CN109762173A - Modified carbon nano-tube array and its preparation method and application - Google Patents
Modified carbon nano-tube array and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of modified carbon nano-tube arrays and its preparation method and application.The preparation method of above-mentioned modified carbon nano-tube array includes: that methacrylate monomers are carried out homopolymerization, obtains structural formula and isMethacrylate based polymers, wherein n be 1~11 any integer, R=CmH2m+1, m be 1~4 any integer；And carbon nano pipe array and methacrylate based polymers are subjected to graft reaction, obtain modified carbon nano-tube array.Above-mentioned carbon nano pipe array is modified by methacrylate based polymers, carbon nano pipe array can be made to be uniformly dispersed.Ester group in methacrylate based polymers can react with natural polymer, and the double bond in methacrylate based polymers further can be such that macromolecule crosslinks and form modified hydrogel, and preferable by the mechanical property of the modification hydrogel of above-mentioned modified carbon nano-tube array preparation.
Description
Technical field
The present invention relates to field of carbon nanotubes, more particularly to a kind of modified carbon nano-tube array and preparation method thereof and answer
With.
Background technique
Series of advantages that carbon nanotube has that density is low, intensity is high etc., are ideal high tensile strength fibrous materials, therefore often quilt
The mechanical property for enhancing hydrogel is added in hydrogel.However, since carbon nanotube has the property reunited, so that carbon is received
Mitron is difficult to evenly dispersed.It is not able to satisfy still in traditional technology by the mechanical property of the modification hydrogel of carbon nanotube preparation simultaneously
It needs.
Summary of the invention
Based on this, it is necessary to provide a kind of modified carbon nano tube that can be used in preparing the preferably modified hydrogel of mechanical property
The preparation method of pipe array.
In addition, also providing the application of a kind of modified carbon nano-tube array and modified carbon nano-tube array.
A kind of preparation method of modified carbon nano-tube array, comprising the following steps:
Methacrylate monomers are subjected to homopolymerization, obtaining structural formula isMethyl-prop
Olefin(e) acid esters polymer, wherein any integer that n is 1~11, R=CmH2m+1, m be 1~4 any integer；And
Carbon nano pipe array and the methacrylate based polymers are subjected to graft reaction, obtain modified carbon nano-tube
Array.
It is described in one of the embodiments, that methacrylate monomers progress homopolymerization is obtained into methacrylate
The step of quasi polymer include: by the methacrylate monomers, catalyst, initiator and solvent under the conditions of water bath with thermostatic control
Homopolymerization is carried out, the methacrylate based polymers are obtained.
The catalyst is cobaltous chelate, the catalyst and the methyl-prop in one of the embodiments,
The mass ratio of olefin(e) acid ester monomer is 4.0: 100~4.2: 100.
The catalyst is selected from tetramethoxy phenyl Cobalt Porphyrin, four (tert-butyl) Cobalt Phthalocyanines in one of the embodiments,
And two at least one of bis- (boron difluorodiphenyl base glyoxime) cobalts of hydration.
The initiator is azo-compound in one of the embodiments, and the initiator and the metering system
The mass ratio of acid ester monomer is 2.0: 100~2.2: 100.
It is different to be selected from azodiisobutyronitrile, azobisisoheptonitrile and azo two for the initiator in one of the embodiments,
At least one of butyric acid dimethyl ester.
The solvent is selected from one of chloroform, ethyl alcohol, ether and acetone, the solvent in one of the embodiments,
Volume ratio with the methacrylate monomers is 6.5: 1~7.5: 1.
The temperature of the water bath with thermostatic control is 70 DEG C~80 DEG C in one of the embodiments,.
A kind of modified carbon nano-tube array is prepared by the preparation method of above-mentioned modified carbon nano-tube array.
A kind of above-mentioned modified carbon nano-tube array is preparing the application in modified hydrogel.
