CN114057962A - Polymer double-chain/inorganic nano-particle asymmetric compound and preparation method thereof - Google Patents

Polymer double-chain/inorganic nano-particle asymmetric compound and preparation method thereof Download PDF

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CN114057962A
CN114057962A CN202010744971.2A CN202010744971A CN114057962A CN 114057962 A CN114057962 A CN 114057962A CN 202010744971 A CN202010744971 A CN 202010744971A CN 114057962 A CN114057962 A CN 114057962A
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杨振忠
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Tsinghua University
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    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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Abstract

The invention relates to a polymer double-chain/inorganic nanoparticle asymmetric compound and a preparation method thereof, wherein the compound comprises a composite structure of a polymer single-chain A-inorganic nanoparticle-polymer single-chain B, wherein the polymer single-chains A and B are respectively connected with nanoparticles at the tail ends of the chains through chemical bonds; the single polymer strand a and the single polymer strand B optionally further comprise functional segments or groups to make the double polymer strand/inorganic nanoparticle asymmetric complex more functional.

Description

Polymer double-chain/inorganic nano-particle asymmetric compound and preparation method thereof
Technical Field
The invention relates to the technical field of inorganic and high-molecular composite materials, in particular to a polymer double-chain/inorganic nano-particle asymmetric composite which comprises a composite structure of a polymer single chain A-inorganic nano-particle-polymer single chain B.
Background
Janus material is commonly used in the polymer field to describe microparticles with asymmetric structure in composition and nature, and its name is derived from the god of diplex in the ancient roman mystery. Janus was first used by the polymer physicist De Gennes in 1991 to describe such microparticles (De Gennes. science 1992, 256: 495-. Due to the characteristics of strong autonomy and the like, the monomolecular Janus nano-particles with the micro-scale have great advantages in the aspects of synthesizing monomolecular reactors and the like. The properties can be widely adjusted by selecting different nanoparticles and polymer chains.
On the other hand, inorganic nanoparticles have special properties in the fields of light, electricity, magnetism, catalysis and the like, and have attracted great interest. If the polymer is grafted on one side or two sides of the inorganic nano-particles, the anisotropy is endowed, and the method has important significance for preparing the composite Janus nano-particles.
Recently, a new method for preparing single-side polymer single chains based on a rapid termination reaction was proposed, which can graft polymer single chains on one side of nanoparticles (X.Yao, J.Jing, F.Liang, Z.Yang, Macromolecules,2016,49, 9618-. The nanoparticles obtained by the method are limited by the number of molecular weights, and can be modified to a limited extent, so that the microstructure design of the asymmetric composite particles is limited.
Disclosure of Invention
Problems to be solved by the invention
The polymer double-chain/inorganic nano-particle asymmetric compound and the preparation method thereof are provided, wherein two polymer chains of the polymer double-chain/inorganic nano-particle asymmetric compound optionally further comprise functional groups or chain segments according to needs; in addition, the preparation method can accurately design the composite asymmetric structure of the polymer chain and the inorganic nano-particles, and can prepare the composite with low cost and high efficiency.
Means for solving the problems
A first aspect of the present invention provides: a polymer double-stranded/inorganic nanoparticle asymmetric complex comprising a composite structure of a polymer single-stranded A-an inorganic nanoparticle-a polymer single-stranded B, wherein the polymer single-stranded A and the polymer single-stranded B are connected to the inorganic nanoparticle at a chain tail end through a chemical bond, the kind of monomer unit constituting the polymer single-stranded A and the kind of monomer unit constituting the polymer single-stranded B may be the same or different, and the polymer single-stranded A and the polymer single-stranded B each independently optionally further comprise a functional segment or a functional group.
The composite of any preceding claim, wherein the inorganic nanoparticles are selected from the group consisting of metals, metal compounds, and non-metal compounds, and have a particle size of 1 to 20 nm.
The composite of any of the above, wherein the metal is selected from the group consisting of Au, Ag, Pt, Pd, Fe, Co, Ni, Sn, In, and alloys thereof; the metal compound is selected from Fe3O4、TiO2、Al2O3、BaTiO3、SrTiO3(ii) a The non-metallic compound is SiO2。
According to the above composite, the inorganic nanoparticles have amino groups on the surface.
According to the above composite, each of the single polymer chain a and the single polymer chain B independently contains a structural unit derived from a styrene-based monomer or a vinyl ether-based monomer.
According to the above composite, the styrenic monomer is selected from styrene and C1-5Alkyl-substituted styrenes, C1-5Alkenyl-substituted styrene, halogen-substituted C1-5Alkyl substituted styrene, halogen substituted C1-5One or more of alkenyl substituted styrene and acrylate vinyl benzene; the vinyl ether monomer is selected from one or more of alkyl vinyl ether, halogen-substituted alkyl vinyl ether, alkyl styrene vinyl ether, halogen-substituted alkyl styrene vinyl ether, vinyl phenyl alkoxy alkyl vinyl ether, vinyl ether alkyl ethylene and acrylate vinyl ether.
