CN100503651C - Method for preparing carbon nano-tube used for RAFT polymerization chain transfer agent - Google Patents
Method for preparing carbon nano-tube used for RAFT polymerization chain transfer agent Download PDFInfo
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- CN100503651C CN100503651C CNB2006100288372A CN200610028837A CN100503651C CN 100503651 C CN100503651 C CN 100503651C CN B2006100288372 A CNB2006100288372 A CN B2006100288372A CN 200610028837 A CN200610028837 A CN 200610028837A CN 100503651 C CN100503651 C CN 100503651C
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Abstract
The invention relates to a preparation method of a functionalized carbon nano tube which can be used in reversible addition-fragmentation chain transfer free radical (RAFT) polymerization. The RAFT polymerization as a free radical living controllable polymerization is characterized in controllable structure and molecular weight of the product. The carbon nano-tube becomes a purified and dispersed carbon nano tube after treated by oleum; bromo carbon nano tube is obtained by the modification on the surface of the carbon nano tube with aromatic diazonium salt containing bromos. Grignard reagent is prepared by the bromo carbon nano tube, and has reaction with carbon disulfide and coupling reaction with organic bromide to produce chain transfer agent-dithioester which contains the carbon nano-tube and can be used as RAFT polymerization. The dithioester containing the carbon nano tube has a high chain transfer constant and a special structure, and can make the RAFT polymerization realize successfully the living controllable polymerization. The invention proves possibilities for controlling molecules design, structure and components of the carbon nano-tube-polymers material, thereby the invention has a wider application prospect.
Description
Technical field
The invention belongs to the material field, relate to the carbon nanotube of surface modification, particularly can be used as the preparation method of the functionalized carbon nano-tube of RAFT (reversible addition-fragmentation chain transfer free radical) polymeric chain transfer agent.
Background technology
Carbon nanotube has the extremely good intrinsic property of graphite, as heat-resisting, corrosion-resistant, heat transfer and good conductivity, hot strength height, self lubricity with give birth to a series of over-all propertieies such as the body consistency is good.Its most outstanding characteristic has: the superelevation mechanical property that special electrical properties that the fine structure that nanoscale forms, nanostructure bring up and carbon bond are constructed etc.
Because the high-performance of carbon nanotube, the application prospect of carbon nanotube is inestimable.But, water insoluble and other solvents of carbon nanotube.In solvent or matrix material, carbon nanotube is assembled agglomerating, dispersed extreme difference.These characteristics have seriously limited the basic research and the application of carbon nanotube.Therefore, carbon nanotube being carried out finishing obtains various soluble or functionalized carbon nanotube and has caused more and more scientists' interest.Wherein, because the various superperformances of polymer materials coat the carbon nano-tube modified research focus that also becomes this field gradually with polymkeric substance by chemical bonding or physics.
With polymkeric substance carbon nanotube is carried out chemical bonding and mainly comprise two big classes.One is first synthetic polymer, then this polymkeric substance is keyed on the carbon nanotube in the grafted mode; Another kind of then is that the polymer monomer in-situ polymerization is grafted on the carbon nanotube, and promptly polymer chain increases on carbon nanotube.Both respectively have relative merits, and the former used polymericular weight can determine but cause being not easy to produce chemical bonding owing to the reactive behavior of carbon nanotube is very for a short time that latter reaction's activity is big slightly but molecular weight is uncontrollable.Because the molecular weight of polymkeric substance can produce a very large impact its performance, therefore how controlling the molecular weight that is grafted on the polymkeric substance on the carbon nanotube under the condition that guarantees reactive behavior is an important research contents.
RAFT is as a kind of active controllable free radical polymerization process, because its polymerisate has structure and molecular weight is controlled, also becomes a research focus in recent years.Make the RAFT polymerization realize that successfully the key of controllable free-radical polymerisation is to find a kind of chain-transfer agent with high chain transfer constant and ad hoc structure---two thioesters.
