CN100549070C - A kind of preparation method of carbon nano-tube/polymer conducing composite material - Google Patents
A kind of preparation method of carbon nano-tube/polymer conducing composite material Download PDFInfo
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- CN100549070C CN100549070C CNB2007100188951A CN200710018895A CN100549070C CN 100549070 C CN100549070 C CN 100549070C CN B2007100188951 A CNB2007100188951 A CN B2007100188951A CN 200710018895 A CN200710018895 A CN 200710018895A CN 100549070 C CN100549070 C CN 100549070C
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Abstract
The invention discloses a kind of preparation method of carbon nano-tube/polymer conducing composite material, 0.3～0.8 part in polymkeric substance is joined in 18.9～57.8 parts of solvents, also constantly be stirred to polymkeric substance fully dissolves cool to room temperature to constant temperature under 110～150 ℃ temperature; Get the solvent of 0.054～0.008 part of carbon nanotube and 80.746～41.392 parts, ultra-sonic dispersion is distributed in the solvent even carbon nanotube in the ultrasonic grinding instrument; Formed two kinds of solution are mixed, place ultrasonic grinding instrument ultra-sonic dispersion that it is mixed; Use qualitative filter paper suction filtration mixing solutions at a slow speed; The gained solid mixture vacuumized under 80～100 ℃ be dried to constant weight; The gained dry solids is hot-forming, can obtain the carbon nano-tube/polymer conducing composite material.The invention enables carbon nanotube being uniformly dispersed in polymkeric substance.
Description
Technical field
The present invention relates to a kind of chemical industry preparation method, especially a kind of preparation method of conducing composite material.
Background technology
Conductive polymeric composite is many to be formed by conductive filler material and polymer blending, and they are used widely in fields such as antistatic and electromagnetic shieldings.Resistivity positive temp coefficient effect (PTC) material is wherein a kind of conductive polymer composite with specific function.The ultimate principle of this specific function material be utilize the conductive network that forms by conductive filler material to external world the response (showing as the variation of resistivity) done of variation of temperature play and control or the sensing effect.The high molecular PTC material is used widely in fields such as communication, microelectronics as overload protection or from the temperature control element.The high molecular PTC material is formed by carbon black filled polyethylene usually, as the overload protection element, requires material to have alap room temperature resistivity and sufficiently high PTC intensity.People can improve electric conductivity by increasing content of carbon black, but tend to reduce the PTC intensity of material like this, cause processing difficulties and mechanical property variation simultaneously.Therefore, develop the emphasis that a kind of new high molecular PTC material becomes present research.
Carbon nanotube has the nanostructure of one dimension hollow, and caliber is generally several nanometers to tens nanometers, and pipe range can reach tens microns even longer, specific surface area is big, physical strength height, electric property excellence, also have unique metal or semi-conductor electroconductibility simultaneously, have a wide range of applications.And because carbon nanotube and polymkeric substance have structural similarity; the two mixing can be maximized favourable factors and minimized unfavourable ones; prepare the matrix material of high-performance even some specific function; can be used for fields such as conduction, antistatic, electromagnetic shielding, microwave absorbing; even carbon nanotube and some polymkeric substance are compound has a resistivity-temperature characteristics; can be used for from temperature control heating and recover overload protection certainly, have broad application prospects.But also just because of specific surface area of carbon nanotube is big, add the intensive Van der Waals force, it is tangled mutually, the dispersion effect in polymkeric substance is poor, and the application of carbon nanotube in polymer composites is restricted.Chinese patent 02113457.X and 200410011336.4 discloses the original position mass polymerization preparation method of carbon nano-tube/polymer and the in-situ polymerization method for preparing of carbon nanotube/PE matrix material respectively, but these two kinds of methods all are to prepare matrix material by monomer polymerization under the condition that carbon nanotube exists.Domestic also have the method for human melt blending to prepare carbon nanotube/HDPE composite conducting material, but this method is difficult to make carbon nanotube to obtain good dispersion effect.The Shenyang chemistry institute adopts solution deposit, with carbon nanotube with ultrasonic dispersing in ethanolic soln, mix with the xylene solution that is dissolved with HDPE then, ultra-sonic dispersion, stirring once more, last sedimentation and filtration prepares carbon nanotube/HDPE conducing composite material, but carbon nanotube dispersion stabilization in ethanolic soln is relatively poor, reunites again easily.Especially for the carbon nano-tube/polymer composite material of high filler loading capacity, can't realize homodisperse with above-mentioned the whole bag of tricks at all.
