CN102515141A - Method for synthesizing modified SWCNTs (Single Wall Carbon Nano Tubes) based on Bergman cyclizing reaction - Google Patents
Method for synthesizing modified SWCNTs (Single Wall Carbon Nano Tubes) based on Bergman cyclizing reaction Download PDFInfo
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Abstract
The invention relates to a method for synthesizing modified SWCNTs (Single Wall Carbon Nano Tubes) based on Bergman cyclizing reaction. The method is characterized by comprising the following steps: weighting 10mg purified SWCNTs, of which the purity is more than or equal to 95%; placing the SWCNTs into a dry Schlenk bottle; adding anhydrous N-methyl pyrrolidone; ultrasonically dispersing; adding a 1.0g compound G1 or G2 equivalent to 4eq SWCNTs; keeping on ultrasonically dispersing; under the protection of nitrogen, heating the reacting mixture at 170-190 DEG C and flowing back; stirring and reacting for 3-4 days; cooling the products to room temperature; filtering the obtained greenblack products with a 0.22 micron polytetrafluoroethylene filtering film; washing the products with a large amount of ethyl ether and tetrahydrofuran in turn till the filtrate is colorless; and lastly, vacuum-drying, thereby obtaining about 14mg products of SWCNTs-G1 or SWCNTs-G2. After the modified CNTs (Carbon Nano Tubes) and PCL (Polycaprolactam) are mixed and dispersed in a tetrahydrofuran solution, the electrostatic spinning operation is performed. Observed from a transmission electron microscope, the CNTs are axially arrayed in PCL silk fibers and are excellently dispersed. A way for applying the modified CNTs in a compound material is supplied.
Description
Technical field
The present invention relates to the compound method of the functionalization SWCN of cyclization, particularly a kind of method based on Bergman cyclization modification SWCN.
Background technology
Carbon nanotube (CNTs) because it has unique chemical, electronics and mechanical property, has made it obtain extensive concern in many research fields since finding in 1991.Be included in the research and the application of aspects such as high performance composite, chemical sensor, nanoelectronic element, photovoltaic device and biological medicine.Yet, owing to have the effect of stronger Van der Waals force and pi-pi bond between the carbon nanotube, so that tight agglomeration takes place, caused carbon nanotube indissoluble and be difficult to dispersion in solvent, finally limited its use.Therefore, many investigators are devoted to carbon nanotube is carried out modification, through the whole bag of tricks the limit wall of carbon nanotube are modified solvability and dispersiveness to increase it.At present, the functional modification of carbon nanotube is mainly studied through covalent linkage method and two kinds of methods of non covalent bond method.Wherein, the non covalent bond method is through surfactant modified, polymkeric substance parcel and polymkeric substance absorption etc. carbon nanotube to be carried out finishing; Several different methods attack carbon tube edge walls such as the finishing of covalent linkage method then is through controllable free-radical polymerisation, free radical addition, fluoridize, cycloaddition and drumming reaction are with sp
2The chemical bond of form hydridization reaches the purpose to the modification of carbon pipe.
The Bergman cyclization is meant that the compound that contains the enediyne structure can produce 1 under heating, ultraviolet lighting and certain pH value condition, the reaction of 4-diradical, and Fig. 1 is seen in concrete reaction.This reaction system can combine radical formation six-ring compounds such as Wasserstoffatoms, thereby can impel the cracking of DNA in the targeted cells, and therefore, the enediyne compound is widely used in the research of cancer therapy drug at first.In addition, the Bergman cyclization also is used to the synthetic and preparation of matrix material.But the research that SWCN carries out modification is not also appeared in the newspapers up to now, through the Bergman cyclization.
Summary of the invention
The dendritic compound that the present invention utilizes synthetic to contain the enediyne structure produces diradical through the Bergman cyclization, and reaches the purpose of modification carbon pipe with the unsaturated double-bond on " grafting onto " method attack SWCN (SWCNTs) surface.Preliminary study the dispersiveness of modified carbon nano-tube in the electrospun fibers of polycaprolactone (PCL), to explore its application in nano composite material.
The method that the present invention is based on Bergman cyclization modification SWCN is following:
Used instrument of the present invention and reagent:
Nucleus magnetic resonance (Ultra Shield 400 spectrometer types, the U.S.); Liquid chromatography/flight time mass spectrum combined instrument (Micromass LCTTM type, Britain); Thermogravimetric analyzer (SDT Q600 type, the U.S.); Ultraviolet-visible spectrophotometer (UV-2550PC type, Japan); Fourier transformation infrared spectrometer (Nicolet 5700 types, the U.S.); Transmission electron microscope (JEM-2010/INCA type, Britain); Electrospinning device (self-control, spinning voltage: 30kV).
SWCN SWCNTs, purity >=95%, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences produces.Carry out purifying before the use.Dendritic G1 and G2, concrete compound method be prior art, the applicant has delivered pertinent literature, repeats no more here.The full name of G1 is: 4-(2-phenylacetylene base) butyl-3-alkynes 3, and 5-two (n-Hexadecane oxygen base) benzoic ether, the full name of G2 is: 4-(2-phenylacetylene base) butyl-3-alkynes 3,5-two (3,5-two (n-Hexadecane oxygen base) phenoxy) benzoic ether.Polycaprolactone (PCL) molecular weight is 105g/mol, Shenzhen brilliance chemistry ltd, and all purified processing before organic solvents such as N-Methyl pyrrolidone, THF and methylene dichloride use, other reagent directly uses.
