CN100389147C - Process for preparing rare earth modified carbon nanotube/polypropylene composite materials - Google Patents
Process for preparing rare earth modified carbon nanotube/polypropylene composite materials Download PDFInfo
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- CN100389147C CN100389147C CNB2006100264382A CN200610026438A CN100389147C CN 100389147 C CN100389147 C CN 100389147C CN B2006100264382 A CNB2006100264382 A CN B2006100264382A CN 200610026438 A CN200610026438 A CN 200610026438A CN 100389147 C CN100389147 C CN 100389147C
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Abstract
The present invention relates to a preparation method of a rare earth modification carbon nanotube/ polypropylene composite material, which comprises the following steps: firstly, modifying the surfaces of carbon nanotubes by a rare earth modifying agent under room temperature; secondly, putting the processed carbon nanotubes into a ball mill to be milled; thirdly, blending the carbon nanotube and polypropylene granular materialmechanically, and controlling the weight proportion of the carbon nanotube to be 1 to 10% of blended powder material; then, putting the blended powder material into a mould to be shaped by pressing; finally, hot pressing and solidifying the blended powder material for preparing composite material, wherein the rare earth modifying agent comprises rare earth compounds, alcohol, ethylenediamine tetraacetic acid, ammonium chloride, nitric acid and urea. The present invention has the advantages of simple technological method, low cost and no environmental pollution; the rare earth modification carbon nanotube/ polypropylene composite material has good mechanical performance and tribology performance.
Description
Technical field
The present invention relates to a kind of preparation method of matrix material, relate in particular to a kind of preparation method of rare earth modified carbon nanotube pipe/polypropylene composite material, adopt through the carbon nano-tube filled polypropylene composite material of rare earth surface-treated, to obtain than higher interface binding power, improve the hardness of acrylic resin matrix, and then improve the mechanical property and the abrasion resistance properties of matrix material.
Background technology
Polypropylene (PP) is a kind of thermoplasticity synthetic resins of excellent property, have advantages such as little, nontoxic, the easy processing of proportion, resistance to impact shock, anti-interference song and electrical insulating property are good, be widely used in every field such as packing, daily necessities, chemical industry, automobile, medical treatment, become one of present most widely used plastics.But polypropylene also has some shortcomings, as have bigger molding shrinkage, fragile under low temperaturely split, wear resistance deficiency, heat-drawn wire be not high.The normal method of modification that adopts gives polypropylene new performance in actual production, wherein mainly comprises and uses modification by copolymerization, graft modification, cross-linking modified and filling-modified method to improve polyacrylic performance.Used in filling-modified that talcum powder is filling-modified, method such as calcium carbonate filling modification, wollastonite are filling-modified, glass micro-bead filling modified, but also do not have a kind of novel method that relates to carbon nano-tube filled modification.
Nano material is the type material of being attached great importance in recent years, and many excellent properties that it had can be applicable to many fields, comprising being applied to polymeric material field.Carbon nanotube is a kind of of nano material, and carbon nanotube is the seamless hollow tube that is rolled into by the graphite flake that carbon atom forms, and has peculiar electric property, superpower mechanical property, good adsorption property, thereby has caused very big attention in the material field.
But carbon nanotube radial nano-grade size and high surface energy cause it to reunite easily in polymkeric substance, and be dispersed relatively poor, not only reduced the effective L D ratio of carbon nanotube.And cause slippage between the tube and tube easily, make the reinforced effects variation of carbon nanotube.In addition, the carbon nano tube surface feature is similar to graphite, and insoluble in most solvents, wet performance is poor, is difficult to be formed with effective adhesive with polymeric matrix.In order to improve the dispersed of carbon nanotube and to increase it and the bonding force of polymer interface, must be by to methods such as the physics of the surface modification of carbon nanotube and matrix, chemical modifications, improve the wetting property between carbon nanotube and the matrix, even between carbon nanotube and matrix, form Chemical bond, to improve the interface combination degree between carbon nanotube and the matrix, obtain the high matrix material of interlaminar shear strength.
Summary of the invention
The objective of the invention is at existing Filling and modifying of polypropylene technology, a kind of preparation method of rare earth modified carbon nanotube pipe/polypropylene composite material is provided, it is simple to have technology, the characteristics that reinforced effects is good, can well improve the interface binding power of carbon nanotube and polypropylene matrix, thereby improve the over-all properties of matrix material.
