CN101439854B - Preparation of boric acid or borate modified nano-carbon tube - Google Patents
Preparation of boric acid or borate modified nano-carbon tube Download PDFInfo
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- CN101439854B CN101439854B CN2008102072615A CN200810207261A CN101439854B CN 101439854 B CN101439854 B CN 101439854B CN 2008102072615 A CN2008102072615 A CN 2008102072615A CN 200810207261 A CN200810207261 A CN 200810207261A CN 101439854 B CN101439854 B CN 101439854B
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Abstract
The invention belongs to the technical field of materials and particularly relates to a method for preparing a carbon nano tube modified by boric acid or borate. The method comprises the following concrete steps: firstly, a carboxylcarbon nano tube reacts with diamine to obtain an aminated carbon nano tube; and then the aminated carbon nano tube reacts with the boric acid or the borate under the action of a catalyst to obtain the carbon nano tube grafted and modified by the boric acid or the borate. The method realizes the covalent grafting of the boric acid or the borate to the carbon nano tube. An obtained product has good dispersion in a high-performance resin matrix, can improve various mechanical properties, the thermal property and the friction property of the resin matrix, and realize the upgrading and updating to products such as a phenolic resin, bimaleimide and ethylene rhodanate or develop novel application fields.
Description
Technical field
The invention belongs to the material technology field, relate to carbon nanotube, especially the method on the carbon nano-tube modified surface of chemical method.
Background technology
Carbon nanotube has excellent mechanical property, electrical property, and it all has huge potential using value in a lot of fields.Prepare carbon nano-tube/polymer composite material, can improve mechanical property, photoelectric properties, high thermal resistance and the frictional property etc. of polymkeric substance.Carbon nano-tube/polymer composite material has become the research direction of a hot topic of matrix material at present.But the water insoluble and organic solvent of the carbon nanotube of micron order length is very easily reunited again, occurs unfavorable state of aggregation in final matrix material, causes the excellent properties of carbon nanotube not give full play to.
Therefore, domestic and international research person is just attempting chemically modified is carried out on the surface of carbon nanotube, the covalent linkage functionalization, non covalent bond that comprises tube wall coats fills in foreign matter and the pipe etc., with improve carbon nanotube in organic solvent dispersiveness and the consistency in the polymeric matrix.Wherein, the covalent linkage functionalization of carbon nanotube is the chemistry that grew up in recent years and the cross discipline of materialogy, because the stability of chemical bond, the research space of diversity and wide region is more and more attracting the very big interest of scientist's research.
The chemical modification method that sees report at present is mainly by strong acid treatment introduces hydroxy-acid group in carbon nano tube surface, carries out chloride, alcoholization or amination then, and then introduces polymer molecule in carbon nano tube surface.The weak point of this method is the strong oxidising process meeting destroying carbon nanometer tube self structure of acidification and cuts off carbon nanotube, influences the performance of carbon nanotube self.Thereby in actual applications, the modifying method that needs to seek the reaction conditions gentleness is introduced suitable group, thereby improves dispersiveness and certain aspect property of carbon nanotube.
Summary of the invention
The preparation method who the purpose of this invention is to provide the boric acid or the borate modified carbon nanotube of reaction conditions gentleness.
The preparation method of boric acid that the present invention proposes or borate modified carbon nanotube at first carries out condensation reaction with carboxyl carbon nanotube and two amine materials, obtains amido modified carbon nanotube; Then boric acid or borate and amido modified carbon nanotube are reacted, reaction finishes after filtering with microporous membrane promptly obtains boric acid or borate modified carbon nanotube.Concrete steps are as follows:
(1) with carboxyl carbon nanotube and diamine is 1: 1～1: 1000 mixed in molar ratio, with the carbodiimide class is condensing agent, in the high boiling solvent system in 50～150 ℃ of temperature oil baths reflux, stir, mixing time is 8～96h, clean unnecessary amine with ethanol, vacuum drying promptly obtains the amination carbon nanotube;
(2) with step (1) gained amination carbon nanotube and boric acid or borate be 1: 1～100 mixed by weight, with alkali is catalyzer, aprotic solvent is a solvent, under the dewatering agent effect, back flow reaction 5～16h under 80～105 ℃ of temperature cleans unnecessary small molecules boric acid or borate with tetrahydrofuran (THF), vacuum drying, promptly obtain boric acid or borate modified carbon nanotube, products therefrom adopts infrared spectrum characterization, 1434cm occurred
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band.