Summary of the invention
The objective of the invention is to propose a kind of new preparation method who can be used for RAFT polymeric functionalized carbon nano-tube.Thereby can utilize the structure and the controlled characteristics of molecular weight of RAFT polymerisate, make the controlled possibility that becomes of molecular designing, structure and composition of " carbon nanotube-polymkeric substance " material.
For achieving the above object, solution of the present invention is:
Can be used as carbon nanotube of RAFT polymeric chain-transfer agent and preparation method thereof, may further comprise the steps: the oleum with trioxygen-containing sulphur 20%～50% carries out acidifying to carbon nanotube, carry out finishing with the aromatic diazo salt pair carbon nanotube that contains bromo again, promptly connect from the teeth outwards and go up various organic groups or macromolecular chain, thereby obtain the bromination carbon nanotube.Again with bromination made of carbon nanotubes Grignard reagent, react with dithiocarbonic anhydride then and organic bromide generation linked reaction, generation has the carbon nanotube that can be used for reversible addition-fragmentation chain transfer free radical (RAFT) polymeric chain-transfer agent (two thioesters) structure.
Further, the preparation process of described bromination carbon nanotube is as follows: the oleum of 1 weight part exsiccant carbon nanotube and 0.1～100 weight part mixes, behind magnetic agitation 1～100h, add the phenyl amines bromide of 10～100 weight parts, the nitrite of 10～100 weight parts and the initiator of 1～10 weight part successively, be heated to 20～200 ℃, react 0.5～50h in magnetic agitation and under refluxing.Product is with the filter membrane suction filtration, and with coordinative solvent washing 3～10 times.Behind 20～100 ℃ of following vacuum-drying 10～40h, obtain the bromination carbon nanotube.
The step of the described carbon nanotube that has two thioesters structures with the bromination made of carbon nanotubes is as follows: get the bromination carbon nanotube that 1 weight part makes according to preceding method, the metal magnesium rod through polishing of 1～100 weight part, the organic solvent of 0.1～100 weight part, be heated to 20～50 ℃, reflux under the logical condition of nitrogen gas, dropwise drip the dithiocarbonic anhydride of 0.1～100 weight part with separating funnel, insulation 0.5～20h.Be warming up to 50～150 ℃ then, add the organic bromide of 1～100 weight part, react 1～100h in magnetic agitation and under refluxing.Products therefrom is used distilled water wash 3～10 times with the filter membrane suction filtration, washs 3～10 times with ether or tetrahydrofuran (THF) again.At 0～50 ℃ of following vacuum-drying 10～100h, the carbon nanotube that obtains having two thioesters structures.
Used carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; The sulfur trioxide content of used oleum is 20%～50%; Used phenyl amines bromide comprises 2-bromaniline, 3-bromaniline, 4-bromaniline, 4-bromo-3-monomethylaniline, 4-bromo-3-ethylaniline, 4-bromo-3-n-propyl aniline, 4-bromo-3-isopropyl aniline or 4-bromo-3-n-butyl aniline; Used nitrite comprises Sodium Nitrite, potassium nitrite and barium nitrite; Used initiator comprises peroxide initiator, azo-initiator and redox class initiator; Wash used solvent and comprise tetrahydrofuran (THF), acetone, N, dinethylformamide.
Used organic solvent comprises anhydrous tetrahydro furan or absolute ether during the preparation Grignard reagent, and used organic bromide comprises isopropyl benzene bromine, 1-bromo ethyl phenenyl, itrile group isopropyl bromide.
The used millipore filtration of suction filtration is methylcellulose gum film, polyvinylidene fluoride film or the poly tetrafluoroethylene of aperture at 0.22～0.60 μ m.
The present invention can be applicable to aspects such as molecular designing, structure and the composition of " carbon nanotube-polymkeric substance " material be controlled.
Owing to adopted such scheme, the present invention has the following advantages:
The prepared RAFT polymeric functionalized carbon nano-tube that can be used for of the present invention, good dispersion in organic solvent, has the structure that can realize the required chain-transfer agent of RAFT polymerization (two thioesters), for the controlled possibility that provides of molecular designing, structure and composition of " carbon nanotube-polymkeric substance " material is provided.