In some embodiments, the monomers forming the single polymer chain a or the single polymer chain B are each independently selected from one or more of n-butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, methylphenyl vinyl ether, benzyl chloride vinyl ether, vinylphenyl methoxyethyl vinyl ether, vinyl ether alkyl ethylene, ethyl acrylate vinyl ether, styrene, p-methylstyrene, α -methylstyrene, chloromethylstyrene, 4- (vinylphenyl) -1-butene (VSt), acrylate-based vinylbenzene.
In some embodiments, the single polymer chain a and the single polymer chain B are each independently composed of a structural unit derived from a styrene-based monomer or a vinyl ether-based monomer.
The complex according to the above, wherein the degree of polymerization of the single polymer chain A and the single polymer chain B is each independently 10 to 10000, preferably 50 to 1000; the size of the polymer single chain A and the size of the polymer single chain B are respectively 1-20 nm.
The composite of any preceding claim, wherein the functional segments comprise polyethylene glycol segments, PNIPAM segments, PDMAEMA segments, and/or PDEAEMA segments; the functional group is selected from at least one of carboxyl, amine, hydroxyl, halogen and silane group.
A second aspect of the present invention is to provide: a method of making the above-described composite, the method comprising:
the inorganic nano-particles are modified to obtain amino on the surface, and the inorganic nano-particles with amino on the surface are dispersed in a solvent to obtain inorganic nano-particle dispersion liquid;
preparing a polymer single chain A with an active center at the tail end by cationic polymerization;
adding the polymer single chain A with the active center at the tail end into the inorganic nano-particle dispersion liquid to obtain dispersion liquid containing a polymer single chain A-inorganic nano-particle compound;
and preparing a polymer single chain B with an active center at the tail end through cationic polymerization, and adding the polymer single chain B into a dispersion liquid containing the polymer single chain A-inorganic nano particle composite to obtain the polymer single chain A-inorganic nano particle-polymer single chain B composite.
The production method described above, wherein the modification of the inorganic nanoparticles is performed by aminosilane.
The preparation method according to the above, wherein the method further optionally comprises a step of further modifying the polymer single chain a and/or the polymer single chain B in the polymer single chain a-inorganic nanoparticle-polymer single chain B complex to introduce a functional segment or a functional group.
According to the above production method, wherein the substance providing the functional segment or the functional group is at least one selected from the group consisting of N-bromosuccinimide, thioglycolic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), N-dimethylaminoethyl mercaptopolymethacrylate segment, N-diethylaminoethyl mercaptopolymethacrylate, and 3-mercaptopropyltrimethoxysilane.
The above preparation process, wherein the initiator for cationic polymerization is selected from the group consisting of boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, iron trichloride, alkylaluminum chlorides, trifluoromethanesulfonic acid, HCl, HI/I2、HI/ZnI2、HI/ZnBr2、AlEt2Cl、EtAlCl2EtOAc, preferably tin tetrachloride or boron trifluoride.
The production method as described above, wherein the temperature during the production is controlled in the range of-100 ℃ to 100 ℃, preferably-50 ℃ to 40 ℃; the polymerization time of the polymer single chains is 1 to 60 minutes, preferably 5 to 20 minutes.
The preparation method, wherein the solid content of the dispersion liquid containing the polymer single-chain A-inorganic nanoparticle composite is 1-40%, preferably 5-30%.
The production method as described above, wherein the modification is performed by click reaction of a carbon-carbon double bond in the polymer single chain a and/or B with a substance that provides a functional segment or a functional group.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer double-chain/inorganic nanoparticle composite can be used for preparing various Janus materials with chain-sphere-chain structures with different functional combinations by respectively modifying or modifying two polymer single-chains in the Janus materials subsequently, so that the Janus materials can be suitable for various applications. The preparation method can accurately design the composite asymmetric structure of the polymer chain and the inorganic nano-particles. In addition, the preparation method of the invention has the advantages of complete polymerization reaction conversion rate in each step, no interference to subsequent steps, simple method and suitability for batch production.
Detailed Description
The present invention will be described in detail below. The technical features described below are explained based on typical embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.
< terms and definitions >
The "size" defined herein for a single polymer chain is the hydrodynamic diameter as determined by light scattering.
In the present specification, "cationic characteristic color" means a color that the active center exhibits in solution during cationic polymerization.
In the present specification, the numerical range represented by "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, the numerical ranges indicated by "above" or "below" mean the numerical ranges including the numbers.
In the present specification, the meaning of "may" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
As used herein, the use of "optionally" or "optional" means that certain materials, components, performance steps, application conditions, and the like are used or not used.
In the present specification, the unit names used are all international standard unit names, and the "%" used means weight or mass% content, if not specifically stated.
Reference throughout this specification to "a preferred embodiment," "an embodiment," and so forth, means that a particular element (e.g., feature, structure, property, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments. In addition, it is to be understood that the described elements may be combined in any suitable manner in the various embodiments.
The invention provides a polymer double-chain/inorganic nanoparticle asymmetric composite, which comprises a composite structure of a polymer single-chain-inorganic nanoparticle-polymer single-chain, wherein the two polymer single-chains are connected with the inorganic nanoparticle at the tail ends of the chains through chemical bonds.
< Polymer Single Strand >
The single polymer chain is formed by polymerizing monomers, is obtained by subsequent modification, is continuous, and is a linear or branched single molecular chain.
