CN1583572A - Preparing method for polymer grafting and modifying titanium dioxide nanometer tube - Google Patents
Preparing method for polymer grafting and modifying titanium dioxide nanometer tube Download PDFInfo
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- CN1583572A CN1583572A CN 200410024688 CN200410024688A CN1583572A CN 1583572 A CN1583572 A CN 1583572A CN 200410024688 CN200410024688 CN 200410024688 CN 200410024688 A CN200410024688 A CN 200410024688A CN 1583572 A CN1583572 A CN 1583572A
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Abstract
A polymer graft modified Tio2 nanotube is prepared form ordinary TiO2 nanotube through modifying by surfactant to make its surface carry amino groups, reacting on acylating agent to obtain active TiO2 nanotube containing acylhalogen groups, and polymerizing reaction on methyl acrylate, acrylate, or styrene.
Description
Technical field: the present invention relates to a kind of preparation method of polymer graft modification titania nanotube, particularly prepare the polymer graft modification titania nanotube by the controlled free crowd method of activity.
Background technology: because nano material has characteristics such as dimensional effect, surface effects, quantum effect, macro quanta tunnel effect, thereby show the notable feature that is different from general macroscopic material at aspects such as optics, mechanics, electricity, magnetics, developed rapidly in recent years.
Nano TiO 2 powder and receive the aspects such as pollutent of mould material in the storage of sun power and utilization, opto-electronic conversion, the photochromic and big G﹠W of photocatalytic degradation and have widespread use.Titania nanotube is a kind of novel tubular nano material of development in recent years, have than the nano TiO 2 powder and the bigger specific surface area of mould material of receiving, have more tempting application prospect, its preparation method mainly contains template synthesis method, hydro-thermal reaction synthesis method etc.In order to be fit to the needs of different purposes, the sodium titanium mitron that adopts the diverse ways preparation to have specified property causes people's interest gradually, and various modifying titanium dioxide nanotubes and composite structure thereof are produced out.
On the other hand, the discovery of various controllable polymerization methods, controlling polymers molecular weight and narrow molecular weight distribution thereof become possibility.Transition metal-catalyzed " activity " controllable free-radical polymerisation of particularly a kind of usefulness is atom transfer radical polymerization (ATRP), the polymerization single polymerization monomer that this method is suitable for is extensive, and to the control of order molecular weight of product with keep and be better than traditional polymerization greatly aspect the lower molecular weight distributing index, also avoided in the traditional method harsh requirement to the polymerization environment.Simultaneously,, can in product, introduce functional group easily, also can synthesize multiple block polymer because the popularity of initiator especially has the participation of the initiator of functional group.After this polymerization process is found, become the research focus of polymer chemistry in the world soon, and be described as " the recent studies on method of 21 century ".
Along with science and technology development, have the nano structural material of unique texture and function and the attention that nano-device has obtained people gradually, the annual report that a large amount of preparations, modified Nano structured material and nano-device are all arranged.For example, utilize the advantage of ATRP method come graft modification single or multiple lift carbon nanotube (J.Am.Chem.Soc.2004,126,170-176.).Because carbon nanotube has different performances and purposes with titania nanotube, adopt the ATRP method to come the graft modification titania nanotube and in conjunction with the specified property of titania nanotube, just can synthesize various titanium dioxide nano material and nano-devices with ad hoc structure and specified property, can promote the development and application of nano material and nano-device like this, drive the development of nano science and technical field.
Summary of the invention: the objective of the invention is to utilize methods such as atom transfer radical polymerization, at first prepare the titania nanotube that polymer surfaces is modified, to satisfy the needs in different application field by molecular designing.
