CN100569851C - A kind of preparation method of carbon nano tube/epoxy resin matrix material - Google Patents
A kind of preparation method of carbon nano tube/epoxy resin matrix material Download PDFInfo
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- CN100569851C CN100569851C CNB2007100521206A CN200710052120A CN100569851C CN 100569851 C CN100569851 C CN 100569851C CN B2007100521206 A CNB2007100521206 A CN B2007100521206A CN 200710052120 A CN200710052120 A CN 200710052120A CN 100569851 C CN100569851 C CN 100569851C
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Abstract
The invention discloses a kind of preparation method of carbon nano tube/epoxy resin matrix material, the step that comprises has: carboxylated after primary carbon nanotube airflow milling, under the effect of condensing agent, introduce polyhydric aliphatic amine in carbon nano tube surface with flexible structure.Adopt hot melt process with Resins, epoxy, carbon nanotube mixing, high-speed stirring, supersound process,, make the carbon nano tube/epoxy resin matrix material, detect its stretching, impact property adding the aromatic amine curing molding.The invention has the beneficial effects as follows: carry out grafting polyhydric aliphatic amine in carbon nano tube surface, improve the functionalisation of surfaces efficient of carbon nanotube, reduce the surface energy of carbon nanotube, reduced the reunion of carbon nanotube self, promoted carbon nanotube in Resins, epoxy, to disperse; The active amido that carbon nano tube surface is introduced has strengthened both avidity, by with the chemical reaction of resin, carbon nanotube organically is connected with Resins, epoxy.Preparation technology of the present invention is simple, and the composite materials property that makes is good, is convenient to the later industrial applications of carbon nanotube.
Description
Technical field
The present invention relates to a kind of preparation method of carbon nano tube/epoxy resin matrix material.
Background technology
Resins, epoxy (EP) is since 20th century, abroad brought into use the thirties, and through 60 years of development, epoxy resin product kind, quality and application thereof have all entered the stage of maturity.Resins, epoxy contains various polarity group and active very big epoxy group(ing), thereby with various polarity materials such as metal, glass, cement, timber, plastics, especially the material that surfactivity is high has very strong bonding force, the cohesive strength of curable epoxide thing is also very big simultaneously, so its Joint strength is very high.Essentially no low molecular weight volatile deposits yields during epoxy resin cure, the volumetric shrinkage of glue-line is little, and is about 1%～2%, can drop to below 0.2% after adding filler.Can have good consistency and reactivity with multiple organism (monomer, resin, rubber) and inorganics (as filler etc.), erosion resistance and dielectric properties are good, can acid-and base-resisting, the corrosion of multiple media such as salt, solvent.Volume specific resistance 10
13～10
16Ω cm, dielectric strength 16-35kV/mm.Since Resins, epoxy have good mechanical characteristic and electrical insulating property, with the cohesiveness of various materials, with and use the handiness of technology.Therefore it can make coating, matrix material, casting material, sizing agent, grind one's teeth in sleep material and injecting forming material, is widely used in the every field of national economy.But Resins, epoxy also has many weak points.From economic angle, its price comparison height; From the material property angle, its poor toughness, cured article is general crisp partially, and antistripping, cracking resistance, shock resistance, tensile property are poor.These shortcomings are very restricted its Application Areas of further expansion.So, be necessary to study the impact, the tensile strength that how to improve Resins, epoxy, prepare better matrix material.
Carbon nanotube (Carbon Nanotubes, CNTs) be one of the focus of Materials science research in recent years, be divided into multi-walled carbon nano-tubes (Multi-walled nanotubes, MWNTs) and Single Walled Carbon Nanotube (Single-walled nanotubes, SWNTs) two kinds.Because of its high length-to-diameter ratio and superpower mechanical property become the monodimension nanometer material that has application potential, it is used and has related to many-sides such as nano electron device, electrochemical material, hydrogen storage material and composite material reinforcement body.The superpower mechanical property of carbon nanotube can greatly improve the intensity and the toughness of matrix material; Specific conductivity that unique conduction and photoelectric properties can be improved polymer materials and the novel opto-electrical polymers material of preparation; Its particular structure can prepare the one-dimensional nano-composite material of metal or metal oxide filling.The emergence of these brand-new materials will produce great effect to people's production and life.
