CN114057962B - 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 PDFInfo
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- CN114057962B CN114057962B CN202010744971.2A CN202010744971A CN114057962B CN 114057962 B CN114057962 B CN 114057962B CN 202010744971 A CN202010744971 A CN 202010744971A CN 114057962 B CN114057962 B CN 114057962B
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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
- C08F292/00—Macromolecular compounds obtained by polymerising monomers on to inorganic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- 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
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/025—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyether sequences
Abstract
The invention relates to a polymer double-chain/inorganic nanoparticle asymmetric compound and a preparation method thereof, wherein the compound comprises a compound structure of a polymer single-chain A-inorganic nanoparticle-polymer single-chain B, wherein the polymer single-chain A and the polymer single-chain B are respectively connected with the nanoparticle at the tail end of the chain through chemical bonds; the polymer single strand a and the polymer single strand B optionally further comprise functional segments or groups to render the polymer double strand/inorganic nanoparticle asymmetric composite more functional.
Description
Technical Field
The invention relates to the technical field of inorganic and high polymer composite materials, in particular to a polymer double-chain/inorganic nanoparticle asymmetric composite which comprises a composite structure of a polymer single chain A, inorganic nanoparticles and a polymer single chain B.
Background
Janus materials are commonly used in the polymer field to describe microparticles with asymmetric structures in composition and nature, the name of which derives from the double sided god in the ancient roman myth. The first use of Janus by the high molecular physicist De genes in 1991 to describe such microparticles (De genes. Science 1992, 256:495-497). The monomolecular Janus nano particles with the micro-scale have great advantages in the aspects of a synthetic monomolecular reactor and the like due to the characteristics of strong autonomy and the like. The properties can be widely adjusted by selecting different nano particles and polymer chains.
On the other hand, inorganic nanoparticles have special properties in terms of light, electricity, magnetism, catalysis, etc., and are attracting great interest. If the polymer is grafted on one side or two sides of the inorganic nano-particle, the anisotropy is endowed to the inorganic nano-particle, and the method has important significance for preparing the composite Janus nano-particle.
Recently, new methods for preparing single-stranded polymers with single sides based on rapid termination reactions have been proposed, which are capable of grafting single-stranded polymers on one side of nanoparticles (X.Yao, J.Jing, F.Liang, Z.Yang, macromolecules,2016,49,9618-9625.). The nano particles obtained by the method are limited by the number of molecular weights, can be modified limitedly, and limit the microstructure design of the asymmetric composite particles.
Disclosure of Invention
Problems to be solved by the invention
Providing a polymer double-strand/inorganic nanoparticle asymmetric composite, and a preparation method thereof, wherein two polymer chains of the polymer double-strand/inorganic nanoparticle asymmetric composite can optionally further comprise functional groups or chain segments according to requirements; 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.
Solution for solving the problem
A first aspect of the invention is to provide: a polymer double strand/inorganic nanoparticle asymmetric composite comprising a composite structure of a polymer single strand a-inorganic nanoparticle-polymer single strand B, wherein the polymer single strand a and the polymer single strand B are connected to the inorganic nanoparticle at a chain tail end by a chemical bond, the kind of monomer units constituting the polymer single strand a and the kind of monomer units constituting the polymer single strand B may be the same or different, and the polymer single strand a and the polymer single strand B each independently optionally further comprise a functional segment or a functional group.
The composite according to the above, wherein the inorganic nanoparticles are selected from the group consisting of metals, metal compounds and nonmetallic compounds, and the particle size of the inorganic nanoparticles is 1 to 20nm.
The above composite, wherein the metal is selected from Au, ag, pt, pd, fe, co, ni, sn, in and combinations thereofGold; the metal compound is selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 、SrTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The nonmetallic compound is SiO 2 。
According to the above complex, the inorganic nanoparticle has amino groups on the surface.
According to the above complex, the polymer single chain a and the polymer single chain B each independently contain a structural unit derived from a styrenic monomer or a vinyl ether monomer.
According to the above complex, the styrenic monomer is selected from styrene, C 1-5 Alkyl-substituted styrenes, C 1-5 Alkenyl-substituted styrenes, halogen-substituted C 1-5 Alkyl-substituted styrenes, halogen-substituted C 1-5 One or more of alkenyl-substituted styrenes, acrylate-based vinylbenzenes; 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 vinyl and acrylic ester vinyl ether.
In some embodiments, the monomers forming polymer single chain a or polymer single 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 vinyl, ethyl acrylate vinyl ether, styrene, p-methyl styrene, alpha-methyl styrene, chloromethylstyrene, 4- (vinyl phenyl) -1-butene (VSt), acrylate vinyl benzene.
