CN105111467A - Preparation method of polyetherimide ultrafine powder controllable in particle size - Google Patents
Preparation method of polyetherimide ultrafine powder controllable in particle size Download PDFInfo
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Abstract
The invention relates to a preparation method of polyetherimide ultrafine powder controllable in particle size, and belongs to the technical field of 3D printing powder. The preparation method comprises the following steps: adding original carbon nanotube into a well-prepared thick sulfuric acid and thick nitric acid mixed solution, ultrasonically dispersing, heating, stirring and reacting for a period of time; then washing a reaction product to be neutral, filtering and drying to obtain acidified carbon nanotube; collectively adding the acidified carbon nanotube and polyetherimide into a solvent, heating and stirring until polyetherimide is completely dissolved; and finally atomizing the obtained solution into a solution containing polyvinylpyrrolidone under high-speed stirring, and washing, filtering and drying. By changing the addition amount stirring speed of polyvinylpyrrolidone, the particle size of the polyetherimide powder is controlled to prepare the ultrafine powder suitable for 3D printing.
Description
Technical field:
The present invention relates to a kind of preparation method of polyetherimide ultrafine powder of size tunable, belong to 3D and print powder technology field.
Background technology:
Polyetherimide be the earliest 20th century the seventies succeed in developing, and achieving suitability for industrialized production at early eighties, the field of its application is very extensive, comprises electron and electrician, aerospace etc., mainly be made into the component of machine of high strength, corrosion-resistant, radiation-resistant special product.The reason that polyetherimide can be widely used is that it has very outstanding performance, from the angle of molecular chain, it introduces at polyimide chain the class superpolymer that ehter bond formed, belong to noncrystallizable polymer, there is higher fusing point, dimensional stability under mechanical property resistance toheat, radiation resistance, flame retardant properties and high temperature is similar to general aromatic heterocyclic polymer, but its processing characteristics is but very outstanding compared with other aromatic heterocyclic polymers.
The development of 3D printing technique is in the last few years very rapid, and application is in the industrial production also more and more extensive.Kind and its forming principle of 3D printing consumables have close relationship, wherein the consumptive material of Selective Laser Sintering (i.e. SLS technology) is powder body material, mainly comprise macromolecular material powder and metal, ceramic powder, wherein macromolecular material mainly comprises nylon, PS, PP, PLA, ABS and PETG etc., but their over-all properties is not very strong, and such as nylon material water-absorbent is too strong; ABS material and PETG material easily warp when printing big area product; The product shock resistance that PLA material prints is lower, and intensity is lower; The resistance toheat of PP material is bad, antistatic property difference etc.
Summary of the invention:
The object of the invention is to overcome above-mentioned defect, the present invention by spray method preparation through the particle diameter of carbon nano-tube modification at the polyetherimide powder of 40 ~ 60um, make it can also overcome heat conduction not available for macromolecular material and antistatic property on the basis having outstanding performance itself.Control the particle diameter of polyetherimide powder by changing the addition of polyvinylpyrrolidone and stirring velocity thus make the ultrafine powder that applicable 3D prints.
The preparation method of the polyetherimide ultrafine powder of a kind of size tunable provided by the invention, specifically comprises the following steps:
(1) preparation of acidifying carbon nanotube, joins original carbon nanotubes in the vitriol oil prepared and concentrated nitric acid mixing solutions, and after ultrasonic disperse 0.5 ~ 1h, puts into stirring reaction for some time in the oil bath with certain temperature; Finally reaction product deionized water is washed till neutrality, and suction filtration, oven dry, namely obtain the carbon nanotube of acidifying;
(2) carbon nanotube good for step (1) acidifying and polyetherimide are together joined in solvent, stir until polyetherimide dissolves completely 100 ~ 130 DEG C of oil bath high speeds after ultrasonic disperse for some time; Afterwards with Dey-Dose by solution spray obtained above in high-speed stirring containing polyvinylpyrrolidone solution in; In the mixture system finally obtained, the polyetherimide microballoon containing carbon pipe of precipitation is disperse phase, and its Surface coating has polyvinylpyrrolidone; Anlistatig polyetherimide microballoon can be obtained after eventually passing washing, suction filtration and drying.
