CN108530582A - Multi-component Janus composite nano materials and preparation method thereof - Google Patents

Multi-component Janus composite nano materials and preparation method thereof Download PDF

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CN108530582A
CN108530582A CN201710123118.7A CN201710123118A CN108530582A CN 108530582 A CN108530582 A CN 108530582A CN 201710123118 A CN201710123118 A CN 201710123118A CN 108530582 A CN108530582 A CN 108530582A
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janus
polymer
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methyl
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CN108530582B (en
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杨振忠
杨雯智
贾凡
姜秉寅
井静云
姚晓辉
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Institute of Chemistry CAS
University of Chinese Academy of Sciences
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University of Chinese Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
    • C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

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  • Polymers & Plastics (AREA)
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  • Polymerisation Methods In General (AREA)
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Abstract

The present invention relates to a kind of multi-component Janus composite nano materials and preparation method thereof.The Janus composite nano materials of the present invention are based on by polymer is single-stranded and the molecular Janus nano particles of nanoparticle, as to multi-component nano material obtained from the growing mixed functional materials of its nanoparticle fraction and/or polymer single stranded portion graft polymers molecular brush.By polymer is single-stranded and the molecular Janus nano particles of nanoparticle are prepared by ionic polymerization, it is single-stranded with any one in the arbitrary assembled arrangement model of the ball-type nano-particle order of connection that structural model can be selected from polymer.Functional materials are selected from metal, metallic compound and nonmetallic compound.The present invention realize composition, structure accuracy controlling Janus composite nano materials controllable preparation, the excellent properties of bonded composite and nano material have great importance in fields such as catalysis, medicine controlled releasing, the fixation of enzyme, pollutant process.

Description

Multi-component Janus composite nano materials and preparation method thereof
Technical field
The present invention relates to field of material technology, more particularly to a kind of multi-component Janus composite nano materials and its preparation Method.
Background technology
Janus is derived from ancient Roman's mythology, is had the god of two faces, is looked at on one side, and another side will be towards future. 1991, de Gennes quoted mono- words of Janus to describe with anisotropic particle for the first time in the prize-winning speech of Nobel (P.G.de Gennes.Rev.Mod.Phys.1992,64,645-648.).Janus materials are different compositions and property partition set At anisotropic material (A.Perrro, S.Reculusa, S.Ravaine, E.Bourgeat-Lamic, E.Duguet.J.Mater.Chem.2005,15,3745-3760.).In the past 20 years, Janus materials have obtained high speed development, exhibition Many novel properties and tempting application prospect are shown, although achieving weight in terms of the preparation method of associated materials and performance study Be in progress (F.X.Liang, C.L.Zhang, Z.Z.Yang.Adv.Mater.2014,26,6944-6949.), but existing preparation The method of Janus materials still has problem.Such as：The preparation side of the current spherical Janus polymer colloids particle of chain at present Method is mainly block copolymer crosslinking, i.e., obtains nano-colloid and height by some block in intramolecular crosslinking block copolymer The single-stranded Janus composite materials coexisted of molecule, but the shortcomings that such method (≤1%) relatively low there is solid content (S.Mavila, O.Eivgi,I.Berkovich,N.G.Lemcof.Chem.Rev.2016,116,878-961.).It is easy to the side of mass production Method is phase separation method and interface nucleation process, but the Janus materials prepared are difficult to realize the strict partition and micro-structure of chemical composition Precise controlling (T.Tanaka.Langmuir 2010,26,11732-11736.).Therefore, Janus material structures and function Complexity leads to the limitation of preparation method, how quickly, easily realize Janus materials chemical composition strict partition and The finely regulating of micro-structure is that researcher extremely pays close attention to and fails well to be solved the problems, such as always, it would be highly desirable to further research.
Invention content
The purpose of the present invention is in view of above-mentioned problems of the prior art, it is compound to provide a kind of multi-component Janus Nano material and preparation method thereof.
Multi-component Janus composite nano materials provided by the present invention are based on by polymer is single-stranded and nanoparticle subgroup At Janus nano particles, by growing mixed functional materials of nanoparticle fraction to the Janus nano particles and/ Or multi-component nano material obtained from polymer single stranded portion graft polymers molecular brush.
It is described by polymer is single-stranded and the molecular Janus nano particles of nanoparticle are prepared by ionic polymerization, Structural model can be selected from that ball (polymer is single-stranded very short at this time, can ignore), (polymer of connected ball is single-stranded very for ball/ball Short, can ignore), chain/ball, chain/ball/chain, ball/chain/ball, chain/ball/chain/ball/chain, the nano-particles such as ball/chain/ball/chain/ball With any one in the model of the arbitrary assembled arrangement of the single-stranded order of connection；The single-stranded chemical composition of the polymer, the degree of polymerization can It adjusts；Chemical composition, the size of the nano-particle are controllable.
The single-stranded ionic polymerization monomer of the polymer can be selected from cationically polymerizable monomer, can ring-opening polymerisation monomer With one kind in anionic polymerizable monomer.
The monomer of the cationically polymerizable can be selected from styrene, p- methyl styrenes, α-methylstyrene, 4- tertiary butyls Styrene, 4- 1-chloro-4-methyl-benzenes, styrene ethyl trimethoxy silane, methyl styrene silane, isobutyl vinyl ether, uncle Butyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl, one kind in N- vinyl carbazoles or its arbitrary group It closes；
It is described can the monomer of ring-opening polymerisation can be selected from propylene oxide, epoxy butane, decamethylene, Epoxydodecane, epoxy Chloropropane, n-butyl glycidyl ether, phenyl glycidyl ether, phenyl ethylene oxide, 4- tert-butyl-phenyls glycerin ether, α-are in oneself One kind in ester, beta-propiolactone or its arbitrary combination；
The anionic polymerizable monomer can be selected from styrene, p- methyl styrenes, α-methylstyrene, Alpha-Methyl third E pioic acid methyl ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, propylene oxide, epoxy butane, Toluene di-isocyanate(TDI), n-hexyl isocyanates, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, styrene first One kind in aldehyde or its arbitrary combination.
The nano-particle be by a kind of containing functional group can ionic polymerization monomer and another functional group's number be more than Equal to 2 can ionic polymerization monomer carry out ionic polymerization preparation the nano-particle with spherical model.
It is described containing functional group can ionic polymerization monomer can be selected from cationically polymerizable monomer, can ring-opening polymerisation list One kind in body and anionic polymerizable monomer；
The monomer of the cationically polymerizable can be selected from styrene, p- methyl styrenes, α-methylstyrene, p- methoxyl groups Styrene, p- chlorostyrenes, 4- t-butyl styrenes, 4- 1-chloro-4-methyl-benzenes, divinylbenzene, isoprene, butadiene, Styrene ethyl trimethoxy silane, methyl styrene silane, vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, uncle Butyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl, vinyl methyl dimethoxysilane, vinyl Trimethoxy silane, vinyltriethoxysilane, new alkoxy three (methacryloxy) zirconate, new alkoxy three (acryloxy) zirconate, diisopropoxy acetoacetate oleic acid ester group Aluminate, (two is pungent for two oleic acid acyloxy of isopropoxy Base phosphoric acid acyloxy) titanate esters, N- vinyl carbazoles, one kind in vinyl pyrrolidone or its arbitrary combination；
It is described can the monomer of ring-opening polymerisation can be selected from ethylene oxide, propylene oxide, epoxy butane, decamethylene, epoxy ten Dioxane, epoxychloropropane, n-butyl glycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, phenyl epoxy In ethane, 4- tert-butyl-phenyls glycerin ether, 3- glycidyl ether oxypropyltrimethoxysilanes, α-caprolactone, beta-propiolactone One kind or its arbitrary combine；
The anionic polymerizable monomer can be selected from styrene, p- methyl styrenes, α-methylstyrene Alpha-Methyl third E pioic acid methyl ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, toluene di-isocyanate(TDI), just oneself Based isocyanate, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, one kind in styrene formaldehyde or it is arbitrary Combination.
Functional group's number more than or equal to 2 can the monomer of ionic polymerization can be selected from divinylbenzene, butadiene, isoamyl Diene, 1,2,4,5- diepoxies pentane, 1,2,5,6- diepoxies hexane, 1,2,6,7- diepoxies heptane, 1,2,7,8- diepoxies Octane, 1,2,4,5- bicyclopentadiene dioxide, 1,4- butanediol diglycidyl ethers, bisphenol A diglycidyl ether, isophthalic two Phenol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerol dimethacrylate, ethylene glycol dimethacrylate In ester, triethylene glycol dimethacrylate, phthalic acid ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI) One kind at least one or its it is arbitrary combine, be added content be calculated as being added with percent by volume form nano-particle contain official Can group can ionic polymerization amount of monomer 5-30%.
The functional materials can be selected from one or more of metal, metallic compound and nonmetallic compound and appoint Meaning combination.
The metal can be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Any one of Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two kinds Any of the above combines；
The metallic compound can be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, The oxide of Mn, Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, vulcanization Object, tellurides or the two or more arbitrary combinations in them；
The nonmetallic compound is silica.
The polymer molecule brush segment can be selected from polyacrylic acid, the polyacrylic acid tert-butyl ester, polymethylacrylic acid, poly- methyl Tert-butyl acrylate, poly- (methacrylic acid -2- dimethylamino ethyl esters), poly- (methacrylic acid -2- diethylaminos ethyl ester), Poly- (2- vinylpyridines), P4VP, Vinylcaprolactam homopolymer, poly- (2- hydroxypropyl acrylates), poly- (N- L- (1- hydroxymethylpropyls) Methacrylamide), poly- (N- propyl Methacrylamides), poly- (3- acryloxypropyl trimethoxies Base silane), poly- (3- acryloxypropyls triethoxysilane), poly- (γ-methacryloxypropyl trimethoxy silicon Alkane), poly- (γ-methacryloxypropyl), poly- (acryloxy diisopropoxy aluminium), poly- (methyl Acryloxy diisopropoxy aluminium), poly- (three titanium isopropoxide of acryloxy), poly- (three isopropyl oxygen of methacryloxy Base titanium), poly- (three isopropoxy zirconium of acryloxy), poly- (three isopropoxy zirconium of methacryloxy), poly- (N- isopropyls third Acrylamide) any one of or two or more arbitrary combinations.
