CN100425653C - Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube - Google Patents
Preparation of low density(0.03-0.2g/cm3)conductive polyurethane foam material containing carbon nanometer tube Download PDFInfo
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- CN100425653C CN100425653C CNB2006100212867A CN200610021286A CN100425653C CN 100425653 C CN100425653 C CN 100425653C CN B2006100212867 A CNB2006100212867 A CN B2006100212867A CN 200610021286 A CN200610021286 A CN 200610021286A CN 100425653 C CN100425653 C CN 100425653C
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Abstract
The present invention discloses a method and a device for preparing low-density (0.03-0.2 g/cm<3>) conductive polyurethane foam material plastic containing carbon nanometer tubes. In the method, the surface of carbon nanometer tube is processed; through a certain technology, the carbon nanometer tubes whose surfaces are modified are uniformly dispersed in polyalcohol to obtain the mixed solution of the carbon nanometer tubes and the polyalcohol; according to a certain proportion, various auxiliary agents are added to the mixed solution of the carbon nanometer tubes and the polyalcohol; after being uniformly stirred and mixed, the mixed solution fully reacts with a certain amount of polyisocyanate and is poured into moulds, and the module cover is closed; finally, finished products are obtained through maturing processing. The prepared low-density carbon nanometer tube / polyurethane foam material composite material has advantages of good electrical conductivity, about 10<1> omega. Cm of volume resistivity and 0.03 to 0.2 g/cm<3> of density; the density and the electrical conductivity can meet the requirements of electric conduction foam in the fields of national defence, electron information industries, etc.
Description
One, technical field
The invention belongs to the novel conductive technical field of polymer materials, is that (CarbonNanotubes, (resistivity is 10 for conduction CNTs) for a kind of preparation carbon nanotubes
6Ω cm is following) and antistatic (resistivity is 10
6-10
9In the Ω cm scope) low density (0.03-0.2g/cm
3) method of urethane foam.
Two, background technology
Urethane foam because of its porousness, field such as relative density is little, thermal insulation good, the specific tenacity advantages of higher is widely used in national defence, automobile, transportation, medical and health, energy-conservation, interstellar flight, the disposal of three wastes, daily life.Conventional polyurethanes porous plastics volume resistivity is usually 10
13-10
17Between the Ω cm, use very good beyond doubt as insulating material.But with urethane foam in the further application aspect the wrapping material such as national defence leading-edge field, sophisticated electronics, medical facilities, the accumulation of static electric charge be released in products productions such as high explosive, electronics, unicircuit, communication equipment, command system, medical facilities, storage, transportation, loading and unloading and use in caused people's extensive concern.Can influence product works better such as electronics, unicircuit, communication equipment, command system, medical facilities because of electrostatic discharges, and can cause the catastrophic failures such as blast, fire of military hazardous substance.According to incompletely statistics, only in electronic industry, annual because static discharges the loss that causes, and the U.S. is up to 10,000,000,000 dollars, Britain is 2,000,000,000 pounds.In addition along with to performance demands such as weapon electromagnetic shielding, wave-absorbing and camouflages, the demand of foam materials with conductive capability is more and more urgent.Therefore, countries in the world are that academia or industrial community have all dropped into a large amount of human and material resources researchs, exploitation conduction and anti-electrostatic polymer foam materials, and are especially outstanding in recent years.
Because foam densities is low, be vesicular structure, conductive path is difficult to form, and therefore, it is very difficult to improve its electroconductibility.Reported mainly that at present following three kinds of approach improve its electroconductibility.