Above-mentioned steps (1) is described to be prepared in the method for acidifying carbon nanotube, and in mixing solutions, the vitriol oil and concentrated nitric acid mass ratio are preferably 1:1, plays the effect improving carbon pipe dispersiveness, and the mass ratio of itself and original carbon pipe is preferably 40:1.
Above-mentioned steps (1) is described to be prepared in the method for acidifying carbon nanotube, and oil bath temperature is at 125 ~ 145 DEG C.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, carbon nanotube plays the effect improving polyetherimide electroconductibility, and addition is 0.5 ~ 4wt% of polyetherimide, is preferably 1wt%.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, polyetherimide accounts for 10 ~ 30wt% of carbon nanotube, polyetherimide and solvent mixture.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, solvent is the one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, the polyetherimide that polyvinylpyrrolidone plays coated precipitation makes the effect of its stable dispersion balling-up, and addition is 20 ~ 80wt% of polyetherimide.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, polyvinylpyrrolidonesolution solution, its solvent is the one in deionized water, ethanol, methyl alcohol, play and reduce polyetherimide solubleness thus the effect of separating out, polyvinylpyrrolidonesolution solution consumption is preferably 100 ~ 300wt% of carbon nanotube, polyetherimide and solvent institute composition mixture.
In the method for the antistatic polyetherimide ultrafine powder of above-mentioned steps (2) described preparation, high-speed stirring, play dispersion polyetherimide microballoon in time, avoid the effect that microballoon is reunited, its rotating speed is 500 ~ 700r/min.
First carbon nanotube joins in the mixed solvent of the vitriol oil and concentrated nitric acid composition by the present invention, puts into oil bath reacting by heating, then reaction product deionized water is washed to neutrality, obtain acidifying carbon nanotube after ultrasonic.Polyetherimide and acidifying carbon nanotube are joined heating for dissolving in solvent, is sprayed in polyvinylpyrrolidonesolution solution with Dey-Dose subsequently, finally obtain particle diameter at 40 ~ 60um and be mixed with the polyetherimide microballoon of carbon nanotube.The polyetherimide microballoon that the inventive method obtains can be used as the starting material that 3D prints.
The polyetherimide powder body material obtained by this method, when printing for 3D, not only has outstanding processing characteristics, and the product obtained has lighter weight compared with metallic article, and and performance in no way inferior.Stronger mechanical property, shock resistance, high temperature resistant, radiation hardness, resistance to deformation and heat conduction and antistatic property is then had compared with the macromolecular material printed for 3D with other.Can be used for the web member, high-precision optical fiber element etc. that manufacture intensity height and dimensional stabilizing.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 1;
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 2;
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 3;
Fig. 4 is the scanning electron microscope (SEM) photograph of embodiment 5.
Embodiment:
The invention provides a kind of preparation method of polyetherimide ultrafine powder of size tunable.First the preparation vitriol oil and concentrated nitric acid mass ratio are the mixing solutions of 1, the carbon nanotube of certain mass to be joined in mixing solutions after ultrasonic disperse for some time, put in the oil bath of certain temperature, after stirring reaction 1h, product deionized water is washed till neutrality, and suction filtration, oven dry, obtain the carbon nanotube of acidifying.Again polyetherimide and acidifying carbon nanotube are joined in solvent, oil bath heated and stirred is put into until dissolve completely after ultrasonic disperse for some time, with Dey-Dose polyetherimide solution is sprayed to subsequently in the polyvinylpyrrolidonesolution solution in stirring, eventually passes suction filtration, drying thus obtain the polyetherimide microballoon of carbon nano-tube modification.
Following examples further illustrate of the present invention, but the present invention is not limited in following examples.
Embodiment 1:
(1) preparation of acidifying carbon nanotube: first added in the 1.0mL/1.0mL vitriol oil/concentrated nitric acid mixing solutions by 0.05g original carbon nanotubes, then puts into ultrasonic disperse 0.5h in ultrasonic cleaner, makes carbon pipe be uniformly dispersed as far as possible.Stirring heating condensing reflux 1h in 140 DEG C of oil baths afterwards, after reaction stops with washed with de-ionized water carbon nanotube to pH in neutral, last suction filtration, drying obtain acidifying carbon nanotube.