The degree of polymerization of the polymer single stranded portion is 10-10000, preferably 30-3000, more preferably 50-1000.
The nano-particles size is in 1-20nm, preferably 2-15nm.
The degree of polymerization of the polymer of the polymer molecule brush segment be 5-10000, preferably 30-1000, more preferably 50-500。
The present invention also provides the preparation methods of multi-component Janus composite nano materials, include the following steps：
Step 1) is based on by polymer is single-stranded and the molecular Janus nano particles of nanoparticle, at above-mentioned Janus nanometers Nanoparticle fraction in grain introduces reactive group, and it is growing mixed to obtain nanoparticle fraction for growing mixed functional materials The Janus nano particles of functional materials；And/or
Step 2) utilizes free radical polymerisation process, in the Janus of the growing mixed functional materials of above-mentioned nanoparticle fraction Polymer single stranded portion graft polymers molecular brush in nano particle, obtains multi-component Janus composite nano materials.
It is described by polymer is single-stranded and the molecular Janus nano particles of nanoparticle are prepared by ionic polymerization, knot Structure model can be selected from any one in the single-stranded model with the arbitrary assembled arrangement of the ball-type nano-particle order of connection of polymer；It is described The single-stranded chemical composition of polymer, the degree of polymerization is adjustable；Chemical composition, the size of the nano-particle are controllable.
The single-stranded ionic polymerization monomer of the polymer can be selected from cationically polymerizable monomer, can ring-opening polymerisation monomer With one kind in anionic polymerizable monomer.
The monomer of the cationically polymerizable can be selected from styrene, p- methyl styrenes, α-methylstyrene, 4- tertiary butyls Styrene, 4- 1-chloro-4-methyl-benzenes, styrene ethyl trimethoxy silane, methyl styrene silane, isobutyl vinyl ether, uncle Butyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl, one kind in N- vinyl carbazoles or its arbitrary group It closes；
It is described can the monomer of ring-opening polymerisation can be selected from propylene oxide, epoxy butane, decamethylene, Epoxydodecane, epoxy Chloropropane, n-butyl glycidyl ether, phenyl glycidyl ether, phenyl ethylene oxide, 4- tert-butyl-phenyls glycerin ether, α-are in oneself One kind in ester, beta-propiolactone or its arbitrary combination；
The anionic polymerizable monomer can be selected from styrene, p- methyl styrenes, α-methylstyrene, Alpha-Methyl third E pioic acid methyl ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, propylene oxide, epoxy butane, Toluene di-isocyanate(TDI), n-hexyl isocyanates, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, styrene first One kind in aldehyde or its arbitrary combination.
The nano-particle be by a kind of containing functional group can ionic polymerization monomer and another functional group's number be more than Equal to 2 can ionic polymerization monomer carry out ionic polymerization preparation the nano-particle with spherical model.
It is described containing functional group can ionic polymerization monomer can be selected from cationically polymerizable monomer, can ring-opening polymerisation list One kind in body and anionic polymerizable monomer；
The monomer of the cationically polymerizable can be selected from styrene, p- methyl styrenes, α-methylstyrene, p- methoxyl groups Styrene, p- chlorostyrenes, 4- t-butyl styrenes, 4- 1-chloro-4-methyl-benzenes, divinylbenzene, isoprene, butadiene, Styrene ethyl trimethoxy silane, methyl styrene silane, vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, uncle Butyl vinyl ether, octadecyl vinyl ether, dodecyl vinyl, vinyl methyl dimethoxysilane, vinyl Trimethoxy silane, vinyltriethoxysilane, new alkoxy three (methacryloxy) zirconate, new alkoxy three (acryloxy) zirconate, diisopropoxy acetoacetate oleic acid ester group Aluminate, (two is pungent for two oleic acid acyloxy of isopropoxy Base phosphoric acid acyloxy) titanate esters, N- vinyl carbazoles, one kind in vinyl pyrrolidone or its arbitrary combination；
It is described can the monomer of ring-opening polymerisation can be selected from ethylene oxide, propylene oxide, epoxy butane, decamethylene, epoxy ten Dioxane, epoxychloropropane, n-butyl glycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, phenyl epoxy In ethane, 4- tert-butyl-phenyls glycerin ether, 3- glycidyl ether oxypropyltrimethoxysilanes, α-caprolactone, beta-propiolactone One kind or its arbitrary combine；
The anionic polymerizable monomer can be selected from styrene, p- methyl styrenes, α-methylstyrene Alpha-Methyl third E pioic acid methyl ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, toluene di-isocyanate(TDI), just oneself Based isocyanate, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, one kind in styrene formaldehyde or it is arbitrary Combination.
Functional group's number more than or equal to 2 can the monomer of ionic polymerization can be selected from divinylbenzene, butadiene, isoamyl Diene, 1,2,4,5- diepoxies pentane, 1,2,5,6- diepoxies hexane, 1,2,6,7- diepoxies heptane, 1,2,7,8- diepoxies Octane, 1,2,4,5- bicyclopentadiene dioxide, 1,4- butanediol diglycidyl ethers, bisphenol A diglycidyl ether, isophthalic two Phenol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, glycerol dimethacrylate, ethylene glycol dimethacrylate In ester, triethylene glycol dimethacrylate, phthalic acid ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI) One kind at least one or its it is arbitrary combine, be added content be calculated as being added with percent by volume form nano-particle contain official Can group can ionic polymerization amount of monomer 5-30%.
The reactive group can be selected from carboxyl, amino, hydroxyl, one kind of sulfydryl or its arbitrary combination.
It is arbitrary that the functional materials are selected from one or more of metal, metallic compound and nonmetallic compound Combination；
The metal be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, Any one of Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two kinds with Upper arbitrary combination；
The metallic compound be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, The oxide of Mn, Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, vulcanization Object, tellurides or the two or more arbitrary combinations in them；
The nonmetallic compound is silica.
The polymer molecule brush segment is selected from polyacrylic acid, the polyacrylic acid tert-butyl ester, polymethylacrylic acid, poly- methyl-prop Enoic acid ter-butyl ester, poly- (methacrylic acid -2- diethylaminos ethyl ester), gathers poly- (methacrylic acid -2- dimethylamino ethyl esters) (2- vinylpyridines), P4VP, Vinylcaprolactam homopolymer, poly- (2- hydroxypropyl acrylates), poly- (N-L- (1- hydroxymethylpropyls) Methacrylamide), poly- (N- propyl Methacrylamides), poly- (3- acryloxypropyl trimethoxies Silane), poly- (3- acryloxypropyls triethoxysilane), poly- (γ-methacryloxypropyl trimethoxy silane), Poly- (γ-methacryloxypropyl), poly- (acryloxy diisopropoxy aluminium), poly- (metering system Acyloxy diisopropoxy aluminium), poly- (three titanium isopropoxide of acryloxy), poly- (three isopropoxy of methacryloxy Titanium), poly- (three isopropoxy zirconium of acryloxy), poly- (three isopropoxy zirconium of methacryloxy), poly- (N- isopropyl propylene Amide) any one of or two or more arbitrary combinations.
The method may also include introducing reactive functional groups before polymer single stranded portion graft polymers molecular brush The step of；The reactive functional groups are selected from-Br ,-Cl, one kind in-SC (Z) S or its arbitrary combination；Wherein ,-the SC (Z) Z group in S functional groups can be selected from Ph, CH3,PhCH2,-NCH3-,-O,-S。
The polymer single stranded portion degree of polymerization is 10-10000, preferably 30-3000, more preferably 50-1000.
Nano-particles size is in 1-20nm, preferably 2-15nm.
The polymer segment degree of polymerization of the polymer molecule brush is 5-10000, preferably 30-1000, more preferably 50- 500。
The present invention realize composition, structure accuracy controlling Janus composite nano materials controllable preparation, in conjunction with composite wood The excellent properties of material and nano material have important meaning in fields such as catalysis, medicine controlled releasing, the fixation of enzyme, pollutant process Justice.
Description of the drawings
Fig. 1 is that both sides respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes) are single-stranded in the present invention, Centre is the nano-particle i.e. transmission of the Janus nano particles with chain/ball/chain model of polystyrene, polydivinylbenezene Electron microscope.
Fig. 2 be the embodiment of the present invention one in it is single-stranded at poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), Centre is the nano-particle i.e. polyphenyl of the Janus nano particles with chain/ball/chain model of polystyrene, polydivinylbenezene The FTIR spectrum figure of the product of carboxyl is gone up in the nanoparticle fraction modification of ethylene, polydivinylbenezene.
Fig. 3 be the embodiment of the present invention one in it is single-stranded at poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), Centre is the nano-particle i.e. polyphenyl of the Janus nano particles with chain/ball/chain model of polystyrene, polydivinylbenezene The transmission electron microscope picture of the product of the compound Fe3O4 of nanoparticle fraction of ethylene, polydivinylbenezene.
Fig. 4 be the embodiment of the present invention one in it is single-stranded at poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), Centre is the nano-particle i.e. polyphenyl of the Janus nano particles with chain/ball/chain model of polystyrene, polydivinylbenezene The product of the compound Fe3O4 of nanoparticle fraction of ethylene, polydivinylbenezene is by the photo before and after magnet absorption.
Specific implementation mode
A kind of multi-component Janus composite nano materials that first embodiment of the present invention provides are based on by polymerizeing Object is single-stranded and the molecular Janus nano particles of nanoparticle, by the growing mixed functional materials of its nanoparticle fraction and/ Or multi-component nano material obtained from polymer single stranded portion graft polymers molecular brush.
The preparation method of above-mentioned multi-component Janus composite nano materials provided by the invention, includes the following steps：
Step 1) is based on by polymer is single-stranded and the molecular Janus nano particles of nanoparticle, at above-mentioned Janus nanometers Nanoparticle fraction introduces reactive group in grain, and growing mixed functional materials obtain the growing mixed work(of nanoparticle fraction The Janus nano particles of energy property substance；And/or
Step 2) utilizes free radical polymerisation process, in the Janus of the growing mixed functional materials of above-mentioned nanoparticle fraction Polymer single stranded portion graft polymers molecular brush in nano particle and obtain multi-component Janus composite nano materials.