It is the preparation method simple process of above-mentioned modified carbon nano-tube array, easy.By being polymerize with methyl acrylic ester
Carbon nano pipe array is modified by object, so that methacrylate based polymers are grafted to carbon nano pipe array by covalent bond
On, it is capable of increasing the distance between carbon nanotube and reduces the reunion due to caused by the Van der Waals force between carbon nanotube, thus
Keep carbon nano pipe array evenly dispersed.In addition, the ester group in methacrylate based polymers can be for example bright with natural polymer
Glue, chitosan etc. react, and the double bond on methacrylate based polymers end can further make natural polymer
The mechanical property for the hydrogel for crosslinking and forming hydrogel, and obtain is preferable.Therefore, above-mentioned modified carbon nano-tube array energy
It is enough in the preferably modified hydrogel of preparation mechanical property.
Detailed description of the invention
Fig. 1 is the flow chart of the preparation method of the modified carbon nano-tube array of an embodiment；
Fig. 2 is the modified carbon nano tube that the step S120 in the preparation method of modified carbon nano-tube array shown in FIG. 1 is obtained
The schematic diagram of pipe array；
Fig. 3-a is the swarming figure of C1s in the XPS spectrum figure of the pure nano-carbon tube in embodiment 5；Fig. 3-b is in embodiment 5
The swarming figure of O1s in the XPS spectrum figure of pure nano-carbon tube；
Fig. 4-a is the swarming figure of C1s in the XPS spectrum figure of the pure polymethyl methacrylate in embodiment 5；Fig. 4-b is real
Apply the swarming figure of O1s in the XPS spectrum figure of the pure polymethyl methacrylate in example 5；
Fig. 5-a is the swarming figure of Cls in the XPS spectrum figure of the modified carbon nano-tube array in embodiment 5；Fig. 5-b is to implement
The swarming figure of O1s in the XPS spectrum figure of modified carbon nano-tube array in example 5；
Fig. 6 is to prepare answering for hydrogel by modified carbon nano-tube array prepared by 1~embodiment of embodiment 5 and comparative example 1
Power-strain figure.
Specific embodiment
To facilitate the understanding of the present invention, below in conjunction with specific embodiment to invention is more fully described.Tool
Preferred embodiment of the invention is given in body embodiment.But the invention can be realized in many different forms,
It is not limited to the examples described herein.On the contrary, purpose of providing these embodiments is makes to the disclosure
Understanding it is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
Body embodiment purpose, it is not intended that in limitation the present invention.
Referring to Fig. 1, the preparation method of the modified carbon nano-tube array of an embodiment, includes the following steps:
S110: carrying out homopolymerization for methacrylate monomers, and obtaining structural formula is's
Methacrylate based polymers.
Wherein, any integer that n is 1~11, R=CmH2m+1, m be 1~4 any integer.Specifically, methacrylic acid
The degree of polymerization of esters polymer is 2~12, and molecular weight is 200~1200, polydispersity index (Polydispersity Index)
It is 1.10~1.20.
Specifically, the step of methacrylate monomers being subjected to homopolymerization, obtaining methacrylate based polymers
Include:
S111: methacrylate monomers, catalyst, initiator and solvent are added separately in reaction vessel and close
Envelope.
Specifically, methacrylate monomers are being selected from methyl methacrylate, ethyl methacrylate, methacrylic acid just
One of propyl ester and n-BMA.
Wherein, catalyst is cobaltous chelate, and catalyst and the mass ratio of methacrylate monomers are 4.0:
100~4.2: 100.Further, it is double to be selected from tetramethoxy phenyl Cobalt Porphyrin, four (tert-butyl) Cobalt Phthalocyanines and two hydrations for catalyst
At least one of (boron difluorodiphenyl base glyoxime) cobalt.
Wherein, initiator is azo-compound, and initiator and the mass ratio of methacrylate monomers be 2.0: 100~
2.2:100.Further, initiator is in azodiisobutyronitrile, azobisisoheptonitrile and azo-bis-iso-dimethyl
It is at least one.Initiator can generate the free radical centered on carbon, and will not destroy the catalyst of metallo-chelate, favorably
In generation methacrylate oligomers.
