concentration is 0.2g/ml；
2) 1g graphene oxide (GO) is weighed, and make it be dispersed in 100ml N, in dinethylformamide, compound concentration is the graphene oxide dispersion of 0.01g/ml, instill 0.05g (being equivalent to the 5wt% of filer content) Silane coupling agent KH550 simultaneously, in dispersion process, magnetic agitation, each 30 minutes of Ultrasonic Pulverization, owing to dispersion effect is the best, 0.05g (being equivalent to the 5wt% of filer content) lauryl sodium sulfate is added as surfactant in dispersion liquid, continuing stirring makes dispersion liquid add it in configured good PES solution after being uniformly dispersed for 30 minutes, stir 30 minutes；
3) transfer to uniform mixed solution the device that lower section micropore size shown in Fig. 1 is 500 μm continues stirring 10 minutes, then slow device for opening lower valve, makes solution uniformly instill at distance 1cm of lower section equipped with in the collector of deionized water with droplet-like；Meanwhile, slowly the deionized water in agitation collector, prevents the composite premix particle adhesion dripped；
4) after all dripping off, premix particle is leached, continue soaking and washing three times, then it is dried, prepare and follow-up prepare composite, collect dried graphene oxide and strengthen modified poly (ether-sulfone) (PES) based composites premix small size particle and with PES polymer raw material contrast photo as shown in Figure 2；Cleaning fluid distillating recovering solvent.
Embodiment 2
1) weigh 90g polyether sulfone (PES) particle and join in DMF, mechanical agitation so that it is fully dissolve, prepare the polyether sulfone homogeneous solution that 900ml concentration is 0.1g/ml；
2) in PES solution course of dissolution, 30g CaCO is weighed3It is dispersed in DMF, mechanical agitation, prepares the calcium carbonate homogenous disperse liquid that 150ml concentration is 0.2g/ml, during dispersed with stirring, instill 0.06g (being equivalent to the 0.2wt% of filer content) phthalate ester coupling agent；
3) by finely dispersed CaCO3Dispersion liquid joins in the PES solution dissolved, and stirs 20 minutes；Then mixed solution is transferred in the pellet preparation facilities that lower section micropore size is 1000 μm, stirring is continued after fixing, slow device for opening lower valve after 10 minutes, solution is made to become droplet-like to instill in the deionized water at distance 10cm of lower section continuously, in order to prevent particle adhesion from simultaneously facilitating solvent N, quickly oozing out of dinethylformamide, the deionized water being stirred continuously in collector with magnetic stirring apparatus；
4), after mixed solution drips off, leach liquid, and liquid is carried out distillating recovering solvent N, dinethylformamide, leaches deionized water, more repeatedly cleans three times after then prepared particle deionized water being soaked 30 minutes, the most stand-by, gained micron CaCO3Filling-modified polyether sulfone (PES) based composites premix large-size particles photo is as shown in Figure 3.
Embodiment 3
1) weigh bisphenol-a polysulfone (PSF) 90g and join in DMA solvent, mechanical agitation after mixing, prepare the PSF homogeneous solution that 900ml concentration is 0.1g/ml；
2) weigh 2g CNT (CNT) powder and be dispersed in 100ml N, preparing concentration in N-dimethylacetylamide is the carbon nano tube dispersion liquid of 0.02g/ml, first stirring 30 minutes, during Ultrasonic Pulverization adds it to the PSF solution prepared before after 30 minutes again, continuously stir 10 minutes again, the most ultrasonic 20 minutes, it is prepared as finely dispersed mixed solution；
3) transfer to mixed solution the device that lower section micropore size is 200 μm continues to be stirred, then slow device for opening lower valve, make solution uniformly can instill at distance 5cm of lower section equipped with in the collector of deionized water with droplet-like；Deionized water magnetic stirring apparatus uniform stirring；
4) after dripping, the premix particle in deionized water is leached, continue soaking and washing three times, be then dried as composite premix in case follow-up continuation compound use；Cleaning fluid distillating recovering solvent, CNT (CNT) filling-modified polysulfones (PSF) based composites small particle former pellet photo is as shown in Figure 4.