The step 2) may also include introducing reactive functional before polymer single stranded portion graft polymers molecular brush The step of group；The reactive functional groups are selected from-Br ,-Cl, one kind in-SC (Z) S or its arbitrary combination；The wherein described introducing One kind in reactive functional groups-Br ,-Cl or its arbitrary the step of combining, namely with cause the small molecule of functional group into Row is modified, and introduces the step of causing site；It is described with cause functional group small molecule be selected from N-bromosuccinimide, bromine, One kind in chloromethyl methyl ether, bromomethyl methyl ether or its arbitrary combination.The step of introducing reactive functional groups-SC (Z) S, Namely the step of being reacted under alkaline condition with carbon disulfide and carbazole, introducing chain tra nsfer site-SC (Z) S；- SC (Z) S Z group in functional group can be selected from Ph, CH3,PhCH2,-NCH3-,-O,-S。
It is above-described by polymer is single-stranded and the molecular Janus nano particles of nanoparticle are by ionic polymerization system Standby, structural model can be selected from any one in the single-stranded model with the arbitrary assembled arrangement of the ball-type nano-particle order of connection of polymer Kind；The single-stranded chemical composition of the polymer, the degree of polymerization is adjustable；Chemical composition, the size of the nano-particle are controllable.
For example, above-described by the single-stranded structure mould with the molecular Janus nano particles of nanoparticle of polymer Type can be selected from ball (polymer is single-stranded very short at this time, can ignore), (polymer of connected ball is single-stranded very short, can be with for ball/ball Ignore), chain/ball, chain/ball/chain, ball/chain/ball, chain/ball/chain/ball/chain, the nano-particles such as ball/chain/ball/chain/ball and single-stranded company Connect any one in the model of the arbitrary assembled arrangement of sequence.
More specifically, such as above-mentioned chain/ball/chain model, i.e., both sides are that polymer is single-stranded, and centre is nano-particle bead Janus nano materials preparation method, it may include following step：
Step 1) by it is a kind of can ionic polymerization monomer carry out ionic polymerization, it is single-stranded to prepare first segment polymer；
Step 2) by second can ionic polymerization monomer and another functional group's number more than or equal to 2 can ionic polymerization Monomer be sufficiently mixed after be added in the reaction system described in step 1) and carry out ionic polymerization, prepare the single-stranded end group of polymer and connect Receive the Janus materials of rice corpuscles；
Step 3) by the third can ionic polymerization monomer be added step 2) described in reaction system carry out ionic polymerization, system Standby both ends be polymer it is single-stranded, it is intermediate be Janus nano particles that nano-particle has chain/ball/chain model.
Such as above-mentioned chain/spherical model, i.e. side is that polymer is single-stranded, and the other side is the Janus nanometers of nano-particle bead The preparation method of material, it may include following step：
Step 1) by it is a kind of can ionic polymerization monomer carry out ionic polymerization, it is single-stranded to prepare first segment polymer；
Step 2) by second can ionic polymerization monomer and another functional group's number more than or equal to 2 can ionic polymerization Monomer be sufficiently mixed after be added in the reaction system described in step 1) and carry out ionic polymerization, preparation side is polymer list Chain, the other side are the Janus nano materials of nano-particle bead.
The initiator of ionic polymerization described above is selected from the Bronsted acid such as concentrated sulfuric acid, phosphoric acid, perchloric acid, chlorosulfonic acid, fluorine Sulfonic acid, trichloroacetic acid, trifluoroacetic acid, trifluoromethane sulfonic acid；Lewis acid for example boron trifluoride, alchlor, titanium tetrachloride, Butter of tin, zinc chloride, antimony chloride；Iodine, oxonium ion and more stable ion salt such as perchlorate, trityl group salt With in cycloheptatriene salt one kind or its arbitrary combine.Content is added with the volume percentage 0.05- of entire reaction system in it 5%, preferably 0.3-3%, more preferably 0.5-1%.
Ionic polymerization system described above has the advantages that high solids content, and with volume percentage, total monomer contains admittedly Measure 0.1-40%, preferably 5-20%.
In ionic polymerization either step described above, -100-100 DEG C of reaction temperature, preferably -50-40 DEG C；When polymerization Between be 1-120min, preferably 5-30min.
The single-stranded ionic polymerization monomer of the polymer (i.e. it is a kind of can ionic polymerization monomer) be selected from cationically polymerizable Monomer, can be in the monomer and anionic polymerizable monomer of ring-opening polymerisation one kind.
The monomer of the cationically polymerizable is selected from styrene, p- methyl styrenes, α-methylstyrene, 4- tert-butyl benzenes Ethylene, 4- 1-chloro-4-methyl-benzenes, styrene ethyl trimethoxy silane, methyl styrene silane, isobutyl vinyl ether, tertiary fourth Base vinyl ethers, octadecyl vinyl ether, dodecyl vinyl, one kind in N- vinyl carbazoles or its arbitrary group It closes；
It is described can ring-opening polymerisation monomer be selected from propylene oxide, epoxy butane, decamethylene, Epoxydodecane, epoxy chlorine Propane, n-butyl glycidyl ether, phenyl glycidyl ether, phenyl ethylene oxide, 4- tert-butyl-phenyls glycerin ether, α-are in oneself One kind in ester, beta-propiolactone or its arbitrary combination；
The anionic polymerizable monomer is selected from styrene, p- methyl styrenes, α-methylstyrene, Alpha-Methyl propylene Sour methyl esters, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, propylene oxide, epoxy butane, first Phenylene diisocyanate, n-hexyl isocyanates, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, styrene formaldehyde In one kind or its arbitrary combine.
The nano-particle be by a kind of containing functional group can ionic polymerization monomer and another functional group's number be more than Equal to 2 can ionic polymerization monomer carry out ionic polymerization preparation the nano-particle with spherical model；It is described containing functional group Can ionic polymerization monomer of the monomer selected from cationically polymerizable, can be in the monomer and anionic polymerizable monomer of ring-opening polymerisation One kind；The monomer of the cationically polymerizable is selected from styrene, p- methyl styrenes, α-methylstyrene, p- methoxybenzenes Ethylene, p- chlorostyrenes, 4- t-butyl styrenes, 4- 1-chloro-4-methyl-benzenes, divinylbenzene, isoprene, butadiene, benzene Ethylene ethyl trimethoxy silane, methyl styrene silane, vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, tertiary fourth Base vinyl ethers, octadecyl vinyl ether, dodecyl vinyl, vinyl methyl dimethoxysilane, vinyl three Methoxy silane, vinyltriethoxysilane, new alkoxy three (methacryloxy) zirconate, new alkoxy three (third Alkene acyloxy) zirconate, diisopropoxy acetoacetate oleic acid ester group Aluminate, two oleic acid acyloxy (dioctyl of isopropoxy Phosphoric acid acyloxy) titanate esters, N- vinyl carbazoles, one kind in vinyl pyrrolidone or its arbitrary combination；It is described can open loop The monomer of polymerization is selected from ethylene oxide, propylene oxide, epoxy butane, decamethylene, Epoxydodecane, epoxychloropropane, positive fourth Base glycidol ether, glycidyl methacrylate, phenyl glycidyl ether, phenyl ethylene oxide, 4- tert-butyl-phenyls are sweet Oily ether, 3- glycidyl ether oxypropyltrimethoxysilanes, α-caprolactone, one kind in beta-propiolactone or its arbitrary combination； The anionic polymerizable monomer is selected from styrene, p- methyl styrenes, α-methylstyrene Methyl Methacrylate, first Base ethyl acrylate, n-BMA, Tert-butyl Methacrylate, toluene di-isocyanate(TDI), n-hexyl isocyanates, In methyl diphenylene diisocyanate, methacrylonitrile, one kind of benzaldehyde or its arbitrary combine；Functional group's number is more than Equal to 2 can ionic polymerization monomer be selected from divinylbenzene, butadiene, isoprene, 1,2,4,5- diepoxies pentane, 1,2, 5,6- diepoxies hexane, 1,2,6,7- diepoxies heptane, 1,2,7,8- diepoxyoctanes, 1,2,4,5- titanium dioxides bicyclic penta 2 Alkene, 1,4- butanediol diglycidyl ethers, bisphenol A diglycidyl ether, resorcinolformaldehyde resin, trimethylolpropane Triglycidyl ether, glycerol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, One kind at least one of phthalic acid ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI) or its arbitrary group Close, functional group's number more than or equal to 2 can ionic polymerization monomer be added content with percent by volume be calculated as be added form nanometer Particle containing functional group can ionic polymerization amount of monomer 5-30%.
Reactive group described above includes carboxyl, amino, hydroxyl, one kind of sulfydryl or its arbitrary combination.It can utilize The reactive group carries out recombination reaction in subsequent handling with functional materials.For example, it can be nanoparticle fraction Carboxyl is introduced using double bond, using carboxyl as the growing mixed functional materials of reactive group.
Function described above substance is selected from one or more of metal, metallic compound and nonmetallic compound Arbitrary combination；The metal be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Any one of Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two kinds Any of the above combines；The metallic compound be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Oxide, the sulphur of Eu, Mn, Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu Compound, tellurides or the two or more arbitrary combinations in them；The nonmetallic compound is silica.
Polymer molecule brush segment described above is selected from polyacrylic acid, the polyacrylic acid tert-butyl ester, polymethylacrylic acid, poly- first Base tert-butyl acrylate, poly- (methacrylic acid -2- dimethylamino ethyl esters), poly- (methacrylic acid -2- diethylamino second Ester), poly- (2- vinylpyridines), P4VP, Vinylcaprolactam homopolymer, poly- (2- hydroxypropyl acrylates), Poly- (N-L- (1- hydroxymethylpropyls) Methacrylamide), poly- (N- propyl Methacrylamides), poly- (3- acryloxypropyls three Methoxy silane), poly- (3- acryloxypropyls triethoxysilane), poly- (γ-methacryloxypropyl trimethoxy Silane), poly- (γ-methacryloxypropyl), poly- (acryloxy diisopropoxy aluminium), poly- (first Base acryloxy diisopropoxy aluminium), poly- (three titanium isopropoxide of acryloxy), poly- (three isopropyl of methacryloxy Oxygroup titanium), poly- (three isopropoxy zirconium of acryloxy), poly- (three isopropoxy zirconium of methacryloxy), poly- (N- isopropyls Acrylamide) any one of or two or more arbitrary combinations.