Among the present invention, the carboxyl carbon nanotube comprises single wall, double-walled or multi-walled carbon nano-tubes described in the step (1), and its caliber is 1～50nm, and length is 0.1～50 μ m, and through purification process.
Among the present invention, diamine described in the step (1) comprises quadrol, hexanediamine, Ursol D, mphenylenediamine, diaminodiphenyl-methane, Meng alkane diamines, divinyl propylamine, isophorone diamine, two (4-amino-3 methylcyclohexyl) methane, two (4-aminocyclohexyl) methane, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone; Polyamine comprises diethylenetriamine, triethylene tetramine, tetraethylene pentamine, five ethene hexamines, six ethene, seven amine, N-aminoethyl piperazine, Dyhard RU 100, adipic dihydrazide, 3, two (the 3-aminopropyls)-2 of 9-, 4,8,10-four oxaspiro undecanes, 2,4-diamino-6-[2-methylimidazolyl (1)] ethyl cis triazine, 2,4-diamino-6-[2-ethyl-4 methylimidazolyl (1)] ethyl cis triazine or 2,4-diamino-6[2-undecyl imidazole base (1)] in the aminated compounds etc. of ethyl cis triazine any.
Among the present invention, carbodiimide type condensing agent described in the step (1), as N, N-dicyclohexylcarbodiimide, N, N-DIC, the one to multiple kind in 1-ethyl-3-dimethylamine propyl carbodiimide etc.
Among the present invention, high boiling solvent is 1 described in the step (1), 2-dichlorobenzene, chlorobenzene, p-Xylol, o-Xylol, m-xylene, pimelinketone, hexalin, N, accelerine, N, in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or the quinoline etc. any.
Among the present invention, boric acid is inorganic boric acid or borinic acid described in the step (2), and borate is borax, organo-borane and derivative thereof etc.
Among the present invention, aprotic solvent is pimelinketone, toluene, propylene glycol monomethyl ether, propylene-glycol ethyl ether, N described in the step (2), in dinethylformamide or the N,N-dimethylacetamide etc. any one or more.
Among the present invention, alkaline catalysts is NH described in the step (2)
4OH, NaOH, KOH, Ba (OH)
2, Ca (OH)
2, Al
2O
3, MgO, La
2O
3, ThO
2, KF, Na
2CO
3, CsCO
3Deng in any one or more.
Among the present invention, dewatering agent is benzene or toluene described in the step (2).
The present invention carries out condensation reaction with carboxyl carbon nanotube and two amine materials, obtains amido modified carbon nanotube.With boric acid or the amido modified therewith carbon nanotube reaction of borate, prepare boric acid or borate modified carbon nanotube.This preparation method is simple, be easy to control, products obtained therefrom can be scattered in multiple organic solvent, can be used as nanometer additive and is used for polymer modification or directly is used as nano-hybrid material, and with performance resins matrix such as resol etc. good consistency is arranged.Because institute's grafted molecule segment is shorter, can give full play to the nano effect of carbon nanotube, and then in the performance resins matrix, well disperse, improve every mechanical property, thermal characteristics and the frictional behaviour of resin matrix, realize the upgrading of performance resins matrix products such as (resol, bismaleimides, cyanates) or open up new Application Areas.
Description of drawings
Fig. 1 is the infrared spectra of embodiment 1 boric acid grafting and modifying carbon nanotube, 1434cm occurred
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band.
Fig. 2 is many walls carboxyl carbon nanotube-g-quadrol-g-boric acid and comparative example wall more than the 1 amination carbon nanotube (left side: amination carbon nanotube, the right side: many walls carboxyl carbon nanotube-g-quadrol-g-boric acid) of the photo after leaving standstill 6 hours behind the ultra-sonic dispersion in acetone of embodiment 1.
Embodiment
Further specify the present invention below by embodiment.
Embodiment 1: the preparation of many walls carboxyl carbon nanotube-g-quadrol-boric acid
Step 1: get many walls carboxyl carbon nanotube 400mg and place reaction flask, add condensing agent N, N-dicyclohexylcarbodiimide (DCC) 5g, and add quadrol 25ml, uniform mixing.Oil bath backflow 12h under 115 ℃ of temperature, after reaction is finished, with the unnecessary amine of the ultrasonic flush away of dehydrated alcohol, filter with millipore filtration (diameter is 0.45 μ m), repeated washing is neutral up to filtrate Ph value several times, collects carbon nanotube, 40 ℃ of vacuum-drying 24h obtain the amination carbon nanotube of black.