In some embodiments, polymer single chain a and polymer single chain B are each independently composed of structural units derived from styrenic monomers or vinyl ether monomers.
The above complex, wherein the degree of polymerization of the polymer single strand A and the polymer single strand B is each independently 10 to 10000, preferably 50 to 1000; the sizes of the polymer single strand A and the polymer single strand B are each independently 1-20nm.
The composite, wherein the functional segment comprises a polyethylene glycol segment, a PNIPAM segment, a PDMAEMA segment and/or a PDEAEMA segment; the functional group is selected from at least one of carboxyl, amino, hydroxyl, halogen and silane groups.
A second aspect of the invention provides: a method of preparing the above-described complex, the method comprising:
the inorganic nano particles are modified to obtain amino groups on the surface, and the inorganic nano particles with the amino groups 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 through cationic polymerization;
adding the polymer single-chain A with the active center at the tail end into the inorganic nanoparticle dispersion liquid to obtain a dispersion liquid containing a polymer single-chain A-inorganic nanoparticle 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 nanoparticle composite to obtain the polymer single-chain A-inorganic nanoparticle-polymer single-chain B composite.
The preparation method according to the above, wherein the modification of the inorganic nanoparticles is performed by aminosilane.
The preparation method as described above, 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.
The preparation method according to the above, wherein the substance providing the functional segment or the functional group is at least one selected from the group consisting of N-bromosuccinimide, mercaptoacetic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), mercaptopoly-N, N-dimethylaminoethyl methacrylate segment, mercaptopoly-N, N-diethylaminoethyl methacrylate, and 3-mercaptopropyltrimethoxysilane.
The preparation method comprises the following steps ofThe initiator for ionic polymerization is selected from boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, iron trichloride, aluminum alkyl chloride, trifluoromethanesulfonic acid, HCl, HI/I 2 、HI/ZnI 2 、HI/ZnBr 2 、AlEt 2 Cl、EtAlCl 2 Any of EtOAc, preferably tin tetrachloride or boron trifluoride.
The preparation method according to the above, wherein the temperature during the preparation is controlled in the range of-100 ℃ to 100 ℃, preferably-50 ℃ to 40 ℃; the polymerization time of the polymer single strand is 1 to 60 minutes, preferably 5 to 20 minutes.
The preparation method according to the above, wherein the solid content in the dispersion liquid containing the polymer single-chain a-inorganic nanoparticle composite is 1 to 40%, preferably 5 to 30%.
The preparation method according to the above, wherein the modification is performed by click reaction of the carbon-carbon double bond in the polymer single chain A and/or B with a substance providing a functional segment or a functional group.
ADVANTAGEOUS EFFECTS OF INVENTION
The polymer double-chain/inorganic nano-particle compound can be used for preparing a plurality of Janus materials with different functional combinations and chain-ball-chain structures by respectively modifying or modifying two polymer single chains in the Janus materials. The preparation method can accurately design the composite asymmetric structure of the polymer chain and the inorganic nano particles. In addition, the preparation method provided by the invention has the advantages of complete conversion rate of polymerization reaction in each step, no interference to subsequent steps, simple method and suitability for mass production.
Detailed Description
The following describes the present invention in detail. The following description of the technical features is based on the representative 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 strand of polymer is the hydrodynamic diameter as determined by light scattering.
In the present specification, "cationic characteristic color" means a color that an active center exhibits in a solution during cationic polymerization.
In the present specification, the numerical range indicated by the term "numerical value a to numerical value B" means a range including the end point numerical value A, B.
In the present specification, a numerical range indicated by "above" or "below" is a numerical range including the present number.
In the present specification, the meaning of "can" includes both the meaning of performing a certain process and the meaning of not performing a certain process.
In this specification, the use of "optionally" or "optional" means that certain substances, components, steps of performing, conditions of applying, etc. may or may not be used.
In the present specification, unit names used are international standard unit names, and "%" used represent weight or mass% unless otherwise specified.
Reference in the specification to "a preferred embodiment," "an embodiment," and the like, 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 elements may be combined in any suitable manner in the various embodiments.
The invention provides a polymer double-chain/inorganic nanoparticle asymmetric compound, which comprises a composite structure of a polymer single chain, inorganic nanoparticles and a polymer single chain, wherein the two polymer single chains are connected with the inorganic nanoparticles at the tail end of the chain through chemical bonds.
< Single Polymer chain >
The single polymer chains are formed from monomers by polymerization and optionally subsequent modification, and are continuous, linear or branched, single molecular chains.
The polymer double chains forming the polymer double chain/inorganic nano particle asymmetric compound are two polymer single chains connected to two sides of the inorganic nano particle. The two polymer strands are referred to as polymer strand A and polymer strand B, respectively.