The above-described polymer single stranded portion degree of polymerization is 10-10000, preferably 30-3000, more preferably 50- 1000.Nano-particles size is in 1-20nm, preferably 2-15nm.The right polymer poly of the polymer molecule brush segment is 5- 10000, preferably 30-1000, more preferably 50-500.
Preparation method about such polymer molecule brush, for example, can be anti-by atom transfer radical polymerization It answers and/or reversible addion-fragmentation chain transfer free radical polymerization, is connect in polymer single stranded portion using grafting-from methods Branch polymer molecule brush.The grafting-from methods belong to it is well known in the art it is a kind of preparing polymer molecule brush method, The i.e. pre-synthesis line polymer main chain with initiation site, then passes through the polymerisation for causing monomer, synthetic polymer Molecular brush.(H.F.Gao,K.Matyjaszewski.J.Am.Chem.Soc.2007,129,6633-6639.).
The multicomponent be formed by mutually different polymer molecule brush and functional materials composite portion, such as Can be respectively temperature-responsive polymer molecule brush and pH responsive polymers molecular brush and functionality for concrete example Substance composite portion.More specifically, temperature-responsive polymer molecule brush can be selected from poly(N-isopropylacrylamide), poly- second Alkenyl caprolactam, poly- (2- hydroxypropyl acrylates), poly- (N-L- (1- hydroxymethylpropyls) Methacrylamide), poly- (N- is just Propylacrylamide) any one of or two or more arbitrary combinations；PH responsive polymer molecular brush can be selected from polypropylene Acid, polymethylacrylic acid, P4VP, poly- (methacrylic acid -2- dimethylamino ethyl esters), poly- (metering system Acid -2- diethylaminos ethyl ester) any one of or two or more arbitrary combinations.
More specifically, the preparation method of multi-component Janus composite nanometer particles provided by the invention preferably uses down Step 1) is stated to step 4).
Step 1) is single-stranded by both sides respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), and centre is Polystyrene, polydivinylbenezene nano-particle be the Janus nano particles with chain/ball/chain model, and with reactivity The small molecule of group is dissolved in solution, and reactive group, growing mixed functional materials are introduced in nanoparticle fraction.
The wherein described preferred thioacetic acid of small molecule and mercaptoethylmaine for carrying reactive group.
The preferred toluene of solvent, reaction temperature is preferably 60-80 DEG C, and the reaction time is preferably 10-20h.
It is arbitrary that the functional materials are selected from one or more of metal, metallic compound and nonmetallic compound Combination；The metal be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, Zn, Any one of Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two or more Meaning combination；The metallic compound be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Oxide, sulfide, the tellurium of Ca, Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu Compound or the two or more arbitrary combinations in them；The nonmetallic compound is silica.
The functional materials can be metal, metallic compound, nonmetallic compound, or the nanometer containing these components Different complex methods specifically may be used in particle etc., be selected from A)~C) and any one of described in method：
A) make to carry out Electrostatic Absorption in the nanoparticle fraction with the particle with reactive group opposite charges, to Obtain the Janus nano materials for the particle for being compounded with oppositely charged；
B) make metal ion that reduction reaction occur in the nanoparticle fraction, to obtain being compounded with metal or metallization The Janus nano materials of polymer beads；
C) make inorganic matter presoma that reaction be hydrolyzed in the nanoparticle fraction, to obtain compound organic/inorganic substance Janus nano materials.
The method A) in, make to be compounded in the nanoparticle fraction with the particle with reactive group opposite charges Method can be：By described N, N- dimethyl methyls are dissolved in the molecular Janus nano particles of nanoparticle by polymer is single-stranded It in amide, is added and is adsorbed with the particle with reactive group opposite charges, the particle for obtaining the oppositely charged is multiple The Janus nano particles of conjunction.
In the present invention, the nano particle of the band and reactive group opposite charges is preferably selected from SiO2、TiO2、Au、Ag、 Fe、Pd、Pt、FeO、Fe2O3、Fe3O4、Al2O3、SnO2、MnO2、CaCO3, any one in CoO, NiO and ZnO；The band phase The grain size of the nano particle of counter charges is 1-10nm；Solvent is selected from N,N-dimethylformamide, dimethyl sulfoxide (DMSO), N- methylpyrroles One kind in alkanone.
The method B) in, metal in the metal or metal compound particles be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti、Al、Sn、Zr、Cr、Ni、Co、Cu、Pd、Rh、Eu、Mn、Ca、Zn、Fe、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、 Any one of Dy, Ho, Er, Tm, Yb and Lu or two or more arbitrary combinations.Metal ion source can be metal cation salt Solution, such as soluble perchlorate, chloride, nitrate or the sulfate liquor of above-mentioned metal.Reduction reaction institute in the present invention The reducing agent used is without specifically limited, such as reducing agent can be NaBH4、LiB(C2H5)3H or N2H4。
The method B) in, make metal ion the nanoparticle fraction occur reduction reaction method be：It will be described It is placed in the metal ion salt solution with the molecular Janus nano particles of nanoparticle by polymer is single-stranded, makes nano-particle Partial carboxyl interacts with metal ion, to make in the adsorption of metal ions to the nanoparticle fraction, then The metal ion of absorption is set to be contacted with the reducing agent, to make the metal ion be restored in the nanoparticle fraction Reaction.
It, can be by changing about the above-mentioned method for making metal ion in nanoparticle fraction generation reduction reaction is used Become metal ion salt solution concentration, the concentration of reducing agent and reaction condition regulate and control the nanoparticle fraction composition metal or The content and form of metal compound particles.
The condition of the reduction reaction for example can be that reaction temperature is 0-100 DEG C, reaction time 1-24h；Solvent selects One kind from N,N-dimethylformamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone.
The method C) in, so that the method that reaction is hydrolyzed in the nanoparticle fraction in inorganic matter presoma for example may be used Think：By described the inorganic matter precursor solution is placed in the molecular Janus nano particles of nanoparticle by polymer is single-stranded In, so that the inorganic matter presoma is adsorbed or is reacted to the nanoparticle fraction, then with inorganic matter presoma Suitable 2mol/L hydrochloric acid solutions or 28wt% ammonium hydroxide are added in Janus nanoparticles solutions, to make inorganic matter presoma send out Raw hydrolysis, obtains the Janus nano materials of compound organic/inorganic substance.
The inorganic matter presoma is preferably selected from three n-butoxy aluminium, aluminium isopropoxide, four titanium n-butoxides, four isopropyls Oxygroup titanium, four n-butoxy zirconiums, zirconium tetraisopropoxide, isocyanic acid 3- (triethoxy silicon substrate) propyl ester, aminopropyl trimethoxy silicon At least one of alkane and aminopropyl triethoxysilane.In the absorption or reaction step, temperature is preferably 25-90 DEG C, Absorption or reaction time are preferably 1-24h；In the hydrolysis step, temperature is preferably 25-70 DEG C, and the time is preferably 1- 24h。
Step 2) by the monomer solution containing n-isopropyl acrylamide under the effect of the catalyst and starvation Under the conditions of, using above-mentioned Janus nano particles as macromole evocating agent, side band is obtained by atom transfer radical polymerization method There are poly(N-isopropylacrylamide) molecular brush, the Janus nano materials of intermediate nanoparticle fraction composite functional substance.Afterwards End group-the Cl of side chain is converted into-N by the nucleophilic substitution of sodium azide3。
Wherein, the Solvents Solvent of the monomer solution is selected from n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), N- methylpyrroles One kind in alkanone, reaction temperature are preferably 40-50 DEG C, and the reaction time is preferably 20-48h.
The catalyst is preferably made of low-valent transition metals halide and ligand.Wherein, the low-valent transition metals halogen Compound is preferably that cuprous bromide, stannous chloride, frerrous chloride are one such or a variety of；Ligand is selected from 4,4 '-dinonyl -2, 2 '-bipyridyls, 2,2 '-bipyridyls, N, N, N ', N ', N "-five methyl diethylentriamine, triphenylphosphine are one such or more Kind.
The Solvents Solvent of the nucleophilic substitution is selected from N,N-dimethylformamide, dimethyl sulfoxide (DMSO), N- methylpyrroles One kind in alkanone, reaction temperature are preferably 30-50 DEG C.Reaction time is preferably 48-72h.
Janus nano materials after above-mentioned azide substitution are dissolved in solution by step 3), under the effect of the catalyst and nitrogen Gas shielded, by the substitution reaction of N-bromosuccinimide in poly- (p- methyl styrenes) single-stranded side introducing-Br.
Wherein, the solvent of the solution is preferably carbon tetrachloride, and reaction temperature is preferably 80-90 DEG C, and the reaction time is preferred For 5-15h.
Step 4) by the monomer solution containing N- diethylamide amino ethyl methacrylates under the effect of the catalyst and Under conditions of starvation, using the Janus nano materials of above-mentioned introducing-Br as macromole evocating agent, pass through atom transfer freedom Base polymerization obtains side and carries poly(N-isopropylacrylamide) polymer molecule brush, the intermediate compound work(of nanoparticle fraction Energy property substance, the other side carry the multi-component Janus of poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush Nano material.
Wherein, the Solvents Solvent of the monomer solution is selected from n,N-Dimethylformamide, dimethyl sulfoxide (DMSO), N- methylpyrroles One kind in alkanone, reaction temperature are preferably 40-50 DEG C, and the reaction time is preferably 20-48h.
The catalyst is preferably made of low-valent transition metals halide and ligand.Wherein, the low-valent transition metals halogen Compound is preferably that cuprous bromide, stannous chloride, frerrous chloride are one such or a variety of；Ligand is selected from 4,4 '-dinonyl -2, 2 '-bipyridyls, 2,2 '-bipyridyls, N, N, N ', N ', N "-five methyl diethylentriamine, triphenylphosphine are one such or more Kind.
Embodiment
Present invention will be further explained below with reference to specific examples, it should be understood that these embodiments are merely to illustrate the present invention Rather than limit the scope of the invention, in addition, it should also be understood that, after reading the content taught by the present invention, people in the art Member can make the present invention various changes or modification, and such equivalent forms equally fall within the restriction of the application appended claims In the range of.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent etc., are commercially available unless otherwise specified used in following examples.