The polymer double chain forming the polymer double chain/inorganic nanoparticle asymmetric composite is two polymer single chains connected to two sides of the inorganic nanoparticle. The two single polymer chains are respectively called a single polymer chain A and a single polymer chain B.
The polymer single chain A and the polymer single chain B are obtained by cationic polymerization, and each independently optionally further introduces a functional segment or a functional group.
The kind of the monomer unit constituting the single polymer chain a and the kind of the monomer unit constituting the single polymer chain B may be the same or different. In other words, the compositions of the monomer units of the two polymer chains in the above-mentioned complex may be the same or different. In one embodiment of the present invention, the kind of the monomer unit constituting the single polymer chain a is different from that of the monomer unit constituting the single polymer chain B.
The single polymer chain A and the single polymer chain B respectively and independently comprise structural units derived from styrene monomers or vinyl ether monomers; the single polymer chain may contain one or more kinds of structural units, and for example, the single polymer chain may contain two or more kinds of structural units derived from a styrene-based monomer, or the single polymer chain may contain two or more kinds of structural units derived from a vinyl ether-based monomer. In one embodiment of the present invention, each of the single polymer chains a and the single polymer chains B comprises a structural unit derived from a styrenic monomer. In one embodiment of the present invention, one of the single polymer chain a and the single polymer chain B comprises a structural unit derived from a styrene-based monomer, and the other comprises a structural unit derived from a vinyl ether-based monomer.
The styrene monomer comprises styrene, substituted styrene, styrene acrylate monomer and the like. In the case of substituted styrene, the substituent may include an alkyl group, an alkenyl group, an alkoxy group, a halogen atom, etc., the number of carbon atoms of the alkyl group, the alkenyl group, the alkoxy group is preferably 1 to 5, and the alkyl group, the alkenyl group, the alkoxy group may further include a substituent such as halogen, preferably chlorine. Preferably, the substituted styrene is selected from C1-5Alkyl-substituted styrenes, C1-5Alkenyl-substituted styrene, halogen-substituted C1-5Alkyl substituted styrene, halogen substituted C1-5One or more of alkenyl substituted styrene and acrylate vinyl benzene. In some embodiments, the styrenic monomer is selected from the group consisting of styrene, p-methylstyrene, α -methylstyrene, chloromethylstyrene (VBC), 4- (vinylphenyl) -1-butene (VSt).
The vinyl ether monomer is selected from one or more of alkyl vinyl ether, halogen-substituted alkyl vinyl ether, alkyl styrene vinyl ether, halogen-substituted alkyl styrene vinyl ether, vinyl phenyl alkoxy alkyl vinyl ether, vinyl ether alkyl ethylene and acrylate vinyl ether, wherein the acrylate group comprises alkyl acrylate; the number of carbon atoms of the alkyl group or alkoxy group is preferably 1 to 5. In some embodiments, the vinyl ether monomer is selected from n-butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, methylphenyl vinyl ether, benzyl chloride vinyl ether, vinylphenyl methoxyethyl vinyl ether, vinyl ether alkyl vinyl, ethyl acrylate vinyl ether.
The polymer single chain may have a block structure in the case where it contains more than one monomer, and for example, the polymer single chain may contain blocks 1 to 2 to 3 in the order of charge. For example, in one embodiment, the polymeric single chain comprises a block structure of polymethylstyrene-polychloromethylstyrene (PMS-b-PVBC).
The polymerization degree of the single-chain polymer is 10-10000, preferably 50-1000, more preferably 100-800, and the size is 1-20 nm.
In one embodiment, the two polymer single strands obtained by cationic polymerization contained in the polymer double-stranded/inorganic nanoparticle asymmetric complex of the present invention are different in size. In a specific embodiment, the size of the single polymer chain a is larger than the size of the single polymer chain B.
The polymer single chain A and the polymer single chain B are independently optionally further introduced with functional chain segments or functional groups. The functional chain segment comprises at least one selected from a polyethylene glycol chain segment (PEO chain segment), a PNIPAM chain segment (poly (N-isopropylacrylamide) chain segment), a PDMAEMA chain segment (poly (N, N-dimethylaminoethyl methacrylate) chain segment) and a PDEAEMA chain segment (poly (N, N-diethylaminoethyl methacrylate) chain segment); the functional group is selected from carboxyl, amino, hydroxyl, halogen and silane group.
The single polymer chain to which the inorganic nanoparticles are attached may exhibit a parachute structure, which indicates that one linear polymer chain is attached to the inorganic nanoparticles; if parachute structures are formed on both sides of the particle, this means that a linear polymer chain is attached to each side of the particle. In addition, the single polymer chain with the inorganic nanoparticles attached thereto may also exhibit a rod-like structure due to the introduction of more side chains on the linear polymer chain.
The size of the polymer double-chain/inorganic nano-particle asymmetric composite is 10-60nm, and preferably 20-50 nm.
< inorganic nanoparticles >
The inorganic nanoparticles are selected from metals, metal compounds and non-metal compounds, and have a particle size of 1-20 nm.
