CN100558815C - High conductive polyamide/graphite nano conductive composite material and preparation method thereof - Google Patents
High conductive polyamide/graphite nano conductive composite material and preparation method thereof Download PDFInfo
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- CN100558815C CN100558815C CNB2007100238895A CN200710023889A CN100558815C CN 100558815 C CN100558815 C CN 100558815C CN B2007100238895 A CNB2007100238895 A CN B2007100238895A CN 200710023889 A CN200710023889 A CN 200710023889A CN 100558815 C CN100558815 C CN 100558815C
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Abstract
The invention discloses a kind of high conductive polyamide/graphite nano conductive composite material and preparation method thereof, 30-200 purpose natural flake graphite joined in the mixed solution that mass ratio is 4: 1 the vitriol oil and concentrated nitric acid soaked 24 hours, then after washing, drying treatment, heat treated in retort furnace, temperature is 900-1100 ℃, obtains expansion multiple at the expanded graphite more than 200 times; Polyamide resin 90～99 mass parts are joined in the certain amount of solvent, treat that polyamide resin dissolves the back fully to wherein adding above-mentioned expanded graphite 1～10 mass parts, ultrasonic 2h obtains homodisperse mixture, under violent stirring, add precipitation agent then and make mixture precipitation, with throw out suction filtration, drying, prepare high conductive polyamide/graphite nano conductive composite material again.Technology advanced person of the present invention, the matrix material that makes has lower percolation threshold, and higher specific conductivity is expected to use in fields such as antistatic material, electromagnetic shielding material, microwave absorbing.
Description
Technical field
The present invention relates to a kind of conductive poly acid amides (nylon) matrix material, specially refer to the preparation method of the conductive nano composites of polymeric amide and graphite composition.
Background technology
Nylon (polymeric amide) is a kind of thermoplastic engineering plastic of excellent performance, in industrial circle and daily life, use very extensive, its Application Areas from automobile, electronic apparatus, machinery, aerospace field to daily living article.It has excellent mechanical property, electrical property and wear-resisting, oil resistant, anti-solvent, self-lubricating preferably, corrosion-resistant and good processing properties etc.But the electrical insulation capability of nylon causes it to be easy to generate static, has limited its application.Usually adopt the method for adding micron order conductive filler materials such as carbon black to improve the conductivity of polymkeric substance.Though also can improve the conductivity of polymkeric substance, give polymkeric substance ideal conductivity needs bigger loading level, and percolation threshold generally will reach 15～25%, and the result causes the moulding processability of mixture and mechanical property to decline to a great extent.One of method that reduces conductive filler material content is exactly that to adopt particle size be nano level filler, but the huge surface energy of nanoparticle self makes its easy reunion, adopts traditional preparation method to be difficult to make filler to reach the homodisperse of nanoscale.
Expanded graphite (EG) natural flake graphite pyroprocessing after acidifying obtains, has bulk porous structure, the graphite microplate of a large amount of 30～80nm thickness is contained in its inside, carry out itself and polymkeric substance compound, EG can peel off to the nano graphite sheet with big radius-thickness ratio and be aggregated the thing parcel and be fixed up, thereby can overcome the shortcoming that nanoparticle is easily reunited, thus help the formation of conductive channel, significantly reduce the loading level of conductive filler material.
Ou Yuchun etc. have reported the mixture of expanded graphite, caprolactam monomer, initiator after appropriate means is handled, and carry out in-situ polymerization under nitrogen protection, preparation conduction percolation threshold (φ
c) only reach 10 for 0.75vol%, specific conductivity
-4The method of nylon 6/ graphite conductive nano composites that S/cm is above, and with this method application national inventing patent (application number 99108082.3).Chen Guohuas etc. are made complete free Nano graphite thin slice by ultrasonic with expanded graphite, carry out in-situ polymerization with polymer monomer again, prepare percolation threshold (φ equally
c) only be nylon 6/ graphite conductive nano composites of 0.74vol%.Though these two kinds of methods have all been prepared the conductive nano composites with lower filler content and higher conductivity, owing to all be the method that adopts in-situ polymerization, technology more complicated and power consumption and consuming time, thereby be unfavorable for practical application.