Both sides used in following examples respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes) are single Chain, centre be polystyrene, polydivinylbenezene nano-particle be with chain/ball/chain model Janus nano particles according to Following methods are prepared：
25 μ L boron trifluoride ether solutions are added in 5mL dichloromethane by step 1), uniformly rear that 0.25mLp- first is added Base styrene monomer stirs 20min under normal temperature condition；
It is 9 that the volume ratio that 0.25mL has been pre-mixed is added into above-mentioned reaction system for step 2):1 styrene, diethyl Alkenyl benzene monomer, the reaction was continued under the conditions of normal-temperature reaction 20min；
0.25mL 4- (chloromethyl) styrene monomer is added to above-mentioned reaction system in step 3), continues in same reaction item 20min is reacted under part, is after reaction precipitated reaction solution absolute ethyl alcohol, washing, is characterized after sample freeze-drying.Transmission electricity Mirror TEM shows the presence (such as Fig. 1) of 2nm or so nano-particles；Nuclear magnetic resonance spectroscopy is shown in the only spectrogram of chain/ball/chain The characteristic peak that just will appear poly- benzyl chlorostyrene shows successfully to have synthesized second segment polymer single-stranded, poly- (p- methylbenzene second Alkene) the single stranded portion degree of polymerization be 26, poly- (4- 1-chloro-4-methyl-benzenes) the polymer single stranded portion degree of polymerization be 28；Dynamic light scattering DLS results show that particle diameter increases to 6nm by 4nm during chain, chain/ball, chain/ball/chain polymerization and eventually becomes 9nm, into one Step shows the successful synthesis of chain/ball/chain structure.
Side used in following examples is that Hydrin is single-stranded, and the other side is epoxy butane, 1,2,7,8- bis- rings The nano-particle of oxygen octane is that the Janus nano particles with chain/spherical model are prepared in accordance with the following methods：
50 μ L boron trifluoride ether solutions are added in 5mL dichloromethane by step 1), uniformly rear that 1mL epoxy chloropropionates are added Alkane monomer stirs 20min under normal temperature condition；
It is 5.6 that the volume ratio that 1.18mL has been pre-mixed is added into above-mentioned reaction system for step 2):1 epoxy butane, 1,2,7,8- diepoxyoctane monomer, the reaction was continued under the conditions of normal-temperature reaction 30min, after reaction by reaction solution with anhydrous Ethanol precipitation, washing are characterized after sample freeze-drying.Transmission electron microscope TEM shows the presence of 5nm or so nano-particles；Nuclear-magnetism There is the characteristic peak of poly- benzyl chlorostyrene in hydrogen spectrum display of resonating, and the Hydrin single stranded portion degree of polymerization is 30；Dynamic optical Scattering DLS results show that particle diameter increases to 10nm in chain, chain/ball polymerization process by 8nm, show the success of chain/spherical structure Synthesis.
Side used in following examples is that poly- (p- methyl styrenes) is single-stranded, and the other side is styrene and divinylbenzene Nano-particle be to be prepared in accordance with the following methods with the Janus nano particles of chain/spherical model：
2mL p- methyl styrenes are added in 10mL hexamethylenes by step 1), uniformly rear that 0.184mL n-BuLis are added, 30min is stirred at 50 DEG C；
It is 95 that the volume ratio that 2mL has been pre-mixed is added into above-mentioned reaction system for step 2):5 styrene, divinyl Base benzene monomer, the reaction was continued at 50 DEG C 30min after reaction precipitate reaction solution absolute ethyl alcohol, washing, sample freeze-drying After characterized.Transmission electron microscope TEM shows the presence of 7nm or so nano-particles；Poly- (p- methyl styrenes) single stranded portion is poly- Right is 150；Dynamic light scattering DLS results show that particle diameter increases to 8nm in chain, chain/ball polymerization process by 5nm, show The successful synthesis of chain/spherical structure.
【Embodiment one】A kind of preparation of multi-component Janus composite nano materials
Step 1) is single-stranded by the both sides 0.6g respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), in Between for polystyrene, polydivinylbenezene nano-particle be with chain/ball/chain model Janus nano particles (Mn= It 10.6k) is dissolved in 50mL toluene, 240mg azodiisobutyronitriles and 1.2mL thioacetic acid is added into reaction system, in nitrogen Under protection, 70 DEG C of stirring 15h.Reaction solution absolute ethyl alcohol is precipitated after reaction, washing, is characterized after sample freeze-drying. It is formed with FTIR spectrum and is characterized, 1720cm-1There is the characteristic absorption peak of carboxyl in place (see Fig. 2).It proves into Material gain introduces carboxyl with click-reaction on crosslinked nano-particle.0.3g is introduced to the Janus of chain/ball/chain model of carboxyl Nano particle is dissolved in 300mL n,N-Dimethylformamide, is stirred at room temperature and is led to 1h nitrogen.It is 1 by molar ratio:2 seven hydrations Ferrous sulfate 87.6mg and ferric chloride hexahydrate 170.1mg are added in above-mentioned reaction system, are stirred at room temperature under nitrogen protection 5h.Reaction is risen to 83 DEG C with oil bath afterwards, 26.25mL ammonium hydroxide is added into reaction system in batches and is quickly stirred, about 1h is completed. After staying partial reaction stoste, it will be characterized after reaction solution centrifugation, drying.React stoste can use magnet adsorption separation product with it is molten Agent, and solvent is clarified after absorption.Transmission electron microscope TEM shows the presence of 2nm or so nano-particles, it was demonstrated that success nanoparticle sub-portion Divide compound Fe3O4(see Fig. 3).
Fig. 4 is single-stranded at poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes) in the present invention, and centre is poly- The nano-particle i.e. polystyrene of the Janus nano particles with chain/ball/chain model, poly- two of styrene, polydivinylbenezene The compound Fe of nanoparticle fraction of vinyl benzene3O4Product by the photo before and after magnet absorption.It can thus be seen that nanoparticle Subdivision success is compound to have gone up Fe3O4。
Step 2) is by 200mg macromole evocating agents, that is, compound Fe of nanoparticle fraction3O4Janus composite nanometer particles (Mn =15.4k), 2.94g n-isopropyl acrylamide, 0.14mL tri- (2- dimethylaminoethyls) amine, 6.7mL N, N- dimethyl methyls Amide sequentially adds in the Schlenk pipes of the 25mL equipped with magneton, vacuumize by liquid nitrogen frozen-three times-inflated with nitrogen recycles it Afterwards, 74.4mg cuprous bromides are added in a cold or frozen state, deoxidation in triplicate recycles.Then Schlenk pipes are moved into 50 DEG C of perseverances In warm oil bath, stop after reacting 38h.Reaction solution is centrifuged after reaction, is washed to supernatant with n,N-Dimethylformamide Clarification, sample room temperature characterize after being dried under vacuum to constant weight.Transmission electron microscope TEM shows the presence of 3-4nm or so nano-particles；It will Particle is dispersed in water, and particle shows different dissolubilities about 32 DEG C, in conjunction with FTIR spectrum result, it was demonstrated that at Poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side grafting poly-N-isopropyl acrylamide polymer molecule brush, nanoparticle sub-portion is made in work( Divide compound Fe3O4Janus composite nano materials, above-mentioned poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side is measured by thermogravimetric analysis It is grafted poly-N-isopropyl acrylamide polymer molecule brush, the compound Fe of nanoparticle fraction3O4Janus composite nano materials The degree of polymerization of molecular weight Mn=110.5k namely poly(N-isopropylacrylamide) polymer molecule brush segment is 30.
The single-stranded side grafting poly-N-isopropyl acrylamides of 150mg above-mentioned poly- (4- 1-chloro-4-methyl-benzenes) polymerize by step 3) The compound Fe of object molecular brush, nanoparticle fraction3O4Janus composite nano materials (Mn=110.5k) be dissolved in 4.4mLN, N- diformazans In base formamide, after being completely dissolved, 23mg sodium azide is added, 48h is stirred at 40 DEG C.Reaction solution is centrifuged after reaction, It is washed with deionized three times, sample room temperature characterizes after being dried under vacuum to constant weight.Sample room temperature characterizes after being dried under vacuum to constant weight. It is formed with FTIR spectrum and is characterized, 2100cm-1There is the characteristic absorption peak of nitrine in place, it was demonstrated that success is poly- The poly(N-isopropylacrylamide) polymer molecule brush end introducing-N of (4- 1-chloro-4-methyl-benzenes) single-stranded side3.By 80mg Above-mentioned introducing-N3Janus nano materials, 6.24mg N-bromosuccinimides, 0.16mg azodiisobutyronitriles be dissolved in 5mL In carbon tetrachloride, under nitrogen protection, 83 DEG C of return stirring 15h.After reaction.It is diluted with 10 times of N,N-dimethylformamides Reaction solution simultaneously centrifuges, washs to supernatant and clarify, and sample room temperature is dried under vacuum to constant weight.It is single-stranded that poly- (p- methyl styrenes) is made Side carries-Br, the compound Fe of nanoparticle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side be grafted poly- (N- isopropyls third Acrylamide) polymer molecule brush Janus composite nano materials.
Step 4) is by poly- (p- methyl styrenes) single-stranded side band obtained in 40mg macromole evocating agents, that is, above-mentioned steps 3 There is the compound Fe of-Br, nanoparticle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side be grafted poly(N-isopropylacrylamide) The Janus composite nano materials (Mn=111.6k) of polymer molecule brush, 0.162mL N- diethylamide methacrylic acid second Ester, 0.0042mL N, N, N ', N ', N "-five methyl diethylentriamine, 2.6mL N,N-dimethylformamides sequentially add dress Have in the Schlenk pipes of the 25mL of magneton, vacuumize by liquid nitrogen frozen-three times-inflated with nitrogen cycle after, in a cold or frozen state 74.4mg cuprous bromides are added, deoxidation in triplicate recycles.Then Schlenk pipes are moved into 70 DEG C of constant temperature oil baths, reacts 19h After stop.Reaction solution is centrifuged after reaction, is washed to supernatant and is clarified with n,N-Dimethylformamide, sample room temperature in vacuo It is characterized after drying to constant weight.Dynamic light scattering DLS is the results show that have the presence of 14nm or so nano-particles, alkali under acid condition Property under the conditions of sample different degrees of reunion, granularity is in 200nm or so, in conjunction with FTIR spectrum result, it was demonstrated that successfully It is grafted poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush, nanometer to poly- (p- methyl styrenes) single-stranded side The compound Fe of particle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side be grafted poly(N-isopropylacrylamide) polymer molecule The multi-component Janus composite nano materials of brush, measure above-mentioned poly- (p- methyl styrenes) single-stranded side by thermogravimetric analysis and connect Poly- (N- diethylamides amino ethyl methacrylate) the polymer molecule brush of branch, the compound Fe of nanoparticle fraction3O4, poly- (4- chloromethyls Styrene) single-stranded side grafting poly(N-isopropylacrylamide) polymer molecule brush multi-component Janus composite Nanos material The polymerization of the molecular weight Mn=156.1k of material namely poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush segment Degree is 20.