Synthesizing of functionalization SWCN of the present invention
The modification concrete operations of SWCN are following:
The SWCNTs that takes by weighing behind the 10mg purifying places exsiccant Schlenk bottle, adds the anhydrous N-Methyl pyrrolidone of 20～30mL, and ultra-sonic dispersion is about 30 minutes.Add the compound G1 be equivalent to 4eq SWCNTs then, 1.0g continued ultrasonic 10～15 minutes, with reaction mixture under nitrogen protection in 170～190 ℃ of following reflux, stirring reaction 3～4 days.Again product is cooled to room temperature; The blackish green product of gained filters with 0.22 μ m teflon membrane filter; And successively with ether, THF washed product be to filtrating colourless till, at last the black product about 24 hours, is obtained 14mg product S WCNTs-G1 90～100 ℃ of following vacuum-dryings.
In like manner, as grafts,, obtain 11mg SWCNTs-G2 with G2 according to identical modifying method.Above two kinds of modification SWCNs are characterized accordingly.
Respectively with the SWCNTs-G1 after the modification and SWCNTs-G2 and PCL in THF (THF) solution in: the ratio of modification SWCNTs/PCL/THF=0.001/0.1/1 (mass ratio) in 40 ℃ of heating, stirring and dissolving down.Adopt homemade electrostatic spinning apparatus 2.5 * 10 then
4Make the modified carbon nano-tube composite spun fiber under the V voltage, it is collected carbon supporting film copper mesh surface, utilize the doping situation of transmission electron microscope observing carbon pipe.
The present invention utilizes synthetic to have the dendritic compound of enediyne structure; At a certain temperature; In the N-Methyl pyrrolidone solvent, react with SWCN generation free radical addition; Carbon nano tube modified characterizes through thermogravimetric analysis, ir spectra, UV spectrum, nucleus magnetic resonance, and with its pattern of transmission electron microscope observing.The result proves that dendritic compound is the radical attack carbon nano tube surface sp that at high temperature produces through the Bergman cyclization
2The carbon atom of form hydridization is converted into sp
3The carbon atom of hydridization, and then reach purpose to functionalization.And, through the dendritic functionalized carbon nanotube organic solvent commonly used such as THF, N-Methyl pyrrolidone and dichloromethane solution in solvability and good dispersibility.Modified carbon nano-tube is mixed, disperses the back electrostatic spinning with PCL, find that through transmission electron microscope observing it presents axial array in the PCL silky fibre in tetrahydrofuran solution, and good dispersibility.This also provides a kind of approach for the application of modified carbon nano-tube in matrix material.
Description of drawings
Fig. 1 is a Bergman cyclization synoptic diagram;
Fig. 2. for utilization contains the dendritic compound G1 of enediyne structure, the synoptic diagram of G2 functionalization SWCN;
Fig. 3 is the thermogravimetric analysis figure of modified carbon nano-tube, heats 10 ℃/minute of heat-up rates in the air.Original SWCNTs among the figure behind (a) purifying; (b) SWCNTs-G1; (c) SMWNTs-G2; (d) oligopolymer G1;
Fig. 4 is the infrared spectrum of modified carbon nano-tube, the original SWCNTs among the figure behind (a) purifying; (b) SWCNTs-G1;
(c) SMWNTs-G2; (d) oligopolymer G1;
The ultraviolet-visible light spectrogram of Fig. 5 modified carbon nano-tube is made solvent with trichloromethane, the original SWCNTs among the figure behind (a) purifying,
(b)SWCNTs-G1；
Fig. 6 is the 1HNMR nuclear magnetic spectrogram of the modified carbon nano-tube of G1;
Fig. 7 is the 1HNMR nuclear magnetic spectrogram of the modified carbon nano-tube of G2;
Fig. 8 is a modified carbon nano-tube and at dispersive transmission electron microscope observing figure in PCL electrostatic spinning liquid, (A) SWCNTs-G1 among the figure; (B) electrostatic spinning of doping SWCNTs-G1;
Synthesizing of Fig. 9 enediyne compounds;
Synthesizing of the dendritic compound of Figure 10;
Figure 11 contains dendritic compound synthetic of enediyne structure.
Embodiment
The method that the present invention is based on Bergman cyclization modification SWCN is following:
Used instrument of the present invention and reagent:
Nucleus magnetic resonance (Ultra Shield 400 spectrometer types, the U.S.); Liquid chromatography/flight time mass spectrum combined instrument (Micromass LCTTM type, Britain); Thermogravimetric analyzer (SDT Q600 type, the U.S.); Ultraviolet-visible spectrophotometer (UV-2550PC type, Japan); Fourier transformation infrared spectrometer (Nicolet 5700 types, the U.S.); Transmission electron microscope (JEM-2010/INCA type, Britain); Electrospinning device (self-control, spinning voltage: 30kV).
SWCN SWCNTs (purity >=95%, Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences).Carry out purifying according to document before using.Polycaprolactone (PCL) molecular weight is 105g/mol, Shenzhen brilliance chemistry ltd, and all purified processing before organic solvents such as N-Methyl pyrrolidone, THF and methylene dichloride use, other reagent directly uses.