(1) adds the small molecules static inhibitor.Static inhibitor is a kind of small-molecule substance, comprises lipophilic group and hydrophilic radical in the molecule, and lipophilic group connects polymer surfaces, and the water in the hydrophilic radical absorbed air forms moisture film, reduces the surface resistivity of polymkeric substance.Britain ABM chemical company (Davies waits .Resin Technol, and 1988,17 (2): 7) since the eighties in last century, developed Catafor series quaternary ammonium salt static inhibitor.Add the Catafor of 2wt%-3wt% in the low-density polyurethane foam wrapping material, can make surface resistivity and volume specific resistance drop to 10 respectively
11Ω and 10
10-10
11Ω cm.If further improve the molecular weight of this static inhibitor, surface resistivity also can reduce to 1.45 * 10
10Ω.Japanese Kao crystal soda company (Ri Tekaiping 4-298517 (1992)) is since the seventies in last century, adopt a series of quaternary ammonium salt static inhibitor to improve the antistatic property of polyurethane foam, the volume specific resistance of gained foam materials sample was measured after 1～7 day, was respectively 1.8 * 10
7Ω cm and 1.5 * 10
7Ω cm has good antistatic performance, but the less stable of the electrical property of this porous plastics, and with duration of service electroconductibility lose gradually.Germany Semperit company (Ger Offen 2423116 (1975)) goes up and adopts a series of quaternary ammonium salt static inhibitor to improve pre-polymerization method polyurethane foamed material antistatic property the actual seventies, and the surface resistivity of gained foam samples also only reduces to 2 * 10
9～10
10Ω.Jiang Zhiguo etc. (Jiang Zhiguo, etc. Beijing chemical industry, 1993,23 (3): 10) in open-celled rigid polyurethane foams, add 15wt% phosphoric acid ester static inhibitor.The volume specific resistance of goods and surface resistivity are 7.9 * 10
9Ω cm and 1.3 * 10
10Ω is only near the requirement of Antistatic Foam Plastics.
(2) add conductive filler material (as carbon black, graphite, metal-powder etc.).This is that the particle that will have excellent conductive performance is incorporated in the polymkeric substance, overlaps mutually between the particle and forms conductive path, thereby reduce the method for polymer resistive rate.U.S. Bumett company (US Pat4621106 (1986)) proposed in 1986, added conductive carbon black particulate halogenated acetic acid in prescription, and the flexible PU foam surface resistivity of making is 2.4 * 10
6Ω, electrostatic attenuation time 0.65s.Yan Bing etc. (tight ice, etc. New Chemical Materials, 2002,30 (9): 26) Zhi Bei carbon black filled polyurethane foam composite, with the increase of content of carbon black, volume specific resistance decreases, and content of carbon black is 10% o'clock, and volume specific resistance still is 10
8Ω cm.Wu Shuqing etc. (Wu Shuqing, etc. Chinese plastics, 2001,15 (12): 52) also prepared carbon black filled urethane foam, volume specific resistance can reach 10
7-10
9Ω cm.(Jiang Zhiguo such as Jiang Zhiguo, Deng. Beijing chemical industry, 1993,23 (3): 10) studied carbon black filled open-cell polyurethane foam, discovery increases with content of carbon black, product volume resistivity and surface resistivity slowly descend simultaneously. and when the sooty parts by weight reached 7.5%, volume specific resistance and surface resistivity were 1.4 * 10
8Ω cm and 2.6 * 10
8Ω has reached anlistatig requirement.And, when content of carbon black less than 5% the time. the resistivity to sample does not have influence substantially.(stone is of heap of stone, Li Zhongming for the applicant, Deng, Polymer-PlasticsTechnology and Engineering, 2005,44:1323) studied expansible black lead and filled the influence of rigid urethane foam its conductivity, find that volume specific resistance is still up to 1.3 * 10 when expansible black lead content is 20wt%
14Ω cm.