For realizing such purpose, in the technical scheme of the present invention, adopt rare-earth modifier that carbon nanotube is carried out surface modification treatment earlier, carbon nanotube after will handling is again put into the ball mill ball milling, then carbon nanotube is carried out mechanical blending with polypropylene granules, the weight percent of controlling carbon nanotube is 1～10% of a mixed powder, then mixed powder is put into mould compression moulding, obtains rare earth modified carbon nanotube pipe/polypropylene composite material through hot-press solidifying.Can make carbon nanotube/polypropylene composite materials sample or part by mechanical workout more afterwards.Wherein, the component of rare-earth modifier comprises rare earth compound, ethanol, ethylenediamine tetraacetic acid (EDTA), ammonium chloride, nitric acid and urea.
Method concrete steps of the present invention are:
Earlier carbon nanotube is immersed and soak 2～4 hours in the rare-earth modifier, filter the back oven dry.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%.
Carbon nanotube after the rare earth modified processing is mixed with distilled water, and the weight percent that is made into carbon nanotube is 2～10% solution, puts into planetary ball mill ball milling 15～60min, and rotating speed is 100～500r/min.The carbon nanotube that obtains is put into baking oven fully dries.
Then by weight percentage, polypropylene with 90～99% mixes with 1～10% carbon nanotube, carrying out powerful pulverizing of machinery stirs, after stirring mixed powder is put into die for molding, earlier furnace temperature is warming up to 110 ℃, kept 60 minutes, the premolding blank is carried out preformed, this moment, pressure-controlling was at 10～14MPa, and then was warming up to 190～220 ℃ with 60 ℃/hour speed, was incubated 1 hour, make the molding compound moulding, adopt subsequently with the stove temperature reduction way, cool to 80 ℃, pressure remains under the constant pressure in whole process.After temperature drops to below 80 ℃, pressure is removed, the matrix material after the compression molding is taken out together with mould,, obtain rare earth modified carbon nanotube pipe/polypropylene composite material with the room temperature cooling.Can be machined into carbon nanotube/polypropylene composite materials sample or part again.
Rare earth compound of the present invention is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
The present invention is applicable to that various carbon nanotubes strengthens the polypropylene matrix material, and wherein carbon nanotube comprises single wall, double-walled or multi-walled carbon nano-tubes.Polypropylene comprises homopolymerization type polypropylene and copolymerized type propene polymer.
The present invention can solve the problem of carbon nanotube polypropylene composite material interface binding power difference, improves the mechanical property and the tribological property of matrix material, and processing method is simple, and cost is low, environmentally safe.Adopt the matrix material of making through the carbon nano-tube filled polypropylene of rare earth surface-treated to compare, have better mechanical property and tribological property with common same type of material.
Embodiment
Below by specific embodiment technical scheme of the present invention is further described, but do not constitute limitation of the invention.
Embodiment 1:
Used starting material comprise: the polypropylene powder, and PP-K8303, Beijing Yanshan Petrochemical Co. produces.Carbon nanotube: the multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound 0.1%, ethanol 99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05%, ammonium chloride 0.1%, nitric acid 0.02%, urea 0.03%.
At room temperature carbon nanotube is immersed earlier in the rare-earth modifier and soaked 2 hours, filter the back oven dry.Carbon nanotube after handling is mixed with distilled water, and the weight percent that is made into carbon nanotube is 2% solution, puts into planetary ball mill ball milling 30min, and rotating speed is 100r/min.The baking oven of the carbon nanotube that obtains being put into 100 ℃ is fully dried.
Then by weight percentage, polypropylene with 99% mixes with 1% dried carbon nano-tube, carrying out powerful pulverizing of machinery stirs, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 110 ℃, kept 60 minutes, the premolding blank is carried out preformed, this moment pressure-controlling about 10MPa, and then be warming up to about 220 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding, lower the temperature subsequently, adopt with the stove temperature reduction way, cool to 80 ℃, concrete temperature fall time is decided on envrionment conditions.Pressure remains at 10MPa in whole process, after temperature drops to below 80 ℃ pressure is removed, and the matrix material after the compression molding is taken out together with mould, with the room temperature cooling, obtains rare earth modified carbon nanotube pipe/polypropylene composite material.