Summary of the invention
One of the object of the invention will overcome deficiency of the prior art, and a kind of have lower filler content and higher conductivity are provided, and the high conductive polyamide/graphite nano conductive composite material of good moulding processability and mechanical property is arranged.
Two of the object of the invention provides a kind of technology advanced person, simple, and energy-conservation, timesaving prepares the method for high conductive polyamide/graphite nano conductive composite material.
First purpose of the present invention is achieved in that high conductive polyamide/graphite nano conductive composite material, it is characterized in that being made up of polymeric amide and graphite, and the mass percent of polymeric amide and graphite is: polymeric amide 90～99%, graphite 1～10%.
Described graphite is that expansion multiple is a 200-400 expanded graphite doubly.Polymeric amide comprises nylon 6, nylon 66, nylon 1010, Ni Long11, nylon 12, nylon 46, NYLON610, nylon 612, nylon 1212.
The scheme that second purpose of the present invention realizes is that the preparation method of high conductive polyamide/graphite nano conductive composite material is characterized in that comprising the steps:
(1) 30-200 purpose natural flake graphite is joined in the mixed solution that mass ratio is 4: 1 the vitriol oil and concentrated nitric acid and soaked 24 hours, then after washing, drying treatment, heat treated in retort furnace, temperature is 900-1100 ℃, obtains expansion multiple at the expanded graphite more than 200 times;
(2) polyamide resin 90～99 mass parts are joined in the certain amount of solvent, treat that polyamide resin dissolves the back fully to wherein adding above-mentioned expanded graphite 1～10 mass parts, ultrasonic 2h obtains homodisperse mixture, under violent stirring, add a certain amount of suitable deionized water then and make mixture precipitation, with throw out suction filtration, drying, prepare high conductive polyamide/graphite nano conductive composite material at last.
Described solvent is any of formic acid or meta-cresol or dense mineral acid or dimethyl formamide or trifluoroethanol or α-cyanalcohol or methyl alcohol-calcium chloride or hexamethyl phosphoric triamide or 1: 1 phenol-tetrachloroethane.
Technology advanced person of the present invention, simple, energy-conservation, save time, adopt coprecipitation method that polymkeric substance and expanded graphite are dispersed in the solvent, polymer molecule is to the EG intercalation under the effect of solvent, while, EG under ultransonic effect was stripped from the graphite flake into nanometer grade thickness, and was evenly dispersed in the system, and polymkeric substance and graphite flake precipitate simultaneously under the effect of precipitation agent then, thereby the state that nano graphite flakes is dispersed in the polymkeric substance is fixed, and finally obtains nano composite material.
Experimental result shows that the present invention has lower percolation threshold (0.652vol%), is lower than the experimental result of Ou Yuchun and Chen Guohua etc., has higher specific conductivity simultaneously, and when EG content was 2wt%, volume conductance had reached 10
-2S.cm
-1The present invention has kept the mechanical property and the processing characteristics of the excellence of nylon substantially, simultaneously, have static resistance preferably again, therefore have wide industrial prospect, be expected to obtain to use widely in fields such as antistatic material, electromagnetic shielding material, microwave absorbing.
Description of drawings
Fig. 1 is the influence synoptic diagram of EG content to PA6/EG conductive nano composites specific conductivity;
Fig. 2 is the influence synoptic diagram of EG content to PA6/EG conductive nano composites notched Izod impact strength.
Embodiment
Embodiment 1:
Natural flake graphite (30-200 order) is joined middle the immersion 24 hours of mixed solution (mass ratio is 4: 1) of the vitriol oil and concentrated nitric acid, after washing, drying treatment, 900-1100 ℃ of following heat treated in retort furnace obtains expansion multiple 200-400 expanded graphite doubly.Getting Nylon 6 9.9 grams joins in the 200ml formic acid, after treating to dissolve fully, add above-mentioned graphite 0.1 gram, ultrasonic 2h obtains homodisperse mixture, add 200ml deionized water then as precipitation agent, make scattered mixture precipitation,, make the high conductive polyamide/graphite nano conductive composite material that contains EG 1wt% throw out suction filtration, washing, drying.The specific conductivity of gained matrix material and notched Izod impact strength data are seen Fig. 1 and Fig. 2.