Specifically, solvent is selected from one of chloroform, ethyl alcohol, ether and acetone, and solvent and methacrylate monomers
Volume ratio be 6.5: 1~7.5: 1.It further, further include that reaction vessel is subjected to degasification before sealing reaction vessel
The step of.
S112: reaction vessel is immersed in water bath with thermostatic control and is reacted.
Specifically, the temperature of water bath with thermostatic control is 70 DEG C~80 DEG C, reaction time 1h.
S113: removing catalysts and solvents after reaction, obtains methacrylate based polymers.
Specifically, catalyst is precipitated using the mixture or pure ethyl acetone of acetone and water, passes through filtering later
Remove catalyst.Mentioned reagent being capable of effective deposited metal cobalt chelates.The method of above-mentioned removing solvent can be steamed using rotation
Hair method.
Further, the end of methylmethacrylate polymer has unsaturated double-bond, under certain condition can also
Continue that polymerization reaction occurs.
S120: carbon nano pipe array is subjected to graft reaction with methacrylate based polymers, obtains modified carbon nano tube
Pipe array.Modified carbon nano-tube schematic diagram shown in referring to Figure 2 together, wherein any integer that n is 1~11.
Specifically, the step of carbon nano pipe array being carried out graft reaction with methacrylate based polymers include:
S121: carbon nano pipe array is prepared in the first substrate.
Specifically, using chemical vapor deposition for carbon nanotubes array.Further, above-mentioned to prepare carbon nano-pipe array
The step of column include: using electron beam evaporation method in the first substrate deposit catalyst layers, then under protective gas atmosphere,
First substrate is warming up to 550 DEG C~900 DEG C, so that catalyst layer homogeneous nucleation in the first substrate, then it is passed through carbon-source gas
Reaction obtains carbon nano pipe array.
Wherein, catalyst layer is cobalt-nickel alloy layer.Carbon-source gas includes 25%~40% ethylene, 1%~10% hydrogen
Gas and remainder are nitrogen (in terms of partial pressure).The throughput for being passed through carbon-source gas is 1L/min~3L/min, is passed through carbon
The time that source gas is reacted is 2min~5min.
Further, the first substrate is nickel sheet or copper sheet.The main function of first substrate is carrying carbon nano pipe array,
And nickel sheet and copper sheet are good to the stability of carbon nano pipe array, will not react with carbon nano pipe array.A reality wherein
It applies in mode, the diameter of the first substrate is 8 feet.It is appreciated that in other embodiments, the size of the first substrate can be with
It is any other size.
Specifically, protective gas is selected from least one of nitrogen, argon gas and helium.Being passed through protective gas can keep away
Exempt from carbon-source gas under high temperature to be oxidized.
The carbon nano-pipe array deposited in the first substrate in one of the embodiments, is classified as single-walled carbon nanotube battle array
Column.It is appreciated that in other embodiments, the carbon nano pipe array deposited in the first substrate is also possible to multi wall carbon and receives
Mitron array.
The length of the carbon nano pipe array deposited in the first substrate in one of the embodiments, be 0.5 μm~
2.0 μm, the diameter of carbon nanotube is 10nm~15nm in carbon nano pipe array.It is appreciated that in other embodiments, carbon nanometer
The length of pipe array can also be other values.
S122: methacrylate based polymers are deposited in the second substrate.
Specifically, the second substrate is nickel sheet or copper sheet.The main function of second substrate is to carry methyl acrylic ester
Polymer, and nickel sheet and the stability of copper sheet are good, will not react with methacrylate based polymers.A reality wherein
It applies in mode, the size of the second substrate is 50mm*50mm.It is appreciated that in other embodiments, the size of the second substrate is also
It can be any other size.
Further, methacrylate based polymers are deposited in the form of a film in the second substrate.Film with a thickness of
1mm。
S123: while treatment with ultraviolet light is carried out to the first substrate and the second substrate, so that methacrylate based polymers
Graft reaction is carried out with carbon nano pipe array, obtains modified carbon nano-tube array.