The polymer single strand a and the polymer single strand B are obtained by cationic polymerization, and each independently optionally further incorporates a functional segment or a functional group.
The kind of the monomer unit constituting the polymer single chain A may be the same as or different from the kind of the monomer unit constituting the polymer single chain B. In other words, the monomer unit compositions 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 monomer units constituting the polymer single chain A is different from the kind of monomer units constituting the polymer single chain B.
The polymer single chain a and the polymer single chain B each independently contain a structural unit derived from a styrenic monomer or a vinyl ether monomer; the polymer chain may contain one or more structural units, for example, the polymer chain may include two or more structural units derived from a styrenic monomer, or the polymer chain may include two or more structural units derived from a vinyl ether monomer. In one embodiment of the invention, both polymer single chain a and polymer single chain B comprise structural units derived from styrenic monomers. In one embodiment of the invention, one of polymer strands a and B comprises structural units derived from styrenic monomers, and the other comprises structural units derived from vinyl ether monomers.
The styrene monomer includes styrene, substituted styrene, styrene acrylate monomer, etc. For the 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 contain a substituent such as a halogen, and the halogen is preferably chlorine. Preferably, the substituted styrenes are selected from C 1-5 Alkyl substitutionStyrene, C 1-5 Alkenyl-substituted styrenes, halogen-substituted C 1-5 Alkyl-substituted styrenes, halogen-substituted C 1-5 Alkenyl-substituted styrene, acrylate-based vinylbenzene. In some embodiments, the styrenic monomer is selected from styrene, p-methylstyrene, alpha-methylstyrene, chloromethylstyrene (VBC), 4- (vinylphenyl) -1-butene (VSt).
Vinyl ether monomers are 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 vinyl ether, acrylate vinyl ether, wherein the acrylate group comprises alkyl acrylate; the number of carbon atoms of the alkyl group or the alkoxy group is preferably 1 to 5. In some embodiments, the vinyl ether monomer is selected from the group consisting of n-butyl vinyl ether, isobutyl vinyl ether, chloroethyl vinyl ether, methylphenyl vinyl ether, benzyl chlorovinyl ether, vinylphenyl methoxyethyl vinyl ether, vinyl ether alkyl vinyl, ethyl acrylate vinyl ether.
When the single polymer chain contains one or more monomers, the single polymer chain may have a block structure, and for example, the single polymer chain may contain blocks 1 to 2 to 3 in this order. For example, in one embodiment, the single polymer chain comprises a block structure of polymethylstyrene-polychloromethylstyrene (PMS-b-PVBC).
The degree of polymerization of the polymer single strand is 10-10000, preferably 50-1000, more preferably 100-800, and the size thereof is 1-20nm.
In one embodiment, the two cationically polymerized polymer single strands contained in the polymer double strand/inorganic nanoparticle asymmetric composites of the present invention differ in size. In one embodiment, the size of polymer strand A is greater than the size of polymer strand B.
The polymer single strand a and the polymer single strand B are each independently optionally further introduced with a functional segment or a functional group. The functional segment comprises at least one selected from a polyethylene glycol segment (PEO segment), a PNIPAM segment (poly (N-isopropyl acrylamide) segment), a PDMAEMA segment (poly-N, N-dimethylaminoethyl methacrylate segment), and a PDMAEMA segment (poly-N, N-diethylaminoethyl methacrylate segment); the functional group is selected from carboxyl, amino, hydroxyl, halogen and silane groups.
The single polymer strand with the inorganic nanoparticles attached can take on a parachute structure that indicates that a linear polymer strand is attached to the inorganic nanoparticles; if parachute structures are formed on both sides of the particle, it means that both sides of the particle are respectively connected to one linear polymer chain. Furthermore, the single polymer chain to which the inorganic nanoparticles are attached may also take on 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 compound is 10-60nm, preferably 20-50nm.
< inorganic nanoparticles >
The inorganic nano-particles are selected from metals, metal compounds and nonmetallic compounds, and the particle size of the inorganic nano-particles is 1-20nm.
The metal is selected from Au, ag, pt, pd, fe, co, ni, sn, in and alloys thereof; the metal compound is selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 、SrTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The nonmetallic compound is SiO 2 。
The inorganic nanoparticle surface has amino groups by modification. Specifically, the amino group can be introduced by modifying the inorganic nanoparticle with an aminosilane-based substance. Examples of the aminosilanes include γ -aminopropyl trimethoxysilane, γ -aminopropyl methyldimethoxysilane, γ -aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl triethoxysilane, 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- [ 3- (triethoxysilyl) propyl ] hexamethylenediamine, and the like; in some embodiments, preference is given to using aminopropyl triethoxysilane, aminopropyl trimethoxysilane.