Embodiment 4
1) weigh bisphenol-a polysulfone (PSF) 90g and join in DMA solvent, mechanical agitation after mixing, prepare the PSF homogeneous solution that 900ml concentration is 0.1g/ml；
2) at the N of PSF, in N-dimethylacetamide solution course of dissolution, prepare filling-modified filler dispersion liquid: 29g micron order graphite (500 mesh) and 1g CNT (CNT) are dispersed in N, in dinethylformamide, configuration concentration is the filler dispersion liquid of 0.15g/ml, and add 0.6g (being equivalent to the 2wt% of filer content) coupling agent KH550, stir 30 minutes with agitator, the most ultrasonic 30 minutes, then dispersion liquid is transferred in the PSF solution dissolved, continue stirring 30 minutes；
3) transferring to continue in Fig. 1 device stirring after mixed solution stirs, below device, micropore size is 1.5mm, and then device for opening valve is slowly dropped in the collector filling deionized water at distance 20cm of lower section by solution,
4) after solution drips off, being leached by cakey premix particle, then proceed to clean by deionized water, dried for standby, solvent is recovered by distillation, and gained composite premix particle is as shown in Figure 5.
Embodiment 5
1) weigh bisphenol-a polysulfone (PSF) 60g and dose in DMA, mechanical agitation, prepare the uniform PSF solution that 600ml concentration is 0.1g/ml；
2) 20gAl is weighed2O3Powder is dispersed in DMA stirring 30 minutes, and preparation 100ml concentration is 0.2g/ml Al2O3Dispersion liquid, then joins dispersion liquid in PSF solution, is stirred for 30 minutes；
3) mixed solution is transferred in device, and continue stirring, slowly open valve after 5 minutes and make solution be in the feeder equipped with deionized water that droplet-like uniformly instills at distance 5cm of lower section, deionized water magnetic stirring apparatus uniform stirring；
4) after dripping, premix particle is leached, continue soaking and washing three times, then dried for standby；Cleaning fluid distillating recovering solvent.
Embodiment 6
1) weighing 100g polystyrene (PS) particle and dose in acetone solvent, stir with agitator, preparation 500ml concentration is the PS acetone homogeneous solution of 0.2g/ml；
2) weigh 50g powder glass (about 300 mesh) to be dispersed in acetone soln, it is stirred, prepare the powder glass dispersion liquid that 250ml concentration is 0.2g/ml, 0.1g (being equivalent to filer content 2wt%) coupling agent KH560 is instilled in whipping process, after stirring 30 minutes, then ultrasonic disperse 30 minutes；
3) glass dispersion liquid is mixed with PS solution, stir 10 minutes, then mixed solution is transferred to continue in device stirring, slowly opens valve after 5 minutes and make solution uniformly instill in droplet-like as pearl-decorated curtain in the collector equipped with deionized water at distance 5cm of lower section；
4) after mixed solution drips off, premix particle is leached, continue soaking and washing three times, then dried for standby；Cleaning fluid distillating recovering solvent.
Embodiment 7
1) weighing polyimides (PI) 25g to dose and carry out mix and blend in solvent DMA (DMAc), preparation 500ml concentration is the uniform PI solution of 0.05g/ml；
2) at the N of PI, in N-dimethylacetamide solution course of dissolution, prepare filling-modified filler dispersion liquid: 9g carbon fiber powder (fiber size is about 100 mesh) and 1g CNT (CNT) are dispersed in N, in N-dimethylacetylamide, form the filler dispersion liquid that 50ml concentration is 0.2g/ml, in filler dispersion liquid mixing process, add the coupling agent KH550 of 0.5g (being equivalent to filer content 5%), in whole dispersion liquid dispersion process, first stir 30 minutes with agitator, the most ultrasonic 30 minutes, it is then transferred in the PI solution dissolved, continue stirring 30 minutes；
3) transfer to device continues stirring 5 minutes after mixed liquor stirs, then open valve by solution the most uniformly instill below at distance 10cm equipped with in the tank of deionized water, owing to the hydrophobicity of PI own is strong, after in solution entrance water, meeting contraction at once solidifies out into PI, CF and CNT and compounds filling-modified composite premix solidified particle, and solvent can rapidly diffuse in deionized water；
4) after solution drips off, being cleaned by premix particle filtering, dried for standby, solvent is recovered by distillation.