Description of drawings
Fig. 1 is the infrared spectrum of two thioesters of the carbon nanotubes of an embodiment of the present invention
Fig. 2 is the Single Walled Carbon Nanotube (a) and the contrast Raman spectrogram that contains two thioesters (b) of Single Walled Carbon Nanotube of an embodiment of the present invention
Embodiment
Embodiment 1: adding 100mg exsiccant Single Walled Carbon Nanotube and 100mL sulfur trioxide content are 20% oleum in the single neck round-bottomed flask of the 250mL that magnetic stir bar is housed, behind the magnetic agitation 3h, add 5.779g4-bromaniline, 2.318g Sodium Nitrite and 0.28g Diisopropyl azodicarboxylate successively, be heated to 80 ℃, the magnetic agitation and the 1h that refluxes.Products therefrom through the dilution of 1L deionized water, is the tetrafluoroethylene millipore filtration suction filtration of 0.22 μ m with the aperture earlier then, and extremely neutral with the deionized water repetitive scrubbing earlier, again with tetrahydrofuran (THF) washing 5 times.Obtain bromo carbon nanotube 0.129g behind 60 ℃ of vacuum-drying 24h.
Bromo carbon nanotube that adding 100mL anhydrous tetrahydro furan, 100mg make in the 250mL three neck round-bottomed flasks that magnetic stir bar is housed and 0.8g are through the magnesium rod of polishing, be heated to 40 ℃, logical nitrogen also refluxes, dropwise drip dithiocarbonic anhydride 40mL with separating funnel, dropwise follow-up continuation of insurance temperature 1h.Be warming up to 70 ℃ then, add 1-bromo ethyl phenenyl 1g, insulation 60h.Products therefrom is the tetrafluoroethylene millipore filtration suction filtration of 0.22 μ m with the aperture, uses distilled water wash 5 times, again with tetrahydrofuran (THF) washing 5 times.Obtain having the carbon nanotube of two thioesters behind 25 ℃ of vacuum-drying 72h.
Result such as Fig. 1 and Fig. 2.In the infrared spectrum, the C-H vibration absorption peak is at 2925 and 2847cm
-1The place; The C=S vibration absorption peak is at 1637cm
-1The place; The C-S vibration absorption peak is at 1127cm
-1The place; The C-H vibration absorption peak is at 562cm
-1The place.Contrast Raman spectrum figure shows that variation has taken place the structure of Single Walled Carbon Nanotube.
Embodiment 2: adding 50mg exsiccant multi-walled carbon nano-tubes and 100mL sulfur trioxide content are 20% oleum in the single neck round-bottomed flask of the 250mL that magnetic stir bar is housed, behind the magnetic agitation 3h, add 3.125g 4-bromo-3-monomethylaniline, 1.159g Sodium Nitrite and 0.14g Diisopropyl azodicarboxylate successively, be heated to 80 ℃, the magnetic agitation and the 1h that refluxes.Products therefrom through the dilution of 500mL deionized water, is the tetrafluoroethylene millipore filtration suction filtration of 0.22 μ m with the aperture earlier then, and extremely neutral with the deionized water repetitive scrubbing earlier, again with tetrahydrofuran (THF) washing 5 times.Obtain bromo carbon nanotube 0.066g behind 50 ℃ of vacuum-drying 24h.
Bromo carbon nanotube that adding 50mL absolute ether, 50mg make in the 100mL three neck round-bottomed flasks that magnetic stir bar is housed and 0.4g are through the magnesium rod of polishing, be heated to 40 ℃, logical nitrogen also refluxes, and dropwise drips dithiocarbonic anhydride 40mL with separating funnel, dropwises follow-up continuation of insurance temperature 1h.Be warming up to 70 ℃ then, add 1-bromo ethyl phenenyl 1g, insulation 60h.Products therefrom is the tetrafluoroethylene millipore filtration suction filtration of 0.22 μ m with the aperture, uses distilled water wash 5 times, again with tetrahydrofuran (THF) washing 5 times.Obtain having the carbon nanotube of two thioesters behind 25 ℃ of vacuum-drying 72h.
