CN1410475A - Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method - Google Patents
Polymer/carbon nano pipe composite powder and its solid phase shear break up preparation method Download PDFInfo
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Abstract
A polymer/carbon monometre tube composite powder is prepared from granular polymer (average grain size 10 microns-5mm), carbon nanometre tube (0.5-200 nm) and disperser through proportionally mixing in a high-speed stirrer for 5-20 min, and shear-dispersing in a solid-phase shear pulverizing for shear dispersing 1-50 times. It can be used to prepare the plastic, rubber and fibre product with electrically conducting, antistatic, thermally conducting, electromagnetic shielding and microwave absorbing performances.
Description
One, technical field
The present invention relates to polymer/carbon nano-tube composite granule and solid state shear dispersive preparation method thereof
Two, background condition
Carbon nanotube (CNTs) since finding by Japanese scholar Iijima the beginning of the nineties (Iijima S., Nature, 1991,354 (7), 56-58), cause the very big attention of scientific circles and industrial community immediately, be the focus of international scientific research in recent years.Carbon nanotube is divided into multi-walled carbon nano-tubes (MWNTs) and Single Walled Carbon Nanotube (SWNTs), and the graphite flake layer structure of being made up of six-ring is curled and the concentric drums that forms constitutes, different with diameter and spirality, and carbon nanotube can present metal or characteristic of semiconductor.Carbon nanotube has excellent mechanical property, and the strength ratio steel is high 100 times, and proportion has only 1/6 of steel.Carbon nanotube has excellent microwave absorbing characteristic in addition, can be used for electromagnetic shielding or absorbing material etc.Especially, carbon nano-tube/polymer composite material has become focus (AjayanP.M., Stephan O., Colliex C., Tranth D.Science, 1994,265, the 1212-1215 of World Science research since reported first such as Ajayan; Calvert P., Nature, 1999,399,210-211).The compound mutual supplement with each other's advantages or the reinforcement that can realize group element material of carbon nanotube and polymkeric substance, the most economical special performance that effectively utilizes carbon nanotube is the effective way of carbon nanotube stabilization.Carbon nano-tube/polymer composite material has wide application prospect at aspects such as information material, bio-medical material, stealth material, catalyzer, high performance structures material, multifunctional materials, carbon nanotube has the high length-to-diameter ratio and the structure of hollow, has excellent mechanical property, can be used as a kind of super fiber, matrix material is played enhancement.Simultaneously because the carbon nanotube particular electrical, performances such as that the matrix material of formation can have is antistatic, microwave absorbing and electromagnetic shielding.Can application promise in clinical practice be arranged in following field: (1) space vehicle, radar, counting chamber shell, signal processing chamber enclosure, (2) electronic unit, (3) automobile case and parts, (4) nana intelligent fiber etc.The polymer/carbon nano-tube matrix material is generally by solution, melting mixing and in-situ polymerization preparation, but because carbon nanotube is easy to assemble and tangle, up to the present, experimental result and theoretical prediction are still far apart.The key issue that needs to solve is dispersion and the orientation problem of carbon nanotube in polymeric matrix.(Thostenson?E?T，Ren?Z，Chou?T-W，Composites?Science?and?Technology，2001，61，1899-1912)
Three, summary of the invention
The objective of the invention is provides polymer/carbon nano-tube composite granule and solid state shear dispersive preparation method thereof at the deficiencies in the prior art, be characterized in utilizing the solid state mechanochemistry reactor that material is applied powerful pressure, shear-stress and hoop stress, produce high crush efficiency and excellent blending dispersion function, make polymkeric substance and carbon nanotube by rub, shear, break, power is chimeric and process such as power diffusion obtains good polymkeric substance and the carbon nano-tube composite powder of dispersion stabilization.
The objective of the invention is to realize that by following technical measures wherein said raw material mark is parts by weight except that specified otherwise.