(3) prepare conductive foam plastic by preparation conductive gelatin dipping or steam dipping in-situ polymerization.Be that open-cell foamed plastics is immersed in the high molecular monomer of intrinsic conduction, prepare the polyurethane foam composite that the intrinsic conduction polymer runs through by in-situ polymerization; Or open-cell foamed plastics is immersed in the glue that contains conducting particles or static inhibitor, by improving the method for conductivity attached in the urethane these.(Wang such as Wang, et al.Chemistry of Materials, 2003, the open-cell polyurethane foam that 15:375) will soak in iodine reagent is placed in pyrroles's steam, obtain the matrix material of polypyrrole and polyurethane foam by the method for in-situ polymerization, find that the matrix material specific conductivity is from 5 * 10 when polypyrrole-iodine content increases to 270wt% from 25wt% (with respect to the quality of pure polyurethane foam)
-6S/cm (resistivity 2 * 10
5Ω cm) increases to 3 * 10
-4S/cm (resistivity 3.33 * 10
3Ω cm).(Frisch such as Frisch, et al.Journal of Applied Polymer Science, 2001,80 (6): 893) soak soft and rigid urethane foam with polyaniline, absorbed polyaniline fully up to foam, then 0 ℃ with sample bubble hydrochloric acid soln and deionized water at different concns in, with the deionized water cleaning and dipping foam of polyaniline, dried by the fire 48 hours down at 80 ℃ then, found that the specific conductivity of flex foam does not change with the dimensional change of sample, and for the rigid foam sample of same size, its specific conductivity increases sharply with the increase of the concentration of acid, and its specific conductivity has reached anlistatig requirement.Zhang Hongjuan (Zhang Hongjuan, polyurethane industrial, 2002,17 (2): 35) select for use be added with static inhibitor urethane water and milk glue as steeping fluid, the flexible urethane foam goods be impregnated in wherein, preparing surface resistivity is 10
2-10
8The antistatic foam of Ω.(Lu Changzheng such as Lu Changzheng, Deng, plastics, 2003,32 (5): 50) Shawinigan black be dispersed in make conductive gelatin in the acrylic acid adhesive, again urethane foam is impregnated in the conductive gelatin take out after the roll-in repeatedly, drying, make the polyurethane foamed material that has improved electrical property, when the content of Shawinigan black in glue when 3% is increased to 4.5%, the volume specific resistance of foam sample is from 10
6Ω cm drops to 10
3Ω cm.
Though these present several approach can more or less improve the conductivity of polyurethane foam, all have weak point.As: in the method (1), adding static inhibitor can not form conductive path at material internal; Can only improve surface conductivity and can not improve volume conductance, and surface conductivity also only reaches antistatic level; Static inhibitor is with the duration of service of loss gradually, static resistance variation even disappearance, so its weather resistance, stability and security are relatively poor.In the method (2), common conducting particles is because size is difficult to be distributed in the film place between foam greatly, so the conductive path imperfection, and the resistivity of material of acquisition is too high, can not use as electro-conductive material, and the adding of a large amount of conducting particless has a strong impact on foam-formed processing performance.In the method (3), the method for dipping is only effective to open celled foam; Conductive polymers and foam surface cohesive force are very weak, come off easily, so electrical property instability in the use; Complex process, cost are more high.
There is the conductive filler material filled and process of certain length-to-diameter ratio to improve foamy electroconductibility in the recent period and caused people's attention.Charcoal nanofiber (Yang YL.et al.AdvancedMaterials has studied in U.S. Gupta seminar, 2005,17:1999) and carbon nanotube (Yang YL.et al.Nano Letters, 2005,5 (11): 2131) filled polystyrene foamy conductivity (the about 0.56g/cm of density
3), find that the specific conductivity of polystyrene foam is from 1.0 * 10 when adding 5wt% charcoal fiber
-14S/m (resistivity 1.0 * 10
16Ω cm) increases to 4.5 * 10
-4S/m (resistivity 2.22 * 10
5Ω cm); Add the 5wt% carbon nanotube and also can effectively improve the foamy conductivity.The applicant has prepared density 0.20-0.60g/cm
3The conductive polyurethane foam (Li Zhongming, stone are of heap of stone, Yang Mingbo, Chinese invention patent, application number; 2005100221170).But be that the conductive foam that Gupta seminar or applicant prepared in the past all exists the high defective of density, limited this material and used in a lot of fields.In this patent, the applicant is by improving the structure and the power of self-control agitator, and repeatedly oxidation modification and add stage by stage thinner prepared density 0.03-0.20g/cm
3, volume specific resistance is 10
9-10
1The matrix material of polyurethane foam-carbon nanotube of Ω cm.This material is expected in many fields such as electronic component, national defence, space flight as static protective material, electromagnetic shielding material, lightning protection aircraft skin, sealed cell, various transmitters etc.