The application of carbon current nanotube in the polymer matrix composite field is one of important directions of carbon nanotube applied research.Carbon nanotube is because of its light weight, and electric conductivity is good, and mechanical property is strong, and its adding can improve performances such as the mechanics of polymer composites and electricity.But the subject matter that carbon nano tube device and matrix material thereof are used be exactly carbon nanotube in polymer-based carbon dispersion and with the avidity of body material.Because the carbon nano tube surface defective is few, lack active group, the solubleness in all kinds of SOLVENTS is all very low.In addition, there are stronger Van der Waals force its huge specific surface area and very high length-to-diameter ratio in addition between the carbon nanotube, it is reunited or winding easily, had a strong impact on its application.The method that traditional carbon nano-tube/polymer composite material adopts physics to fill or coat, be about to carbon nanotube and organic or inorganic material and carry out the simple physics blend, this method has improved the electroconductibility of matrix material to a certain extent, but the easy reunion of carbon nanotube self, can not in matrix material, well disperse, produce defective in composite inner, even reduced the mechanical property of material sometimes, had a strong impact on its application.Therefore the present invention proposes a kind of method of new carbon nano-tube modification, improve its dispersiveness in polymkeric substance, strengthen the avidity of carbon nanotube and Resins, epoxy, finally improve the mechanical property of matrix material.
Summary of the invention
Purpose of the present invention mainly is at the deficiencies in the prior art, proposes a kind of preparation method of carbon nano tube/epoxy resin matrix material of strong mechanical performance.
The preparation method of carbon nano tube/epoxy resin matrix material of the present invention may further comprise the steps:
(1) primary carbon nanotube is carried out after airflow milling handles, stand-by;
(2) be that 68.0% concentrated nitric acid is according to mass/volume with the carbon nanotube of step (1) and mass concentration
Than mixing for the ratio of 1.0g/50～100ml, behind the ultrasonic 30～120min of mixture, 60～90 ℃ are stirred condensing reflux 20～48h down, cooling, a large amount of deionized water dilutions, the washing of millipore filtration decompress filter is to neutral, and product is 90 ℃ of vacuum-dryings, pulverize, obtain carboxylated carbon nanotube;
(3) with the carbon nanotube in the step (2) and condensing agent, dimethyl formamide and binary or polyhydric aliphatic amine thorough mixing in proportion, by weight/volume is: carbon nanotube: condensing agent: dimethyl formamide: binary or polyhydric aliphatic amine amine=1g: 4～8g: 20～60ml: 20～40g.At 120～130 ℃ of condensing reflux 24～48h.Cooling, with dehydrated alcohol dilution, millipore filtration decompress filter, flush away remaining impurities, 80 ℃ of vacuum-dryings are pulverized, and just obtain the carbon nanotube of grafting binary or polyhydric aliphatic amine;
(4) carbon nanotube that step (3) is obtained mixes the curing reaction aftershaping in proportion with Resins, epoxy and aromatic amine curing agent.
(5) experimentation in the step (4) is first weighing Resins, epoxy and carbon nanotube, at 130～180 ℃ of temperature 20～40min that weigh down, its viscosity is reduced Resins, epoxy.Then the exsiccant carbon nanotube is added wherein, high-speed stirring 10～20min, ultrasonic 10～30min adds wherein at the solidifying agent with fusing, and high-speed stirring 10～20min is cast to curing molding in the Standard Module.Just made the carbon nano tube/epoxy resin matrix material.
Among the present invention, said carbon nanotube is a multi-walled carbon nano-tubes, and caliber is 10～30nm, and pipe range is 0.5～100 μ m, purity 〉=95.0%.
Said binary or polyhydric aliphatic amine can be quadrol, hexanediamine, 1,4-butanediamine, 1, at least a in the polyhydric aliphatic amine such as 5-pentamethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylene pentamine.
Said condensing agent is N, N '-dicyclohexylcarbodiimide, N, N '-carbonyl dimidazoles, 4, at least a in the 5-dicyano imidazole.
Said Resins, epoxy is at least a in bisphenol A-type E-51, E-44, E-42, the E-54 type Resins, epoxy.
Said aromatic curing agent is at least a in mphenylenediamine, two amido ditans, the two amido sulfobenzides.