The preparation method of polymer graft modification titania nanotube of the present invention is specific as follows:
Step (a): 1 weight part exsiccant titania nanotube raw material, 5～100 weight parts have the tensio-active agent of amido and the solvent of 20～100 weight parts, behind 0～100kHz ultrasonication, 5～20min, be heated to 50～100 ℃ under the nitrogen protection, reaction 10～48hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly after, obtain the titania nanotube that the surface has amido behind 40～100 ℃ of vacuum-drying 10～30hr;
Step (b): add titania nanotube 1 weight part that step (a) gained surface has amido, the solvent of alpha-halogen carboxylic acid halides 1～50 weight part and 20～100 weight parts, behind 0～100kHz ultrasonication, 5～20min, be heated to 20～100 ℃ under the nitrogen protection, stir reaction 0.5～100hr down, suction filtration and repetitive scrubbing obtain the titania nanotube that the initiating activity group is with on the surface;
Step (c): the catalyzer that adds 0.01～1 weight part, 0.01 the part of～5 weight parts, titania nanotube 0.01～1 weight part that adds step (b) gained surface band initiating activity group again, solvent 0～50 weight part, sealing, behind 0～100kHz ultrasonication 5-50min, inflated with nitrogen or argon gas 10～1000min, the polymerization single polymerization monomer that adds 0.01～100 parts by weight again, continue logical inflated with nitrogen or argon gas 10～100min, behind reaction 0.1～100hr under 0～150 ℃, behind the stopped reaction, add solvent cut, suction filtration, behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the titania nanotube of polymer graft.
Used titania nanotube is the titania nanotube of template synthesis method or the preparation of hydro-thermal reaction synthetic method in the inventive method step (a).
The used tensio-active agent that has amido of the inventive method step (a) is 3-amido propane triethoxysilicane, N-(2-amido-ethyl)-3-amido propane triethyl oxygen silicon, 3-amido propane trimethoxy silicon or N-(2-amido-ethyl)-3-amido propane trimethyl oxygen silicon; Solvent for use is benzene,toluene,xylene, chlorobenzene or dichlorobenzene.
Used alpha-halogen carboxylic acid halides is alpha-brominated isobutyl acylbromide, alpha-brominated butyryl bromide, alpha-brominated propionyl bromide, alpha-chloro isobutyryl chloride, alpha-chloro butyryl chloride or alpha-chloro propionyl chloride in the inventive method step (b); Solvent for use is methylene dichloride, trichloromethane, tetrahydrofuran (THF), pyridine, N, dinethylformamide or triethylamine.
Used polymerization single polymerization monomer is a methyl acrylic ester in the inventive method step (c), esters of acrylic acid or styrenic, methyl methacrylate is wherein arranged, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, hydroxyethyl methylacrylate, N, N-dimethyl amine Jia Jibingxisuanyizhi, N, N-diethylamide Jia Jibingxisuanyizhi, methyl acrylate, butyl acrylate, isobutyl acrylate, Hydroxyethyl acrylate, N, N-dimethyl amine ethyl propenoate, N, N-diethylamide ethyl propenoate, vinylbenzene, benzene ethyl sulfonic acid monomer, to chloro-styrene, to fluorobenzene ethene, vinyl pyridine, vinyl carbazole, V-Pyrol RC, acrylamide or N,N-DMAA.Catalyst system therefor for contain Cu (I), Ni (I), Fe (II), Ru (II), Pb (II), Mo (V) or Re (V), metallic compound, cuprous bromide, ferrous bromide, cuprous chloride, iron protochloride, lithium molybdate, RuCl are wherein arranged
2, ReO
2I (PPh
3)
2, Pd (OAc)
2Used part is 2,2 '-bipyridine, Tetramethyl Ethylene Diamine, N, N, N ', N ', N " pentamethyl-diethyl triamine, 1,1,4; 7; 10,10-hexamethyl triethyl tetramine, three [2-(N, N-dimethyl amine)-ethyl)]-amine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent for use is chlorobenzene, methyl-phenoxide, phenyl ether, N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), ethyl acetate, butanone or propyl alcohol or contain the mixture of these solvents.
Polymer graft modification titania nanotube produced according to the present invention, the preparation method is simple, and controllability is strong; Titania nanotube has good solubility after the functionalization of gained, and contain the nano level space that regularly arranged, different affine performances, nano level size polymer segments are formed in the structure, can be used as the nano-device of specific function, thereby have a wide range of applications in each side such as nano science, Materials science and biomedicines.