Specifically, the first substrate is in same level and placed side by side with the second substrate.Above-mentioned treatment with ultraviolet light exists
It is carried out under protective gas atmosphere.The irradiation power of ultraviolet light is 15mW~35mW.Under this irradiation power, be conducive to improve anti-
The fuel factor of system is answered, promotes the formation of gaseous state methacrylate based polymers, and under the action of protective gas air-flow
Gaseous state methacrylate based polymers are made to be moved to the surface of carbon nano pipe array, to be grafted with carbon nano pipe array
Reaction.
Further, the illumination wavelength of ultraviolet light is the monochromatic narrow band light of 196nm~350nm.Under this illumination wavelength, energy
It is enough effectively to open C―C bond formation dangling bonds in carbon nano tube surface, while being conducive to guaranteeing methyl acrylic ester polymerization
Object reduces ultraviolet light to methacrylate based polymers and carbon nano-pipe array in the case where capable of being grafted to carbon nano pipe array
The destruction of array structure.The time for the treatment of with ultraviolet light is 20min~50min, the first substrate of ultraviolet source distance and the second substrate
Distance is 2mm~20mm.
It further, further include the step that the first substrate is exposed to protective atmosphere down toward natural cooling after ultraviolet lighting
Suddenly.
The preparation method of above-mentioned modified carbon nano-tube array can obtain finely dispersed modified carbon nano-tube array.Pass through
Carbon nano pipe array is modified with the methacrylate based polymers with unsaturated group end, carbon is capable of increasing and receives
The distance between mitron and reduce the reunion due to caused by the Van der Waals force between carbon nanotube, to make modified carbon nanometer
Pipe array is evenly dispersed.Ester group in methacrylate based polymers can be sent out with natural polymer such as gelatin, chitosan etc.
Raw reaction, and the double bond in methacrylate based polymers further can be such that macromolecule crosslinks and form hydrogel,
And the mechanical property for the modification hydrogel being prepared is preferable.
The modified carbon nano-tube array of one embodiment is prepared by the preparation method of above-mentioned modified carbon nano-tube array
It arrives.The modified carbon nano-tube array is uniformly dispersed, and the active site due to having ester group and unsaturated double-bond, can be as modification
Agent prepares modified hydrogel.
The modified carbon nano-tube array can be used in preparing modified hydrogel, such as preparation is reacted with gelatin as modifying agent
Modified hydrogel.Modified hydrogel is prepared by above-mentioned modified carbon nano-tube array, the mechanics of modified hydrogel can be significantly improved
Performance.
Specifically, preparing the process of modified hydrogel by above-mentioned modified carbon nano-tube array can be following process:
By Gelatin in phosphate buffered saline (PBS), the reaction of modified carbon nano-tube array is then added, obtains carbon nanometer
The modified gelatin prepolymer of pipe.Then the gelatin prepolymer of carbon nano-tube modification is dissolved in phosphate buffered saline (PBS), sufficiently
Photoinitiator is added after stirring, carries out ultraviolet light cross-linking reaction, obtains the hydrogel of carbon nano-tube modification.
The following are specific embodiment parts:
Unless otherwise instructed, following embodiment is without containing other groups not yet explicitly pointed out in addition to inevitable impurity
Point.
Embodiment 1
(1) in the reaction vessel be added 8mg tetramethoxy phenyl Cobalt Porphyrin, 190mg n-BMA monomer,
4mg azodiisobutyronitrile and 1.48mL ether then carry out degassing processing, and reaction vessel are sealed.After sealing
Reaction vessel immerses in 70 DEG C of waters bath with thermostatic control and reacts 1h.Ethyl acetone is added after reaction to urge tetramethoxy phenyl Cobalt Porphyrin
Agent is precipitated, and is carried out rotary evaporation to liquid phase after filtering out sediment, is obtained n-BMA polymer.Methyl
The structural formula of n-butyl acrylate polymer is as follows:
(2) the deposit cobalt alloy nickel catalysis oxidant layer in the first substrate, and it is anti-that the first substrate is placed in chemical vapor deposition
It answers in furnace.It is passed through nitrogen, is warming up to 550 DEG C.It is then passed through 25% ethylene, 5% hydrogen and 70% nitrogen again, reacts 2min, obtains
To carbon nano pipe array.One piece of second substrate is taken, and is formed in the second substrate and is gathered with a thickness of the n-BMA of 1mm
Close object film.It is in nitrogen atmosphere, the first substrate and the second substrate is placed side by side in reacting furnace, the first substrate and the second base
Bottom carries out treatment with ultraviolet light in same level, to the first substrate and the second substrate.The irradiation power of ultraviolet light is 20mW, purple
The illumination wavelength of outer light is 256nm, irradiation time 20min.After reaction, ultraviolet light is closed, the first substrate is exposed to
Nitrogen atmosphere obtains modified Nano pipe array down toward natural cooling.