The concrete compound method of compound G1 and G2 is like accompanying drawing 9,10, shown in 11.Concrete grammar is following:
With adjacent bromo-iodobenzene (14.15g; 50mmol), the trimethyl silicane ethyl-acetylene (5.9g, 60mmol) and anhydrous triethylamine (75mL) add in the 500mL Schlenk bottle, in vacuum line, carry out vacuum-nitrogen circulation operation 6 times; Add dichloro two (triphenylphosphine) palladium (1.1g then respectively; 1.5mmol) and cuprous iodide (0.5805g 3mmol), carries out vacuum-nitrogen circulation operation 6 times again.Under room temperature condition and nitrogen protection, react stirred overnight subsequently.After reaction is accomplished, revolve to steam and remove the part triethylamine, with ETHYLE ACETATE, saturated aqueous common salt, saturated ammonium chloride solution and saturated aqueous common salt product is extracted separatory successively again.Upper organic phase is used the anhydrous magnesium sulfate drying after-filtration, filtrating revolve steam thick product, be pale brown look liquid.Be eluent with sherwood oil (60 ℃～90 ℃) then, thick product through the separation of chromatographic silica gel post, purifying, is got 12.53g yellow transparent oily product, productive rate is 99%.
1H?NMR(CDCl
3，δ，ppm)：7.56-7.58(Ph-H，1H)，7.48-7.50(Ph-H，1H)，7.22-7.24(Ph-H，1H)，7.13-7.17(Ph-H，1H)，0.28(s，Si-CH
3，9H)。
With product 1 (5.5g, 21.7mmol), 3-butine-1-alcohol (1.83g; 26.1mmol) and the 25mL anhydrous triethylamine join in the 100mL Schlenk bottle, in the vacuum line system, carry out vacuum-nitrogen circulation operation 6 times, add cuprous iodide (0.25g then; 1.3mmol) and dichloro two (triphenylphosphine) palladium (0.457g 0.651mmol), carries out vacuum-nitrogen circulation operation 6 times again; The Schlenk bottle is placed 85 ℃ of oil baths, nitrogen protection reaction is down spent the night thereupon.The gained mix products is revolved steaming remove triethylamine, use ETHYLE ACETATE and saturated aqueous common salt respectively successively, saturated ammonium chloride and saturated aqueous common salt extracting and separating resultant product.Separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration; Revolve then and steam filtrating; Again products obtained therefrom is done with ethyl acetate/petroleum ether=1/5 mixed solvent that eluent separates, purifying on silica gel column chromatography, final 2.26g red-brown oily matter, productive rate is 43%.
1H?NMR(CDCl
3，δ，ppm)：7.45-7.47(Ph-H，1H)，7.38-7.40(Ph-H，1H)，7.22-7.24(Ph-H，2H)，3.83(Ph-CC-CH
2-CH
2-，2H)，2.73(Ph-CC-CH
2-CH
2-，2H)，2.16(-OH，1H)，0.28(s，Si-CH
3，9H)。
Synthesizing of compound 3 (3,5-resorcylic acid ester):
Take by weighing 3 earlier, (15.41g 100mmol) places the 250mL round-bottomed flask to the 5-resorcylic acid; With 85mL methyl alcohol it is dissolved, again flask is placed ice-water bath, dropwise add thionyl chloride (17.85g under stirring; 150mmol), add in 10 minutes, react 5h then.The gained reaction mixture is revolved steaming except that desolvating, then extract resultant product successively with saturated sodium bicarbonate and saturated aqueous common salt.Again separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration, filtrating is revolved steaming, obtains light yellow solid powder 14.3g, and productive rate is 85%.
1H?NMR(CDCl
3，δ，.ppm)：7.09(Ph-H，2H)，6.57(Ph-H，1H)，5.16(Ph-OH，2H)，3.91(Ph-CO-O-CH
3，3H)。
Synthesizing of compound 4:
With compound 3 (5.04g, 30mmol), 1-bromohexadecane (22.90g; 75mmol) and Anhydrous potassium carbonate (20.73g 150mmol) is dissolved in the withstand voltage reaction flask of 250mL with the 150mL anhydrous acetonitrile, vacuum-nitrogen circulation operation 6 times; Rapidly with the reaction flask sealing, 100 ℃ are reacted stirred overnight down again.Revolve then to steam and remove the solvent in the reaction product, use methylene dichloride and saturated aqueous common salt extracting and separating product more successively.Separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration, and filtrating is revolved steaming.Do with methylene dichloride/sherwood oil=1/1 and methylene dichloride/sherwood oil=4/1 respectively successively then that eluent separates, purified product on silica gel column chromatography, finally obtain the 18.12g white solid, productive rate is 98%.