Description of drawings:
Fig. 1: the surface has the silicon spectrogram of amido titania nanotube
Fig. 2: the infrared spectrogram of polymethylmethacrylate grafting titania nanotube
Embodiment: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1: the titania nanotube with the preparation of template synthesis method is an initial raw material, obtains the titania nanotube that the surface has amido after surfactant-modified; Have the active titanic dioxide nanotube that the preparation of amido titania nanotube and acylation reaction contains acyl halide group; Cause various methyl acrylic esters, esters of acrylic acid and styrene monomer polymerization with atom transition free radical polymerization reaction then, obtain the titania nanotube of polymer graft.
Step (a): the magnetic agitation rotor is being housed, in the two neck round-bottomed flasks of the 100mL of reflux condensing tube, add 1.0g exsiccant titania nanotube raw material, 8.0mL3-amido propane triethoxysilicane and 30.0mL toluene, behind 40kHz ultrasonication 5min, be heated to 80 ℃ under the nitrogen protection, behind the stirring reaction 24hr, stopped reaction, be cooled to room temperature, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, the toluene repetitive scrubbing repeatedly obtains the titania nanotube 1.1g that the surface has amido behind 80 ℃ of vacuum-drying 24hr;
Step (b): in the two neck round-bottomed flasks of the 100mL that the magnetic agitation rotor is housed, adding step (a) gained surface has the titania nanotube 1.0g of amido, 30mL methylene dichloride and 2.5g triethylamine, behind 40kHz ultrasonication 10min, the frozen water cooling drips the solution of being made up of 10mL methylene dichloride and the alpha-brominated isobutyl acylbromide of 4.0g down, after dropwising, after continuing stirring reaction 24hr under the room temperature, with φ 0.22 μ m tetrafluoroethylene millipore filtration suction filtration, use methyl alcohol successively, acetone, water and washing with acetone are removed ammonium salt and excessive acylbromide, obtain containing the active titanic dioxide nanotube 1.2g of acyl halide group behind 80 ℃ of vacuum-drying 24hr;
Step (c): in the polymerizing pipe that the magnetic agitation rotor is housed, add 0.010g CuBr, step (b) gained contains the active titanic dioxide nanotube 0.100g of acyl halide group, 0.012g PMDETA (N, N, N ', N ', N " pentamethyl--diethyl triamine) and 2.0mL butanone and the mixed solvent (weight ratio is 7: 3) of propyl alcohol, sealing, inflated with nitrogen 15min; behind 40kHz ultrasonication 5min; add the 2.0g methyl methacrylate again behind the continuation inflated with nitrogen 15min, reacts 15hr down at 70 ℃; after viscosity obviously increases; stopped reaction, the dilution of adding tetrahydrofuran (THF), suction filtration; wash with tetrahydrofuran (THF) repeatedly, remove unreacted monomer and catalyzer etc., 80 ℃ of vacuum-dryings obtain polymethylmethacrylate grafted titania nanotube.
Fig. 1 has shown that for the surperficial silicon spectrogram that has the amido titania nanotube 3-amido propane triethoxysilicane reactive grafting is to the titania nanotube surface; Fig. 2 is the infrared spectrogram of polymethylmethacrylate grafting titania nanotube, its charateristic avsorption band (2994cm
-1, 2950cm
-1And 1731cm
-1) proved that polymethylmethacrylate is grafted on the titania nanotube surface.
Claims (6)
1. the preparation method of polymer graft modification titania nanotube, its feature is the preparation method carry out as follows:
Step (a): 1 weight part exsiccant titania nanotube raw material, 5～100 weight parts have the tensio-active agent of amido and the solvent of 20～100 weight parts, behind 0～100kHz ultrasonication, 5～20min, be heated to 50～100 ℃ under the nitrogen protection, reaction 10～48hr, with the filter membrane suction filtration, repetitive scrubbing repeatedly after, obtain the titania nanotube that the surface has amido behind 40～100 ℃ of vacuum-drying 10～30hr;
Step (b): add titania nanotube 1 weight part that step (a) gained surface has amido, the solvent of alpha-halogen carboxylic acid halides 1～50 weight part and 20～100 weight parts, behind 0～100kHz ultrasonication, 5～20min, be heated to 20～100 ℃ under the nitrogen protection, stir reaction 0.5～100hr down, suction filtration and repetitive scrubbing obtain the titania nanotube that the initiating activity group is with on the surface;
Step (c): add 0.01～1 catalyzer with weight part, 0.01 the part of～5 weight parts, titania nanotube 0.01～1 weight part that adds step (b) gained surface band initiating activity group again, solvent 0～50 weight part, sealing, behind 0～100kHz ultrasonication 5-50min, inflated with nitrogen or argon gas 10～1000min, the polymerization single polymerization monomer that adds 0.01～100 parts by weight again, continue logical inflated with nitrogen or argon gas 10～100min, behind reaction 0.1～100hr under 0～150 ℃, behind the stopped reaction, add solvent cut, suction filtration, behind the repetitive scrubbing, 0～180 ℃ of vacuum-drying obtains the titania nanotube of polymer graft.