【Embodiment two】A kind of preparation of multi-component Janus composite nano materials
Poly- (p- methyl styrenes) single-stranded side is made according to step 1) in embodiment one to the identical method of step 3) With-Br, the compound Fe of nanoparticle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side be grafted poly- (N- isopropyl acrylamides Amine) polymer molecule brush Janus composite nano materials.Only step 4) is different from embodiment one.It is specific as follows：
Step 4) is by poly- (p- methyl styrenes) single-stranded side band obtained in 10mg macromole evocating agents, that is, above-mentioned steps 3 There is the compound Fe of-Br, nanoparticle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side be grafted poly(N-isopropylacrylamide) The Janus composite nano materials (Mn=111.6k) of polymer molecule brush, 117.69 μ L tert-butyl acrylates, 5.6 μ L N, N, N ', N ', N "-five methyl diethylentriamines, 1mL toluene sequentially add in the Schlenk pipes of the 25mL equipped with magneton, by three Secondary liquid nitrogen frozen-vacuumizes-inflated with nitrogen cycle after, 3.875mg cuprous bromides, in triplicate deoxidation are added in a cold or frozen state Cycle.Then Schlenk pipes are moved into 80 DEG C of constant temperature oil baths, is stopped after reacting 12h.Reaction solution is centrifuged after reaction, It is washed to supernatant and is clarified with dichloromethane, sample room temperature characterizes after being dried under vacuum to constant weight.Transmission electron microscope TEM shows there is 5nm The presence of left and right nano-particle, in conjunction with FTIR spectrum result, it was demonstrated that successfully obtain poly- (p- methyl styrenes) single-stranded one Side graft polypropylene tert-butyl acrylate polymer molecule brush, the compound Fe of nanoparticle fraction3O4, poly- (4- 1-chloro-4-methyl-benzenes) it is single-stranded Side is grafted the multi-component Janus composite nano materials of poly(N-isopropylacrylamide) polymer molecule brush, passes through thermogravimetric Analysis measures above-mentioned poly- (p- methyl styrenes) single-stranded side graft polypropylene tert-butyl acrylate polymer molecule brush, nanoparticle sub-portion Divide compound Fe3O4, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side grafting poly(N-isopropylacrylamide) polymer molecule brush it is more The molecular weight Mn=142.4k of the Janus composite nano materials of component, namely polyacrylic acid tert-butyl ester polymer molecule brush segment The degree of polymerization be 20.
【Embodiment three】A kind of preparation of multi-component Janus composite nano materials
Step 1) is single-stranded by the both sides 0.6g respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), in Between for polystyrene, polydivinylbenezene nano-particle be with chain/ball/chain model Janus nano particles (Mn= It 10.6k) is dissolved in 50mL toluene, 240mg azodiisobutyronitriles and 1.2mL thioacetic acid is added into reaction system, in nitrogen Under protection, 70 DEG C of stirring 15h.Reaction solution absolute ethyl alcohol is precipitated after reaction, washing, is characterized after sample freeze-drying. It is formed with FTIR spectrum and is characterized, 1720cm-1There is the characteristic absorption peak of carboxyl in place.It proves successfully to utilize point It hits reaction and introduces carboxyl on crosslinked nano-particle.The Janus nano particles of the above-mentioned introducing carboxyls of 0.3g are dissolved in 300mL In n,N-Dimethylformamide, the 50mg/mL aqueous solution of chloraurate of 90 μ L is added, absorption is stirred at room temperature for 24 hours.Then 300 μ are added The 1.4mg/mL sodium borohydride aqueous solutions of L carry out reduction reaction for 24 hours in room temperature, and transmission electron microscope TEM shows 2nm or so nanometers The presence of particle, it was demonstrated that the compound Au of success nanoparticle fraction.
Subsequent step is made poly- (p- methyl styrenes) according to step 2) in embodiment one to the identical method of step 4) Single-stranded side is grafted poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush, the compound Au of nanoparticle fraction, gathers The multi-component Janus of (4- 1-chloro-4-methyl-benzenes) single-stranded side grafting poly(N-isopropylacrylamide) polymer molecule brush is multiple Close nano material.
【Example IV】A kind of preparation of multi-component Janus composite nano materials
Step 1) is single-stranded by the both sides 0.6g respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), in Between for polystyrene, polydivinylbenezene nano-particle be with chain/ball/chain model Janus nano particles (Mn= It 10.6k) is dissolved in 50mL toluene, 240mg azodiisobutyronitriles and 1.2mL thioacetic acid is added into reaction system, in nitrogen Under protection, 70 DEG C of stirring 15h.Reaction solution absolute ethyl alcohol is precipitated after reaction, washing, is characterized after sample freeze-drying. It is formed with FTIR spectrum and is characterized, 1720cm-1There is the characteristic absorption peak of carboxyl in place.It proves successfully to utilize point It hits reaction and introduces carboxyl on crosslinked nano-particle.0.3g is introduced to the Janus nano particles of chain/ball/chain model of carboxyl It is dissolved in 300mL n,N-Dimethylformamide, is stirred at room temperature and leads to 1h nitrogen.It is 1 by molar ratio:2 green vitriol 87.6mg and six water and iron chloride 170.1mg are added in above-mentioned reaction system, and 5h is stirred at room temperature under nitrogen protection.Oil is used afterwards Reaction is risen to 83 DEG C by bath, and 26.25mL ammonium hydroxide is added into reaction system in batches and quickly stirs, about 1h is completed.Stay part anti- After answering stoste, it will be characterized after reaction solution centrifugation, drying.Magnet adsorption separation product and solvent can be used by reacting stoste, and be inhaled Attached solvent clarification.Transmission electron microscope TEM shows the presence of 2nm or so nano-particles, it was demonstrated that success is multiple in nanoparticle fraction Close Fe3O4.By the compound Fe of 0.3g nanoparticle fractions3O4Janus nano materials be scattered in 80mL absolute ethyl alcohols, be added 1h is stirred at room temperature in 20mL distilled water and 20 μ L ethyl orthosilicates, and 1mL ammonium hydroxide is added, 12h is stirred at room temperature.It after reaction will be anti- It answers liquid to centrifuge, is washed to supernatant and clarified with absolute ethyl alcohol, sample room temperature characterizes after being dried under vacuum to constant weight.Transmission electron microscope TEM Show the presence of 4nm or so nano-particles, it was demonstrated that success is in the compound Fe of nanoparticle fraction3O4/SiO2。
Subsequent step is made poly- (p- methyl styrenes) according to step 2) in embodiment one to the identical method of step 4) Single-stranded side is grafted poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush, the compound Fe of nanoparticle fraction3O4/ SiO2, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side grafting poly(N-isopropylacrylamide) polymer molecule brush it is multi-component Janus composite nano materials.
【Embodiment five】A kind of preparation of multi-component Janus composite nano materials
Step 1) is single-stranded by the both sides 0.6g respectively poly- (p- methyl styrenes) single-stranded and poly- (4- 1-chloro-4-methyl-benzenes), in Between for polystyrene, polydivinylbenezene nano-particle be with chain/ball/chain model Janus nano particles (Mn= It 10.6k) is dissolved in 50mL toluene, 240mg azodiisobutyronitriles and 1.2mL thioacetic acid is added into reaction system, in nitrogen Under protection, 70 DEG C of stirring 15h.Reaction solution absolute ethyl alcohol is precipitated after reaction, washing, is characterized after sample freeze-drying. It is formed with FTIR spectrum and is characterized, 1720cm-1There is the characteristic absorption peak of carboxyl in place.It proves successfully to utilize point It hits reaction and introduces carboxyl on crosslinked nano-particle.0.3g is introduced to the Janus nano particles of chain/ball/chain model of carboxyl It is dissolved in 300mL n,N-Dimethylformamide, is stirred at room temperature and leads to 1h nitrogen.It is 1 by molar ratio:2 green vitriol 87.6mg and six water and iron chloride 170.1mg are added in above-mentioned reaction system, and 5h is stirred at room temperature under nitrogen protection.Oil is used afterwards Reaction is risen to 83 DEG C by bath, and 26.25mL ammonium hydroxide is added into reaction system in batches and quickly stirs, about 1h is completed.Stay part anti- After answering stoste, it will be characterized after reaction solution centrifugation, drying.Magnet adsorption separation product and solvent can be used by reacting stoste, and be inhaled Attached solvent clarification.Transmission electron microscope TEM shows the presence of 2nm or so nano-particles, it was demonstrated that success is multiple in nanoparticle fraction Close Fe3O4.By the compound Fe of 0.3g nanoparticle fractions3O4Janus nano materials be scattered in 80mL absolute ethyl alcohols, be added 1h is stirred at room temperature in 20mL distilled water and 20 μ L ethyl orthosilicates, and 1mL ammonium hydroxide is added, 12h is stirred at room temperature.It after reaction will be anti- It answers liquid to centrifuge, is washed to supernatant and clarified with absolute ethyl alcohol, sample room temperature characterizes after being dried under vacuum to constant weight.Transmission electron microscope TEM Show the presence of 4nm or so nano-particles, it was demonstrated that success is in the compound Fe of nanoparticle fraction3O4/SiO2.By 0.25g nanoparticles The compound Fe of subdivision3O4/SiO2Be scattered in 5mL absolute ethyl alcohols, 1.25mL gamma-aminopropyl-triethoxy-silanes, 1.25mL is added Deionized water, 70 DEG C of stirring 15h, reaction solution is centrifuged, washed to supernatant and clarified with absolute ethyl alcohol after reaction, sample room Temperature is dried under vacuum to constant weight, obtains modified Janus nano particles.It takes 48mg palladium bichlorides to exist, under low-grade fever environment, is added extremely 60mL ethanol solutions are configured to solution under ultrasound condition, take the above-mentioned modified Janus nano particles of 0.2g, ultrasonic disperse It is filtered after 4h, sample room temperature characterizes after being dried under vacuum to constant weight.Transmission electron microscope TEM shows depositing for 5-6nm or so nano-particles Energy-dispersive spectroscopy EDS is proved successfully in the compound Fe of nanoparticle fraction3O4/SiO2/Pd。
Subsequent step is made poly- (p- methyl styrenes) according to step 2) in embodiment one to the identical method of step 4) Single-stranded side is grafted poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush, the compound Fe of nanoparticle fraction3O4/ SiO2/ Pd, poly- (4- 1-chloro-4-methyl-benzenes) single-stranded side are grafted the multigroup of poly(N-isopropylacrylamide) polymer molecule brush The Janus composite nano materials divided.