Beneficial effect of the present invention is: the present invention has improved the functionalisation of surfaces efficient of carbon nanotube by carbon nanotube having been carried out grafting snappiness binary or polyhydric aliphatic amine preferably, has reduced the surface energy of carbon nanotube.And the carboxyl that has got around carbon nano tube surface connects the chloride process that amido will pass through, and has both saved processing costs, also makes technology become simple.The modified rear surface of carbon nanotube can reduce greatly, reduced the reunion of carbon nanotube self, the large-area pencil that is gathered into of carbon nanotube in the accompanying drawing after carboxylated as can be seen is behind the grafting polyamine, the pencil carbon nanotube is strutted, and it can better be disperseed in Resins, epoxy.In addition, carbon nano tube surface has been introduced active amido, has strengthened both avidity, by with the chemical reaction of resin, carbon nanotube organically is connected with Resins, epoxy.Preparation technology of the present invention is simple, and the matrix material that makes has excellent mechanical property.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail, be necessary to be pointed out that at this following examples only are used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.
Embodiment 1
(1) takes by weighing the primary carbon nanotube of 5.0g, carry out airflow milling and handle back stand-by;
(2) be that 68.0% concentrated nitric acid mixes than the ratio of 1.0g/50ml according to mass/volume with the carbon nanotube of step (1) and mass concentration, behind the ultrasonic 30min of mixture, 80 ℃ are stirred condensing reflux 24h down, cooling, a large amount of deionized water dilutions, the washing of millipore filtration decompress filter is to neutral, and product is 90 ℃ of vacuum-dryings, pulverize, obtain carboxylated carbon nanotube;
(3) with carbon nanotube and N in the step (2), N '-dicyclohexyl carbimide, dimethyl formamide and quadrol by weight/volume ratio is: carbon nanotube: N, N '-dicyclohexylcarbodiimide: dimethyl formamide: quadrol=1g: 4g: 20ml: 20g mixes.At 125 ℃ of condensing reflux 24h.Cooling, with dehydrated alcohol dilution, millipore filtration decompress filter, flush away remaining impurities, 80 ℃ of vacuum-drying 24h pulverize, and just obtain the carbon nanotube of grafting quadrol;
(4) carbon nanotube that step (3) is obtained and Resins, epoxy and diaminodiphenyl-methane carry out mixing cured moulding in proportion.Weight ratio is: carbon nanotube: Resins, epoxy: diaminodiphenylmethane=1: 77: 23;
(5) experimentation in the step (4) is first weighing Resins, epoxy, diaminodiphenyl-methane and carbon nanotube, at 150 ℃ of warm 30min that weigh down, its viscosity is reduced Resins, epoxy.Then the exsiccant carbon nanotube is added wherein high-speed stirring 10min, ultrasonic 20min, add wherein at the solidifying agent with fusing, high-speed stirring 10min is cast in the Standard Module, 80 ℃ solidify 2h, and 150 ℃ solidify the 4h aftershaping, just make the carbon nano tube/epoxy resin matrix material.
The composite materials property testing method is as follows:
Tensile strength:
Be solidified into the standard testing batten, use the microcomputer control electronics universal testing machine of Shenzhen strong sharp test apparatus company limited, test its tensile strength by GB/T1040-92, test speed is 20mm/min, and pneumatic clamping 5KN, sample marking distance are 50mm.
Shock strength:
The standard testing batten of curing molding uses the XBL-22 overarm shock-testing machine of Shenzhen triumphant strong sharp test apparatus company limited, tests its shock strength by GB/T 1843-1996.
The carbon nano tube/epoxy resin performance of composites test result of embodiment 1 sees Table 1.