The metal is selected from Au, Ag, Pt, Pd, Fe, Co, Ni, Sn, In and alloy thereof; the metal compound is selected from Fe3O4、TiO2、Al2O3、BaTiO3、SrTiO3(ii) a The non-metallic compound is SiO2。
The surface of the inorganic nanoparticles is modified to have amino groups. Specifically, the inorganic nanoparticles may be modified by an aminosilane-based substance to introduce an amino group. As the aminosilane, gamma-aminopropyltrimethoxysilane, gamma-aminopropylmethyldimethoxysilane, gamma-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltriethoxysilane, N '-bis- [ 3- (trimethoxysilyl) propyl ] ethylenediamine, N' -bis- [ 3- (triethoxysilyl) propyl ] ethylenediamine, N '-bis- [ 3- (methyldimethoxysilyl) propyl ] ethylenediamine, N' -bis- [ 3- (trimethoxysilyl) propyl ] hexamethylenediamine, N '-bis- [ 2- (trimethoxysilyl) propyl ] hexamethylenediamine, N' -bis- [ 3- (triethoxysilyl) propyl ] hexamethylenediamine, N '-bis- [ 3- (triethoxy) propyl ] hexamethylenediamine, and N, N' -bis- [ 3- (triethoxy) propyl ] hexamethylenediamine can be used, N, N' -bis- [ 3- (triethoxysilyl) propyl ] hexamethylenediamine, etc.; in some embodiments, aminopropyltriethoxysilane, aminopropyltrimethoxysilane are preferably used.
< preparation method >
A method of preparing a polymer duplex/inorganic nanoparticle asymmetric composite, the method comprising:
the inorganic nano-particles are modified to obtain amino on the surface, and the inorganic nano-particles with amino on the surface are dispersed in a solvent to obtain inorganic nano-particle dispersion liquid;
preparing a polymer single chain A with an active center at the tail end by cationic polymerization;
adding the polymer single chain A with the active center at the tail end into the inorganic nano-particle dispersion liquid to obtain dispersion liquid containing a polymer single chain A-inorganic nano-particle compound;
and preparing a polymer single chain B with an active center at the tail end through cationic polymerization, and adding the polymer single chain B into a dispersion liquid containing the polymer single chain A-inorganic nano particle composite to obtain the polymer single chain A-inorganic nano particle-polymer single chain B composite.
Wherein the modification of the inorganic nanoparticles comprises the introduction of amino groups by means of aminosilanes.
Wherein, preferably, the molecular weight of the polymer single chain A is controlled to be large enough by cationic polymerization, and the asymmetric structure of the polymer single chain A-inorganic nano particles is obtained; when preparing another active chain, namely a polymer single chain B by cationic polymerization, controlling the molecular weight to further bond the polymer single chain B to the surface of the inorganic nanoparticle with the polymer single chain A-inorganic nanoparticle asymmetric structure.
The method optionally further comprises the step of further modifying the single polymer chains a and/or the single polymer chains B in the single polymer chain a-inorganic nanoparticle-single polymer chain B complex to introduce functional segments or functional groups.
The substance providing the functional segment or the functional group may be a substance containing the functional segment or the functional group and capable of reacting with the carbon-carbon double bond in the single polymer chain, and examples thereof include, but are not limited to, N-bromosuccinimide, thioglycolic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), mercaptopolymethacrylic acid-N, N-dimethylaminoethyl ester segment, mercaptopolymethacrylic acid-N, N-diethylaminoethyl ester, 3-mercaptopropyltrimethoxysilane, and the like. The modification is carried out by click reaction of the carbon-carbon double bond in the single polymer chain A and/or B with a substance providing a functional segment or functional group.
In one embodiment, the preparation method of the polymer double-stranded/inorganic nanoparticle asymmetric composite comprises the following steps:
step 1), modifying nanoparticles with amino groups on the surface through amino silane;
step 2), preparing an active chain solution of a polymer single chain A with an active center at the tail end through cationic polymerization;
step 3), dripping the active chain solution obtained in the step 2) into the nano-particle dispersion liquid synthesized in the step 1) to obtain polymer single-chain A-nano-particle composite particles;
step 4), preparing a polymer single chain B with an active center at the tail end by cationic polymerization by using a monomer which can be subjected to cationic polymerization and is different from the monomer in the step 2), and dripping the polymer single chain B into the dispersion liquid of the polymer single chain A-nanoparticle composite particles obtained in the step 3) to obtain the polymer single chain A-inorganic nanoparticle-polymer single chain B composite asymmetric particles;
step 5) further modifying the chain-sphere-chain asymmetric particles obtained in the above way.
Wherein, the nanoparticles In step 1) may be selected from one of metal, metal compound and nonmetal compound, and the metal may be selected from Au, Ag, Pt, Pd, Fe, Co, Ni, Sn, In and alloy thereof; the metal compound may be selected from Fe3O4、TiO2、Al2O3、BaTiO3,SrTiO3(ii) a The non-metallic compound is SiO2. The size is 1-20 nanometers.
The aminosilane is preferably aminopropyltriethoxysilane.
Wherein, the initiator for initiating cationic polymerization in step 2) includes but is not limited to: boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, iron trichloride, alkylaluminum chlorides, trifluoromethylsulfonic acid, HCl, HI/I2，HI/ZnI2，HI/ZnBr2，AlEt2Cl，EtAlCl2EtOAc and the like. Tin tetrachloride and boron trifluoride are preferred. The polymerization degree of the single chain of the polymer is 10-10000, preferably 50-1000, and the size of the single chain of the polymer is 1-20 nm.