The above-mentioned description to embodiment is can understand and apply the invention for ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (6)
1, a kind of preparation method of carbon nanotube of used for RAFT polymerization chain transfer agent, it is characterized in that: at first the diazonium compound by containing bromo is to the prepared by surface modification bromination carbon nanotube of carbon nanotube, prepare Grignard reagent then, by making with the reaction of dithiocarbonic anhydride and the linked reaction of organic bromide.
2, method according to claim 1, it is characterized in that: get the metal magnesium rod through polishing of 1 weight part bromination carbon nanotube, 1～100 weight part, the organic solvent of 0.1～100 weight part, be heated to 20～50 ℃, reflux under the logical condition of nitrogen gas, dropwise drip the dithiocarbonic anhydride of 0.1～100 weight part with separating funnel, insulation 0.5～20h; Be warming up to 50～150 ℃ then, add the organic bromide of 1～100 weight part, react 1～100h in magnetic agitation and under refluxing; Products therefrom is used distilled water wash 3～10 times with the filter membrane suction filtration, washs 3～10 times with ether or tetrahydrofuran (THF) again; At 0～50 ℃ of following vacuum-drying 10～100h, the carbon nanotube that obtains having two thioesters structures.
3, method according to claim 2, it is characterized in that: the preparation process of described bromination carbon nanotube comprises: the oleum of 1 weight part exsiccant carbon nanotube and 0.1～100 weight part mixes, behind magnetic agitation 1～100h, add the phenyl amines bromide of 10～100 weight parts, the nitrite of 10～100 weight parts and the initiator of 1～10 weight part successively, be heated to 20～200 ℃, react 0.5～50h in magnetic agitation and under refluxing; Product is with the filter membrane suction filtration, and with coordinative solvent washing 3～10 times; Behind 20～100 ℃ of following vacuum-drying 10～40h, obtain the bromination carbon nanotube.
4, method according to claim 3 is characterized in that: described carbon nanotube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes; The sulfur trioxide content of described oleum is 20%～50%; Described phenyl amines bromide comprises 2-bromaniline, 3-bromaniline, 4-bromaniline, 4-bromo-3-monomethylaniline, 4-bromo-3-ethylaniline, 4-bromo-3-n-propyl aniline, 4-bromo-3-isopropyl aniline or 4-bromo-3-n-butyl aniline; Described nitrite comprises Sodium Nitrite, potassium nitrite and barium nitrite; Described initiator comprises peroxide initiator, azo-initiator and redox class initiator; The solvent of described washing usefulness is following a kind of in listed: tetrahydrofuran (THF), acetone, N, dinethylformamide.
5, method according to claim 2, it is characterized in that: during the preparation Grignard reagent, described organic solvent comprises anhydrous tetrahydro furan or absolute ether, and described organic bromide is following a kind of in listed: isopropyl benzene bromine, 1-bromo ethyl phenenyl, itrile group isopropyl bromide.
6, method according to claim 2 is characterized in that: the used filter membrane of described suction filtration is methylcellulose gum film, polyvinylidene fluoride film or the poly tetrafluoroethylene of aperture at 0.22～0.60 μ m.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004244490A (en) * | 2003-02-13 | 2004-09-02 | Toray Ind Inc | Carbon nanotube-containing resin composite and method for producing the same, and high-modulus film |
| US20060079626A1 (en) * | 2004-03-19 | 2006-04-13 | Arrowhead Center, Inc. | Thiation of carbon nanotubes and composite formation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004244490A (en) * | 2003-02-13 | 2004-09-02 | Toray Ind Inc | Carbon nanotube-containing resin composite and method for producing the same, and high-modulus film |
| US20060079626A1 (en) * | 2004-03-19 | 2006-04-13 | Arrowhead Center, Inc. | Thiation of carbon nanotubes and composite formation |
Non-Patent Citations (1)
| Title |
|---|
| 用双硫酯链转移法合成嵌段聚合物. 庄荣传等.高分子学报，第3期. 2001 * |
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