It is 37MPa that the matrix material that makes according to the method described above records its tensile strength according to standard.
Routine in contrast, under identical content of carbon nanotubes and composite material preparation process condition, carbon nanotube reinforced polypropylene compound material tensile strength without rare earth modified processing is 32.5MPa, and as can be seen, rare earth modified processing has obviously improved the tensile property of matrix material.
Embodiment 2:
Used starting material comprise: the polypropylene powder: the PP-K8303 resin powder that Beijing Yanshan Petrochemical Co. produces.Carbon nanotube: Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound 1.5%, ethanol 96%, ethylenediamine tetraacetic acid (EDTA) 0.2%, ammonium chloride 0.8%, nitric acid 0.5%, urea 1%.
Earlier carbon nanotube is at room temperature immersed in the rare-earth modifier and soaked 3 hours, filter the back oven dry.Carbon nanotube after handling is mixed with distilled water, and the weight percent that is made into carbon nanotube is 6% solution, puts into planetary ball mill ball milling 15min, and rotating speed is 500r/min.The baking oven of the carbon nanotube that obtains being put into 100 ℃ is fully dried.
Then by weight percentage, polypropylene with 95% mixes with 5% dried carbon nano-tube, carry out the powerful stirring of machinery, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 110 ℃, kept 60 minutes, the premolding blank is carried out preformed, this moment pressure-controlling about 12MPa, and then be warming up to about 200 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding, lower the temperature subsequently, adopt with the stove temperature reduction way, cool to 80 ℃, pressure remains at 12MPa in whole process, after temperature drops to below 80 ℃ pressure is removed, and the matrix material after the compression molding is taken out together with mould, with the room temperature cooling, make rare earth modified carbon nanotube pipe/polypropylene abrasion-proof matrix material.Above-mentioned materials is machined into shock test sample and rub(bing)test sample.
Utilize MMD-10 type metope wear testing machine, matrix material to gained carries out the friction and wear behavior test, and with comparing without the carbon nanotube/polypropylene composite materials of rare earth modified processing, experimental result shows: the friction and wear behavior through the carbon nanotube/polypropylene composite materials of rare earth modified processing is better than undressed carbon nanotube/polypropylene composite materials.
Embodiment 3:
Used starting material comprise: the polypropylene powder: the PP-K8303 resin powder that Beijing Yanshan Petrochemical Co. produces.Carbon nanotube: Single Walled Carbon Nanotube, double-walled carbon nano-tube and multi-walled carbon nano-tubes that Nanometer Port Co., Ltd., Shenzhen produces.The weight percentages of components of the rare-earth modifier that is adopted is: rare earth compound 2%, alcohol 95 %, ethylenediamine tetraacetic acid (EDTA) 0.5%, ammonium chloride 1%, nitric acid 0.5%, urea 1%.
Earlier carbon nanotube is at room temperature immersed in the rare-earth modifier and soaked 4 hours, filter the back oven dry.Carbon nanotube after handling is mixed with distilled water, and the weight percent that is made into carbon nanotube is 10% solution, puts into planetary ball mill ball milling 60min, and rotating speed is 400r/min.The baking oven of the carbon nanotube that obtains being put into 100 ℃ is fully dried.
Then by weight percentage, polypropylene with 90% mixes with 10% dried carbon nano-tube, carry out the powerful stirring of machinery, after stirring mixed powder is put into plate vulcanization machine die for molding, earlier furnace temperature is warming up to about 110 ℃, kept 60 minutes, the premolding blank is carried out preformed, this moment pressure-controlling about 14MPa, and then be warming up to about 190 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding, lower the temperature subsequently, adopt with the stove temperature reduction way, cool to 80 ℃, pressure remains at 14MPa in whole process, after temperature drops to below 80 ℃ pressure is removed, and the matrix material after the compression molding is taken out together with mould, with the room temperature cooling, obtain rare earth modified carbon nanotube pipe/polypropylene composite material.
It is 42MPa that the matrix material that makes according to the method described above records its tensile strength according to standard.