Three, summary of the invention
The objective of the invention is at the deficiency that is widely used in conductive polyurethane foam material both at home and abroad, adopt novel conductive filler material---carbon nanotube (Carbon Nanotubes, CNTs), as the conductive filler material of polyurethane foam, adopt texture improvement self-control agitator and new oxidation processing technique and the dispersing technology hard, the semi-rigid conductive polyurethane foam material that prepare low density, low-resistivity.
Body material of the present invention is hard, the semi-hard polyurethane foam of polyvalent alcohol and polyisocyanates (both are the main raw material component), organotin and aminated compounds (both are catalyzer), distilled water (for whipping agent) prepared in reaction.The performance perameter of reactant and auxiliary agent as shown in Table 1.
Raw material that table one the present invention is used and performance perameter thereof
| Material name | Main effect |
| Polyvalent alcohol | Polymer monomers |
| Polyisocyanates | Polymer monomers |
| Trolamine | Crosslinking catalyst |
| Organotin | Catalysts |
| Distilled water | Whipping agent |
| Silicone oil | Suds-stabilizing agent |
The used conductive filler material of the present invention is carbon nanotube (CNTs), comprise multi-walled carbon nano-tubes (MultiwallCarbon Nanotubes, MWCNTs), Single Walled Carbon Nanotube (Single Wall Carbon Nanotubes, SWCNTs), diameter is respectively 5-40nm and 1-2nm, and pipe range is 0.5-100 μ m.
Purpose of the present invention is realized by following technical measures:
The method that carbon nano tube surface provided by the invention is handled is meant that mainly strong oxidizers such as utilizing nitric acid, sulfuric acid, potassium permanganate handles carbon nano tube surface, increases its surface polarity group.
The dispersing method of carbon nanotube provided by the invention, be meant that mainly the CNTs that utilizes homemade planetary stirrer and dispersion methods such as commercially available sonic oscillation, ultrasonication to handle is dispersed in the polyether glycol in the presence of thinner (mainly being acetone, distilled water, dehydrated alcohol isopolarity non-active solvent).
Mould therefor size of the present invention and shape are looked goods size and shape decision, and material can be used aluminium alloy, stainless steel etc.Need open spilehole in the foaming direction, guarantee that the gas in the mould is discharged smoothly when foaming, its size is advisable not produce excessive overflow.
The density of the polyurethane foam of the present invention's preparation is to control by quality, the proportioning of control reactant, and key step is as follows:
(1) weighing takes by weighing raw material and auxiliary agent by table two prescription.
(2) temperature-controlled drying polyvalent alcohol and polyisocyanates are 80 ℃ of down dry 12 hours (temperature can fluctuate up and down, but is not less than 60 ℃, be not higher than 100 ℃ to be advisable, but the time is looked the moisture content proper extension and the shortening of raw material), and dry postcooling is standby to room temperature.
(3) surface modification of carbon nanotube, and adopt non-activated thinner to reduce the viscosity of polyvalent alcohol, the technology that adopts repeatedly oxidation modification and add thinner stage by stage reaches the homodisperse of carbon nanotube.
(4) powerful mixing is catalyzer trolamine and organotin, suds-stabilizing agent---silicone oil, and whipping agent---distilled water joins in the mixed solution of CNTs and polyvalent alcohol, fully stirs with self-control high-power machinery whipping appts, mixes.