Embodiment 2
(1) 8mg tetramethoxy phenyl Cobalt Porphyrin, 190mg methyl methacrylate monomer, 4mg are added in the reaction vessel
Azodiisobutyronitrile and 1.30mL chloroform then carry out degassing processing, and reaction vessel are sealed.By the reaction after sealing
Container immerses in 70 DEG C of waters bath with thermostatic control and reacts 1h.Ethyl acetone is added after reaction by tetramethoxy phenyl porphyrin Co catalysts
It is precipitated, rotary evaporation is carried out to liquid phase after filtering out sediment, obtains methylmethacrylate polymer.Methacrylic acid
The structural formula of methacrylate polymer is as follows:
(2) the deposit cobalt alloy nickel catalysis oxidant layer in the first substrate, and it is anti-that the first substrate is placed in chemical vapor deposition
It answers in furnace.It is passed through hydrogen, is warming up to 630 DEG C.25% ethylene, 5% hydrogen and 70% are then passed through with the throughput of 2L/min again
Nitrogen reacts 3min, obtains carbon nano pipe array.One piece of second substrate is taken, and forms the first with a thickness of 1mm in the second substrate
Base methyl acrylate polymer film.It is in argon atmosphere, the first substrate and the second substrate is placed side by side in reacting furnace, the
One substrate and the second substrate are in same level, carry out treatment with ultraviolet light to the first substrate and the second substrate.The photograph of ultraviolet light
Penetrating power is 20mW, and the illumination wavelength of ultraviolet light is 216nm, irradiation time 20min.Ultraviolet light is closed after reaction, it will
First substrate is exposed to atmosphere of hydrogen down toward natural cooling, obtains modified Nano pipe array.
Embodiment 3
(1) 8mg tetra- (tert-butyl) Cobalt Phthalocyanine, 200mg ethyl methacrylate monomer, 4.4mg are added in the reaction vessel
Azo-bis-iso-dimethyl and 1.60mL acetone then carry out degassing processing, and reaction vessel are sealed.After sealing
Reaction vessel immerse in 70 DEG C of waters bath with thermostatic control and react 1h, the mixture of acetone and water is added after reaction by four (tert-butyls)
Phthalocyanine cobalt catalyst is precipitated, and is carried out rotary evaporation to liquid phase after filtering out sediment, is obtained ethyl methacrylate polymerization
Object.The structural formula of ethyl methacrylate polymers is as follows:
(2) deposit catalyst layers in the first substrate, and the first substrate is placed in chemical vapour deposition reactor furnace.It is logical
Enter argon gas, is warming up to 750 DEG C.40% ethylene, 1% hydrogen and 59% nitrogen are then passed through with the throughput of 3L/min again, reacted
2min obtains carbon nano pipe array.One piece of second substrate is taken, and forms the methacrylic acid with a thickness of 1mm in the second substrate
Polymerizable methacrylate object film.It is in argon atmosphere, the first substrate and the second substrate is placed side by side in reacting furnace, the first substrate with
Second substrate is in same level, carries out treatment with ultraviolet light to the first substrate and the second substrate.The irradiation power of ultraviolet light is
35mW, the illumination wavelength of ultraviolet light are 196nm, irradiation time 30min.After reaction, ultraviolet light is closed, by the first substrate
Argon atmosphere is exposed to down toward natural cooling, obtains modified Nano pipe array.