Among these, cationically polymerized monomers include, but are not limited to: n-butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, methylphenyl vinyl ether, benzyl chloride vinyl ether, vinyl ether styrene, vinyl ether alkyl ethylene, vinyl ether acrylate, styrene, p-methyl styrene, alpha-methyl styrene, chloromethyl styrene (VBC), 4- (vinylphenyl) -1-butene (VSt). The polymerization degree of the single chain of the polymer is 10-10000, preferably 50-1000, and the size of the single chain of the polymer is 1-20 nm.
Wherein, the reactants of the modification reaction in the step 5) include but are not limited to: n-bromosuccinimide, thioglycolic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol and the like.
In the above preparation process, the temperature should be controlled to be-100 ℃ to 100 ℃. Preferably from-50 ℃ to 40 ℃.
The prepared polymer single-chain A-inorganic nanoparticle-polymer single-chain B compound can be further modified according to the method to obtain the multifunctional Janus composite nanomaterial. The method has important significance in the fields of high performance of composite materials, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carriers, solid emulsifiers and the like.
The invention will be further illustrated with reference to the following specific examples. The experimental procedures used in the examples may be conventional ones unless otherwise specified; the materials, reagents and the like used in the examples are commercially available unless otherwise specified.
The hydrodynamic diameter (DLS size) in the preparation examples and examples was determined by the following method: dissolving or dispersing the polymer single chain or the nano particles in a solvent to prepare a solution or dispersion liquid with the concentration of 5 mg/mL. 1mL of the solution or dispersion was taken in a four-way quartz cuvette and measured using a particle sizer (Malvern Zetasizer ZSE).
Preparation example 1: preparation of 4- (vinylphenyl) -1-butene (VSt)
Step 1) A500 mL round bottom flask was charged with 200mL of 1.7mol/L allyl magnesium chloride (0.34mol), diluted with 160mL of ultra dry tetrahydrofuran, and placed in a 0 ℃ cold bath.
Step 2) 4-chloromethyl styrene overbased alumina column, 40mL (0.28mol) is measured by a syringe, and VBC is dropwise added within 1h by using a syringe pump under stirring. The flask was left to stir at room temperature for an additional 4 hours, after which time the reaction was quenched by slow addition of deionized water.
And 3) washing the mixture for 3 times by using water, adding anhydrous magnesium sulfate into the mixture of the monomer and a small amount of tetrahydrofuran as an upper oil phase, stirring the mixture overnight, filtering the mixture, and performing rotary evaporation to remove the tetrahydrofuran. Distilling the monomer under reduced pressure, freezing, removing oxygen, and storing in a refrigerator at-30 deg.C in glove box.
Hydrogen nuclear magnetic resonance spectroscopy indicated the successful synthesis of monomeric VSt.
Preparation example 2: preparation of aminopropyltriethoxysilane-modified Fe3O4Nanoparticles
Surface modification is carried out on oil-dispersible ferroferric oxide nano-particles with the particle size of 10nm through silane ligand exchange, and the specific steps are as follows. Adding ferroferric oxide into toluene to prepare 0.5g/mL of dispersion, taking 100.0mL of dispersion, adding 0.5mL of aminopropyltriethoxysilane and 0.01mL of acetic acid, and mechanically stirring for 24 hours at room temperature. Separating ferroferric oxide particles by using a magnet, washing the ferroferric oxide particles by using methylbenzene and ethanol respectively, and freeze-drying the washed ferroferric oxide particles to obtain aminopropyltriethoxysilane modified Fe3O4And (3) nanoparticles. DLS size 11nm (toluene).
Preparation example 3: preparation of aminopropyltriethoxysilane-modified gold nanoparticles
Surface modification of 7nm oleylamine protected gold nanoparticles by silane ligand exchange. Dispersing gold nanoparticles in toluene to prepare 0.5g/mL dispersion, taking 100.0mL dispersion, adding 0.5mL 3-mercaptopropyltriethoxysilane and 0.01mL acetic acid, stirring at room temperature for 24h, adding 0.5mL aminopropyltriethoxysilane and 0.01mL acetic acid, and stirring at room temperature for 24 h. And (3) centrifugally washing the product with toluene and ethanol respectively, and freeze-drying to obtain the aminopropyltriethoxysilane-modified gold nanoparticles. DLS size 8nm (toluene).
Preparation example 4: preparation of aminopropyltriethoxysilane-modified silica nanoparticles
The surface modification of 10nm silica particles by silane ligand exchange specifically comprises the following steps: dispersing 0.5g of 10nm silicon dioxide nanoparticles into 100mL of ethanol under ultrasonic waves, adding 0.1mL of aminopropyltriethoxysilane, modifying at 70 ℃ for 24h, respectively centrifugally washing the product with ethanol and water, and freeze-drying to prepare the aminopropyltriethoxysilane-modified silicon dioxide nanoparticles. DLS size 11nm (toluene).