Summary of the invention
In order to overcome the deficiency that prior art can not the homodisperse carbon nanotube, the invention provides a kind of method for preparing the carbon nano-tube/polymer conducing composite material, can realize the homodisperse of carbon nanotube under the high filler loading capacity.
The technical solution adopted for the present invention to solve the technical problems may further comprise the steps, and wherein said raw material umber is mass fraction except that specified otherwise:
Step 1. joins 0.3～0.8 part in polymkeric substance in 18.9～57.8 parts of solvents, constant temperature 1～10h under 110～150 ℃ temperature, and constantly stir, fully be dissolved in the solvent until polymkeric substance, stop to heat cool to room temperature then;
Step 2. is got 0.054～0.008 part of carbon nanotube, with 80.746～41.392 parts solvent, is ultra-sonic dispersion 5～30min in the ultrasonic grinding instrument of 450～900W at power then, and even carbon nanotube is distributed in the solvent;
Step 3. is mixed the formed two kinds of solution of step 1 and step 2, places ultrasonic grinding instrument ultra-sonic dispersion 5～30min of 450～900W, makes carbon nanotube, polymkeric substance, solvent even;
Step 4. is used qualitative filter paper suction filtration step 3 gained mixing solutions at a slow speed;
Step 5. is filtered the gained solid mixture with step 4 and vacuumize dry 10～50h under 80～100 ℃, until constant weight;
Step 6. is hot-forming with step 5 gained dry solids, can obtain the carbon nano-tube/polymer conducing composite material.
Wherein, the polymkeric substance in the above-mentioned steps is at least a in high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), the polypropylene; Carbon nanotube is mean diameter 0.5～200nm, the Single Walled Carbon Nanotube (SWNTs) of mean length 500nm～20 μ m or multi-walled carbon nano-tubes (MWNTs) at least a.Solvent is at least a in toluene, dimethylbenzene, orthodichlorobenzene, naphthane, the perhydronaphthalene.
The invention has the beneficial effects as follows: the invention enables carbon nanotube being uniformly dispersed in polymkeric substance, customer service the melt blending carbon nanotube shortcoming of reuniting, especially solved the homodisperse problem of high filler loading capacity carbon nanotube in polymkeric substance.Operating process of the present invention is simple, can be used for the preparation of many soluble polymers and carbon nano tube compound material.High length-diameter ratio carbon nanotube/high-density polyethylene composite material with the inventive method preparation has lower percolation threshold; The low length-to-diameter ratio carbon nanotube/high-density polyethylene composite material of homodisperse high filler loading capacity has good PTC effect;
The present invention is further described below in conjunction with embodiment.
Embodiment
Embodiment 1:
Step 1. joins high density polyethylene(HDPE) 2g among the orthodichlorobenzene 100g, constant temperature 2～8h under 120 ℃ temperature, and constantly stir, fully be dissolved in the orthodichlorobenzene until polymkeric substance, stop heating then, cool to room temperature;
Step 2. is 10～20nm with mean diameter, mean length is that the MWNTs20mg of 5～15 μ m mixes with orthodichlorobenzene 100g, at power is that 650W, frequency are ultra-sonic dispersion 10min in the ultrasonic grinding instrument of 20～25KHz, and MWNTs is evenly spread in the orthodichlorobenzene;
Step 3. is mixed step 1 and the formed two kinds of solution of step 2, places the ultrasonic grinding instrument ultra-sonic dispersion 10min of 650W, and MWNTs, high density polyethylene(HDPE), orthodichlorobenzene are mixed;
Step 4. is used qualitative filter paper suction filtration step 3 gained mixing solutions at a slow speed;
Step 5. is filtered the gained solid mixture with step 4 and vacuumize dry 10～50h under 80～100 ℃, until constant weight;
Step 6. is hot-forming with step 5 gained dry solids, can obtain the MWNTs/ Conductive Composites.