Embodiment 2:
Implementation step is with embodiment 1, and the Nylon 6 consumption is 9.8 grams, expanded graphite 0.2 gram.The specific conductivity of gained matrix material and notched Izod impact strength data are seen Fig. 1 and Fig. 2.
Embodiment 3:
Implementation step is with embodiment 1, and the Nylon 6 consumption is 9.2 grams, expanded graphite 0.8 gram.The specific conductivity of gained matrix material and notched Izod impact strength data are seen Fig. 1 and Fig. 2.
When polyamide resin adopts nylon 66 or nylon 1010, Ni Long11, nylon 12, nylon 46, NYLON610, nylon 612, nylon 1212, prepare high conductive polyamide/graphite nano conductive composite material equally.
When solvent adopts formic acid, meta-cresol, dimethyl formamide, trifluoroethanol, α-cyanalcohol, methyl alcohol-calcium chloride, hexamethyl phosphoric triamide, 1: 1 phenol-tetrachloroethane, prepare high conductive polyamide/graphite nano conductive composite material too.
Claims (2)
1, a kind of preparation method of high conductive polyamide/graphite nano conductive composite material is characterized in that comprising the steps:
(1) 30-200 purpose natural flake graphite is joined in the mixed solution that mass ratio is 4: 1 the vitriol oil and concentrated nitric acid and soaked 24 hours, then after washing, drying treatment, heat treated in retort furnace, temperature is 900-1100 ℃, obtains expansion multiple at the expanded graphite more than 200 times;
(2) polyamide resin 90～99 mass parts are joined in the certain amount of solvent, treat that polyamide resin dissolves the back fully to wherein adding above-mentioned expanded graphite 1～10 mass parts, ultrasonic 2h obtains homodisperse mixture, under violent stirring, add a certain amount of suitable deionized water then and make mixture precipitation, with throw out suction filtration, drying, prepare high conductive polyamide/graphite nano conductive composite material at last.
2, the preparation method of high conductive polyamide/graphite nano conductive composite material according to claim 2 is characterized in that described solvent is any of formic acid or meta-cresol or dense mineral acid or dimethyl formamide or trifluoroethanol or α-cyanalcohol or methyl alcohol-calcium chloride or hexamethyl phosphoric triamide or 1: 1 phenol-tetrachloroethane.
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| CN100558815C true CN100558815C (en) | 2009-11-11 |
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| CN101608061B (en) * | 2008-06-17 | 2012-06-13 | 东丽纤维研究所（中国）有限公司 | Polyamide/oxidized graphite composite material with high conduction performance and preparation method thereof |
| CN102604372B (en) * | 2012-02-17 | 2013-06-05 | 南京聚隆科技股份有限公司 | Polyamide composite material with flame retardance and heat conduction and preparation method thereof |
| CN102732009B (en) * | 2012-06-15 | 2014-04-02 | 苏州宇度医疗器械有限责任公司 | Flame retardant electroconductive nylon composite material |
| CN103740092B (en) * | 2013-12-18 | 2016-01-20 | 江苏悦达新材料科技有限公司 | A kind of high thermal conductivity graphene/nylon composite material and preparation method thereof |
| CN105801913B (en) * | 2014-12-31 | 2018-05-15 | 上海凯赛生物技术研发中心有限公司 | Antistatic additive, static resistant polyamide composition and preparation method thereof |
| CN106084760B (en) * | 2016-06-22 | 2018-09-18 | 中北大学 | A kind of nylon 6/ thermally expands graphite conducting composite material and preparation method thereof |
| CN106832733A (en) * | 2017-03-07 | 2017-06-13 | 扬州三涧科贸有限公司 | A kind of preparation method of dielectric polyaniline/elastic composite high |
| CN110041898B (en) * | 2019-05-23 | 2021-06-29 | 江苏碳元绿色建筑科技有限公司 | Nano-material in-situ reinforced porous graphite material and preparation method and application thereof |
| CN114481370A (en) * | 2022-02-25 | 2022-05-13 | 山东大学 | Graphite-doped polyacrylonitrile-based nano composite material and preparation method and application thereof |
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