Preparation example 5: preparation of aminopropyltriethoxysilane-modified cobalt nanoparticles
Preparing a diphenyl ether solution from cobalt acetate and oleic acid in a ratio of 1:1, and reducing the cobalt acetate by using a reducing agent 1, 2-dodecanediol to obtain oleic acid-protected cobalt nanoparticles with the diameter of 6 nm. 6nm oleic acid protected cobalt metal nanoparticle surface was modified by silane ligand exchange. Specifically, the cobalt oleate-protected nanoparticles were dispersed in toluene to prepare a 0.5g/mL dispersion, and 0.5mL aminopropyltriethoxysilane and 0.01mL acetic acid were added to 100.0mL of the dispersion, followed by mechanical stirring at room temperature for 24 hours. And (3) after magnet separation, washing with toluene and ethanol respectively, and freeze-drying to prepare the aminopropyltriethoxysilane modified cobalt nanoparticles. DLS size 7nm (toluene).
Example 1:
10.0mg of aminopropyltriethoxysilane-modified ferroferric oxide prepared in preparation example 2 was dispersed in cyclohexane for use. 10.0. mu.L of boron trifluoride was dissolved in 5.0mL of dichloromethane at 0 ℃ and stirred uniformly, then 3.0g of styrene was added and stirred to react for 30min, to obtain a PS active chain with a molecular weight of 36k and a DLS size of 11.0nm (dichloromethane). Slowly dripping the active chain solution into aminopropyltriethoxysilane-modified ferroferric oxide dispersion liquid under the ultrasonic condition, stopping dripping until the characteristic color of light pink cations appears in the dispersion liquid, and preparing to obtain PS-Fe3O4And (c) a complex.
Dissolving 10.0 mu L of boron trifluoride into 5.0mL of cyclohexane at room temperature, uniformly stirring, cooling to 0 ℃, adding 1.0g of p-methylstyrene, and stirring for reaction for 30min to obtain a PMS active chain, wherein the molecular weight of the PMS active chain is 9k, and the DLS size is 5.0nm (dichloromethane). Slowly dropping the active chain solution into the solution containing PS-Fe under the condition of ultrasonic3O4In the system of the compound, the dripping is stopped after the characteristic light pink cationic color appears in the dispersion liquid. Injecting a small amount of methanol to terminate the active polymer, repeatedly washing the particles under the action of a magnet, and preparing to obtain PS-Fe3O4-PMS composite nanoparticles. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on both sides of the magnetic particles (namely, two sides of the particles are respectively connected with a linear polymer chain), and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.
Example 2:
10.0mg of the amino-modified ferriferrous oxide obtained in preparation example 2 was dispersed in cyclohexane for use. 10.0. mu.L of boron trifluoride was dissolved in 5.0mL of methylene chloride at 0 ℃And (3) adding 3.0g of styrene into the alkane after uniformly stirring, and stirring for reacting for 30min to obtain a PS active chain, wherein the molecular weight of the PS active chain is 36k, and the size of DLS is 11.0nm (dichloromethane). Slowly dripping the active chain solution into amino-modified ferroferric oxide dispersion liquid under the ultrasonic condition, stopping dripping until light pink cation characteristic color appears in the dispersion liquid, and preparing PS-Fe3O4And (c) a complex.
Dissolving 10.0 mu L of boron trifluoride into 5.0mL of cyclohexane at room temperature, uniformly stirring, cooling to 0 ℃, adding 0.5g of p-methylstyrene, stirring for reaction for 30min, adding 0.5g of p-chloromethylstyrene, stirring for reaction for 30min, and preparing the PMS-b-PVBC active chain, wherein the molecular weight is 9k, and the DLS size is 5.0nm (dichloromethane). Slowly dropping the active chain solution containing PS-Fe under the condition of ultrasonic3O4And in the reaction system of the compound, stopping dripping after the characteristic light pink cationic color appears in the dispersion liquid. Injecting a small amount of methanol to terminate the active polymer, repeatedly washing the particles under the action of a magnet, and preparing PS-Fe3O4-PVBC-b-PMS composite nanoparticles. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.
Example 3:
10.0mg of the amino-modified ferriferrous oxide obtained in preparation example 2 was dispersed in cyclohexane for use. 10.0. mu.L of stannic chloride is dissolved in 5.0mL of dichloromethane at 0 ℃, after uniform stirring, 2.0g of chloroethyl vinyl ether is added, and stirring reaction is carried out for 30min, thus obtaining the PCVE active chain, wherein the molecular weight is 36k, and the DLS size is 11.0nm (dichloromethane). Slowly dripping the active chain solution into amino-modified ferroferric oxide dispersion liquid under the ultrasonic condition, stopping dripping until light green cation characteristic color appears in the dispersion liquid, and preparing PCVE-Fe3O4And (c) a complex.
10.0. mu.L of boron trifluoride was dissolved in 5.0mL of cyclohexane at room temperature, and after stirring, the solution was cooled to 0 ℃ and 0.5g of VSt was added, and the reaction was stirred for 30min to obtain a PVSt active chain having a molecular weight of 9k and a DLS size of 5.0nm (dichloromethane). Mixing the aboveThe active chain solution is slowly dropped into the solution containing PCVE-Fe under the condition of ultrasound3O4In the system of the compound, the dripping is stopped after the characteristic light pink cationic color appears in the dispersion liquid. Injecting a small amount of methanol to stop the active polymer, repeatedly washing the particles under the action of a magnet, and preparing PCVE-Fe3O4-PVSt composite nanoparticles. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.