【Embodiment six】A kind of preparation of multi-component Janus composite nano materials
The sides 0.5g are that Hydrin is single-stranded by step 1), and the other side is epoxy butane, 1,2,7,8- diepoxies are pungent The nano-particle of alkane is that the Janus nano particles (Mn=9.2k) with chain/spherical model are dissolved in 50mL toluene, to reaction system Middle addition 240mg azodiisobutyronitriles and 1.2mL thioacetic acid, under nitrogen protection, 70 DEG C of stirring 15h.After reaction will Reaction solution absolute ethyl alcohol is precipitated, is washed, and is characterized after sample freeze-drying.It is formed with FTIR spectrum and carries out table Sign, 1720cm-1There is the characteristic absorption peak of carboxyl in place.It proves successfully to introduce carboxylic on crosslinked nano-particle using click-reaction Base.The Janus nano particles that 0.2g is introduced into chain/spherical model of carboxyl are dissolved in 200mL n,N-Dimethylformamide, room temperature It stirs and leads to 1h nitrogen.It is 1 by molar ratio:2 green vitriol 58.4mg and six water and iron chloride 113.4mg are added to In above-mentioned reaction system, 5h is stirred at room temperature under nitrogen protection.Reaction is risen to 83 DEG C with oil bath afterwards, in batches into reaction system 17.5mL ammonium hydroxide is added and quickly stirs, about 1h is completed.After staying partial reaction stoste, table will be carried out after reaction solution centrifugation, drying Sign.Magnet adsorption separation product and solvent can be used by reacting stoste, and solvent is clarified after absorption.Transmission electron microscope TEM shows 5-6nm The presence of left and right nano-particle, it was demonstrated that the compound Fe of success nanoparticle fraction3O4。
Step 2) is by 100mg macromole evocating agents, that is, compound Fe of nanoparticle fraction3O4Janus composite nanometer particles (Mn =14k), 1.47g n-isopropyl acrylamide, 70 μ L tri- (2- dimethylaminoethyls) amine, 6.7mL n,N-Dimethylformamide In the Schlenk pipes for sequentially adding the 25mL equipped with magneton, vacuumize by liquid nitrogen frozen-three times-inflated with nitrogen cycle after, 37.2mg cuprous bromides are added under freezing state, deoxidation in triplicate recycles.Then Schlenk pipes are moved into 50 DEG C of constant temperature oil baths In, stop after reacting 38h.Reaction solution is centrifuged after reaction, is washed to supernatant and is clarified with n,N-Dimethylformamide, sample Product room temperature in vacuo characterizes after drying to constant weight.Transmission electron microscope TEM shows the presence of 10nm or so nano-particles；Particle is disperseed In water, particle shows different dissolubilities about 32 DEG C, it was demonstrated that the single-stranded side grafting of Hydrin is successfully made Poly(N-isopropylacrylamide) polymer molecule brush, the compound Fe of nanoparticle fraction3O4Janus composite nano materials, pass through Thermogravimetric analysis measures the single-stranded side grafting poly(N-isopropylacrylamide) polymer molecule brush of above-mentioned Hydrin, nanometer The compound Fe of particle fraction3O4Janus composite nano materials molecular weight Mn=115.9k namely poly- (N- isopropyl acrylamides Amine) polymer molecule brush segment the degree of polymerization be 30.
【Embodiment seven】A kind of preparation of multi-component Janus composite nano materials
The sides 0.5g are that poly- (p- methyl styrenes) is single-stranded by step 1), and the other side is receiving for styrene and divinylbenzene Rice corpuscles is that the Janus nano particles (Mn=28.9k) with chain/spherical model are dissolved in 50mL toluene, is added into reaction system Enter 400mg azodiisobutyronitriles and 2mL thioacetic acid, under nitrogen protection, 70 DEG C of stirring 15h.After reaction by reaction solution With absolute ethyl alcohol precipitation, washing, characterized after sample freeze-drying.It is formed with FTIR spectrum and is characterized, 1720cm-1There is the characteristic absorption peak of carboxyl in place.It proves successfully to introduce carboxyl on crosslinked nano-particle using click-reaction. The Janus nano particles that 0.3g is introduced into chain/spherical model of carboxyl are dissolved in 200mL n,N-Dimethylformamide, are stirred at room temperature And logical 1h nitrogen.It is 1 by molar ratio:2 green vitriol 140mg and six water and iron chloride 272mg are added to above-mentioned anti- It answers in system, 5h is stirred at room temperature under nitrogen protection.Reaction is risen to 83 DEG C with oil bath afterwards, is added in batches into reaction system 26.25mL ammonium hydroxide simultaneously quickly stirs, and about 1h is completed.After staying partial reaction stoste, it will be characterized after reaction solution centrifugation, drying. Magnet adsorption separation product and solvent can be used by reacting stoste, and solvent is clarified after absorption.Transmission electron microscope TEM shows 9nm or so The presence of nano-particle, it was demonstrated that the compound Fe of success nanoparticle fraction3O4。
Step 2) is by the compound Fe of the above-mentioned nanoparticle fractions of 80mg3O4Janus nano particles, 34.3mg N- bromo ambers Acid imide, 0.88mg azodiisobutyronitriles are dissolved in 10mL carbon tetrachloride, under nitrogen protection, 83 DEG C of return stirring 15h.Reaction After.It with 10 times of n,N-Dimethylformamide dilute reaction solutions and centrifuges, wash to supernatant and clarify, sample room temperature in vacuo is dry It is dry to constant weight.Poly- (p- methyl styrenes) single-stranded side is made and carries-Br, the compound Fe of nanoparticle fraction3O4Janus it is compound Nano material.
Step 3) is by poly- (p- methyl styrenes) single-stranded side band obtained in 40mg macromole evocating agents, that is, above-mentioned steps 2 There is the compound Fe of-Br, nanoparticle fraction3O4Janus composite nano materials (Mn=42.5k), 1.34mL N- diethyl amidos Ethyl methacrylate, 0.035mL N, N, N ', N ', N "-five methyl diethylentriamine, 21.6mL N, N- dimethyl formyls Amine sequentially adds in the Schlenk pipes of the 25mL equipped with magneton, vacuumize by liquid nitrogen frozen-three times-inflated with nitrogen cycle after, 0.5g cuprous bromides are added in a cold or frozen state, deoxidation in triplicate recycles.Then Schlenk pipes are moved into 70 DEG C of constant temperature oil baths In, reaction stops afterwards for 24 hours.Reaction solution is centrifuged after reaction, is washed to supernatant and is clarified with n,N-Dimethylformamide, sample Product room temperature in vacuo characterizes after drying to constant weight.Dynamic light scattering DLS is the results show that there is 20nm or so nano-particles under acid condition Presence, the different degrees of reunion of sample under alkaline condition, granularity is in 250nm or so, in conjunction with FTIR spectrum as a result, card Bright poly- (p- methyl styrenes) the single-stranded side that successfully obtains is grafted poly- (N- diethylamides amino ethyl methacrylate) polymer point Son brush, the compound Fe of nanoparticle fraction3O4Janus composite nano materials, above-mentioned poly- (p- methylbenzenes are measured by thermogravimetric analysis Ethylene) to be grafted poly- (N- diethylamides amino ethyl methacrylate) polymer molecule brush, nanoparticle fraction compound for single-stranded side Fe3O4Multi-component Janus composite nano materials molecular weight Mn=298.5k namely poly- (N- diethylamide ylmethyl propylene Acetoacetic ester) polymer molecule brush segment the degree of polymerization be 20.
It is to be particularly noted that the invention belongs to pioneering inventions, although only describing and most holding to save space The multi-component Janus composite nano materials of industry are easily applied to, still, the mechanism recorded from description of the invention and citing From the point of view of illustrating, those skilled in the art will envision that the invention thought can be readily applied to prepare it is other multi-component The multicomponent Janus composite nano materials of preparation easily can also be applied to catalysis, medicine by Janus composite nano materials The fields such as object controlled release, the fixation of enzyme, pollutant process.
Such as both sides are respectively poly(N-isopropylacrylamide) molecular brush and poly- (N- diethyl amido first in embodiment one Base ethyl acrylate) molecular brush multi-component Janus composite nano materials.But understand can also by those skilled in the art Both ends are prepared for other polymer molecule brushes, to obtain having other multicomponent by changing reaction monomers and reaction condition Nano particle.

Claims (14)

1. a kind of multi-component Janus composite nano materials, it is characterised in that：The Janus composite nano materials be based on by Polymer is single-stranded and the molecular Janus nano particles of nanoparticle, by the growing mixed functional object of its nanoparticle fraction Multi-component nano material obtained from matter and/or polymer single stranded portion graft polymers molecular brush.
2. Janus composite nano materials according to claim 1, it is characterised in that：It is described by polymer is single-stranded and nanometer The molecular Janus nano particles of grain are prepared by ionic polymerization, and it is single-stranded with ball-type nanometer that structural model is selected from polymer Any one in the model of the arbitrary assembled arrangement of the particle order of connection；The single-stranded chemical composition of the polymer, the degree of polymerization is adjustable； Chemical composition, the size of the nano-particle are controllable.