1H?NMR(CDCl
3，δ，ppm)：7.16(Ph-H，2H)，6.63(Ph-H，1H)，3.96(-O-CH
2-，4H)，3.90(-CO-O-CH
3，3H)，1.75-1.79(-O-CH
2-CH
2-CH
2-，4H)，1.42-1.44(-O-CH
2-CH
2-，4H)，1.26(-CH
2-CH
2-CH
2-，48H)，0.88(-CH
2-CH
3，6H)。
Synthesizing of compound 5:
(6.17g 10mmol) places the 100mL round-bottomed flask, adds the 40mL THF with compound 4; 8mL methyl alcohol, complete dissolved compound 4 adds the Pottasium Hydroxide (2.24g of 8mL dissolved in distilled water again; 40mmol), then reaction mixture is spent the night 56 ℃ of refluxed, again the product mixing solutions is cooled to room temperature; Drip 1mol/L hydrochloric acid soln regulator solution acidity to pH=3～5, then solution is revolved steaming, resultant product is utilized methylene dichloride and saturated aqueous common salt extracting and separating successively.Separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration, and filtrating is revolved steaming, obtains the 5.90g white solid, and productive rate is 98%.
1H?NMR(CDCl
3，δ，ppm)：7.18(Ph-H，2H)，6.65(Ph-H，1H)，3.94(-O-CH
2-，4H)，1.78-1.74(-O-CH
2-CH
2-，4H)，1.41-1.43(-O-CH
2-CH
2-，4H)，1.24(-CH
2-CH
2-CH
2-，48H)，0.86(-CH
2-CH
3，6H)。
Synthesizing of compound 6:
(0.86g 22.5mmol) places 250mL Schlenk bottle, adds the 2mL anhydrous tetrahydro furan and makes it become pasty state, and vacuum-nitrogen circulation is operated 6 times with Lithium Aluminium Hydride.(9.26g 15.0mmol), and utilizes constant pressure funnel slowly it to be joined in the Schlenk bottle, feeds in raw material to finish, and vacuum-nitrogen circulation is operated 6 times, and mixture reaction spends the night under nitrogen protection to use an amount of anhydrous tetrahydro furan dissolved compound 4 again.After reaction is accomplished, slowly drip the excessive Lithium Aluminium Hydride of deionized water cancellation, again with the hydrochloric acid of 1mol/L with the pH value of system be adjusted to 7 backs a zeyssatite short column, and precipitate with an amount of washed with dichloromethane.Gained filtrating is used the saturated aqueous common salt extracting and separating, and separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration, revolve and steam filtrating, obtain white solid 8.65g, productive rate is 97%.
1H?NMR(CDCl
3，δ，ppm)：6.50(Ph-H，2H)，6.38(Ph-H，1H)，4.62(Ph-CH
2-OH，2H)，3.95(Ph-O-CH
2-，4H)，2.17(Ph-CH
2-OH，1H)，1.76(-O-CH
2-CH
2-，4H)，1.43(-CH
2-CH
2-CH
3，4H)，1.26(-CH
2-CH
2-CH
2-，48H)，0.88(-CH
2-CH
3，6H)。
Synthesizing of compound 7:
Utilize an amount of anhydrous methylene chloride dissolved compound 6 (8.0g, 13.6mmol)), carbon tetrabromide (4.15g; 12.5mmol) in 250mL Schlenk bottle, vacuum-nitrogen circulation is operated 6 times, subsequently at following minute several parts of slow triphenylphosphine (7.13g that add of nitrogen protection; 27.2mmol), adding in 3～5 minutes, vacuum-nitrogen circulation is operated 6 times again; Make then to be reflected under the nitrogen protection, room temperature condition is reaction 15min down.With saturated aqueous common salt cancellation reaction, again mix products is utilized methylene dichloride and saturated aqueous common salt extracting and separating successively after reaction is accomplished, separating obtained organic phase is used the anhydrous magnesium sulfate drying after-filtration, and filtrating is revolved steaming.Make eluent with sherwood oil and methylene dichloride/sherwood oil=4/1 successively respectively again and on silica gel column chromatography, separate enriched product, get the thick oily matter of 6.92g white, productive rate is 78%.
1H?NMR(CDCl
3，δ，ppm)：6.50(Ph-H，2H)，6.38(Ph-H，1H)，4.40(Ph-CH
2-OH，2H)，3.94(Ph-O-CH
2-，4H)，1.76(-O-CH
2-CH
2-，4H)，1.42(-CH
2-CH
2-CH
3，4H)，1.26(-CH
2-CH
2-CH
2-，48H)，0.88(-CH
2-CH
3，6H)。
Synthesizing of compound 8:
With compound 3 (0.76g, 4.54mmol), compound 7 (6.52g; 10mmol) insert in the 100mL Schlenk bottle, add the complete dissolving mixt of 25mL anhydrous propanone with 18-hat-6 ethers (0.24g, 0.9mmol)); Add Anhydrous potassium carbonate (12.58g again; 91mmol), vacuum-nitrogen circulation is operated 6 times then, reaction backflow 48h under nitrogen protection.Revolve after reaction stops and steaming reaction mixture, use methylene dichloride and saturated aqueous common salt extracting and separating resultant product successively, separating obtained organic phase is used anhydrous magnesium sulfate drying, filter, revolve steaming except that desolvating.Do with methylene dichloride/sherwood oil=1/4 and methylene dichloride/sherwood oil=4/1 successively respectively again that eluent separates, purified product on silica gel column chromatography, finally obtain the 4.76g light yellow solid.Productive rate is 80%.