< preparation method >
A method of preparing a polymer double-stranded/inorganic nanoparticle asymmetric complex, the method comprising:
the inorganic nano particles are modified to obtain amino groups on the surface, and the inorganic nano particles with the amino groups 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 through cationic polymerization;
adding the polymer single-chain A with the active center at the tail end into the inorganic nanoparticle dispersion liquid to obtain a dispersion liquid containing a polymer single-chain A-inorganic nanoparticle 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 nanoparticle composite to obtain the polymer single-chain A-inorganic nanoparticle-polymer single-chain B composite.
Wherein the modification of the inorganic nanoparticles comprises introducing an amino group via an aminosilane.
Wherein, preferably, the molecular weight of the polymer single chain A is controlled to be large enough by cationic polymerization, so as to obtain an asymmetric structure of the polymer single chain A-inorganic nano-particle; when the cationic polymerization is used for preparing another active chain, namely the polymer single chain B, the molecular weight is controlled, so that the surface of the inorganic nano-particle with the asymmetric structure of the polymer single chain A-inorganic nano-particle is further bonded with the polymer single chain B.
The method optionally further comprises the 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 functional segments or functional groups.
The substance providing the functional segment or functional group may be a substance containing the functional segment or functional group and capable of reacting with a carbon-carbon double bond in a single chain of the polymer, and for example, include, but are not limited to, N-bromosuccinimide, thioglycolic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), mercaptopoly (N, N-dimethylaminoethyl methacrylate) segment, mercaptopoly (N, N-diethylaminoethyl methacrylate), 3-mercaptopropyltrimethoxysilane, and the like. The modification is carried out by click reaction of the carbon-carbon double bonds in the polymer single chains a and/or B with a substance providing a functional segment or functional group.
In a specific embodiment, the method of preparing the asymmetric polymer double-stranded/inorganic nanoparticle composite comprises the steps of:
step 1), modifying the nano particles by aminosilane to form amino groups on the surfaces;
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 nanoparticle dispersion liquid synthesized in the step 1) to obtain single-chain polymer A-nanoparticle composite particles;
step 4) preparing a single polymer chain B with an active center at the tail end by cationic polymerization by using a monomer which is different from the monomer in the step 2) and can be cationic polymerized, and dripping the single polymer chain B into the dispersion liquid of the single polymer chain A-nanoparticle composite particles obtained in the step 3) to obtain single polymer chain A-inorganic nanoparticle-single polymer chain B composite asymmetric particles;
step 5) the chain-ball-chain asymmetric particles obtained above are further modified.
Wherein the nanoparticle in step 1) may be selected from one of a metal, a metal compound and a non-metal compound, and the metal may be selected from Au, ag, pt, pd, fe, co, ni, sn, in and an alloy thereof; the metal compound may be selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 ,SrTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The nonmetallic compound is SiO 2 . The size is 1-20 nanometers.
The aminosilane is preferably aminopropyl triethoxysilane.
Wherein, the initiator for initiating cationic polymerization in the step 2) includes but is not limited to: boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, iron trichloride, alkyl aluminum chlorides, trifluoromethane sulfonic acid, HCl, HI/I 2 ，HI/ZnI 2 ，HI/ZnBr 2 ，AlEt 2 Cl，EtAlCl 2 EtOAc, etc. Tin tetrachloride and boron trifluoride are preferred. The single-chain polymerization degree of the polymer is 10-10000, preferably 50-1000, and the size is 1-20nm.
Wherein cationically polymerized monomers, including but 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 vinyl, vinyl ether acrylate, styrene, p-methyl styrene, alpha-methyl styrene, chloromethyl styrene (VBC), 4- (vinyl phenyl) -1-butene (VSt). The single-chain polymerization degree of the polymer is 10-10000, preferably 50-1000, and the size is 1-20nm.
Wherein the reactants of the modification reaction described in step 5) include, but are not limited to: n-bromosuccinimide, mercaptoacetic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, and the like.
In the above preparation process, the temperature should be controlled at-100℃to 100 ℃. Preferably-50 ℃ to 40 ℃.
The prepared polymer single-chain A-inorganic nano particle-polymer single-chain B compound can be further modified according to the method to obtain the multifunctional Janus composite nano material. The method has important significance in the fields of composite material high performance, catalysis, oil-water separation, environmental response, drug control release, catalyst carrier, solid emulsifier and the like.
The invention will be further illustrated with reference to specific examples. The experimental procedure used in the examples may be conventional, unless otherwise specified; materials, reagents and the like used in the examples are commercially available unless otherwise specified.