(5) polymerization foaming joins polyisocyanates rapidly in the blending ingredients, fully stirs simultaneously, produces as gas, is poured in the mould after when reactant begins to raise, and closes die cap.
(6) the later stage slaking mould that will be full of polyurethane foam is put into baking oven, solidifies 4 hours down at 100 ℃.
(7) sample is taken out in the sample preparation die sinking, removes the surface skining layer, obtains the low density (0.03-0.2g/cm of carbon nanotubes
3) urethane foam.
The amount ranges of each component is as shown in table 2 in the present invention's prescription:
The amount ranges of each component of table two
| Form | Polyvalent alcohol part | Polyisocyanates part | Organotin part | Trolamine part | Silicone oil part | Distillation moisture content | Carbon nanotube part |
| - | 100 | 98～180 | 0.05～0.2 | 0.05～0.2 | 1～10 | 0.1～1 | 0.5～4 |
Annotate: at 0.03-0.2g/cm
3In the density range, when the polyvalent alcohol umber is 100 parts, when the polyisocyanates umber was 98～120 parts, the conductive polyurethane foam material of preparation was a semi-rigid foam; When the polyvalent alcohol umber is 100 parts, when the polyisocyanates umber was 121～180 parts, the conductive polyurethane foam material of preparation was a rigid foam.
Four, advantage of the present invention
(1) conductive polyurethane foam material of the present invention's preparation, the conductive foam plastic of having filled up permanent conduction is difficult to the deficiency of preparation aspect.
What (2) the present invention mainly prepared is the low density conductive polyurethane foam material, and density is at 0.03-0.2g/cm
3, with respect to the density 0.2-0.6g/cm that prepared in the past
3Conductive foam plastic, density is low, the electromagnetic shielding material as wrapping material such as precise electronic device, high explosive, sophisticated weapons preferably, electronic component, the shell of lightning protection aircraft, various transmitters etc.
(3) can to prepare conductivity good in the present invention, and the low conductive polyurethane foam material of conductive agent content.Content as carbon nanotube is 0.5-4wt%, and volume conduction exceedes and oozes threshold values only for 0.05vol%, and volume specific resistance can reach 10
1Ω cm.
(4) conductive polyurethane foam material that makes of the present invention when low density, forms two-dimentional conductive network; Along with the increase of density, transform to three-dimensional conductive network from two-dimentional conductive network.
(5) the conductive polyurethane bubble material plastics that make of the present invention, in use, resistivity is safe from harm to human body, equipment and environment not with duration of service and temperature variation, and is especially significant in environment protection.
Five, the specific embodiment of the invention
Embodiment given below is to specific descriptions of the present invention, is necessary to be pointed out that at this following examples only are used for that the present invention is described further, can not be interpreted as limiting the scope of the invention.
Density 0.05g/cm
3About the prescription of embodiment 1～10 of urethane foam see Table three
The prescription of table three embodiment 1～10
Annotate: 1. what embodiment 3,5,7 and 10 adopted is Single Walled Carbon Nanotube, and caliber is 1～2nm, and pipe range is 50～100 μ m.
2. what all the other not marked embodiment adopted is multi-walled carbon nano-tubes, and caliber is 5～40nm, and pipe range is 0.5～50 μ m density 0.12g/cm
3About the prescription of embodiment 11～20 of urethane foam see Table four
The prescription of table four embodiment 11～20
Annotate: 1. what embodiment 14,15,16 and 19 adopted is Single Walled Carbon Nanotube, and caliber is 1～2nm, and pipe range is 50～100 μ m.
2. what all the other not marked embodiment adopted is multi-walled carbon nano-tubes, and caliber is 5～40nm, and pipe range is 0.5～50 μ m density 0.2g/cm
3About the prescription of embodiment 21～30 of urethane foam see Table five
The prescription of table five embodiment 21～30
Annotate: 1. what embodiment 23,25,26 and 27 adopted is Single Walled Carbon Nanotube, and caliber is 1～2nm, and pipe range is 50～100 μ m.