Embodiment 4
(1) 7.6mg bis- is added in the reaction vessel and is hydrated bis- (boron difluorodiphenyl base glyoxime) cobalts and four (tert-butyl) phthaleins
The mixture of cyanines cobalt, 190mg n propyl methacrylate monomer, 3.8mg azobisisoheptonitrile, azodiisobutyronitrile and azo two
The mixture of isobutyl dimethyl phthalate, 1.37mL ethyl alcohol then carry out degassing processing, and reaction vessel are sealed.After sealing
Reaction vessel immerses in 80 DEG C of waters bath with thermostatic control and reacts 1h.Ethyl acetone is added after reaction by two bis- (the boron difluorodiphenyls of hydration
Base glyoxime) Co catalysts are precipitated, and rotary evaporation is carried out to liquid phase after filtering out sediment, obtains methacrylic acid positive third
Ester polymer.The structural formula of n propyl methacrylate polymer is as follows:
(2) deposit catalyst layers in the first substrate, and the first substrate is placed in chemical vapour deposition reactor furnace.It is logical
Enter helium, is warming up to 850 DEG C.30% ethylene, 10% hydrogen and 60% nitrogen are passed through with the throughput of 1L/min again, reacted
5min obtains carbon nano pipe array.Take one piece of second substrate, in the second substrate formed with a thickness of 1mm methacrylic acid just
Propyl ester thin polymer film.It is in helium atmosphere, the first substrate and the second substrate is placed side by side in reacting furnace, the first substrate with
Second substrate is in same level, carries out treatment with ultraviolet light to the first substrate and the second substrate.The irradiation power of ultraviolet light is
35mW, the illumination wavelength of ultraviolet light are 256nm, irradiation time 20min.Ultraviolet light is closed after reaction, by the first substrate
Helium atmosphere is exposed to down toward natural cooling, obtains modified Nano pipe array.
Embodiment 5
(1) mixture of 8.2mg tetramethoxy phenyl Cobalt Porphyrin and four (tert-butyl) Cobalt Phthalocyanines is added in the reaction vessel,
The mixture and 1.59mL chloroform of 200mg methyl methacrylate monomer, 4.4mg azodiisobutyronitrile and azobisisoheptonitrile,
Degassing processing is then carried out, and reaction vessel is sealed.Reaction vessel after sealing is immersed in 70 DEG C of waters bath with thermostatic control and reacts 1h.
Ethyl acetone is added after reaction to precipitate catalyst, rotary evaporation is carried out to liquid phase after filtering out sediment, is obtained
Methylmethacrylate polymer.The structural formula of methylmethacrylate polymer is as follows:
(2) deposit catalyst layers in the first substrate, and the first substrate is placed in chemical vapour deposition reactor furnace.It is logical
Enter nitrogen, be warming up to 900 DEG C, then 30% ethylene, 10% hydrogen and 60% nitrogen are passed through with the throughput of 2L/min, reacts
3min obtains carbon nano pipe array.One piece of second substrate is taken, forms the methyl methacrylate with a thickness of 1mm in the second substrate
Ester polymer film.It is in nitrogen atmosphere, the first substrate and the second substrate is placed side by side in reacting furnace, the first substrate and the
Two bases carry out treatment with ultraviolet light in same level, to the first substrate and the second substrate.The irradiation power of ultraviolet light is
15mW, the illumination wavelength of ultraviolet light are 350nm, irradiation time 30min.After reaction, ultraviolet light is closed, by the first substrate
Nitrogen atmosphere is exposed to down toward natural cooling, obtains modified Nano pipe array.