The hydrodynamic diameter (DLS size) in the preparations and examples was determined by the following method: the polymer single chains or nano particles are dissolved or dispersed in a solvent to prepare a solution or dispersion with the concentration of 5 mg/mL. 1mL of the solution or dispersion was placed in a four-way quartz cuvette and measured by a particle diameter meter (Malvern Zetasizer ZSE).
Preparation example 1: preparation of 4- (vinylphenyl) -1-butene (VSt)
Step 1) 500mL round bottom flask was charged with 200mL of 1.7mol/L allyl magnesium chloride (0.34 mol), diluted with 160mL of ultra-dry tetrahydrofuran and placed in a 0℃cold bath.
Step 2) 4-chloromethylstyrene overbased alumina column, 40mL (0.28 mol) was metered in by syringe and VBC was added dropwise over 1h with stirring using a syringe pump. The flask was left to stir for an additional 4 hours at room temperature after which time the reaction was stopped by slowly adding deionized water.
The mixture in the step 3) is washed by water for 3 times, the upper oil phase is the mixed solution of the monomer and a small amount of tetrahydrofuran, anhydrous magnesium sulfate is added to stir overnight, and the tetrahydrofuran is removed by rotary evaporation after filtration. And (3) distilling the monomer under reduced pressure, freezing, pumping and deoxidizing, and then placing the monomer into a refrigerator with the temperature of minus 30 ℃ in a glove box for standby.
Nuclear magnetic resonance hydrogen spectrum indicates successful synthesis of monomer VSt.
Preparation example 2: preparation of aminopropyl triethoxysilane modified Fe 3 O 4 Nanoparticles
The 10nm oil-dispersible ferroferric oxide nanoparticles were surface modified by silane ligand exchange, as follows. The ferroferric oxide is added into toluene to prepare a dispersion liquid with the concentration of 0.5g/mL, 100.0mL of the dispersion liquid is taken, 0.5mL of aminopropyl triethoxysilane and 0.01mL of acetic acid are added, and the mixture is mechanically stirred for 24 hours at room temperature. Separating ferroferric oxide particles by using a magnet, respectively washing with toluene and ethanol, and freeze-drying to obtain the aminopropyl triethoxysilane modified Fe 3 O 4 And (3) nanoparticles. The DLS size was 11nm (toluene).
Preparation example 3: preparation of aminopropyl triethoxysilane modified gold nanoparticles
The surface modification of the 7nm oleylamine protected gold nanoparticles was performed by silane ligand exchange. Dispersing gold nanoparticles in toluene to prepare a dispersion liquid with the concentration of 0.5g/mL, taking 100.0mL of the dispersion liquid, adding 0.5mL of 3-mercaptopropyl triethoxysilane and 0.01mL of acetic acid, stirring at room temperature for 24h, adding 0.5mL of aminopropyl triethoxysilane and 0.01mL of acetic acid, and stirring at room temperature for 24h. And (3) centrifugally washing the product by toluene and ethanol respectively, and freeze-drying to obtain the aminopropyl triethoxysilane modified gold nanoparticles. The DLS size was 8nm (toluene).
Preparation example 4: preparation of aminopropyl triethoxysilane modified silica nanoparticles
Surface modification of 10nm silica particles by silane ligand exchange, specifically comprises: dispersing 0.5g of 10nm silicon dioxide nano particles in 100mL of ethanol under ultrasonic, adding 0.1mL of aminopropyl triethoxysilane, modifying for 24 hours at 70 ℃, centrifugally washing the product by ethanol and water respectively, and freeze-drying to prepare the aminopropyl triethoxysilane modified silicon dioxide nano particles. The DLS size was 11nm (toluene).
Preparation example 5: preparation of aminopropyl triethoxysilane modified cobalt nanoparticles
Cobalt acetate and oleic acid are prepared into diphenyl ether solution in a ratio of 1:1, and a reducing agent of 1, 2-dodecanediol is used for reducing the cobalt acetate to obtain oleic acid protection cobalt nano particles with the diameter of 6 nm. Surface modification of 6nm oleic acid protected cobalt metal nanoparticles by silane ligand exchange. Specifically, oleic acid-protected cobalt nanoparticles were dispersed in toluene to prepare a dispersion of 0.5g/mL, 100.0mL of the dispersion was taken and 0.5mL of aminopropyl triethoxysilane and 0.01mL of acetic acid were added thereto, and the mixture was mechanically stirred at room temperature for 24 hours. After magnet separation, washing with toluene and ethanol respectively, and freeze-drying to prepare the aminopropyl triethoxysilane modified cobalt nano particles. The DLS size was 7nm (toluene).