2. the preparation method of polymer graft modification titania nanotube according to claim 1 is characterized in that titania nanotube used in the step (a) is the titania nanotube of template synthesis method or the preparation of hydro-thermal reaction synthesis method.
3. the preparation method of polymer graft modification titania nanotube according to claim 1 is characterized in that the used tensio-active agent that has amido of step (a) is 3-amido propane triethoxysilicane, N-(2-amido-ethyl)-3-amido propane triethoxysilicane, 3-amido propane trimethoxy silicon or N-(2-amido-ethyl)-3-amido propane trimethoxy silicon; Solvent for use is benzene,toluene,xylene, chlorobenzene or dichlorobenzene.
4. the preparation method of polymer graft modification titania nanotube according to claim 1 is characterized in that used alpha-halogen carboxylic acid halides is alpha-brominated isobutyl acylbromide, alpha-brominated butyryl bromide, alpha-brominated propionyl bromide, alpha-chloro isobutyryl chloride, alpha-chloro butyryl chloride or alpha-chloro propionyl chloride in the step (b); Solvent for use is methylene dichloride, trichloromethane, tetrahydrofuran (THF), pyridine, N, dinethylformamide or triethylamine.
5. the preparation method of polymer graft modification titania nanotube according to claim 1, it is characterized in that catalyst system therefor in the step (c) for contain Cu (I), Ni (I), Fe (II), Ru (II), Pb (II), Mo (V) or Re (V), metallic compound, cuprous bromide, ferrous bromide, cuprous chloride, iron protochloride, lithium molybdate, RuCl are wherein arranged
2, ReO
2I (PPh
3)
2, Pd (OAc)
2Used part is 2,2 '-bipyridine, Tetramethyl Ethylene Diamine, N, N, N ', N ', N " pentamethyl-diethyl triamine, 1,1,4; 7; 10,10-hexamethyl triethyl tetramine, three [2-(N, N-dimethyl amine)-ethyl)]-amine, oxalic acid, propanedioic acid, Succinic Acid, phthalic acid, triphenylphosphine or tri-n-butyl phosphine; Solvent for use is chlorobenzene, methyl-phenoxide, phenyl ether, N, dinethylformamide, N,N-dimethylacetamide, N-N-methyl-2-2-pyrrolidone N-, dimethyl sulfoxide (DMSO), ethyl acetate, butanone or propyl alcohol or contain the mixture of these solvents.
6. the preparation method of polymer graft modification titania nanotube according to claim 1, it is characterized in that polymerization single polymerization monomer used in the step (c) is a methyl acrylic ester, esters of acrylic acid or styrenic, comprising methyl methacrylate, butyl methacrylate, Propenoic acid, 2-methyl, isobutyl ester, hydroxyethyl methylacrylate, N, N-dimethyl amine Jia Jibingxisuanyizhi, N, N-diethylamide Jia Jibingxisuanyizhi, methyl acrylate, butyl acrylate, isobutyl acrylate, Hydroxyethyl acrylate, N, N-dimethyl amine ethyl propenoate, N, N-diethylamide ethyl propenoate, vinylbenzene, benzene ethyl sulfonic acid monomer, to chloro-styrene, to fluorobenzene ethene, vinyl pyridine, vinyl carbazole, V-Pyrol RC, acrylamide or N,N-DMAA.