1HNMR(CDCl
3，δ，ppm)：7.28(Ph-H，2H)，6.79(Ph-H，1H)，6.55(Ph-H，4H)，6.40(Ph-H，2H)，4.98(Ph-O-CH
2-Ph-，4H)，3.93(Ph-O-CH
2-CH
2-，8H)，3.90(-CO-O-CH
3，3H)，1.78(-O-CH
2-CH
2-，8H)，1.43(-CH
2-CH
3，8H)，1.26(-CH
2-CH
2-CH
2-，96H)，0.88(-CH
2-CH
3，12H)。
Synthesizing of compound 9:
(3.93g 3mmol) joins in the 100mL round-bottomed flask, and with 10mL THF and 2mL dissolve with methanol, then (0.23g is added dropwise in the round-bottomed flask 56 ℃ of reaction backflows down, stirred overnight after 8mmol) with 2mL deionized water dissolving KOH with compound 8.Add 3mL deionized water cancellation reaction after reaction is accomplished, use pH=3～5 of the hydrochloric acid regulation system of 0.1mol/L again, revolve steaming then.Use methylene dichloride and saturated aqueous common salt extracting and separating enriched product successively, the gained organic phase is used the anhydrous magnesium sulfate drying after-filtration, and filtrating is revolved steaming, obtains white powdery solid 3.76g, and productive rate is 97%.
1H?NMR(CDCl
3，δ，ppm)：7.32(Ph-H，2H)，6.82(Ph-H，1H)，6.55(Ph-H，4H)，6.41(Ph-H，2H)，4.99(Ph-O-CH
2-Ph-，4H)，3.75(Ph-O-CH
2-CH
2-，8H)，1.78(-O-CH
2-CH
2-，8H)，1.44(-CH
2-CH
3，8H)，1.25(-CH
2-CH
2-CH
2-，96H)，0.88(-CH
2-CH
3，12H)。
Synthesizing of compound 10:
With compound 2 (1.10g, 4.57mmol), 5 (4.13g; 6.85mmol) and 4-DMAP (0.11g; 0.91mmol) be dissolved in the 50mL round-bottomed flask with the 40mL anhydrous methylene chloride, again with 8mL anhydrous methylene chloride dissolving DCC (1.32g, 6.40mmol); And it is dropwise joined in the above-mentioned mixed solution, add in the 10min.Reaction mixture is stirring reaction 24h at room temperature.With the sedimentation and filtration in the mixture, use a little washed with dichloromethane after the end, and revolve steaming, concentrated filtrate.Then enriched product is done with ethyl acetate/petroleum ether=1/25 that eluent separates, purified product on silica gel column chromatography, obtained the 3.60g yellow oil, productive rate is 95%.
1H?NMR(CDCl
3，δ，ppm)：7.38-7.46(Ph-H，2H)，7.21-7.23(Ph-H，2H)，7.19(Ph-H，2H)，6.63(Ph-H，1H)，4.52(-CC-CH
2-CH
2-，2H)，3.95(Ph-O-CH
2-，4H)，2.95(-CC-CH
2-，2H)，1.75(Ph-O-CH
2-CH
2-，4H)，1.43(Ph-O-CH
2-CH
2-，4H)，1.26(-CH
2-CH
2-CH
2-，48H)，0.88(-CH
2-CH
3，6H)，0.26(s，Si-CH
3，9H)。
13C?NMR(CDCl
3，δ，ppm)：166.1，160.1，132.0，131.7，128.1，126.2，107.7，106.6，103.5，98.2，89.5，80.8，68.3，62.8，31.9，29.7，29.4，26.0，22.7，20.2，14.1，-0.03。MS (ESI+): m/z, C
54H
86O
4Si (theoretical value): 827.6374 [(M+H)
+]; Measured value: 827.6411 [(M+H)
+].
Compound G1's is synthetic:
Earlier with compound 10 (3.30g; 4mmol) be dissolved in the 100mL Schlenk bottle with the 30mL anhydrous tetrahydro furan, under nitrogen protection, add then TBAF (5.20g, be equivalent to 5eq-the TMS group); Mixture at ambient temperature, nitrogen protection and lucifuge reaction 30min.After mix products is crossed a silica gel short column, and use a large amount of ETHYLE ACETATE drip washing to elutant be colourless till.Gained filtrating is revolved inspissation contract, the gained crude product is that eluent separates on silica gel column chromatography, purifying with ethyl acetate/petroleum ether=1/20, obtains faint yellow oily product 2.01g, and productive rate is 66%.
1H?NMR(CDCl
3，δ，.ppm)：7.40-7.48(Ph-H，2H)，7.24(Ph-H，2H)，7.20(Ph-H，2H)，6.63(Ph-H，1H)，4.52(-CC-CH
2-CH
2-，2H)，3.95(Ph-O-CH
2-，4H)，3.26(-CC-H，1H)，2.96(-CC-CH
2-，2H)，1.76(Ph-O-CH
2-CH
2-，4H)，1.43(Ph-O-CH
2-CH
2-，4H)，1.26(-CH
2-CH
2-CH
2-，48H)，0.88(-CH
2-CH
3，6H)。
13C?NMR(CDCl
3，δ，.ppm)：166.3，160.1，132.5，131.7，128.4，126.4，107.8，106.5，89.9，82.1，80.9，80.5，68.3，62.9，31.9，29.7，29.4，26.0，22.7，20.3，14.1。MS (ESI+): m/z, C
51H
78O
4(theoretical value): 793.5537 [(M+K)
+]; Measured value: 793.5552 [(M+K)
+].