The recipe ingredient of polymer/carbon nano-tube composite granule starting raw material is:
5～300 parts in polymkeric substance
0.1～600 part of carbon nanotube
0～10 part of dispersion agent
Wherein polymkeric substance is that median size is that polyethylene, polypropylene, polycarbonate, polymethylmethacrylate, polybutylene terephthalate, polyethylene terephthalate, polyether-ether-ketone, urethane, polymeric amide, polystyrene, polyvinyl chloride, polyoxymethylene, chloroprene rubber, paracril, styrene-butadiene rubber(SBR) and/or poly-(acrylonitrile-butadiene-styrene (ABS)) multipolymer of 100nm～5mm is at least a.Carbon nanotube is that average caliber is 0.5-200nm, and length is that Single Walled Carbon Nanotube and/or the multi-walled carbon nano-tubes of 200nm-20 μ m is at least a.Dispersion agent is higher fatty acid, silane coupling agent, titanate coupling agent, class of department, and tween, OP, hexadecyl trimethyl ammonium bromide, polyacrylate and/or poly-methyl acrylate are at least a.
The solid state shear dispersive preparation method of polymer/carbon nano-tube composite granule:
A: with median size is the polyethylene of 100nm～5mm, polypropylene, polycarbonate, polymethylmethacrylate, polybutylene terephthalate, polyethylene terephthalate, polyether-ether-ketone, urethane, polymeric amide, polystyrene, polyvinyl chloride, polyoxymethylene, chloroprene rubber, paracril; 5～300 parts of styrene-butadiene rubber(SBR) and/or poly-(acrylonitrile-butadiene-styrene (ABS)) multipolymers; average caliber is 0.5-200nm; length is 0.1～600 part of the Single Walled Carbon Nanotube of 200nm-20 μ m and/or multi-walled carbon nano-tubes; dispersion agent is a higher fatty acid; silane coupling agent; titanate coupling agent; class of department; tween; OP; hexadecyl trimethyl ammonium bromide; 0～10 part of polyacrylate and/or poly-methyl acrylate; add in the high-speed stirring mixer; mixed rotating speed 50～500rpm 5～20 minutes;
B: the above-mentioned polymkeric substance and carbon nanotube and/or dispersion agent of mixing sent in the solid state shear disintegrating apparatus, static cutting disk outer side cavity feeds recirculated water, 5～40 ℃ of water temperatures, start millstone type and shear disintegrating apparatus, 10～1000 rev/mins of control rotating speeds, shear grinding dispersion and mix 1～50 time, obtain the polymer/carbon nano-tube composite granule.
This composite granule by extrude, injection moulding or hot-forming, perhaps join in other resin compounds as a kind of component, by extrude, injection moulding or hot-formingly obtain having conduction, plastics, rubber and the fibre product of antistatic, heat conduction, electromagnetic shielding, microwave absorbing characteristic; Perhaps be attached on other base material, form the polymer/carbon nano-tube composite coating by methods such as electrostatic spraying, hot dipping stain, fluidized-beds.
The present invention has following advantage:
1, the present invention utilizes solid state mechanochemistry reactor particular structure and material is applied powerful shear-stress, and crushing medium (mill) closely contacts with crushed material, the crush efficiency height; Can realize the miniaturization and compoundization of polymkeric substance and carbon nanotube simultaneously, form composite nano-powder.
2, solve carbon nanotube and be easy to assemble and tangle, be difficult to the dispersive problem.
3, present method prepares the polymer/carbon nano-tube composite granule under solid conditions, need not heating or deep cooling, have energy-conservation, technology is simple, easy to operate, low cost of manufacture, can realize the mass-producing continuous production; It is a kind of eco-friendly method for preparing ultrafine powder.
4, can obtain high carbon nano-tube/polymer composite material of filling.
Four, embodiment
By the following examples the present invention is specifically described; be necessary that being pointed out that at this that following embodiment only is applicable to further specifies the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment:
1. with median size the polyethylene 300g of～100 μ m, with average caliber be 20～40nm, be about the carbon nanotube 6g of 1 μ m～10 μ m, add in the high speed agitator and mix, mixing time 20 minutes, rotating speed 400rpm, wherein every stirring stopped three minutes in 5 minutes, to prevent that frictional heating from making polymkeric substance softening, adhesion.Feed recirculated water at millstone type force chemical reactor (Chinese patent ZL95111258.9) static cutting disk outer side cavity, 15～20 ℃ of water temperatures start the millstone type force chemical reactor, 40～50 rev/mins of control rotating speeds.By charging opening, add the mixture of forming by polyethylene powder and carbon nanotube, the pulverizing of milling, control feed rate and speed of grinding plate make the residence time of material in mill between 20～40 seconds.Mixture after last time pulverizing is carried out pan-milling once more, collect the fine powder that obtains, mill to death 30 times promptly obtains the uniform polyethylene/carbon nano-tube composite powder of appearance color.With composite granule by the hot-forming polyethylene/carbon nano tube compound material that obtains.Test-results shows: compare with pure polyethylene, tensile strength improves～20%, and shock strength improves 15～30%, and specific conductivity reaches 10
-6S.cm
-1.