Example 1:
10.0mg of aminopropyl triethoxysilane modified ferroferric oxide prepared in preparation example 2 is dispersed in cyclohexane for use. Dissolving 10.0 mu L of boron trifluoride in 5.0mL of dichloromethane alkane at 0 ℃, stirring uniformly, adding 3.0g of styrene, stirring and reacting for 30min to obtain PS active chain with molecular weight of36k, DLS size 11.0nm (dichloromethane). Slowly dripping the active chain solution into aminopropyl triethoxysilane modified ferroferric oxide dispersion liquid under the condition of ultrasound, stopping dripping after the light pink cation characteristic color appears in the dispersion liquid, and preparing the PS-Fe 3 O 4 A complex.
10.0. Mu.L of boron trifluoride was dissolved in 5.0mL of cyclohexane at room temperature, stirred uniformly, cooled to 0℃and 1.0g of p-methylstyrene was added thereto, and the reaction was carried out for 30 minutes with stirring to give a PMS active chain having a molecular weight of 9k and a DLS size of 5.0nm (methylene chloride). Slowly dripping the active chain solution into the solution containing PS-Fe under the condition of ultrasonic 3 O 4 In the system of the compound, the dripping is stopped after the cation characteristic color of light pink 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 to obtain PS-Fe 3 O 4 -PMS composite nanoparticles. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles (namely, two sides of the particles are respectively connected with a linear polymer chain), which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Example 2:
10.0mg of the amino-modified ferroferric 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 alkane at 0℃and stirred uniformly, then 3.0g of styrene was added thereto and the reaction was carried out for 30 minutes with stirring to obtain a PS chain having a molecular weight of 36k and a DLS size of 11.0nm (methylene chloride). Slowly dripping the active chain solution into amino modified ferroferric oxide dispersion liquid under the condition of ultrasound, stopping dripping after the light pink cation characteristic color appears in the dispersion liquid, and preparing PS-Fe 3 O 4 A complex.
10.0 mu L of boron trifluoride is dissolved in 5.0mL of cyclohexane at room temperature, stirred uniformly, cooled to 0 ℃, added with 0.5g of p-methylstyrene, stirred and reacted for 30min, added with 0.5g of p-chloromethylstyrene, stirred and reacted for 30min to prepare PMS-b-PVBC active chain with the molecular weight of 9k and the DLS size of 5.0nm (dichloromethane). Strips of the active strand solution described above in ultrasoundSlowly drop-in the component under the component and contain PS-Fe 3 O 4 In the reaction system of the compound, dripping is stopped after the cation characteristic color of light pink 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 to prepare PS-Fe 3 O 4 -PVBC-b-PMS composite nanoparticles. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Example 3:
10.0mg of the amino-modified ferroferric oxide obtained in preparation example 2 was dispersed in cyclohexane for use. 10.0. Mu.L of tin tetrachloride was dissolved in 5.0mL of methylene chloride at 0℃and stirred uniformly, then 2.0g of chloroethyl vinyl ether was added thereto, and the reaction was carried out for 30 minutes with stirring to give a PCVE active chain having a molecular weight of 36k and a DLS size of 11.0nm (methylene chloride). Slowly dripping the active chain solution into amino modified ferroferric oxide dispersion liquid under the condition of ultrasound, stopping dripping after light green cation characteristic color appears in the dispersion liquid, and preparing PCVE-Fe 3 O 4 A complex.
10.0. Mu.L of boron trifluoride was dissolved in 5.0mL of cyclohexane at room temperature, stirred uniformly, cooled to 0℃and then 0.5g of VSt was added thereto, and the reaction was carried out for 30 minutes with stirring to give PVSt active chain having a molecular weight of 9k and a DLS size of 5.0nm (methylene chloride). Slowly dripping the active chain solution into a solution containing PCVE-Fe under the condition of ultrasonic 3 O 4 In the system of the compound, the dripping is stopped after the cation characteristic color of light pink 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 to prepare PCVE-Fe 3 O 4 PVSt composite nanoparticles. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Example 4:
the double bond of PVSt polymer side group and 2, 2-dimethoxy-2-phenyl acetophenone are used as photoinitiator, and the click reaction between 3-mercaptopropionic acid and the double bond of polymer side chain is carried out as follows.