Synthesizing of compound 12:
Compound 2 (0.40g, 1.67mmol), 9 (3.24g; 2.5mmol) and 4-DMAP (0.04g 0.33mmol) is dissolved in the 50mL round-bottomed flask with the 6mL anhydrous methylene chloride, again with 1mL anhydrous methylene chloride dissolving DCC (0.48g; 2.34mmol); It is dropwise joined in the above-mentioned mixed solution, add in the 10min, then reaction mixture stirring reaction 24h at room temperature.With the sedimentation and filtration in the mixture, and use a little washed with dichloromethane after reaction finishes, filtrate and revolve steaming.Make the product of eluent after separation on the silica gel column chromatography, purifying concentrate with ethyl acetate/petroleum ether=1/25, obtain the 2.30g yellow oil, productive rate is 90%.
1H?NMR(CDCl
3，δ，.ppm)：7.38-7.44(Ph-H，2H)，7.32(Ph-H，2H)，7.19-7.21(Ph-H，2H)，6.80(Ph-H，1H)，6.54(Ph-H，4H)，6.41(Ph-H，2H)，4.96(Ph-O-CH
2-Ph-，4H)，4.52(-CC-CH
2-CH
2-，2H)，3.93(Ph-O-CH
2-CH
2-，8H)，2.94(-CC-CH
2-，2H)，1.76(-O-CH
2-CH
2-，8H)，1.43(Ph-O-CH
2-CH
2-，8H)，1.26(Ph-O-CH
2-CH
2-CH
2-，96H)，0.88(-CH
2-CH
3，12H)，0.26(s，Si-CH
3，9H)。
13C?NMR(CDCl
3，δ，.ppm)：165.9，160.5，159.8，138.5，132.1，131.8，128.1，126.2，108.5，107.3，105.8，103.5，100.9，98.3，89.4，80.9，70.3，68.1，62.9，31.9，29.7，29.4，26.1，22.7，20.2，14.1，-0.007。MS (ESI+): m/z, C
100H
162O
8Si (theoretical value): 1542.1937 [(M+H)
+]; Measured value: 1542.2075 [(M+H)
+].
Compound G2's is synthetic:
Earlier with compound 12 (2.0g 1.32mmol) is dissolved in the 25mL Schlenk bottle with the 10mL anhydrous tetrahydro furan, then under nitrogen protection adding TBAF (1.73g, be equivalent to 5eq-the TMS group), make reaction system lucifuge under nitrogen protection react 1h.Then mix products is crossed a silica gel short column, and use a large amount of ETHYLE ACETATE drip washing to elutant be colourless till.Gained filtrating is revolved steaming, concentrated, and is that eluent separates on silica gel column chromatography, purifying with ethyl acetate/petroleum ether=1/25, obtains faint yellow oily product 1.78g, and productive rate is 93%.
1H?NMR(CDCl
3，δ，ppm)：7.41-7.46(Ph-H，2H)，7.32(Ph-H，2H)，7.21(Ph-H，2H)，6.80(Ph-H，1H)，6.54(Ph-H，4H)，6.40(Ph-H，2H)，4.97(Ph-O-CH
2-Ph-，4H)，4.53(-CC-CH
2-CH
2-，2H)，3.93(Ph-O-CH
2-CH
2-，8H)，3.24(-CC-H，1H)，2.94(-CC-CH
2-，2H)，1.78(-O-CH
2-CH
2-，8H)，1.43(Ph-O-CH
2-CH
2-，8H)，1.26(Ph-O-CH
2-CH
2-CH
2-，96H)，0.88(-CH
2-CH
3，12H)。
13C?NMR(CDCl
3，δ，.ppm)：166.0，160.5，159.7，138.5，132.5，131.9，128.4，126.3，108.5，107.2，105.7，100.9，89.8，82.1，80.9，80.6，70.3，68.1，62.9，31.9，29.7，29.4，26.1，22.7，20.2，14.1。MS (ESI+): m/z, C
97H
154O
8(theoretical value): 1470.1439 [(M+Na)
+]; Measured value: 1470.1561 [(M+Na)
+].
The modification of SWCN is as shown in Figure 2, and concrete operations are following:
The SWCNTs that takes by weighing behind the 10mg purifying places exsiccant Schlenk bottle, adds the anhydrous N-Methyl pyrrolidone of 20～30mL, and ultra-sonic dispersion is about 30 minutes.Add the compound G1 be equivalent to 4eq SWCNTs then, 1.0g continued ultrasonic 10～15 minutes, with reaction mixture under nitrogen protection in 170～190 ℃ of following reflux, stirring reaction 3～4 days.Again product is cooled to room temperature; The blackish green product of gained filters with 0.22 μ m teflon membrane filter; And successively with a large amount of ether, THF washed product be to filtrating colourless till; At last the black product about 24 hours, is obtained about 14mg product S WCNTs-G1 90～100 ℃ of following vacuum-dryings.