2. be 20～40nm for～50 μ m polypropylene 300g with average caliber with median size, be about the carbon nanotube 6g of 1 μ m～10 μ m, add in the high speed agitator and mix, mixing time 20 minutes, rotating speed 400rpm, wherein every stirring stopped three minutes in 5 minutes, made polymkeric substance softening to prevent frictional heating, adhesion.Static cutting disk outer side cavity feeds recirculated water, and 15～20 ℃ of water temperatures start the millstone type force chemical reactor, 40～50 rev/mins of control rotating speeds.By charging opening, add the mixture of forming by polypropylene powder and carbon nanotube, the pulverizing of milling, control feed rate and speed of grinding plate make the residence time of material in mill between 20～40 seconds.Mixture after last time pulverizing is carried out pan-milling once more, collect the fine powder that obtains, mill to death 20 times promptly obtains the uniform polypropylene/carbon nano-tube composite powder of appearance color, with composite granule by the hot-forming polypropylene/carbon nano tube compound material that obtains.Test-results shows: compare with virgin pp, tensile strength improves 25%, and shock strength improves 20%, and specific conductivity reaches 10
-6S.cm
-1.
3. nylon 6 300g that with median size are～100 μ m are 10～20nm with average caliber, be about the carbon nanotube 3g of 1 μ m～5 μ m, add in the high speed agitator and mix, mixing time 20 minutes, rotating speed 400rpm, wherein every stirring stopped three minutes in 5 minutes, made polymkeric substance softening to prevent frictional heating, adhesion.Static cutting disk outer side cavity feeds recirculated water, and 15～20 ℃ of water temperatures start the millstone type force chemical reactor, 40～50 rev/mins of control rotating speeds.By charging opening, add the mixture of forming by nylon 6 powders and carbon nanotube, the pulverizing of milling, control feed rate and speed of grinding plate make the residence time of material in mill between 20～40 seconds.Mixture after last time pulverizing is carried out pan-milling once more, collect the fine powder that obtains, mill to death 20 times promptly obtains uniform nylon 6/ carbon nano-tube composite powder of appearance color, and composite granule is obtained nylon 6/ carbon nano tube compound material by injection molding.Test-results shows: compare with pure nylon 6, tensile strength improves 30%, and shock strength improves 25%, and specific conductivity reaches 10
-6S.cm
-1
4. be that 2～4mm polyurethane elastomer is milled 4 times at the millstone type force chemical reactor with median size, make its shaped flatization and form the thin slice that specific surface increases.Is 20～40nm with the sheet of polyurethane 400g that obtains with average caliber, be about the carbon nanotube 20g of 1 μ m～10 μ m, span-80 2g places high-speed stirring mixer to mix, mixing time 30 minutes, rotating speed 400rpm, every stirring stopped three minutes in 5 minutes, made polymkeric substance softening to prevent frictional heating, adhesion.Static cutting disk outer side cavity feeds recirculated water, and 18～23 ℃ of water temperatures start the millstone type force chemical reactor, 40～50 rev/mins of control rotating speeds.Add the mixture of being made up of sheet of polyurethane, carbon nanotube and Si Ban 80 by charging opening, carry out pan-milling and pulverize, control feed rate and speed of grinding plate make the residence time of material in mill between 20～40 seconds.With the powder mill to death that obtains 50 times, promptly obtain the polyurethane/carbon nano-tube composite granule, with composite granule by the hot-forming conductive polyurethane/carbon nano tube compound material that obtains.Test-results shows: compare with pure urethane, tensile strength improves 25%, and shock strength improves 15%, and specific conductivity reaches 10
-2S.cm
-1, thermally-stabilised raising～20 ℃.