(2) preparation of polyetherimide ultrafine powder: under room temperature, 4.5g polyetherimide and 0.045g acidifying carbon nanotube are joined 25.5gN, in N-N,N-DIMETHYLACETAMIDE, and with after ultrasonic cleaner ultrasonic disperse 5min, put into 130 DEG C of oil baths and be stirred under 200r/min condition and dissolve completely.0.9g polyvinylpyrrolidone is dissolved in 59.1g deionized water simultaneously, is stirred under 550r/min condition and dissolves completely.To be sprayed to by polyetherimide solution with Dey-Dose subsequently in the polyvinylpyrrolidonesolution solution in stirring, the microballoon suction filtration washing will separated out afterwards, finally puts in 45 DEG C of vacuum drying ovens and can obtain the microballoon of particle diameter at 105 ~ 120um after vacuum-drying 3h.
Embodiment 2:
(1) preparation of acidifying carbon nanotube: first added in the 1.0mL/1.0mL vitriol oil/concentrated nitric acid mixing solutions by 0.05g original carbon nanotubes, then puts into ultrasonic disperse 0.5h in ultrasonic cleaner, makes carbon pipe be uniformly dispersed as far as possible.Stirring heating condensing reflux 1h in 140 DEG C of oil baths afterwards, after reaction stops with washed with de-ionized water carbon nanotube to pH in neutral, last suction filtration, drying obtain acidifying carbon nanotube.
(2) preparation of polyetherimide ultrafine powder: under room temperature, 4.5g polyetherimide and 0.045g acidifying carbon nanotube are joined 25.5gN, in N-N,N-DIMETHYLACETAMIDE, and with after ultrasonic cleaner ultrasonic disperse 5min, put into 130 DEG C of oil baths and be stirred under 200r/min condition and dissolve completely.1.58g polyvinylpyrrolidone is dissolved in 58.42g deionized water simultaneously, is stirred under 550r/min condition and dissolves completely.To be sprayed to by polyetherimide solution with Dey-Dose subsequently in the polyvinylpyrrolidonesolution solution in stirring, the microballoon suction filtration washing will separated out afterwards, finally puts in 45 DEG C of vacuum drying ovens and can obtain the microballoon of particle diameter at 80 ~ 100um after vacuum-drying 3h.
Embodiment 3:
(1) preparation of acidifying carbon nanotube: first added in the 1.0mL/1.0mL vitriol oil/concentrated nitric acid mixing solutions by 0.05g original carbon nanotubes, then puts into ultrasonic disperse 0.5h in ultrasonic cleaner, makes carbon pipe be uniformly dispersed as far as possible.Stirring heating condensing reflux 1h in 140 DEG C of oil baths afterwards, after reaction stops with washed with de-ionized water carbon nanotube to pH in neutral, last suction filtration, drying obtain acidifying carbon nanotube.
(2) preparation of polyetherimide ultrafine powder: under room temperature, 4.5g polyetherimide and 0.045g acidifying carbon nanotube are joined 25.5gN, in N-N,N-DIMETHYLACETAMIDE, and with after ultrasonic cleaner ultrasonic disperse 5min, put into 130 DEG C of oil baths and be stirred under 200r/min condition and dissolve completely.2.25g polyvinylpyrrolidone is dissolved in 57.75g deionized water simultaneously, is stirred under 550r/min condition and dissolves completely.To be sprayed to by polyetherimide solution with Dey-Dose subsequently in the polyvinylpyrrolidonesolution solution in stirring, the microballoon suction filtration washing will separated out afterwards, finally puts in 45 DEG C of vacuum drying ovens and can obtain the microballoon of particle diameter at 50 ~ 62um after vacuum-drying 3h.