Example 4:
the double bond of the PVSt polymer side group and 2, 2-dimethoxy-2-phenylacetophenone are used as a photoinitiator, and the click reaction is carried out on the 3-mercaptopropionic acid and the double bond of the polymer side chain, which is specifically as follows.
Sequentially adding DMF, 3-thioglycolic acid and 2, 2-dimethoxy-2-phenylacetophenone into a single-mouth bottle, introducing nitrogen for 30min to remove oxygen, initiating reaction under the irradiation of a 365nm ultraviolet lamp, and slowly dropwise adding the PCVE-Fe prepared in example 33O4-DMF solution of PVSt composite nanoparticles, reaction at room temperature for 4 h. Washing the particles under the action of a magnet to prepare PCVE-Fe3O4-PVSt @ COOH composite nanoparticles. DLS size 30.0nm (toluene). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, characteristic peaks of carboxyl can be seen through characterization of Fourier infrared spectrum, and the fact that carboxyl functional groups are successfully introduced into double bonds on polymer chains through click reaction is proved. The particles have amphipathy, can be well divided in water and toluene, and can be used as a solid emulsifier.
Example 5:
the double bond of the PVSt polymer side group, 2, 2-dimethoxy-2-phenylacetophenone as a photoinitiator, and mercapto polyethylene glycol and the double bond of the polymer side chain are subjected to click reaction, which is specifically as follows.
DMF, mercaptopolyethylene glycol (Mw 1000k/mol) and 2, 2-dimethoxy-2-phenylacetophenone were sequentially added to a single-neck flask, nitrogen was introduced for 30min to remove oxygen, a reaction was initiated under the irradiation of a 365nm ultraviolet lamp, and PCVE-Fe prepared in example 3 was slowly added dropwise3O4DMF solution of-PVSt composite nanoparticlesThe reaction solution was reacted at room temperature for 4 hours. Washing the particles under the action of a magnet to prepare PCVE-Fe3O4- (PVSt-g-PEO) composite nanoparticles. DLS size 30.0nm (toluene). Under a transmission electron microscope, one side of the magnetic particles forms a parachute structure (namely, a linear polymer chain), and the other side forms a rod structure (namely, a large number of polyethylene glycol chains are introduced through double bonds distributed on PVSt side chains). The characteristic peak of polyethylene glycol can be seen by Fourier infrared spectrum characterization, which proves that the double bond on the polymer chain successfully introduces the polyethylene glycol side chain through click reaction. The particles have amphipathy, can be well divided in water and toluene, and can be used as a solid emulsifier.
Example 6:
10.0mg of the amino-modified gold particles prepared in production example 3 were dispersed in cyclohexane to be used. 10.0. mu.L of boron trifluoride was dissolved in 5.0mL of dichloromethane at 0 ℃ and stirred uniformly, then 3.0g of methylstyrene was added and stirred to react for 30min to obtain PMS active chain having a molecular weight of 36k and a DLS size of 11.0nm (dichloromethane). And slowly dripping the active chain solution into the amino modified gold dispersion liquid under the ultrasonic condition, and stopping dripping until the characteristic light pink cationic color appears in the dispersion liquid to prepare the PMS-Au compound. The system was cooled to 0 ℃ until use.
Dissolving 10.0 μ L of stannic chloride in 5.0mL of cyclohexane at room temperature, stirring uniformly, cooling to 0 ℃, adding 1.0g of vinyl ether styrene, stirring and reacting for 30min to obtain the PVBVE active chain, wherein the molecular weight is 9k, and the DLS size is 5.0nm (dichloromethane). And slowly dripping the active chain solution into the reaction system containing PMS-Au under the ultrasonic condition, and stopping dripping when the characteristic color of light yellow cations appears in the dispersion liquid. And (3) injecting a small amount of methanol to terminate the active polymer, and repeatedly washing the particles to prepare the PMS-Au-PVBVE composite nano-particles. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the particles, and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.
Example 7:
10.0mg of the amino-modified silica particles prepared in preparation example 4 were dispersed in cyclohexane and were used.
PMS-SiO production was carried out in the same manner as in example 6 except that the amino-modified silica particles of production example 4 were used2-PVBVE composite nanoparticles. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.
Example 8:
10.0mg of aminopropyltriethoxysilane-modified cobalt nanoparticles prepared in preparation example 5 were dispersed in cyclohexane for use.
Except for using the aminopropyltriethoxysilane-modified cobalt nanoparticles of preparation example 5, PMS-Co-PVBVE composite nanoparticles were prepared in the same manner as in example 6. DLS size 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, and the fact that the polymer double chains are successfully grafted to the surfaces of the particles is shown.

Claims (18)

1. A polymer double-stranded/inorganic nanoparticle asymmetric complex comprising a composite structure of a polymer single-stranded A-an inorganic nanoparticle-a polymer single-stranded B, wherein the polymer single-stranded A and the polymer single-stranded B are connected to the inorganic nanoparticle at a chain tail end through a chemical bond, the kind of monomer unit constituting the polymer single-stranded A and the kind of monomer unit constituting the polymer single-stranded B may be the same or different, and the polymer single-stranded A and the polymer single-stranded B each independently optionally further comprise a functional segment or a functional group.