5. the polycarbonate 300g that with median size is～100 μ m is 10～20nm with average caliber, be about the carbon nanotube 9g of 1 μ m～5 μ m, add in the high speed agitator and mix, mixing time 20 minutes, rotating speed 400rpm, wherein every stirring stopped three minutes in 5 minutes, made polymkeric substance softening to prevent frictional heating, adhesion.Static cutting disk outer side cavity feeds recirculated water, and 15～20 ℃ of water temperatures start the millstone type force chemical reactor, 40～50 rev/mins of control rotating speeds.By charging opening, add the mixture of forming by polycarbonate powder and carbon nanotube, the pulverizing of milling, control feed rate and speed of grinding plate make the residence time of material in mill between 20～40 seconds.Mixture after last time pulverizing is carried out pan-milling once more, collect the fine powder that obtains, mill to death 20 times promptly obtains the uniform polycarbonate/carbon nano-tube composite powder of appearance color, and composite granule is obtained polycarbonate/carbon nano tube compound material by injection molding.Test-results shows: compare with polycarbonate, tensile strength improves 20%, and shock strength improves 20%, and specific conductivity reaches 10
-4S.cm
-1
Claims (3)
1, polymer/carbon nano-tube composite granule is characterized in that the recipe ingredient (by weight) of starting raw material is:
5～300 parts in polymkeric substance
0.1～600 part of carbon nanotube
0～10 part of dispersion agent
Wherein polymkeric substance is that median size is the polyethylene of 100nm～5mm, polypropylene, polycarbonate, polymethylmethacrylate, polybutylene terephthalate, polyethylene terephthalate, polyether-ether-ketone, urethane, polymeric amide, polystyrene, polyvinyl chloride, polyoxymethylene, chloroprene rubber, paracril; styrene-butadiene rubber(SBR) and/or poly-(acrylonitrile-butadiene-styrene (ABS)) multipolymer are at least a; carbon nanotube is that average caliber is 0.5-200nm; length is that Single Walled Carbon Nanotube and/or the multi-walled carbon nano-tubes of 200nm-20 μ m is at least a; dispersion agent is a higher fatty acid; silane coupling agent; titanate coupling agent; class of department; tween; OP; hexadecyl trimethyl ammonium bromide, polyacrylate and/or poly-methyl acrylate are at least a.
2. according to the solid state shear dispersive preparation method of claims 1 described polymer/carbon nano-tube composite granule, it is characterized in that:
A: with median size is the polyethylene of 100nm～5mm, polypropylene, polycarbonate, polymethylmethacrylate, polybutylene terephthalate, polyethylene terephthalate, polyether-ether-ketone, urethane, polymeric amide, polystyrene, polyvinyl chloride, polyoxymethylene, chloroprene rubber, paracril; 5～300 parts of styrene-butadiene rubber(SBR) and/or poly-(acrylonitrile-butadiene-styrene (ABS)) multipolymers; average caliber is 0.5-200nm; length is Single Walled Carbon Nanotube and/or the multi-walled carbon nano-tubes of 200nm-20 μ m; 0.1～600 part; dispersion agent is a higher fatty acid; silane coupling agent; titanate coupling agent; class of department; tween; OP; hexadecyl trimethyl ammonium bromide; polyacrylate and/or poly-methyl acrylate; 0～10 part; add in the high-speed stirring mixer and mixed rotating speed 50～500rpm 5～20 minutes;
B: the above-mentioned polymkeric substance and carbon nanotube and/or dispersion agent of mixing sent in the solid state shear disintegrating apparatus, static cutting disk outer side cavity feeds recirculated water, 5～40 ℃ of water temperatures, start the solid state shear disintegrating apparatus, 10～1000 rev/mins of control rotating speeds, shear grinding dispersion and mix 1～50 time, obtain the polymer/carbon nano-tube composite granule.
3. according to the purposes of claims 1 or 2 described polymer/carbon nano-tube composite granules, it is characterized in that this composite granule by extrude, injection moulding or hot-forming, perhaps join in other resin compounds as a kind of component, by extrude, injection moulding or hot-formingly obtain having conduction, plastics, rubber and the fibre product of antistatic, heat conduction, electromagnetic shielding, microwave absorbing characteristic; Perhaps be attached on other base material, form the polymer/carbon nano-tube composite coating by methods such as electrostatic spraying, hot dipping stain, fluidized-beds.
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