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| CN1299999C (en) * | 2005-10-20 | 2007-02-14 | 华中师范大学 | Base metal stannate nanometer tube and its production thereof |
| CN100392025C (en) * | 2005-05-30 | 2008-06-04 | 河南大学 | In situ method for preparing modified Nano powder of hydrate, hydroxy salt, and oxide |
| CN102807655A (en) * | 2012-05-25 | 2012-12-05 | 常州大学 | Method for preparing nano-TiO2-poly (methyl methacrylate) hybrid particles |
| CN103143068A (en) * | 2013-03-18 | 2013-06-12 | 上海交通大学 | TiO2 nano-tube drug sustained-release material with PHA (phytohematoagglutinin) coating and application thereof |
| CN103861649A (en) * | 2014-03-19 | 2014-06-18 | 合肥工业大学 | Preparation method of titanium dioxide based composite photocatalyst with visible-light response function |
| CN105970121A (en) * | 2016-06-11 | 2016-09-28 | 宋介珍 | Aluminum-base material for brake disc of electrical vehicle |
| CN111718450A (en) * | 2020-06-29 | 2020-09-29 | 绍兴迪飞新材料有限公司 | Organic-inorganic electrically polarized particle and preparation method and application thereof |
| CN113120955A (en) * | 2019-12-31 | 2021-07-16 | 南京理工大学 | Preparation method of grafted sulfonated butyl titanium dioxide nanotube |
| CN114540984A (en) * | 2022-04-08 | 2022-05-27 | 杭州麒隆化纤有限公司 | High-strength coated yarn and production method thereof |
| CN114984784A (en) * | 2022-06-10 | 2022-09-02 | 宁夏清研高分子新材料有限公司 | Modified titanium dioxide nanotube and polysulfone hybrid membrane and preparation method thereof |
-
2004
- 2004-05-27 CN CN 200410024688 patent/CN1256282C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100392025C (en) * | 2005-05-30 | 2008-06-04 | 河南大学 | In situ method for preparing modified Nano powder of hydrate, hydroxy salt, and oxide |
| CN1299999C (en) * | 2005-10-20 | 2007-02-14 | 华中师范大学 | Base metal stannate nanometer tube and its production thereof |
| CN102807655A (en) * | 2012-05-25 | 2012-12-05 | 常州大学 | Method for preparing nano-TiO2-poly (methyl methacrylate) hybrid particles |
| CN103143068A (en) * | 2013-03-18 | 2013-06-12 | 上海交通大学 | TiO2 nano-tube drug sustained-release material with PHA (phytohematoagglutinin) coating and application thereof |
| CN103143068B (en) * | 2013-03-18 | 2015-10-14 | 上海交通大学 | There is the TiO of PHA overlay film 2nanotube Thermosensitive Material Used for Controlled Releasing of Medicine and application thereof |
| CN103861649A (en) * | 2014-03-19 | 2014-06-18 | 合肥工业大学 | Preparation method of titanium dioxide based composite photocatalyst with visible-light response function |
| CN105970121A (en) * | 2016-06-11 | 2016-09-28 | 宋介珍 | Aluminum-base material for brake disc of electrical vehicle |
| CN113120955A (en) * | 2019-12-31 | 2021-07-16 | 南京理工大学 | Preparation method of grafted sulfonated butyl titanium dioxide nanotube |
| CN113120955B (en) * | 2019-12-31 | 2023-03-31 | 南京理工大学 | Preparation method of grafted sulfonated butyl titanium dioxide nanotube |
| CN111718450A (en) * | 2020-06-29 | 2020-09-29 | 绍兴迪飞新材料有限公司 | Organic-inorganic electrically polarized particle and preparation method and application thereof |
| CN111718450B (en) * | 2020-06-29 | 2021-10-26 | 绍兴迪飞新材料有限公司 | Organic-inorganic electrically polarized particle and preparation method and application thereof |
| CN114540984A (en) * | 2022-04-08 | 2022-05-27 | 杭州麒隆化纤有限公司 | High-strength coated yarn and production method thereof |
| CN114540984B (en) * | 2022-04-08 | 2023-08-18 | 杭州麒隆化纤有限公司 | High-strength coated yarn and production method thereof |
| CN114984784A (en) * | 2022-06-10 | 2022-09-02 | 宁夏清研高分子新材料有限公司 | Modified titanium dioxide nanotube and polysulfone hybrid membrane and preparation method thereof |
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