Embodiment 8
1) weigh 90g PES particle and dose in DMF, stir with agitator, prepare the PES homogeneous solution that 900ml concentration is 0.1g/ml；
2) at the N of PES, in dinethylformamide solution course of dissolution, prepare filling-modified filler dispersion liquid: first weigh 10g phenolic resin and be dissolved in 100ml ethanol, and instill 0.5g (being equivalent to filer content 5wt%) coupling agent KH550, stirring makes it dissolve, then weigh in the ethanol novolac solution after 30g carbon fiber powder (fiber size is about 100 mesh) joins dissolving, it is stirred, the mixture stirred is placed in 50 DEG C of baking ovens, ethanol is made to volatilize, after being evaporated completely Deng ethanol, the carbon fiber powder processed is joined N, in dinethylformamide, preparation 400ml concentration is the filler dispersion liquid of 0.1g/ml, stir 30 minutes, it is then added in the PES solution dissolved, continue stirring 30 minutes.
3) transferring in device by the mixed solution stirred, below device, aperture is 1.5mm, after stirring 5 minutes, slowly opens valve, and making solution is that droplet-like instills at distance 10cm of lower section continuously equipped with in the particle collection trough in deionized water；
4) after dripping, the premix particle in deionized water is leached, continue soaking and washing three times, then dried for standby；Cleaning fluid distillating recovering solvent.
Claims (8)
1. a polymer base micro-/ nano filling modifier compound premix preparation method of granules, its uniform particle sizes
Controlled, preparation process is as follows:
1) the non-soluble polymer matrix dissolution being dissolved completely in water-soluble solvent is obtained in the first water-soluble solvent
To homogeneous polymer solution；Described homogeneous polymer solution concentration is 0.05～0.2g/ml；
2) micro-/ nano filler is scattered in the second water-soluble solvent, is stirred；And heated process, ultrasonic point
Dissipate process, add solubilizer or add coupling agent, obtain homogeneous micro-/ nano filler dispersion liquid, described homogeneous micro-/ nano
Filler dispersion liquid concentration is 0.01～0.2g/ml；Described micro-/ nano filler is CNT, graphene oxide, oxidation
Aluminium powder, calcium carbonate powder, powder carbon fiber, pulverized glass fibres or graphite powder；
Described first water-soluble solvent and the second water-soluble solvent are identical or the water-soluble solvent of similar nature；Described
First water-soluble solvent and the second water-soluble solvent are DMF, DMA or third
Ketone；
3) homogeneous micro-/ nano filler dispersion liquid is added step 1) in homogeneous polymer solution in, agitated make the two
Mixing and obtain homogeneous solution system solution, the viscosity of described homogeneous solution system solution controls 25～35Pa.s；
4) transfer to homogeneous solution system solution, in the liquid separatnig container with orifice or micropore of the bottom, continue stirring,
Immediately below liquid separatnig container, 1cm～20cm position is placed the pellet equipped with deionized water and is collected container, stirs with magnetic force
Mixing the deionized water that device is slowly stirred in pellet collection container, the valve then opening liquid separatnig container makes homogeneous mixing molten
Liquid system solution is that droplet-like instills equipped with in the pellet collection container of deionized water；Instill the homogeneous in deionized water
The drop quick solidification of mixed solution system solution becomes the spheric granules of uniform particle sizes；Described first water-soluble solvent
Separate out from spheric granules with the second water-soluble solvent；
5) after homogeneous mixed solution all drips off, the spheric granules collected by pellet in container leaches, and spend from
Sub-water cleans 3 to 5 times repeatedly, and drying obtains polymer base micro-/ nano filling modifier compound premix afterwards
Particle；The first described water-soluble solvent and the second water-soluble solvent are recovered by distillation.
2. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described non-soluble polymer be polysulfones, Merlon, polyimides, polyether sulfone or
Polystyrene.
3. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described solubilizer and coupling agent are surface conditioning agent；
Described surface conditioning agent is titanate coupling agent, silane coupler or surfactant, described surface conditioning agent
Addition is the 0.2%～5wt% of micro-/ nano filer content.
4. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 3
Method, it is characterised in that described silane coupler is KH550 or KH560.
5. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described step 2) ultrasonic disperse be processed as at ultrasonic cell disruptor or Ultrasonic Cleaning
The ultrasonic disperse carried out in device processes, and the ultrasonic disperse process time controlled within 2 hours.
6. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described step 2) heat treatment temperature less than high molecular polymer and micro-/ nano filler
Degradation temperature.
7. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described step 3) mixing time be 10～30 minutes.
8. the polymer base micro-/ nano filling modifier compound premix particle preparation side as described in claim 1
Method, it is characterised in that described step 5) deionized water repeatedly clean as with 5 times of spheric granules material volumes
Deionized water soaking and washing repeatedly, cleans for the first time and need to first soak 30 minutes.
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| CN104844066B (en) * | 2015-03-27 | 2017-03-01 | 中国科学院深圳先进技术研究院 | Boron nitride paper and preparation method thereof |
| CN105153639B (en) * | 2015-07-09 | 2017-07-18 | 河海大学 | A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite |
| CN105060268B (en) * | 2015-07-09 | 2017-06-16 | 河海大学 | A kind of preparation method of CNT microballoon |
| CN105482511A (en) * | 2015-11-10 | 2016-04-13 | 西南石油大学 | Aluminium oxide/graphene oxide sheet-shaped hybrid and preparation method thereof |
| CN106832500A (en) * | 2017-01-24 | 2017-06-13 | 南京科孚纳米技术有限公司 | A kind of preparation method of Graphene toughness reinforcing latex composite |
| CN109251495B (en) * | 2018-09-12 | 2021-03-02 | 泉州市康馨化工科技有限公司 | Method for 3D printing and molding graphene composite material |
| CN109824993B (en) * | 2019-01-29 | 2021-09-14 | 新奥石墨烯技术有限公司 | Nano material/polymer composite material and preparation method thereof |
| AU2020307169A1 (en) * | 2019-06-28 | 2022-02-24 | Grafoid Inc. | Graphene based filters and systems comprising same |
| CN112442232B (en) * | 2019-09-03 | 2021-11-05 | 中国科学院化学研究所 | Nano material composite polymer powder and preparation method thereof |
| CN114750331A (en) * | 2021-01-12 | 2022-07-15 | 上海芯密科技有限公司 | Method for preparing micron-grade or submicron-grade filler by adopting high polymer material |
| CN115895147B (en) * | 2022-10-24 | 2023-10-24 | 中国电子科技集团公司第四十三研究所 | All-organic polymer nanocomposite and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706890A (en) * | 2004-06-07 | 2005-12-14 | 清华大学 | Prepn process of composite material based on carbon nanotube |
| CN1760269A (en) * | 2004-10-13 | 2006-04-19 | 上海扬泽纳米新材料有限公司 | Electric polymer and preparation method |
| CN101121791A (en) * | 2006-08-09 | 2008-02-13 | 清华大学 | Method for preparing carbon nano-tube/polymer composite material |
-
2014
- 2014-09-28 CN CN201410509472.XA patent/CN104194007B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1706890A (en) * | 2004-06-07 | 2005-12-14 | 清华大学 | Prepn process of composite material based on carbon nanotube |
| CN1760269A (en) * | 2004-10-13 | 2006-04-19 | 上海扬泽纳米新材料有限公司 | Electric polymer and preparation method |
| CN101121791A (en) * | 2006-08-09 | 2008-02-13 | 清华大学 | Method for preparing carbon nano-tube/polymer composite material |
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