Embodiment 2:
Step 1. joins high density polyethylene(HDPE) 1g among the orthodichlorobenzene 70g, constant temperature 2～8h under 120 ℃ temperature, and constantly stir, fully be dissolved in the solvent until polymkeric substance, stop to heat cool to room temperature then;
Step 2. is 60～100nm with mean diameter, mean length is that the MWNTs0.2g of 5～25 μ m mixes with orthodichlorobenzene 300g, at power is that 900W, frequency are ultra-sonic dispersion 20min in the ultrasonic grinding instrument of 20～25KHz, and MWNTs is evenly spread in the orthodichlorobenzene;
Step 3. is mixed step 1 and the formed two kinds of solution of step 2, places the ultrasonic grinding instrument ultra-sonic dispersion 30min of 900W, and MWNTs, high density polyethylene(HDPE), orthodichlorobenzene are mixed;
Step 4. is used qualitative filter paper suction filtration step 3 gained mixing solutions at a slow speed;
Step 5. is filtered the gained solid mixture with step 4 and vacuumize dry 10～50h under 80～100 ℃, until constant weight;
Step 6. is hot-forming with step 5 gained dry solids, can obtain the MWNTs/ Conductive Composites.
Embodiment 3:
Step 1. joins high density polyethylene(HDPE) 2g among the dimethylbenzene 100g, constant temperature 2～8h under 110 ℃ temperature, and constantly stir, fully be dissolved in the dimethylbenzene until polymkeric substance, stop to heat cool to room temperature then;
Step 2. is 10～20nm with mean diameter, mean length is that the MWNTs20mg of 1～20 μ m mixes with dimethylbenzene 100g, at power is that 650W, frequency are ultra-sonic dispersion 10min in the ultrasonic grinding instrument of 20～25KHz, and MWNTs is evenly spread in the dimethylbenzene;
Step 3. is mixed step 1 and the formed two kinds of solution of step 2, places the ultrasonic grinding instrument ultra-sonic dispersion 10min of 650W, and MWNTs, high density polyethylene(HDPE), dimethylbenzene are mixed;
Step 4. is used qualitative filter paper suction filtration step 3 gained mixing solutions at a slow speed;
Step 5. is filtered the gained solid mixture with step 4 and vacuumize dry 10～50h under 80～100 ℃, until constant weight;
Step 6. is hot-forming with step 5 gained dry solids, can obtain the MWNTs/ Conductive Composites.
Embodiment 4:
Step 1. joins ultrahigh molecular weight polyethylene(UHMWPE) 1g among the dimethylbenzene 100g, constant temperature 2～8h under 110 ℃ temperature, and constantly stir, fully be dissolved in the dimethylbenzene until polymkeric substance, stop to heat cool to room temperature then;
Step 2. is 40～60nm with mean diameter, and mean length is that the SWNTs20mg of 1～2 μ m mixes with dimethylbenzene 100g, is that 650W, frequency are ultra-sonic dispersion 15min in the ultrasonic grinding instrument of 20～25KHz at power, and SWNTs is evenly spread in the dimethylbenzene;
Step 3. is mixed step 1 and the formed two kinds of solution of step 2, places the ultrasonic grinding instrument ultra-sonic dispersion 10min of 650W, and SWNTs, ultrahigh molecular weight polyethylene(UHMWPE), dimethylbenzene are mixed;
Step 4. is used qualitative filter paper suction filtration step 3 gained mixing solutions at a slow speed;
Step 5. is filtered the gained solid mixture with step 4 and vacuumize dry 10～50h under 80～100 ℃, until constant weight;
Step 6. is hot-forming with step 5 gained dry solids, can obtain SWNTs/ ultrahigh molecular weight polyethylene(UHMWPE) conducing composite material.