Embodiment 4:
(1) preparation of acidifying carbon nanotube: first added in the 1.0mL/1.0mL vitriol oil/concentrated nitric acid mixing solutions by 0.05g original carbon nanotubes, then puts into ultrasonic disperse 0.5h in ultrasonic cleaner, makes carbon pipe be uniformly dispersed as far as possible.Stirring heating condensing reflux 1h in 140 DEG C of oil baths afterwards, after reaction stops with washed with de-ionized water carbon nanotube to pH in neutral, last suction filtration, drying obtain acidifying carbon nanotube.
(2) preparation of polyetherimide ultrafine powder: under room temperature, 4.5g polyetherimide and 0.045g acidifying carbon nanotube are joined 25.5gN, in N-N,N-DIMETHYLACETAMIDE, and with after ultrasonic cleaner ultrasonic disperse 5min, put into 130 DEG C of oil baths and be stirred under 200r/min condition and dissolve completely.2.93g polyvinylpyrrolidone is dissolved in 57.07g deionized water simultaneously, is stirred under 550r/min condition and dissolves completely.With Dey-Dose polyetherimide solution is sprayed in the polyvinylpyrrolidonesolution solution in stirring subsequently, afterwards by separate out microballoon suction filtration, washing, finally put in 45 DEG C of vacuum drying ovens and can obtain the microballoon of particle diameter at 45 ~ 57um after vacuum-drying 3h.
Embodiment 5:
(1) preparation of acidifying carbon nanotube: first added in the 2.0mL/2.0mL vitriol oil/concentrated nitric acid mixing solutions by 0.1g original carbon nanotubes, then puts into ultrasonic disperse 0.5h in ultrasonic cleaner, makes carbon pipe be uniformly dispersed as far as possible.Stirring heating condensing reflux 1h in 140 DEG C of oil baths afterwards, after reaction stops with washed with de-ionized water carbon nanotube to pH in neutral, last suction filtration, drying obtain acidifying carbon nanotube.
(2) preparation of polyetherimide ultrafine powder: under room temperature, 4.5g polyetherimide and 0.0675g acidifying carbon nanotube are joined 25.5gN, in N-N,N-DIMETHYLACETAMIDE, and with after ultrasonic cleaner ultrasonic disperse 5min, put into 130 DEG C of oil baths and be stirred under 200r/min condition and dissolve completely.2.93g polyvinylpyrrolidone is dissolved in 57.07g deionized water simultaneously, is stirred under 550r/min condition and dissolves completely.With Dey-Dose polyetherimide solution is sprayed in the polyvinylpyrrolidonesolution solution in stirring subsequently, afterwards by separate out microballoon suction filtration, washing, finally put in 45 DEG C of vacuum drying ovens and can obtain the microballoon of particle diameter at 40 ~ 55um after vacuum-drying 3h.
Claims (9)
1. a preparation method for the polyetherimide ultrafine powder of size tunable, is characterized in that, specifically comprise the following steps:
Original carbon nanotubes to be joined in the mixing solutions of the vitriol oil and the concentrated nitric acid prepared, and after ultrasonic disperse 0.5 ~ 1h, put into stirring reaction for some time in the oil bath with certain temperature and last reaction product deionized water be washed till neutrality; Namely the carbon nanotube of acidifying is obtained after suction filtration, oven dry; The carbon nanotube good by acidifying and polyetherimide together join in solvent, stir until polyetherimide dissolves completely after ultrasonic disperse for some time 100 ~ 130 DEG C of oil bath high speeds; Afterwards with Dey-Dose by solution spray obtained above in high-speed stirring containing polyvinylpyrrolidone solution in; Anlistatig polyetherimide microballoon can be obtained after eventually passing washing, suction filtration and drying.
2. according to the method for claim 1, it is characterized in that, in step (2), the addition of carbon nanotube is 0.5 ~ 4wt% of polyetherimide.
3. according to the method for claim 1, it is characterized in that, in step (2), the addition of carbon nanotube is the 1wt% of polyetherimide.
4. according to the method for claim 1, it is characterized in that, in step (2), the mass percent of polyetherimide in carbon nanotube, polyetherimide and solvent mixture is 10 ~ 30%.
5. according to the method for claim 1, it is characterized in that, in step (2), the solvent of dissolving polyetherimide is the one in N-Methyl pyrrolidone, DMF, N,N-dimethylacetamide.