Embodiment 2
(1) takes by weighing the primary carbon nanotube of 5.0g, carry out airflow milling and handle back stand-by;
(2) be that 68.0% concentrated nitric acid mixes than the ratio of 1.0g/50ml according to mass/volume with the carbon nanotube of step (1) and mass concentration, behind the ultrasonic 30min of mixture, 75 ℃ are stirred condensing reflux 24h down, cooling, a large amount of deionized water dilutions, the washing of millipore filtration decompress filter is to neutral, and product is 90 ℃ of vacuum-dryings, pulverize, obtain carboxylated carbon nanotube;
(3) with carbon nanotube and N in the step (2), N '-carbonyl dimidazoles, dimethyl formamide and hexanediamine by weight/volume ratio is: carbon nanotube: N, N '-carbonyl dimidazoles: dimethyl formamide: hexanediamine=1g: 4g: 20ml: 30g mixes.At 125 ℃ of condensing reflux 24h.Cooling, with dehydrated alcohol dilution, millipore filtration decompress filter, flush away remaining impurities, 80 ℃ of vacuum-dryings are pulverized, and just obtain the carbon nanotube of grafting hexanediamine amine;
(4) carbon nanotube that step (3) is obtained and Resins, epoxy and diaminodiphenyl-methane carry out mixing cured moulding in proportion.Weight ratio is: carbon nanotube: Resins, epoxy: diaminodiphenyl-methane=2: 77: 23;
(5) experimentation in the step (4) is first weighing Resins, epoxy, diaminodiphenyl-methane and carbon nanotube, at 150 ℃ of warm 30min that weigh down, its viscosity is reduced Resins, epoxy.High-speed stirring 10min, ultrasonic 20min will be added wherein then in dry carbon nanotube, add wherein at the solidifying agent with fusing, high-speed stirring 10min is cast in the Standard Module, 80 ℃ solidify 2h, and 150 ℃ solidify the 4.5h aftershaping, just make moulding carbon nano tube/epoxy resin matrix material
The composite materials property testing method is with implementing 1.
The carbon nano tube/epoxy resin performance of composites of embodiment 2 sees Table 1.
Embodiment 3
(1) takes by weighing the primary carbon nanotube of 5.0g, carry out airflow milling and handle back stand-by;
(2) be that 68.0% concentrated nitric acid mixes than the ratio of 1.0g/50ml according to mass/volume with the carbon nanotube of step (1) and mass concentration, behind the ultrasonic 0.5h of mixture, 75 ℃ are stirred condensing reflux 24h down, cooling, a large amount of deionized water dilutions, the washing of millipore filtration decompress filter is to neutral, and product is 90 ℃ of vacuum-dryings, pulverize, obtain carboxylated carbon nanotube;
(3) with the carbon nanotube and 4 in the step (2), 5-dicyano imidazole, dimethyl formamide and diethylenetriamine by weight/volume ratio is: carbon nanotube: 4,5-dicyano imidazole: dimethyl formamide: mphenylenediamine=1g: 4g: 20ml: 20g mixes.At 125 ℃ of condensing reflux 24h.Cooling, with dehydrated alcohol dilution, millipore filtration decompress filter, flush away remaining impurities, 80 ℃ of vacuum-drying 24h pulverize, and just obtain the carbon nanotube of grafting diethylenetriamine;
(4) carbon nanotube that step (3) is obtained and Resins, epoxy and diaminodiphenyl-methane carry out mixing cured moulding in proportion.Weight ratio is: carbon nanotube: Resins, epoxy: diaminodiphenyl-methane=3: 77: 23;
(5) experimentation in the step (4) is first weighing Resins, epoxy, diaminodiphenyl-methane and carbon nanotube, at 150 ℃ of warm 30min that weigh down, its viscosity is reduced Resins, epoxy.Then the exsiccant carbon nanotube is added wherein high-speed stirring 10min, ultrasonic 20min, add wherein at the solidifying agent with fusing, high-speed stirring 10min is cast in the Standard Module, 80 ℃ solidify 2h, and 150 ℃ solidify the 5h aftershaping, just make the carbon nano tube/epoxy resin matrix material.
The composite materials property testing method is with implementing 1.
The carbon nano tube/epoxy resin performance of composites of embodiment 3 sees Table 1.
The material mechanical performance test data of each embodiment correspondence sees Table 1
Table 1
| Sample | Tensile strength/MPa | Unnotched impact strength/KJ/m 2 | Elongation at break/% |
| Pure EP | 38.62 | 16.1 | 0.86 |
| Embodiment 1 | 43.12 | 17.5 | 1.76 |
| Embodiment 2 | 69.42 | 46.7 | 2.24 |
| Embodiment 3 | 45.58 | 18.2 | 1.03 |
By table as seen, the mechanical property of carbon nano tube/epoxy resin matrix material of the present invention is significantly improved than the Resins, epoxy that does not add carbon nanotube.Tensile strength brings up to 69.42 from 38.62Mpa, and non-notch impacts from 16.1KJ/m
2Bring up to 46.7KJ/m
2, elongation at break brings up to 2.24% from 0.86%.