2. what all the other not marked embodiment adopted is multi-walled carbon nano-tubes, caliber is 5～40nm, pipe range is the electric property of 0.5～50 μ m for the CNTs/ urethane foam of investigation the present invention preparation, and the porous plastics of preparation is pressed its electric property of following standard testing:
Volume specific resistance: with volume specific resistance less than 10
8The sample of Ω cm is processed into 100 * 10 * 5mm
3Batten, test by ASTM D-991.With volume specific resistance greater than 10
8The sample of Ω cm is processed into 100 * 100 * 4mm
3Sample blocks, with the test of ZC36 type high resistant instrument.
Test result sees Table six
The volume specific resistance of table six CNTs/ urethane foam
| Description of materials | Volume specific resistance (Ω cm) |
| |
5.6×10 7 |
| Embodiment 2 | 7.8×10 4 |
| Embodiment 3 | 8.6×10 9 |
| |
5.4×10 7 |
| Embodiment 5 | 7.3×10 4 |
| Embodiment 6 | 8.7×10 3 |
| |
8.3×10 2 |
| Embodiment 8 | 7.4×10 6 |
| Embodiment 9 | 4.3×10 2 |
| Embodiment 10 | 7.9×10 1 |
| Embodiment 11 | 5.3×10 9 |
| Embodiment 12 | 4.9×10 9 |
| Embodiment 13 | 4.3×10 7 |
| Embodiment 14 | 5.8×10 6 |
| Embodiment 15 | 6.7×10 4 |
| Embodiment 16 | 6.5×10 2 |
| Embodiment 17 | 2.7×10 2 |
| |
4.9×10 1 |
| Embodiment 19 | 6.3×10 4 |
| Embodiment 20 | 5.1×10 9 |
| Embodiment 21 | 3.3×10 9 |
| Embodiment 22 | 4.1×10 4 |
| Embodiment 23 | 2.6×10 3 |
| Embodiment 24 | 3.7×10 2 |
| Embodiment 25 | 1.1×10 7 |
| Embodiment 26 | 1.2×10 2 |
| Embodiment 27 | 1.7×10 1 |
| Embodiment 28 | 3.6×10 2 |
| Embodiment 29 | 3.9×10 6 |
| Embodiment 30 | 2.8×10 9 |
Six, description of drawings
Fig. 1 is the low power electron scanning micrograph of embodiment 5 gained CNTs/ urethane foams; Fig. 2 is the high power electron scanning micrograph of embodiment 5 gained CNTs/ urethane foams; Fig. 3 is the low power electron scanning micrograph of embodiment 15 gained CNTs/ urethane foams; Fig. 4 is the high power electron scanning micrograph of embodiment 15 gained CNTs/ rigid urethane foams; Fig. 5 is embodiment 22 gained CNTs/ urethane foam low power electron scanning micrographs.Fig. 6 embodiment 22 gained CNTs/ urethane foam high power electron scanning micrographs.
Claims (5)
1. the density of preparation carbon nanotubes is 0.03-0.2g/cm
3The method of conductive polyurethane foam material is characterized in that preparing by following processing step and condition the urethane foam of carbon nanotubes:
(1) weighing takes by weighing polyvalent alcohol and polyisocyanates by following prescription:
100 parts of polyvalent alcohols; Polyisocyanates 98-180 part; Organotin 0.05-0.2 part; Trolamine 0.05-0.2 part; Silicone oil 1-10 part; Distilled water 0.1-1 part; Carbon nanotube 0.5-4 part
(2) temperature-controlled drying polyvalent alcohol and polyisocyanates descended dry 12 hours at 80 ℃, and dry postcooling is standby to room temperature;
(3) surface modification of carbon nanotube, and adopt non-activated thinner to reduce the viscosity of polyvalent alcohol, thus reach the homodisperse of carbon nanotube;
(4) catalyzer trolamine and organotin, silicone oil, and distilled water joins in the mixed solution of carbon nanotube and polyvalent alcohol powerful mixing, fully stirs with mechanical stirring device, mixes by as above prescription;
(5) the polymerization foaming joins polyisocyanates rapidly in the blending ingredients, fully stirs simultaneously, produces as gas, is poured into when reactant begins to raise in the mould, closes die cap;
(6) the later stage slaking mould that will be full of polyurethane foam is put into baking oven, 100 ℃ solidify 4 hours down after, take out cooling;
(7) sample is taken out in the sample preparation die sinking, removes the surface skining layer, and the density that obtains carbon nanotubes is 0.03-0.2g/cm
3Urethane foam.