Claims (2)
1, a kind of preparation method of carbon nano-tube/polymer conducing composite material is characterized in that comprising the steps:
(a) polymkeric substance 0.3～0.8 weight part is joined in 18.9～57.8 parts by weight solvent, constant temperature 1～10h under 110～150 ℃ temperature, and constantly stir, fully be dissolved in the solvent until polymkeric substance, stop to heat cool to room temperature then; Described polymkeric substance is at least a in high density polyethylene(HDPE), ultrahigh molecular weight polyethylene(UHMWPE), the polypropylene, and described solvent is at least a in toluene, dimethylbenzene, orthodichlorobenzene, naphthane, the perhydronaphthalene;
(b) getting 0.054～0.008 weight part carbon nanotube, with the solvent of 80.746～41.392 weight parts, is ultra-sonic dispersion 5～30min in the ultrasonic grinding instrument of 450～900W at power then, and even carbon nanotube is distributed in the solvent;
(c) the formed two kinds of solution of step (a) and step (b) mix, and place ultrasonic grinding instrument ultra-sonic dispersion 5～30min of 450～900W, make carbon nanotube, polymkeric substance, solvent even;
(d) using at a slow speed, qualitative filter paper suction filtration step (c) gained mixes a solution;
(e) step (d) is filtered the gained solid mixture and under 80～100 ℃, vacuumize dry 10～50h, until constant weight;
(f) step (e) gained dry solids is hot-forming, can obtain the carbon nano-tube/polymer conducing composite material.
2, the preparation method of a kind of carbon nano-tube/polymer conducing composite material according to claim 1, it is characterized in that: described carbon nanotube is mean diameter 0.5～200nm, the Single Walled Carbon Nanotube of mean length 500nm～20 μ m or multi-walled carbon nano-tubes at least a.
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| CN101831103B (en) * | 2010-05-24 | 2012-10-03 | 哈尔滨理工大学 | High-conductivity polyolefin composite material and preparation method thereof |
| US9748016B2 (en) * | 2011-11-28 | 2017-08-29 | Zeon Corporation | Process for producing carbon nanotube composition and carbon nanotube composition |
| CN103165742B (en) * | 2011-12-16 | 2016-06-08 | 清华大学 | The preparation method of solar cell |
| ES2404780B1 (en) * | 2013-03-25 | 2014-02-13 | Asociación De La Industria Navarra (Ain) | Manufacturing procedure of electrically conductive composites |
| CN103903819A (en) * | 2014-04-14 | 2014-07-02 | 黄河科技学院 | Preparation method of flexible transparent conducting film |
| CN104260514B (en) * | 2014-09-12 | 2017-01-25 | 哈尔滨工业大学 | Preparation method of high-conductivity carbon nano tube paper composite material with infrared stealth and lightning protection performance and application of high-conductivity carbon nano tube paper composite material |
| WO2016134984A1 (en) * | 2015-02-26 | 2016-09-01 | Philips Lighting Holding B.V. | Thermally conductive composites |
| CN107011561A (en) * | 2017-03-22 | 2017-08-04 | 华东理工大学 | A kind of high-impact, antistatic ultra-high molecular weight polyethylene composite material and preparation method thereof |
| GB2564454A (en) * | 2017-07-11 | 2019-01-16 | Rapid Powders Ltd | A method, treated or modified polymer and article of manufacture |
| CN107652504A (en) * | 2017-09-27 | 2018-02-02 | 中玺新材料（安徽）有限公司 | A kind of preparation method of ultra-high molecular weight polyethylene/graphite alkene composite |
| CN107987550A (en) * | 2017-12-27 | 2018-05-04 | 江苏飞博尔新材料科技有限公司 | A kind of preparation method of conducing composite material |
| CN109215833A (en) * | 2018-08-29 | 2019-01-15 | 清华大学深圳研究生院 | A kind of carbon nanotube and PDMS electrically conductive composite and preparation method thereof |
| CN109411760A (en) * | 2018-11-01 | 2019-03-01 | 珠海光宇电池有限公司 | A kind of PTC safety coatings and the preparation method and application thereof |
| CN109575405B (en) * | 2018-12-14 | 2020-05-26 | 中山大学 | Modified ultrahigh molecular weight polyethylene and preparation method thereof, and polyethylene composite material and preparation method thereof |
| CN110184573B (en) * | 2019-06-28 | 2021-10-22 | 成都先锋材料有限公司 | Binding material and binding method of sputtering target material |
| CN111564236B (en) * | 2020-04-28 | 2022-11-29 | 清华大学 | Conductive paste, preparation method and preparation method of conductive film |
| CN112852226A (en) * | 2021-01-15 | 2021-05-28 | 神美科技有限公司 | Sewage pipe network repairing material and preparation method thereof |
| CN114470972A (en) * | 2021-12-28 | 2022-05-13 | 盐城工学院 | Preparation method of carbon nano tube polyester composite filter material |
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