Claims (1)
1. the preparation method of a carbon nano tube/epoxy resin matrix material is characterized in that may further comprise the steps:
(1) takes by weighing the primary carbon nanotube of 5.0g, carry out airflow milling and handle back stand-by;
(2) be that 68.0% concentrated nitric acid mixes than the ratio of 1.0g/50ml according to mass/volume with the carbon nanotube of step (1) and mass concentration, behind the ultrasonic 30min of mixture, 80 ℃ are stirred condensing reflux 24h down, cooling, a large amount of deionized water dilutions, the washing of millipore filtration decompress filter is to neutral, and product is 90 ℃ of vacuum-dryings, pulverize, obtain carboxylated carbon nanotube;
(3) with carbon nanotube and N in the step (2), N '-dicyclohexyl carbimide, dimethyl formamide and quadrol by weight/volume ratio is: carbon nanotube: N, N '-dicyclohexylcarbodiimide: dimethyl formamide: quadrol=1g: 4g: 20ml: 20g mixes, at 125 ℃ of condensing reflux 24h, and cooling, dilute with dehydrated alcohol, the millipore filtration decompress filter, flush away remaining impurities, 80 ℃ of vacuum-drying 24h, pulverize, just obtain the carbon nanotube of grafting quadrol;
(4) carbon nanotube that step (3) is obtained and Resins, epoxy and diaminodiphenyl-methane carry out mixing cured moulding in proportion, and weight ratio is: carbon nanotube: Resins, epoxy: diaminodiphenylmethane=1: 77: 23;
(5) experimentation in the step (4) is first weighing Resins, epoxy, diaminodiphenyl-methane and carbon nanotube, with Resins, epoxy at 150 ℃ of following constant temperature 30min, its viscosity is reduced, then the exsiccant carbon nanotube is added wherein high-speed stirring 10min, ultrasonic 20min adds wherein at the solidifying agent with fusing, high-speed stirring 10min is cast in the Standard Module, and 80 ℃ solidify 2h, 150 ℃ solidify the 4h aftershaping, just make the carbon nano tube/epoxy resin matrix material.
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| CN101289569B (en) * | 2008-06-16 | 2012-05-09 | 南昌大学 | Method for preparing multi-wall carbon nano-tube/epoxide resin wave- absorbing and camouflage composite material |
| CN101429422B (en) * | 2008-12-01 | 2012-07-04 | 南昌大学 | Method for improving heat conductivity of heat-conduction silicone grease |
| CN101695995B (en) * | 2009-11-11 | 2011-08-31 | 上海交通大学 | Carbon nano tube with grafted amine functional groups and preparation method |
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| CN103396568B (en) * | 2013-08-15 | 2016-01-20 | 上海理工大学 | The preparation method of a kind of multi-walled carbon nano-tubes/epoxy resin laminated film and device used thereof |
| CN103881137A (en) * | 2014-03-06 | 2014-06-25 | 北京化工大学 | Melamine flame retardant graft modified carbon nanotube and manufacturing method thereof |
| CN104341719A (en) * | 2014-10-23 | 2015-02-11 | 衡水学院 | Method for preparing carbon-nanotube epoxy-resin composite material |
| CN104592713A (en) * | 2014-12-31 | 2015-05-06 | 吉林化工学院 | Method for preparing functional carbon nanotube/epoxy resin composite material |
| CN104830027A (en) * | 2015-05-20 | 2015-08-12 | 叶芳 | Method for preparing novel epoxy resin laminated composite material for sports equipment |
| CN105542620B (en) * | 2015-12-24 | 2018-08-10 | 西北工业大学 | Three component carbon nanotube anticorrosive coatings of one kind and preparation method |
| CN106084705B (en) * | 2016-06-09 | 2018-02-23 | 扬州润友复合材料有限公司 | A kind of high intensity antistatic composite material sheet material and preparation method thereof |
| CN108623845A (en) * | 2017-03-24 | 2018-10-09 | 天津大学 | The method and its application of polysiloxane-modified carbon nanotube |
| CN108586809B (en) * | 2018-05-16 | 2019-08-09 | 西北工业大学 | A kind of carbon nanotube base compounded mix and preparation method thereof and a kind of epoxy resin base electro-magnetic screen nanocomposite |
| CN112029240B (en) * | 2020-09-07 | 2023-05-16 | 吉祥三宝高科纺织有限公司 | High-heat-conductivity polymer carbon nano tube composite material and preparation method thereof |
| CN113214603B (en) * | 2021-05-12 | 2022-11-04 | 云南中烟工业有限责任公司 | Carbon nanotube epoxy resin composite material electrode, preparation method and application thereof |
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