In like manner, as grafts,, obtain about 11mg SWCNTs-G2 with G2 according to identical modifying method.Above two kinds of modification SWCNs are characterized accordingly.
Respectively with the SWCNTs-G1 after the modification and SWCNTs-G2 and PCL in THF (THF) solution in: the ratio of modification SWCNTs/PCL/THF=0.001/0.1/1 (mass ratio) in 40 ℃ of heating, stirring and dissolving down.Adopt homemade electrostatic spinning apparatus under 2.5 * 104V voltage, to make the modified carbon nano-tube composite spun fiber then, it is collected carbon supporting film copper mesh surface, utilize the doping situation of transmission electron microscope observing carbon pipe.
The thermogravimetric analysis of functionalized carbon nano-tube of the present invention characterizes as follows.
Thermogravimetry mainly is to utilize the difference of the thermostability between carbon pipe and the grafts to distinguish carbon pipe and graft compound.Can find out through thermogravimetric analysis Fig. 3, (a) the original SWCNTs behind the purifying; (b) SWCNTs-G1; (c) SMWNTs-G2; (d) oligopolymer G1.When SWCN after modification, compare with the original SWCN behind the purifying, original SWCN begins weightlessness in the time of 480 ℃, corresponding modified product SMWNTs-G1 and the weightlessness of SWCNTs-G2 in the time of 480 ℃ are respectively 15% and 12.5%.And corresponding oligopolymer G1 that in the filtrating of aftertreatment, obtains and G2 almost completely burn down in the time of 600 ℃.In addition, comparison curves b, c can find that two generations, dendritic compound was lower than the percentage of grafting of the dendritic compound of a generation at the percentage of grafting of carbon pipe, and the sterically hindered percentage of grafting that causes more greatly when this mainly is two generations dendritic compound grafting changes.
Infrared spectrum such as Fig. 4 of functionalized carbon nano-tube of the present invention characterize as follows.
Through the mensuration of IR, the result is: (a) the original SWCNTs behind the purifying; (b) SWCNTs-G1; (c) SMWNTs-G2; (d) oligopolymer G1.Can know, through dendritic compound-modified after SWCNTs-G1 and SMWNTs-G2 about 2923cm-1, locate all to occur a C-H stretching vibration peak, what this peak was corresponding is the stretching vibration peak of methylene radical among compound G1 and the G2.Do not occur among the original SWCNTS of this peak behind purifying.Explain that the Bergman cyclization has taken place single wall carbon tube edge wall.In addition, the scissoring vibration peak of SWCNTs-G1 and the SMWNTs-G2 enhanced methylene radical of appearance at the 1444cm-1 place has explained that also covalence graft has taken place carbon tube edge wall.These all explained be generation arborescence or two generation arborescence the covalence graft of radical has all taken place at the carbon tube-surface.
The uv-visible absorption spectroscopy method of functionalized carbon nano-tube of the present invention characterizes as follows.
Uv-visible absorption spectroscopy figure is as shown in Figure 5, and the changes in surface of carbon pipe modification front and back can be described.Generally speaking, a large amount of structures of matter on the surface of carbon nanotube all can produce corresponding absorption spectrum peak, and these are referred to as van hove singularity.The variation of carbon nano tube modified front and back absorption peak draws the evidence of modifying success or not in these corresponding wavelength range through comparing.After the carbon pipe is modified, will cause a large amount of van hove singularities in surface to disappear, just ultraviolet absorption peak reduces.Variation on this surface tissue shows that the π key system of carbon tube-surface is destroyed because of covalent modification has taken place, thereby has reduced van hove singularity.We have selected the SWCNTs behind generation grafts SWCNTs-G1 and the original purifying to carry out the ultraviolet-visible spectrum sign, and the ultraviolet-visible light spectrogram (making solvent with trichloromethane) of result's modified carbon nano-tube as shown in Figure 5 is the original SWCNTs behind the purifying (a); (b) SWCNTs-G1.Can know through curve a, b in the comparison diagram; Relatively amplitude ratio is bigger for the absorption curve of original SWCNTs in the 250-800nm wavelength region of curve a representative; The non-constant of its model Hough regularity is described; And smoother through the SWCNTs-G1 absorption curve in this wavelength region after the modification, model Hough regularity is relatively good.Explain from the side that thus dendritic on the SWCNTs surface Bergman reaction has taken place.
The 1HNMR nucleus magnetic resonance of functionalized carbon nano-tube of the present invention characterizes as follows.
Nmr spectrum can prove the grafting success or not through the grafted functional group that characterizes the carbon tube-surface like Fig. 6, shown in 7.We utilize the single-wall carbon tube SWCNTs-G1 after the NMR test obtains graft modification, the 1H NMR of SWCNTs-G2 to compose like Fig. 6.Wherein, The oligopolymer nucleus magnetic hydrogen spectrum proton peak of spectral line a representation compound G1; The chemical shift of the oligopolymer that its expression compound G1 produces in solution through the Bergman cyclization, among the figure chemical shift 0.82 with the proton peak of 1.22ppm position be respectively to cause by methyl and methylene radical in the long chain alkane functional group of dendritic compound G1.The SWCN of the modification of curve b representative also 0.82 with 1.22ppm about the chemical shift position on have corresponding proton peak to occur, this explains that dendritic compound G1 has been grafted on the carbon nano tube surface.Equally, similar situation also appears in the nuclear magnetic resonance peak of the oligopolymer of Fig. 7 comparison G2 and its carbon pipe modified product SWCNTs-G2.The Bergman cyclization has all taken place in this enediyne group that enediyne verivate G1 and G2 are described from the side; And in the radical attack carbon nanotube that utilize to produce with the carbon atom of sp2 form hydridization, thereby the free radical addition reaction takes place and dendritic compound is grafted on the wall of carbon nanotube limit.