DMF, 3-thioglycollic acid and 2, 2-dimethoxy-2-phenyl acetophenone are sequentially added into a single-mouth bottle, nitrogen is introduced for 30min to deoxidize, the reaction is initiated under the irradiation of 365nm ultraviolet lamp, and PCVE-Fe prepared in the example 3 is slowly added dropwise 3 O 4 -DMF solution of PVSt composite nanoparticles, reacted for 4h at room temperature. Washing the particles under the action of a magnet to prepare PCVE-Fe 3 O 4 PVSt@COOH composite nanoparticles. The DLS size was 30.0nm (toluene). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, and a characteristic peak of carboxyl can be seen by using Fourier infrared spectrum characterization, so that the double bonds on the polymer chain are proved to be successfully introduced into carboxyl functional groups through click reaction. The particles have amphipathy, can be well separated in water and toluene, and can be used as a solid emulsifier.
Example 5:
the double bond of PVSt polymer side group and 2, 2-dimethoxy-2-phenyl acetophenone are used as photoinitiator, and the mercapto polyethylene glycol and the double bond of polymer side chain produce click reaction as follows.
DMF, mercaptopolyethylene glycol (mw=1000k/mol) and 2, 2-dimethoxy-2-phenylacetophenone are sequentially added into a single-mouth bottle, nitrogen is introduced for 30min to deoxidize, the reaction is initiated under irradiation of 365nm ultraviolet lamp, and PCVE-Fe prepared in example 3 is slowly added dropwise 3 O 4 -DMF solution of PVSt composite nanoparticles, reacted for 4h at room temperature. Washing the particles under the action of a magnet to prepare PCVE-Fe 3 O 4 - (PVSt-g-PEO) composite nanoparticles. The DLS size was 30.0nm (toluene). Under transmission electron microscopy, the magnetic particles formed a parachute structure (i.e., a linear polymer chain) on one side and a rod-like structure (i.e., a large number of polyethylene glycol chains were introduced through double bonds distributed on the PVSt side chains) on the other side. Characteristic peaks of polyethylene glycol can be seen by Fourier infrared spectrum characterization, which proves that double bonds on a polymer chain are successfully introduced into polyethylene glycol side chains through click reaction. The particles have amphipathy, can be well separated in water and toluene, and can be used as a solid emulsifier.
Example 6:
10.0mg of the amino-modified gold particles prepared in preparation example 3 were dispersed in cyclohexane for use. 10.0. Mu.L of boron trifluoride was dissolved in 5.0mL of methylene chloride at 0℃and stirred uniformly, then 3.0g of methylstyrene was added thereto, and the mixture was reacted with stirring for 30 minutes to obtain a PMS active chain having a molecular weight of 36k and a DLS size of 11.0nm (methylene chloride). Slowly dripping the active chain solution into an amino modified gold dispersion liquid under the condition of ultrasound, and stopping dripping after the light pink cation characteristic color appears in the dispersion liquid to prepare the PMS-Au compound. The system was cooled to 0 ℃ for use.
10.0. Mu.L of tin tetrachloride was dissolved in 5.0mL of cyclohexane at room temperature, stirred uniformly, cooled to 0℃and 1.0g of vinyl ether styrene was added thereto, and stirred and reacted for 30 minutes to give PVBVE active chain having a molecular weight of 9k and a DLS size of 5.0nm (methylene chloride). Slowly dripping the active chain solution into the reaction system containing PMS-Au under the condition of ultrasound, and stopping dripping after pale yellow cation characteristic color 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. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the particles, which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Example 7:
10.0mg of the amino-modified silica particles prepared in preparation example 4 were dispersed in cyclohexane for use.
The procedure was the same as in example 6 except that the amino-modified silica particles of preparation example 4 were used, to obtain PMS-SiO 2 PVBVE composite nanoparticles. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Example 8:
10.0mg of aminopropyl triethoxysilane modified cobalt nanoparticles prepared in preparation example 5 were dispersed in cyclohexane for use.
The procedure of example 6 was followed except that the aminopropyl triethoxysilane-modified cobalt nanoparticle of preparation 5 was used, to prepare a PMS-Co-PVBVE composite nanoparticle. The DLS size was 24.0nm (dichloromethane). Under a transmission electron microscope, parachute structures are formed on two sides of the magnetic particles, which indicates that the polymer double chains are successfully grafted to the surfaces of the particles.
Claims (19)
1. A polymer double strand/inorganic nanoparticle asymmetric composite comprising a composite structure of a polymer single strand a-inorganic nanoparticle-polymer single strand B, wherein the polymer single strand a and the polymer single strand B are connected to the inorganic nanoparticle at a chain tail end by a chemical bond, a kind of monomer units constituting the polymer single strand a is different from a kind of monomer units constituting the polymer single strand B, the polymer single strand a and the polymer single strand B each independently optionally further comprising a functional segment or a functional group; one of the polymer single chain a and the polymer single chain B contains a structural unit derived from a styrenic monomer, and the other contains a structural unit derived from a vinyl ether monomer;
the size of the polymer single strand A is larger than that of the polymer single strand B;
the inorganic nano particles are selected from metals, metal compounds and nonmetallic compounds, and the particle size of the inorganic nano particles is 1-20nm.