Step 2: get step (1) gained amination carbon nanotube 100mg and place reaction flask, add 3g boric acid, add catalyzer 5ml ammoniacal liquor, the 50ml propylene glycol monomethyl ether is a solvent, 20ml toluene is as dewatering agent, the 4h that refluxes under 95 ℃ of temperature is the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture after reaction is finished, and tetrahydrofuran (THF) is washed till the limpid neutrality of filtrate.Product places vacuum drying oven, and 40 ℃ of following vacuum-drying 12h promptly get the multi-walled carbon nano-tubes that boric acid is modified.1434cm has appearred in infrared spectra
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band.
The reaction process of boric acid grafting carbon nanotube is as follows:
Embodiment 2: the preparation of many walls carboxyl carbon nanotube-g-quadrol-borax.
Step 1: get many walls carboxyl carbon nanotube 400mg and place reaction flask, add condensing agent N, N-dicyclohexylcarbodiimide (DCC) 5g, and add quadrol 30ml, uniform mixing.At 140 ℃ of backflow 8h, after reaction is finished, with the unnecessary amine of the ultrasonic flush away of dehydrated alcohol, filter with millipore filtration (diameter is 0.45 μ m), repeated washing is neutral up to filtrate Ph value several times, collect carbon nanotube, 40 ℃ of vacuum-drying 24h obtain the amination carbon nanotube of black.
Step 2: get above-mentioned amination carbon nanotube 100mg and place reaction flask, add the 4g borax, 20% (quality) NaOH aqueous solution of 5ml is catalyzer, the 50ml propylene glycol monomethyl ether is a solvent, 20ml toluene is as dewatering agent, in 100 ℃ of backflow 5h, be the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture after reaction is finished, tetrahydrofuran (THF) is washed till the limpid neutrality of filtrate.Product places vacuum drying oven, and 40 ℃ of following vacuum-drying 24h promptly get the multi-walled carbon nano-tubes that borax is modified.1434cm has appearred in infrared spectra
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band, products therefrom has dispersion stabilization preferably in acetone soln.
Embodiment 3: the preparation of many walls carboxyl carbon nanotube-g-diaminodiphenyl-methane-boric acid.
Step 1: get many walls carboxyl carbon nanotube 300mg and place reaction flask, add condensing agent N, N-DIC (DIC) 6g, and add diaminodiphenyl-methane 20g, uniform mixing.At 120 ℃ of backflow 36h.After reaction is finished,, filter with millipore filtration (diameter is 0.45 μ m) with the unnecessary amine of the ultrasonic flush away of dehydrated alcohol, repeated washing is neutral up to filtrate Ph value several times, collects carbon nanotube, 40 ℃ of vacuum-drying 24h obtain the amination multi-walled carbon nano-tubes of black.
Step 2: get above-mentioned amination carbon nanotube 100mg and place reaction flask, add 3g boric acid, 10% (quality) Ba (OH) of 5ml
2The aqueous solution is catalyzer, and the 50ml propylene glycol monomethyl ether is a solvent, and 20ml toluene is dewatering agent, in 95 ℃ of backflow 5h, is the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture after reaction is finished, and tetrahydrofuran (THF) is washed till the limpid neutrality of filtrate.Product places vacuum drying oven, and 40 ℃ of following vacuum-drying 24h promptly get the multi-walled carbon nano-tubes that boric acid is modified.1434cm has appearred in infrared spectra
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band, products therefrom has dispersion stabilization preferably in acetone soln.
Embodiment 4: the preparation of single wall carboxyl carbon nanotube-g-hexanediamine-borax.
Step 1: get single wall carboxyl carbon nanotube 300mg and place reaction flask, add condensing agent N, N-DIC (DIC) 6g, and add hexanediamine 15g, uniform mixing.At 120 ℃ of backflow 36h.After reaction is finished,, filter with millipore filtration (diameter is 0.45 μ m) with the unnecessary amine of the ultrasonic flush away of dehydrated alcohol, repeated washing is neutral up to filtrate Ph value several times, collects carbon nanotube, 40 ℃ of vacuum-drying 24h obtain the amination multi-walled carbon nano-tubes of black.
