CN1847283A - Prepn process of carbon nanotube epoxy resin curing agent - Google Patents
Prepn process of carbon nanotube epoxy resin curing agent Download PDFInfo
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- CN1847283A CN1847283A CN 200610026002 CN200610026002A CN1847283A CN 1847283 A CN1847283 A CN 1847283A CN 200610026002 CN200610026002 CN 200610026002 CN 200610026002 A CN200610026002 A CN 200610026002A CN 1847283 A CN1847283 A CN 1847283A
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Abstract
The preparation process of carbon nanotube epoxy resin curing agent includes the following steps: reaction of carbon nanotube and sulfuric acid/ nitric acid at 50-170 deg.c under the ultrasonic action for 10-120 min to obtain carboxylated carbon nanotube; dissolving the carboxylated carbon nanotube in N, N'-dimethyl formamide solution to reaction at 60-200 deg.c under the ultrasonic action for 10-120 min, and adding aromatic amino compound and N, N'-dicyclohexyl carbimide shinking agent to prepare the aromatic carboxylated carbon nanotube. The epoxy resin curing agent with aromatic amino compound grafted to the surface of carbon nanotube can raise the mechanical performance of epoxy resin, raise the heat stability of epoxy resin, raise the dispersivity and content of carbon nanotube inside epoxy resin and improve the interface between carbon nanotube and epoxy resin.
Description
Technical field
The invention belongs to the organic polymer material field, relate to a kind of preparation method of epoxy curing agent, particularly relate to a kind of preparation method of carbon nano tube epoxy resin curing agent.
Background technology
Carbon nanotube has unique atomic structure, very high specific surface area, and performances such as good electricity, magnetics, mechanics, therefore in scientific research and practical application, carbon nanotube has broad application prospects in various fields.
Resins, epoxy is a kind of thermoset oligopolymer, poor performance.Except that as the stablizer of polyvinyl chloride etc., there is not direct use value.But after it and solidifying agent are cured reaction and form the three-dimensional crosslinked network structure, then present the performance of a series of excellences.So the chemical reaction performance of solidifying agent and Resins, epoxy is basis, core that Resins, epoxy is used.Behavior and the performance of cured article of Resins, epoxy in solidification process depends on influencing each other and rationally cooperate between curing agents and it and the resin to a great extent, and these depend on the molecular structure of solidifying agent, therefore, being applied in of Resins, epoxy of research is exactly the problem of studying epoxy curing agent in a way.
In epoxy resin composite material, an important factor is the hardness of balance solidifying agent degree of crosslinking and Resins, epoxy.Usually the degree of crosslinking raising will cause impact capacity to descend.Carbon nanotube is the highest nano material of intensity, if carbon nanotube can be used as epoxy curing agent, the mechanical property of epoxy resin composite material will be significantly increased so.
J.Zhu (Adv.Funct.Mater.2004,14, No.7, July) and Man-Lung Sham (Carbon2005, in press) carbon nano tube surface is inserted alicyclic and the fatty amine based compound, be used for epoxy curing agent and come cured epoxy resin, improve the mechanical property of Resins, epoxy.But add the thermotolerance variation that alicyclic or aliphatics amido solidifying agent can make Resins, epoxy in Resins, epoxy, though therefore alicyclic and adding aliphatics amido carbon nano tube improves the mechanical property of Resins, epoxy, thermostability descends.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method of carbon nanotube epoxy resin curing agent, to remedy the deficiencies in the prior art or defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method of carbon nanotube epoxy resin curing agent comprises the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, with volume ratio 3: 1 the at room temperature ultrasonic 10～120min of sulfuric acid/nitric acid, temperature of reaction is 50～170 ℃, reaction times is 10～120min, extremely neutral with deionized water wash, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube.
(2) preparation of aromatic series amido carbon nano tube solidifying agent: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 10～120min under the room temperature; in temperature is 60～200 ℃, and the reaction times is 12～120h; add aromatic amine based compound and N, N '-dicyclohexyl carbimide dehydrating agent is under the nitrogen protection condition; preparation aromatic series amido carbon nano tube; product is through N, N '-dimethyl formamide, tetrahydrofuran (THF); absolute ethanol washing, vacuum-drying.