6. according to the method for claim 1, it is characterized in that, in step (2), the addition of polyvinylpyrrolidone is 20 ~ 80wt% of polyetherimide.
7. according to the method for claim 1, it is characterized in that, the solvent of polyvinylpyrrolidonesolution solution is the one in deionized water, ethanol, methyl alcohol in step (2), and the consumption of polyvinylpyrrolidonesolution solution is carbon nanotube, 100 ~ 300wt% of polyetherimide and solvent institute composition mixture.
8. according to the method for claim 1, it is characterized in that, the rotating speed that step (2) high speed stirs is 500 ~ 700r/min.
9. the polyetherimide ultrafine powder of size tunable is prepared according to any one method of claim 1-8.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057090A (en) * | 2017-04-27 | 2017-08-18 | 万华化学集团股份有限公司 | A kind of preparation method of nylon powder |
| CN107263855A (en) * | 2017-06-19 | 2017-10-20 | 中国航发北京航空材料研究院 | A kind of high-strength high temperature-resistant 3D printing material, wire rod are prepared and Method of printing |
| CN112552556A (en) * | 2020-12-09 | 2021-03-26 | 四川华造宏材科技有限公司 | Degradable high-thermal-conductivity composite material and preparation method thereof |
| CN115266853A (en) * | 2022-08-02 | 2022-11-01 | 哈尔滨工业大学（威海） | Electrochemical biosensor and preparation method and application thereof |
| CN115873424A (en) * | 2022-11-29 | 2023-03-31 | 江西悦安新材料股份有限公司 | Carbon nano tube modified particle and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353130A (en) * | 2001-11-21 | 2002-06-12 | 中国科学院生态环境研究中心 | High-molecular microspheres or acicular microparticles with uniform granularity and its shaping process |
| CN102936357A (en) * | 2012-10-31 | 2013-02-20 | 北京化工大学 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
| CN103201321A (en) * | 2010-09-07 | 2013-07-10 | 拜耳知识产权有限责任公司 | Process for producing polymer-CNT composites |
-
2015
- 2015-08-27 CN CN201510536282.1A patent/CN105111467B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1353130A (en) * | 2001-11-21 | 2002-06-12 | 中国科学院生态环境研究中心 | High-molecular microspheres or acicular microparticles with uniform granularity and its shaping process |
| CN103201321A (en) * | 2010-09-07 | 2013-07-10 | 拜耳知识产权有限责任公司 | Process for producing polymer-CNT composites |
| CN102936357A (en) * | 2012-10-31 | 2013-02-20 | 北京化工大学 | Antistatic agent made from silver nanowire and functional carbon nano tube (CNT) and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| 汪洋等: "聚吡咯包覆碳纳米管的制备及其抗静电性能的研究", 《2013 年全国高分子学术论文报告会论文摘要集—主题J：高分子复合体系》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107057090A (en) * | 2017-04-27 | 2017-08-18 | 万华化学集团股份有限公司 | A kind of preparation method of nylon powder |
| CN107057090B (en) * | 2017-04-27 | 2019-07-23 | 万华化学集团股份有限公司 | A kind of preparation method of nylon powder |
| CN107263855A (en) * | 2017-06-19 | 2017-10-20 | 中国航发北京航空材料研究院 | A kind of high-strength high temperature-resistant 3D printing material, wire rod are prepared and Method of printing |
| CN112552556A (en) * | 2020-12-09 | 2021-03-26 | 四川华造宏材科技有限公司 | Degradable high-thermal-conductivity composite material and preparation method thereof |
| CN112552556B (en) * | 2020-12-09 | 2022-07-01 | 四川华造宏材科技有限公司 | Degradable high-thermal-conductivity composite material and preparation method thereof |
| CN115266853A (en) * | 2022-08-02 | 2022-11-01 | 哈尔滨工业大学（威海） | Electrochemical biosensor and preparation method and application thereof |
| CN115873424A (en) * | 2022-11-29 | 2023-03-31 | 江西悦安新材料股份有限公司 | Carbon nano tube modified particle and preparation method and application thereof |
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