2. The composite of claim 1, wherein the inorganic nanoparticles are selected from the group consisting of metals, metal compounds, and non-metal compounds, and have a particle size of 1-20 nm.
3. The composite of claim 1 or 2, wherein the metal is selected from Au, Ag, Pt, Pd, Fe, Co, Ni, Sn, In, and alloys thereof; the metal compound is selected from Fe3O4、TiO2、Al2O3、BaTiO3、SrTiO3(ii) a The non-metallic compound is SiO2。
4. The composite of any of claims 1-3, wherein the inorganic nanoparticles have amino groups on the surface.
5. The complex according to any one of claims 1 to 4, wherein the single polymer chain A and the single polymer chain B each independently comprise a structural unit derived from a styrenic monomer or a vinyl ether monomer.
6. A composite according to claim 5, wherein the styrenic monomer is selected from styrene, C1-5Alkyl-substituted styrenes, C1-5Alkenyl-substituted styrene, halogen-substituted C1-5Alkyl substituted styrene, halogen substituted C1-5One or more of alkenyl substituted styrene and acrylate vinyl benzene; the vinyl ether monomer is selected from one or more of alkyl vinyl ether, halogen-substituted alkyl vinyl ether, alkyl styrene vinyl ether, halogen-substituted alkyl styrene vinyl ether, vinyl phenyl alkoxy alkyl vinyl ether, vinyl ether alkyl ethylene and acrylate vinyl ether.
7. The composite according to any one of claims 1 to 5, wherein the monomers forming the single polymer chains A or B are each independently selected from one or more of n-butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, methylphenyl vinyl ether, benzyl chloride vinyl ether, vinylphenyl methoxyethyl vinyl ether, vinyl ether alkyl vinyl, ethyl acrylate vinyl ether, styrene, p-methylstyrene, α -methylstyrene, chloromethylstyrene, 4- (vinylphenyl) -1-butene (VSt), acrylate vinyl benzene.
8. The complex according to any one of claims 1 to 6, wherein the single polymer chain A and the single polymer chain B are each independently composed of a structural unit derived from a styrene-based monomer or a vinyl ether-based monomer.
9. The complex according to any one of claims 1 to 8, wherein the degree of polymerization of the single polymer chain A and the single polymer chain B is each independently 10 to 10000, preferably 50 to 1000; the size of the polymer single chain A and the size of the polymer single chain B are respectively 1-20 nm.
10. The composite of any one of claims 1-9, wherein the functional segments comprise polyethylene glycol segments, PNIPAM segments, PDMAEMA segments, and/or PDEAEMA segments; the functional group is selected from at least one of carboxyl, amine, hydroxyl, halogen and silane group.
11. A method of preparing a complex according to any one of claims 1 to 10, the method comprising:
the inorganic nano-particles are modified to obtain amino on the surface, and the inorganic nano-particles with amino on the surface are dispersed in a solvent to obtain inorganic nano-particle dispersion liquid;
preparing a polymer single chain A with an active center at the tail end by cationic polymerization;
adding the polymer single chain A with the active center at the tail end into the inorganic nano-particle dispersion liquid to obtain dispersion liquid containing a polymer single chain A-inorganic nano-particle compound;
and preparing a polymer single chain B with an active center at the tail end through cationic polymerization, and adding the polymer single chain B into a dispersion liquid containing the polymer single chain A-inorganic nano particle composite to obtain the polymer single chain A-inorganic nano particle-polymer single chain B composite.
12. The production method according to claim 11, wherein the modification of the inorganic nanoparticles is performed by aminosilane.
13. The production method according to claim 11 or 12, wherein the method further optionally comprises a step of further modifying the polymer single strand a and/or the polymer single strand B in the polymer single strand a-inorganic nanoparticle-polymer single strand B complex to introduce a functional segment or a functional group.
14. The method according to claim 13, wherein the substance providing the functional segment or the functional group is at least one selected from the group consisting of N-bromosuccinimide, thioglycolic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), mercaptopoly (N, N-dimethylaminoethyl methacrylate), mercaptopoly (N, N-diethylaminoethyl methacrylate), and 3-mercaptopropyltrimethoxysilane.
15. The production process according to claim 11 or 12, wherein the initiator for cationic polymerization is selected from the group consisting of boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, ferric trichloride, alkylaluminum chlorides, trifluoromethanesulfonic acid, HCl, HI/I2、HI/ZnI2、HI/ZnBr2、AlEt2Cl、EtAlCl2EtOAc, preferably tin tetrachloride or boron trifluoride.
16. The production method according to claim 11 or 12, wherein the temperature during the production is controlled in the range of-100 ℃ to 100 ℃, preferably-50 ℃ to 40 ℃; the polymerization time of the polymer single chains is 1 to 60 minutes, preferably 5 to 20 minutes.
17. The preparation method according to claim 11 or 12, wherein the dispersion comprising the polymer single-chain a-inorganic nanoparticle composite has a solid content of 1 to 40%, preferably 5 to 30%.
18. The production method according to claim 13 or 14, wherein the modification is performed by click reaction of a carbon-carbon double bond in the polymer single chain a and/or B with a substance that provides a functional segment or a functional group.
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