Step 2: get above-mentioned amination carbon nanotube 100mg and place reaction flask, add the 4g Sodium Tetraborate, 10% (quality) Ba (OH) of 5ml
2The aqueous solution is catalyzer, and the 50ml propylene glycol monomethyl ether is a solvent, and 20ml toluene is dewatering agent, in 95 ℃ of backflow 5h, is the inclined to one side fluorine membrane filtration of 0.45 μ m with the aperture after reaction is finished, and tetrahydrofuran (THF) is washed till the limpid neutrality of filtrate.Product places vacuum drying oven, and 40 ℃ of following vacuum-drying 24h promptly get the multi-walled carbon nano-tubes that boric acid is modified.1434cm has appearred in infrared spectra
-1, 1309cm
-1And 1085cm
-1The boric acid ester charateristic avsorption band, products therefrom has dispersion stabilization preferably in acetone soln.
Comparative example 1: the preparation of many walls amino-carbon nanotube
Get many walls carboxyl carbon nanotube 300mg and place reaction flask, add condensing agent dicyclohexylcarbodiimide (DCC) 6g, and add Ursol D 20g, uniform mixing.At 110 ℃ of backflow 30h.After reaction is finished, with the ultrasonic flush away of dehydrated alcohol unnecessary amine, filter with millipore filtration (diameter is 0.45 μ m), repeated washing is neutrality up to filtrate Ph value several times, the collection carbon nanotube, and 40 ℃ of vacuum-drying 24h obtain the amino multi-walled carbon nano-tubes of black.
Claims (7)
1. the preparation method of boric acid or borate modified carbon nanotube is characterized in that at first carboxyl carbon nanotube and diamine being carried out condensation reaction, obtains amido modified carbon nanotube; Then boric acid or borate and amido modified carbon nanotube are reacted, reaction finishes after filtering with microporous membrane promptly obtains boric acid or borate modified carbon nanotube, and concrete steps are as follows:
(1) with carboxyl carbon nanotube and diamine is 1: 1～1: 1000 mixed in molar ratio, with the carbodiimide class is condensing agent, in the high boiling solvent system in 50～150 ℃ of temperature oil baths reflux, stir, mixing time is 8～96h, clean unnecessary amine with ethanol, vacuum drying promptly obtains the amination carbon nanotube;
(2) with step (1) gained amination carbon nanotube and boric acid or borate be 1: 1～100 mixed by weight, with the bases is catalyzer, aprotic solvent is a solvent, under the dewatering agent effect, back flow reaction 5～16h under 80～105 ℃ of temperature, clean unnecessary small molecules boric acid or borate with tetrahydrofuran (THF), vacuum drying promptly obtains boric acid or borate modified carbon nanotube; Wherein: described boric acid is inorganic boric acid or borinic acid, and described borate is a borax; Described high boiling solvent is 1,2-dichlorobenzene, chlorobenzene, p-Xylol, o-Xylol, m-xylene, pimelinketone, hexalin, N, accelerine, N, in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone or the quinoline any.
2. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube, it is characterized in that the carboxyl carbon nanotube comprises single wall or multi-walled carbon nano-tubes described in the step (1), its caliber is 1～50nm, and length is 0.1～50 μ m, and through purification process.
3. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube is characterized in that diamine described in the step (1) comprises quadrol, hexanediamine, Ursol D, mphenylenediamine, diaminodiphenyl-methane, Meng alkane diamines, isophorone diamine, two (4-amino-3 methylcyclohexyl) methane, two (4-aminocyclohexyl) methane, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone.
4. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube, it is characterized in that carbodiimide type condensing agent is N described in the step (1), N-dicyclohexylcarbodiimide, N, the one to multiple kind in N-DIC or 1-ethyl-3-dimethylamine propyl carbodiimide.
5. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube, it is characterized in that aprotic solvent is pimelinketone, toluene, propylene glycol monomethyl ether, propylene-glycol ethyl ether, N described in the step (2), in dinethylformamide or the N,N-dimethylacetamide any one or more.
6. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube is characterized in that alkaline catalysts is NH described in the step (2)
4OH, NaOH, KOH, Ba (OH)
2Or Ca (OH)
2In any one or more.
7. the preparation method of boric acid according to claim 1 or borate modified carbon nanotube is characterized in that dewatering agent is benzene or toluene described in the step (2).
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