Carry out composite material impact test by GB GB1415-83 regulation, the XCJ-40 type charpy impact test machine that adopts Chengde trier factory to produce, obtaining material impact toughness is 46.8kJ/m
2Example under identical content of carbon nanotubes and composite material preparation process condition, is 39.7kJ/m without the matrix material impelling strength of rare earth modified processing in contrast
2Matrix material impelling strength through rare-earth modifier for treatment of the present invention as can be seen is good.
Claims (2)
1. the preparation method of a rare earth modified carbon nanotube pipe/polypropylene composite material is characterized in that earlier carbon nanotube being immersed soaking 2～4 hours in the rare-earth modifier, filters the back oven dry; Carbon nanotube after the rare earth modified processing is mixed with distilled water, the weight percent that is made into carbon nanotube is 2～10% solution, put into planetary ball mill ball milling 15～60min, rotating speed is 100～500r/min, and the baking oven of the carbon nanotube that obtains being put into 100 ℃ is fully dried; Then by weight percentage, polypropylene with 90～99% mixes with 1～10% carbon nanotube, carrying out powerful pulverizing of machinery stirs, after stirring mixed powder is put into die for molding, earlier furnace temperature is warming up to 110 ℃, kept 60 minutes, the premolding blank is carried out preformed, and pressure-controlling is at 10～14MPa, and then is warming up to 190～220 ℃ with 60 ℃/hour speed, be incubated 1 hour, make the molding compound moulding, adopt subsequently and pressure is removed after cooling to 80 ℃ with the stove temperature reduction way, the matrix material after the compression molding is taken out together with mould, with the room temperature cooling, obtain rare earth modified carbon nanotube pipe/polypropylene composite material; The weight percentages of components of wherein said rare-earth modifier is: rare earth compound 0.1～2%, alcohol 95～99.7%, ethylenediamine tetraacetic acid (EDTA) 0.05～0.5%, ammonium chloride 0.1～1%, nitric acid 0.02～0.5%, urea 0.03～1%; Wherein, described rare earth compound is Lanthanum trichloride, Cerium II Chloride, lanthanum trioxide or cerium oxide.
2. according to the preparation method of the rare earth modified carbon nanotube pipe/polypropylene composite material of claim 1, it is characterized in that described carbon nanotube is Single Walled Carbon Nanotube, double-walled carbon nano-tube or multi-walled carbon nano-tubes; Described polypropylene is homopolymerization type polypropylene or copolymerized type propene polymer.
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| CN102743753B (en) * | 2012-07-20 | 2013-11-13 | 上海交通大学 | Preparation method of rare earth-modified oxygen-carrying carbon nanotube |
| CN105602113A (en) * | 2016-02-02 | 2016-05-25 | 宁波美代进出口有限公司 | Flexible tear-resistant hydrophobic garbage bag and preparation method thereof |
| CN105566761A (en) * | 2016-02-03 | 2016-05-11 | 安徽紫金新材料科技股份有限公司 | Environment-friendly macromolecular plastic film and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016257A2 (en) * | 2000-08-24 | 2002-02-28 | William Marsh Rice University | Polymer-wrapped single wall carbon nanotubes |
| JP2004143276A (en) * | 2002-10-24 | 2004-05-20 | Masaru Matsuo | Electroconductive and antistatic polymer film and fiber containing carbon nanotube and method for producing the same |
| CN1654528A (en) * | 2005-01-27 | 2005-08-17 | 中国石油化工股份有限公司 | Carbon nanotube/polypropylene composite materials and process for preparing same |
| KR20060025432A (en) * | 2004-09-16 | 2006-03-21 | 김형수 | A method for improving compatibility of thermoplastic polymer blends |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002016257A2 (en) * | 2000-08-24 | 2002-02-28 | William Marsh Rice University | Polymer-wrapped single wall carbon nanotubes |
| JP2004143276A (en) * | 2002-10-24 | 2004-05-20 | Masaru Matsuo | Electroconductive and antistatic polymer film and fiber containing carbon nanotube and method for producing the same |
| KR20060025432A (en) * | 2004-09-16 | 2006-03-21 | 김형수 | A method for improving compatibility of thermoplastic polymer blends |
| CN1654528A (en) * | 2005-01-27 | 2005-08-17 | 中国石油化工股份有限公司 | Carbon nanotube/polypropylene composite materials and process for preparing same |
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