Comparative example 1
The deposit cobalt alloy nickel catalysis oxidant layer in the first substrate, and the first substrate is placed in chemical vapour deposition reactor furnace
In.It is passed through hydrogen, is warming up to 630 DEG C.25% ethylene, 5% hydrogen and 70% nitrogen are then passed through with the throughput of 2L/min again,
3min is reacted, carbon nano pipe array is obtained.One piece of second substrate is taken, and forms the poly- methyl with a thickness of 1mm in the second substrate
Methylacrylate Film (molecular weight is 8000~10000).It is in atmosphere of hydrogen, the first substrate and the second substrate is placed side by side
In reacting furnace, the first substrate and the second substrate are in same level, carry out at ultraviolet light to the first substrate and the second substrate
Reason.The irradiation power of ultraviolet light is 20mW, and the illumination wavelength of ultraviolet light is 216nm, irradiation time 20min.After reaction
Ultraviolet light is closed, the first substrate is exposed to atmosphere of hydrogen down toward natural cooling, obtains modified Nano pipe array.
The modified carbon nano-tube array that 1~embodiment of above-described embodiment 5 is prepared is tested, test result is such as
Under:
(1) degree of polymerization test of methacrylate based polymers
Using the molecular weight of the methacrylate based polymers of 1~embodiment of gel permeation chromatography testing example 5,
And divided by monomer molecule amount, to obtain the degree of polymerization of methacrylate based polymers.Experimental result is as shown in table 1.
The degree of polymerization of 1 methacrylate based polymers of table
| Sample | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| The degree of polymerization | 3 | 3 | 5 | 8 | 12 |
As shown in Table 1, there is 3~12 degree of polymerization by the methacrylate based polymers that this method is prepared.
(2) change to prepared by raw material pure nano-carbon tube, methylmethacrylate polymer and the embodiment 5 in embodiment 5
Property carbon nano pipe array carry out XPS spectrum test with characterize embodiment 5 preparation modified carbon nano-tube array whether be grafted upper first
Base methyl acrylate polymer.Test result is respectively as shown in Fig. 3-a, Fig. 3-b, Fig. 4-a, Fig. 4-b, Fig. 5-a and Fig. 5-b.
As can be seen that the XPS spectrum figure of modified carbon nano-tube array is pure nano-carbon tube and methyl from Fig. 5-a and Fig. 5-b
The superposition of the XPS spectrum figure of methyl acrylate polymer, illustrating can be effectively by methyl methacrylate polymerization through treatment with ultraviolet light
Object is grafted on carbon nano pipe array.
Modified carbon nano-tube array obtained in 1~embodiment of embodiment 5 and comparative example 1 is reacted and handed over gelatin
Connection, obtains carbon nano-tube modification hydrogel.And obtained carbon nano-tube modification hydrogel is subjected to tensile mechanical properties survey respectively
Examination, it is as shown in Figure 6 to obtain stress-strain diagram.
Wherein, the process for modified carbon nano-tube array being prepared modified hydrogel is as follows:
By Gelatin in phosphate buffered saline (PBS), the modified carbon nano-tube for being 1: 13 with gelatin mass ratio is then added
Array is diluted with phosphate buffered saline (PBS) after stirring 2h to stop reacting.Then by above-mentioned solution in 45 DEG C of deionized waters
In carry out removing small molecule and salt in 1 week of dialysis, be then freeze-dried, obtain the gelatin pre-polymerization of carbon nano-tube modification
Object.
The gelatin prepolymer of carbon nano-tube modification is dissolved in phosphate buffered saline (PBS), after 30min is sufficiently stirred, is added
The Irgacure 2959 that gelatin prepolymer mass ratio with carbon nano-tube modification is 8: 100, carries out ultraviolet light cross-linking reaction
60min obtains the hydrogel of carbon nano-tube modification.Wherein, the irradiation power of ultraviolet light is 10mW, and the illumination wavelength of ultraviolet light is
365nm。
Specifically, the tensile strength (MPa) of above-mentioned hydrogel is tested using ASTM D-412 method.Using ASTM D-412
Method tests the elongation at break (%) of above-mentioned hydrogel.