In addition, can see that through the nuclear magnetic spectrogram of the oligopolymer among Fig. 6,7 chemical shift place at 7.2～7.5ppm also has tangible proton peak, this also can prove in carbon nano tube surface and have the poly aromatic ring functional group that is produced by the Bergman cyclization.But the proton peak that the functional group of these poly aromatic rings and some other dendritic compound produces is also not obvious in the nuclear magnetic spectrogram of modification carbon pipe; This mainly is because on the one hand; Dendritic compound takes place to form stiff poly aromatic chain at the carbon tube-surface behind the Bergman cyclization in carbon nano tube surface; And become very slow near the inhibition that the proton athletic meeting of the functional group of the graft compound of these chains receives chain; Therefore the proton nuclei magnetic hill that produces very wide or very a little less than, cause out the peak not obvious.On the other hand,, dendritic compound structure reason shielded by the outer end group owing to causing the aromatic nucleus of its core enediyne and the nuclear magnetic signal peak of adjacent functional group, thereby a little less than making its nucleus magnetic resonance peak-to-peak signal very.
Transmission electron microscope observing functionalized carbon nano-tube of the present invention and composite electrostatic spinning fiber product pattern thereof.
Be to observe more intuitively the morphology change of carbon pipe after the modification, the SWCN SWCNTs-G1 that we choose after the modification dissolves with THF, behind the ultra-sonic dispersion, drips and is coated on the copper mesh with carbon supporting film, and nitrogen dries up.Utilize transmission electron microscope that its structure is observed then, shown in the following Fig. 8 A of appearance structure.Obviously can find out on carbon tube edge wall, all have tangible amorphous substance to adhere to by figure, these amorphous substances are owing to the free radical addition of the diradical of Bergman cyclization generation and carbon nano tube surface generation is reacted the organic polymer that produces.Explained that thus dendritic compound is successful in the grafting of carbon nano tube surface.
In addition; For the dispersiveness of further investigating carbon nanotube after the modification and favorable solubility whether; We select with modified carbon nano-tube SWCNTs-G1 and PCL in tetrahydrofuran solution according to SWCNTs-G1/PCL/THF=1/10/100 (mass ratio) ratio mix, dissolving, dispersed with stirring, carry out electrostatic spinning then.Through the dispersion situation of transmission electron microscope observing SWCNTs-G1 in electrospun fibers, result such as Fig. 8 B.Can find out that by figure the modification SWCN is arranged vertically, can be dispersed in preferably in the PCL electrospun fibers in the PCL electrospun fibers.This also proved modified carbon nano-tube in the THF organic solvent solvability and dispersiveness well improved, for its reinforcement applications in matrix material is had laid a good foundation.
Claims (1)
1. method based on Bergman cyclization modification SWCN is characterized in that: take by weighing the SWCN (SWCNTs) behind the 10mg purifying, purity >=95%; Place exsiccant Schlenk bottle, add the anhydrous N-Methyl pyrrolidone of 20～30mL, ultra-sonic dispersion 30 minutes; Add the compound G1 that is equivalent to 4eqSWCNTs then, 1.0g continued ultrasonic 10～15 minutes; With reaction mixture under nitrogen protection in 170～190 ℃ of following reflux; Stirring reaction 3～4 days is cooled to room temperature with product again, and the blackish green product of gained filters with 0.221 μ m teflon membrane filter; And successively with a large amount of ether, THF washed product be to filtrating colourless till; At last the black product about 24 hours, is obtained about 14mg product S WCNTs-G1 90～100 ℃ of following vacuum-dryings, all purified processing before organic solvents such as N-Methyl pyrrolidone, THF and methylene dichloride use; Equally, as grafts,, obtain 11mg SWCNTs-G2 with G2 according to identical modifying method.
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| CN103980177A (en) * | 2014-05-20 | 2014-08-13 | 华东理工大学 | Acetylene compound as well as preparation method and application thereof |
| CN104310378A (en) * | 2014-10-14 | 2015-01-28 | 成都柏森松传感技术有限公司 | Preparation method of carbon nanotube modified by alkynyl on surface |
| CN106698400A (en) * | 2016-12-23 | 2017-05-24 | 浙江大学常州工业技术研究院 | Methacrylic acid graphene polymers and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103980177A (en) * | 2014-05-20 | 2014-08-13 | 华东理工大学 | Acetylene compound as well as preparation method and application thereof |
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| CN104310378A (en) * | 2014-10-14 | 2015-01-28 | 成都柏森松传感技术有限公司 | Preparation method of carbon nanotube modified by alkynyl on surface |
| CN106698400A (en) * | 2016-12-23 | 2017-05-24 | 浙江大学常州工业技术研究院 | Methacrylic acid graphene polymers and preparation method thereof |
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