As optimized technical scheme: comprise the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, is 3: 1 the at room temperature ultrasonic 20～30min of sulfuric acid/nitric acid with volume ratio, and temperature of reaction is 100～140 ℃, and the reaction times is 20～40min; To neutral, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube with deionized water wash.
(2) preparation of aromatic series amido carbon nano tube solidifying agent: carboxylated carbon nanotube is dissolved in N, and in N '-dimethyl formamide solution, ultrasonic 20～30min is 80～120 ℃ in temperature under the room temperature; reaction times is under 24～72h condition; add aromatic amine based compound and N, N '-dicyclohexyl carbimide dehydrating agent is under the nitrogen protection condition; preparation aromatic series amido carbon nano tube; product is through N, N '-dimethyl formamide, tetrahydrofuran (THF); absolute ethanol washing, vacuum-drying.
Described aromatic amine based compound is one or more in m-xylene diamine, mphenylenediamine, two amido ditans and the two amido sulfobenzides.
Described carbon nanotube is many walls or Single Walled Carbon Nanotube.
In a word, the present invention is a starting raw material with single wall or multi-walled carbon nano-tubes,, uses the nitration mixture oxide treatment under certain condition, makes its surface insert functional groups such as carboxyl, hydroxyl.The aminated of carbon nanotube passes through at a certain temperature, adding is as aromatic amine based compound such as m-xylene diamine, mphenylenediamine, two amido ditans and the two amido sulfobenzides etc. of epoxy curing agent, use N, N '-dicyclohexyl carbimide (DCC) makes the carbon nanotube epoxy resin curing agent that the surface has aromatic series amido functional group as dehydrating agent.
Reaction process is as follows:
The chemically modified of carbon nanotube carboxyl:
The chemically modified of carbon nanotube aromatic series amido:
DCC is as dehydrating agent:
The invention has the beneficial effects as follows: connect aromatic amine based compound as epoxy curing agent in carbon nano tube surface, make aminated carbon nanotube as neo-epoxy resin solidifying agent cured epoxy resin, not only the mechanical property of Resins, epoxy can be improved but also the thermostability of Resins, epoxy can be improved, and dispersiveness and the content of raising carbon nanotube in Resins, epoxy, the interface of improving carbon nanotube and Resins, epoxy.
Description of drawings
The infrared spectrogram of Fig. 1 embodiment 1 prepared carboxylic carbon nano-tube
The infrared spectrogram of the multi-walled carbon nano-tubes of two amido sulfobenzides is contained on the surface that Fig. 2 embodiment 1 makes
The infrared spectrogram of the multi-walled carbon nano-tubes of two amido ditans is contained on the surface of Fig. 3 embodiment 3 preparations
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.
Embodiment 1:
With 3g purity is that 95% multi-walled carbon nano-tubes adds and has in the 500ml there-necked flask of whipping appts, and adding volume ratio then is 3: 1 the vitriol oil and the mixture of nitric acid, ultrasonic 30min.At 140 ℃, the reaction times is oxide/carbon nanometer tube under the 20min condition.Gained carboxylic carbon nano-tube (infrared spectrogram such as Fig. 1) is extremely neutral with deionized water wash.Dry in 50 ℃ of vacuum drying ovens.The 1g carboxylic carbon nano-tube is dissolved in N; ultrasonic 30min among the N '-dimethyl formamide (DMF); add 2g N; N '-two amido sulfobenzide, 2g N, N '-dicyclohexyl carbimide; under 120 ℃; nitrogen protection, the reaction times is 72h, the carbon nanotube (infrared spectrogram such as Fig. 2) of amido is contained on the preparation surface.With products therefrom through solution washings such as DMF, THF, dehydrated alcohol, vacuum drying oven drying.Reaction equation is as follows:
To be that 50% aromatic series amido carbon nano tube is dissolved in the acetone soln with the Resins, epoxy mass percent, ultrasonic 30min under the room temperature, add Resins, epoxy after, magnetic agitation is fully disperseed solution.Drips of solution is ground on the sheet at KBr, treat solution evaporation after, infrared tracking curing reaction heats up.Solidify 1h down at 140 ℃, 180 ℃ solidify 2h down, every 20min, carry out examination of infrared spectrum one time.After reaction finishes, stop test.By the infrared spectra graph discovery, the epoxide group of Resins, epoxy exists before the curing reaction, and after the curing reaction end, the epoxide group of Resins, epoxy disappears, the epoxide group that aromatic series amido carbon nano tube and Resins, epoxy are described carries out chemical reaction, and carbon nanotube can be employed as epoxy curing agent.