From fig. 6 it can be seen that the hydrogel of carbon nano modification prepared by 1~embodiment of embodiment 5 is relative to comparative example 1
Obtained in carbon nano-tube modification hydrogel, tensile strength dramatically increases.Illustrate to use in comparative example 1 molecular weight for 8000~
10000 polymethyl methacrylate modified carbon nano-tube, and the high polymer of methyl methacrylate does not contain unsaturated double-bond,
It subsequent cannot be crosslinked, and intermolecular mutual crosslinking can produce bigger effect mechanical property, the modified hydrogel because obtained from
Mechanical property is poor.And the modified carbon nano-tube array that 1~embodiment of above-described embodiment 5 is prepared has ester group and unsaturation double
The active site of key can be used as the modifying agent of hydrogel, and the mechanical property of the modification hydrogel of embodiment preparation is preferable.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of preparation method of modified carbon nano-tube array, which comprises the following steps:
Methacrylate monomers are subjected to homopolymerization, obtaining structural formula isMethacrylic acid
Esters polymer, wherein any integer that n is 1~11, R=CmH2m+1, m be 1~4 any integer；And
Carbon nano pipe array and the methacrylate based polymers are subjected to graft reaction, obtain modified carbon nano-tube battle array
Column.
2. the preparation method of modified carbon nano-tube array according to claim 1, which is characterized in that described by metering system
The step of acid ester monomer progress homopolymerization includes: by the methacrylate monomers, catalyst, initiator and solvent in perseverance
Homopolymerization is carried out under the conditions of tepidarium.
3. the preparation method of modified carbon nano-tube array according to claim 2, which is characterized in that the catalyst is two
The mass ratio of the chelate of valence cobalt, the catalyst and the methacrylate monomers is 4.0: 100~4.2: 100.
4. the preparation method of modified carbon nano-tube array according to claim 3, which is characterized in that the catalyst is selected from
At least one in tetramethoxy phenyl Cobalt Porphyrin, four (tert-butyl) Cobalt Phthalocyanines and two bis- (the boron difluorodiphenyl base glyoxime) cobalts of hydration
Kind.
5. the preparation method of modified carbon nano-tube array according to claim 2, which is characterized in that the initiator is even
Nitrogen compound, and the initiator and the mass ratio of the methacrylate monomers are 2.0: 100~2.2: 100.
6. the preparation method of modified carbon nano-tube array according to claim 5, which is characterized in that the initiator is selected from
At least one of azodiisobutyronitrile, azobisisoheptonitrile and azo-bis-iso-dimethyl.
7. the preparation method of modified carbon nano-tube array according to claim 2, which is characterized in that the solvent is selected from chlorine
The volume ratio of one of imitative, ethyl alcohol, ether and acetone, the solvent and the methacrylate monomers is 6.5: 1~7.5
∶1。
8. the preparation method of modified carbon nano-tube array according to claim 2, which is characterized in that the water bath with thermostatic control
Temperature is 70 DEG C~80 DEG C.
9. a kind of modified carbon nano-tube array, which is characterized in that the modified carbon nano-tube array is any by claim 1~8
The preparation method of modified carbon nano-tube array described in is prepared.
10. modified carbon nano-tube array as claimed in claim 9 is preparing the application in modified hydrogel.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108727A (en) * | 2006-07-18 | 2008-01-23 | 中国科学院化学研究所 | Polymer inarching carbon nano-tube and method of manufacturing the same |
| CN101693125A (en) * | 2009-10-12 | 2010-04-14 | 北京科技大学 | Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel |
| CN105315456A (en) * | 2015-08-03 | 2016-02-10 | 杭州师范大学 | Carbon nano tube in-situ modification polylactam composite material and preparation method and application thereof |
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101108727A (en) * | 2006-07-18 | 2008-01-23 | 中国科学院化学研究所 | Polymer inarching carbon nano-tube and method of manufacturing the same |
| CN101693125A (en) * | 2009-10-12 | 2010-04-14 | 北京科技大学 | Process for preparing biocompatible directional carbon nanotube array reinforced composite hydrogel |
| CN105315456A (en) * | 2015-08-03 | 2016-02-10 | 杭州师范大学 | Carbon nano tube in-situ modification polylactam composite material and preparation method and application thereof |
| CN108314009A (en) * | 2018-03-30 | 2018-07-24 | 深圳烯湾科技有限公司 | The surface modification method of carbon nano pipe array |
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