2. the density of preparation carbon nanotubes according to claim 1 is 0.03-0.2g/cm
3When the method for conductive polyurethane foam material, step (3) in it is characterized in that carry out claim 1, carbon nanotube adopts that in strong oxidizer nitric acid, sulfuric acid, the potassium permanganate one or more are compound to carry out surface treatment.
3. the density of preparation carbon nanotubes according to claim 1 is 0.03-0.2g/cm
3When the method for conductive polyurethane foam material, step (3) in it is characterized in that carry out claim 1, select any one of carbon nanotube Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, the weight percentage of carbon nanotube is 0.5-4.0%.
4. the density of preparation carbon nanotubes according to claim 1 is 0.03-0.2g/cm
3The method of conductive polyurethane foam material, during the step in it is characterized in that carry out claim 1 (3), adopt in nonactive polar solvent acetone, distilled water, the dehydrated alcohol any one or several compound as thinner, thereby the reduction system viscosity, and reach carbon nanotube homodisperse in polyvalent alcohol by sonic oscillation, ultrasonication, mechanical stirring dispersing method.
5. the density of preparation carbon nanotubes according to claim 1 is 0.03-0.2g/cm
3The method of conductive polyurethane foam material is characterized in that the adding of carbon nanotube improves the conductivity of urethane foam, and the density of the urethane foam of preparation only is 0.03-0.2g/cm
3, volume specific resistance is 10
9-10
1Ω cm.
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| CN101259741B (en) * | 2007-03-06 | 2010-12-08 | 鎔利兴业股份有限公司 | Method for preparing antistatic high foaming material |
| CN101440208B (en) * | 2008-12-09 | 2011-01-12 | 东华大学 | Preparation of functionalized carbon nano-tube modification polyurethane elastomer |
| CN101787109B (en) * | 2009-10-30 | 2012-10-31 | 上海交通大学 | Polyurethane heat insulation foaming material and preparation method thereof |
| CN101866794B (en) * | 2010-03-26 | 2013-04-03 | 电子科技大学 | New application of conductive polyurethane foam plastic of carbon-doped nanotube in vacuum electronic component |
| KR101538056B1 (en) * | 2013-10-02 | 2015-07-20 | 한화케미칼 주식회사 | Prepartion method of polyurethane composite containing carbon nanotube |
| CN106220821B (en) * | 2016-08-23 | 2019-08-09 | 中国科学院合肥物质科学研究院 | A kind of nano combined foam of multifunctional light and its preparation method and application |
| CN108102135A (en) * | 2017-12-30 | 2018-06-01 | 郑州峰泰纳米材料有限公司 | A kind of preparation method of the continuous compound of melamine bubble with anti-static function |
| CN109898107B (en) * | 2019-02-28 | 2021-02-19 | 昆明理工大学 | Foam metal copper-doped carbon nanotube electromagnetic shielding material and preparation method thereof |
| CN113402694A (en) * | 2021-07-02 | 2021-09-17 | 中国人民解放军空军特色医学中心 | Fiber-reinforced flame-retardant polyurethane foam wave-absorbing composite material and preparation method thereof |
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| CN1597792A (en) * | 2004-07-23 | 2005-03-23 | 上海交通大学 | Nano pipe of functional carbon with branching or linear condensation type polymer graft and its preparation process |
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