Embodiment 2:
Prepare carboxylated Single Walled Carbon Nanotube by embodiment 1 described method.Get carboxylated Single Walled Carbon Nanotube 1g; the 1g carboxylic carbon nano-tube is dissolved in ultrasonic 10min among the DMF; add 2g N; N '-two amido sulfobenzide, 2g N, N '-dicyclohexyl carbimide; under 200 ℃; nitrogen protection, the reaction times is 12h, the Single Walled Carbon Nanotube solidifying agent of amido is contained on the preparation surface.
Embodiment 3:
Prepare carboxylated multi-walled carbon nano-tubes by embodiment 1 described method.The 1g carboxylic carbon nano-tube is dissolved in ultrasonic 120min among the DMF; add 2g N; N '-two amido ditan; 2g N; N '-dicyclohexyl carbimide, under 60 ℃, nitrogen protection; reaction times is 120h, and the multi-walled carbon nano-tubes solidifying agent (infrared spectrogram 3.) of amido is contained on the preparation surface.Reaction equation is as follows:
Claims (4)
1, a kind of preparation method of carbon nanotube epoxy resin curing agent is characterized in that: comprise the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, with volume ratio 3: 1 the at room temperature ultrasonic 10～120min of sulfuric acid/nitric acid, temperature of reaction is 50～170 ℃, reaction times is 10～120min, extremely neutral with deionized water wash, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube;
(2) preparation of aromatic series amido carbon nano tube solidifying agent: carboxylated carbon nanotube is dissolved in N, in N '-dimethyl formamide solution, and ultrasonic 10～120min under the room temperature; in temperature is 60～200 ℃, and the reaction times is 12～120h, adds aromatic amine based compound and N; N '-dicyclohexyl carbimide dehydrating agent; under the nitrogen protection condition, preparation aromatic series amido carbon nano tube, product is through N; N '-dimethyl formamide; tetrahydrofuran (THF), absolute ethanol washing, vacuum-drying.
2, preparation method according to claim 1 is characterized in that: comprise the steps:
(1) preparation of carboxylic carbon nano-tube: carbon nanotube is added in the reaction vessel, is 3: 1 the at room temperature ultrasonic 20～30min of sulfuric acid/nitric acid with volume ratio, and temperature of reaction is 100～140 ℃, and the reaction times is 20～40min; To neutral, under 50 ℃, the vacuum drying oven drying obtains carboxylic carbon nano-tube with deionized water wash;
(2) preparation of aromatic series amido carbon nano tube solidifying agent: carboxylated carbon nanotube is dissolved in N, and in N '-dimethyl formamide solution, ultrasonic 20～30min is 80～120 ℃ in temperature under the room temperature; reaction times is under 24～72h condition; add aromatic amine based compound and N, N '-dicyclohexyl carbimide dehydrating agent is under the nitrogen protection condition; preparation aromatic series amido carbon nano tube; product is through N, N '-dimethyl formamide, tetrahydrofuran (THF); absolute ethanol washing, vacuum-drying.
3, preparation method according to claim 1 and 2 is characterized in that: described aromatic amine based compound is one or more in m-xylene diamine, mphenylenediamine, two amido ditans and the two amido sulfobenzides.
4, preparation method according to claim 1 and 2 is characterized in that: described carbon nanotube is many walls or Single Walled Carbon Nanotube.
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| CN111825832A (en) * | 2020-08-04 | 2020-10-27 | 江苏利宏科技发展有限公司 | Epoxy resin curing agent and preparation method thereof |
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| CN1234746C (en) * | 2003-12-04 | 2006-01-04 | 上海交通大学 | Multi-carboxyl polymer grafted water-soluble carbon nanometer tube and preparation method thereof |
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