3. Janus composite nano materials according to claim 1 or 2, it is characterised in that：The single-stranded ion of the polymer Monomer of the polymerized monomer selected from cationically polymerizable, one kind that can be in the monomer and anionic polymerizable monomer of ring-opening polymerisation；
The monomer of the cationically polymerizable is selected from styrene, p- methyl styrenes, α-methylstyrene, 4- tert-butyl benzene second Alkene, 4- 1-chloro-4-methyl-benzenes, styrene ethyl trimethoxy silane, methyl styrene silane, isobutyl vinyl ether, tertiary butyl Vinyl ethers, octadecyl vinyl ether, dodecyl vinyl, one kind in N- vinyl carbazoles or its arbitrary combination；
It is described can ring-opening polymerisation monomer be selected from propylene oxide, epoxy butane, decamethylene, Epoxydodecane, epoxychloropropane, N-butyl glycidyl ether, phenyl glycidyl ether, phenyl ethylene oxide, 4- tert-butyl-phenyls glycerin ether, α-caprolactone, β-the third One kind in lactone or its arbitrary combination；
The anionic polymerizable monomer is selected from styrene, p- methyl styrenes, α-methylstyrene, α-methacrylic acid first Ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, propylene oxide, epoxy butane, toluene two In isocyanates, n-hexyl isocyanates, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, styrene formaldehyde A kind of or its arbitrary combination.
4. Janus composite nano materials according to any one of claim 1-3, it is characterised in that：The nano-particle Be by a kind of containing functional group can ionic polymerization monomer and another functional group's number more than or equal to 2 can ionic polymerization list Body carries out the nano-particle with spherical model of ionic polymerization preparation；
It is described containing functional group can ionic polymerization monomer be selected from cationically polymerizable monomer, can ring-opening polymerisation monomer and can One kind in the monomer of anionic polymerisation；
The monomer of the cationically polymerizable is selected from styrene, p- methyl styrenes, α-methylstyrene, p- methoxybenzene second Alkene, p- chlorostyrenes, 4- t-butyl styrenes, 4- 1-chloro-4-methyl-benzenes, divinylbenzene, isoprene, butadiene, benzene second Alkene ethyl trimethoxy silane, methyl styrene silane, vinyl ethers, methyl vinyl ether, isobutyl vinyl ether, tertiary butyl Vinyl ethers, octadecyl vinyl ether, dodecyl vinyl, vinyl methyl dimethoxysilane, vinyl front three Oxysilane, vinyltriethoxysilane, new alkoxy three (methacryloxy) zirconate, three (propylene of new alkoxy Acyloxy) zirconate, diisopropoxy acetoacetate oleic acid ester group Aluminate, two oleic acid acyloxy (dioctyl phosphorus of isopropoxy Sour acyloxy) titanate esters, N- vinyl carbazoles, one kind in vinyl pyrrolidone or its arbitrary combination；
It is described can ring-opening polymerisation monomer be selected from ethylene oxide, propylene oxide, epoxy butane, decamethylene, Epoxydodecane, ring Oxygen chloropropane, n-butyl glycidyl ether, glycidyl methacrylate, phenyl glycidyl ether, phenyl ethylene oxide, 4- Tert-butyl-phenyl glycerin ether, 3- glycidyl ether oxypropyltrimethoxysilanes, α-caprolactone, one kind in beta-propiolactone or It is arbitrarily combined；
The anionic polymerizable monomer is selected from styrene, p- methyl styrenes, α-methylstyrene α-methacrylic acid first Ester, ethyl methacrylate, n-BMA, Tert-butyl Methacrylate, toluene di-isocyanate(TDI), n-hexyl isocyanide Acid esters, methyl diphenylene diisocyanate, methacrylonitrile, benzaldehyde, one kind in styrene formaldehyde or its arbitrary combination；
Functional group's number more than or equal to 2 can ionic polymerization monomer be selected from divinylbenzene, butadiene, isoprene, 1,2,4,5- diepoxies pentane, 1,2,5,6- diepoxies hexane, 1,2,6,7- diepoxies heptane, 1,2,7,8- diepoxyoctanes, 1,2,4,5- bicyclopentadiene dioxide, 1,4- butanediol diglycidyl ethers, bisphenol A diglycidyl ether, resorcinol two Glycidol ether, trihydroxymethylpropanyltri diglycidyl ether, glycerol dimethacrylate, ethylene glycol dimethacrylate, In triethylene glycol dimethacrylate, phthalic acid ester, hexamethylene diisocyanate, toluene di-isocyanate(TDI) at least A kind of one kind in or its it is arbitrary combine, functional group's number more than or equal to 2 can the monomer of ionic polymerization content is added with volume Percentages be added formed nano-particle containing functional group can ionic polymerization amount of monomer 5-30%.
5. the Janus composite nano materials according to any one of claim 1-4, it is characterised in that：The functionality object Matter is selected from the arbitrary combination of one or more of metal, metallic compound and nonmetallic compound；
The metal be selected from Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, Zn, Any one of Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two or more Meaning combination；
The metallic compound be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, The oxide of Zn, Fe, Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, sulfide, telluride Object or the two or more arbitrary combinations in them；
The nonmetallic compound is silica.
6. Janus composite nano materials according to any one of claims 1-5, it is characterised in that：The polymer point Sub- brush segment is selected from polyacrylic acid, the polyacrylic acid tert-butyl ester, polymethylacrylic acid, polymethyl tert-butyl acrylate, poly- (methyl-prop Olefin(e) acid -2- dimethylamino ethyl esters), poly- (methacrylic acid -2- diethylaminos ethyl ester), poly- (2- vinylpyridines), poly- (4- Vinylpyridine), Vinylcaprolactam homopolymer, poly- (2- hydroxypropyl acrylates), poly- (N-L- (1- hydroxymethylpropyls) methyl-prop Acrylamide), poly- (N- propyl Methacrylamides), poly- (3- acryloyloxypropyltrimethoxysilanes), poly- (3- acryloxies Propyl-triethoxysilicane), poly- (γ-methacryloxypropyl trimethoxy silane), poly- (γ-methacryloxy Propyl-triethoxysilicane), poly- (acryloxy diisopropoxy aluminium), poly- (methacryloxy diisopropoxy aluminium), Poly- (three titanium isopropoxide of acryloxy), poly- (three titanium isopropoxide of methacryloxy), poly- (three isopropyl of acryloxy Oxygroup zirconium), poly- (three isopropoxy zirconium of methacryloxy), any one of poly(N-isopropylacrylamide) or two kinds Any of the above combines.
7. the Janus composite nano materials according to any one of claim 1-6, it is characterised in that：The polymer list The degree of polymerization of chain part is 10-10000, preferably 30-3000, more preferably 50-1000；
Nano-particles size is in 1-20nm, preferably 2-15nm；
The degree of polymerization of the polymer molecule brush segment is 5-10000, preferably 30-1000, more preferably 50-500.
8. the preparation method of the multi-component Janus composite nano materials described in any one of claim 1-7, including following steps Suddenly：
Step 1) is based on by polymer is single-stranded and the molecular Janus nano particles of nanoparticle, in the Janus nano particles Nanoparticle fraction introduce reactive group, growing mixed functional materials obtain the growing mixed function of nanoparticle fraction The Janus nano particles of property substance；And/or
Step 2) utilizes free radical polymerisation process, in the Janus nanometers of the growing mixed functional materials of above-mentioned nanoparticle fraction Polymer single stranded portion graft polymers molecular brush in particle, obtains multi-component Janus composite nano materials.
9. the preparation method of Janus composite nano materials according to claim 8, it is characterised in that：The reactivity base Group is selected from carboxyl, amino, hydroxyl, one kind of sulfydryl or its arbitrary combination.
10. the preparation method of Janus composite nano materials according to claim 8 or claim 9, it is characterised in that：The function Property substance be selected from the arbitrary combination of one or more of metal, metallic compound and nonmetallic compound；The metal choosing From Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, Zn, Fe, Sc, Y, La, Ce, Any one of Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu or two or more arbitrary combinations；The gold Category compound be Au, Ag, Pt, Ba, Cd, Pb, Ti, Al, Sn, Zr, Cr, Ni, Co, Cu, Pd, Rh, Eu, Mn, Ca, Zn, Fe, Sc, Y, the oxide of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu, sulfide, tellurides or they In two or more arbitrary combinations；The nonmetallic compound is silica.
11. the preparation method of the Janus composite nano materials according to any one of claim 8-10, it is characterised in that： The polymer molecule brush segment is selected from polyacrylic acid, the polyacrylic acid tert-butyl ester, polymethylacrylic acid, the tertiary fourth of polymethylacrylic acid Ester, poly- (methacrylic acid -2- dimethylamino ethyl esters), poly- (methacrylic acid -2- diethylaminos ethyl ester), poly- (2- ethylene Yl pyridines), P4VP, Vinylcaprolactam homopolymer, poly- (2- hydroxypropyl acrylates), poly- (N-L- (1- hydroxyl first Base propyl) Methacrylamide), poly- (N- propyl Methacrylamides), poly- (3- acryloyloxypropyltrimethoxysilanes), poly- (3- acryloxypropyls triethoxysilane), poly- (γ-methacryloxypropyl trimethoxy silane), poly- (γ-first Base acryloxypropyl triethoxysilane), poly- (acryloxy diisopropoxy aluminium), poly- (methacryloxy two Aluminum isopropoxide), poly- (three titanium isopropoxide of acryloxy), poly- (three titanium isopropoxide of methacryloxy), poly- (propylene Three isopropoxy zirconium of acyloxy), poly- (three isopropoxy zirconium of methacryloxy), appointing in poly(N-isopropylacrylamide) One or two kinds of any of the above combination.
12. the preparation method of the Janus nano materials according to any one of claim 8-11, it is characterised in that：It is described Step 2) further includes the steps that introducing reactive functional groups before polymer single stranded portion graft polymers molecular brush；
The reactive functional groups are selected from-Br ,-Cl, one kind in-SC (Z) S or its arbitrary combination；
Z group in-SC (Z) S functional groups is selected from Ph, CH3,PhCH2,-NCH3-,-O,-S。
13. the preparation method of the Janus nano materials according to any one of claim 8-12, it is characterised in that：Polymerization The object single stranded portion degree of polymerization is 10-10000, preferably 30-3000, more preferably 50-1000；
Nano-particles size is in 1-20nm, preferably 2-15nm；The right polymer poly of the polymer molecule brush segment is 5- 10000, preferably 30-1000, more preferably 50-500.
14. multi-component Janus composite nano materials described in any one of claim 1-7 are in catalysis, medicine controlled releasing, enzyme Application fixed, in pollutant process.
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