2. The composite of claim 1, wherein the metal is selected from Au, ag, pt, pd, fe, co, ni, sn, in and alloys thereof; the metal compound is selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 、SrTiO 3 The method comprises the steps of carrying out a first treatment on the surface of the The nonmetallic compound is SiO 2 。
3. The composite of claim 1 or 2, wherein the inorganic nanoparticle surface has amino groups.
4. The compound of claim 1 or 2, wherein the styrenic monomer is selected from styrene, C 1-5 Alkyl-substituted styrenes, C 1-5 Alkenyl-substituted styrenesHalogen-substituted C 1-5 Alkyl-substituted styrenes, halogen-substituted C 1-5 One or more of alkenyl-substituted styrenes, acrylate-based vinylbenzenes; 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 vinyl and acrylic ester vinyl ether.
5. The compound of claim 1 or 2, wherein the monomers forming polymer strands 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, a-methylstyrene, chloromethylstyrene, 4- (vinyl phenyl) -1-butene (VSt), acrylate vinyl benzene.
6. The compound according to claim 1 or 2, wherein one of the polymer single chain a and the polymer single chain B is constituted of a structural unit derived from a styrenic monomer, and the other is constituted of a structural unit derived from a vinyl ether-based monomer.
7. The complex according to claim 1 or 2, wherein the degree of polymerization of polymer single strand a and polymer single strand B is each independently 10-10000; the sizes of the polymer single strand A and the polymer single strand B are each independently 1-20nm.
8. The composite according to claim 1 or 2, wherein the degree of polymerization of polymer single strand a and polymer single strand B is each independently 50-1000.
9. The composite of claim 1 or 2, wherein the functional segments comprise polyethylene glycol segments, PNIPAM segments, PDMAEMA segments, and/or pdeae ema segments; the functional group is selected from at least one of carboxyl, amino, hydroxyl, halogen and silane groups.
10. A method of preparing a complex according to any one of claims 1-9, the method comprising:
the inorganic nano particles are modified to obtain amino groups on the surface, and the inorganic nano particles with the amino groups 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 through cationic polymerization;
adding the polymer single-chain A with the active center at the tail end into the inorganic nanoparticle dispersion liquid to obtain a dispersion liquid containing a polymer single-chain A-inorganic nanoparticle 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 nanoparticle composite to obtain the polymer single-chain A-inorganic nanoparticle-polymer single-chain B composite.
11. The method of claim 10, wherein the modification of the inorganic nanoparticles is performed by aminosilane.
12. The preparation method according to claim 10 or 11, 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.
13. The method according to claim 12, wherein the substance providing a functional segment or a functional group is at least one selected from the group consisting of N-bromosuccinimide, mercaptoacetic acid, mercaptoethylamine, mercaptoethanol, mercaptopolyethylene glycol, mercaptopoly (N-isopropylacrylamide), mercaptopoly-N, N-dimethylaminoethyl methacrylate, mercaptopoly-N, N-diethylaminoethyl methacrylate, and 3-mercaptopropyltrimethoxysilane.
14. The process according to claim 10 or 11, wherein the initiator for cationic polymerization is selected from boron trifluoride, aluminum trichloride, zinc dichloride, titanium tetrachloride, tin tetrachloride, antimony trichloride, chromium tetrachloride, iron trichloride, aluminum alkyl chloride, trifluoromethanesulfonic acid, HCl, HI/I 2 、HI/ZnI 2 、HI/ZnBr 2 、AlEt 2 Cl、EtAlCl 2 Any of EtOAc.
15. The production method according to claim 10 or 11, wherein the temperature during the production is controlled in the range of-100 ℃ to 100 ℃; the polymerization time of the single strand of polymer is 1 to 60 minutes.
16. The preparation method according to claim 10 or 11, wherein the solid content in the dispersion liquid containing the polymer single-chain a-inorganic nanoparticle composite is 1 to 40%.
17. The production method according to claim 12, wherein the modification is performed by a click reaction of the carbon-carbon double bond in the polymer single chain a and/or B with a substance providing a functional segment or a functional group.
18. The production process according to claim 10 or 11, wherein the initiator of cationic polymerization is tin tetrachloride or boron trifluoride; the temperature in the preparation process is controlled in the range of-50 ℃ to 40 ℃; the polymerization time of the single strand of polymer is 5-20 minutes.
19. The method of preparing according to claim 16, wherein the solid content in the dispersion liquid comprising the polymer single-chain a-inorganic nanoparticle composite is 5 to 30%.
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