CN113563684B - Amphiphilic single-chain Janus composite nanoparticle and preparation method and application thereof - Google Patents
Amphiphilic single-chain Janus composite nanoparticle and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an amphiphilic single-chain Janus composite nanoparticle and a preparation method and application thereof. The composite nano-particles comprise oleophylic macromolecule single chains, polymer molecule brushes, hydrophilic macromolecule single chains and inorganic nano-particles compounded on the polymer molecule brushes in situ. Sequentially adding lipophilic monomers, macromonomers and hydrophilic monomers according to an active sequence by using an anion active polymerization method, and carrying out sectional polymerization to obtain a polymer with a polymer molecular brush in the middle and hydrophilic chain segments and lipophilic chain segment structures at the end parts; and modifying the polymer molecular brush in the polymer, introducing carboxyl, and carrying out in-situ composite growth on inorganic nano particles to obtain the composite nano particles. The invention realizes the mass preparation of the amphiphilic single-chain Janus composite nano-particles, combines the excellent properties of the composite material and the nano-material, and has important significance in the fields of catalysis, drug controlled release, enzyme immobilization, pollutant treatment and the like.
Description
Technical Field
The invention belongs to the technical field of inorganic, organic and high polymer materials, and particularly relates to an amphiphilic single-chain Janus composite nanoparticle as well as a preparation method and application thereof.
Background
The Single-Chain Janus composite Nanoparticles integrate Polymer performance and nanoparticle function, and especially tadpole-shaped asymmetric Nanoparticles taking functional solid Nanoparticles as heads and Single-Chain polymers as tails attract attention (J.A. Pomposo, single-Chain Polymer Nanoparticles: synthesis, characterisation, simulination, and applications.first edition; wiley-VCH: weinheim, 2017). By selecting different nano particles and polymer chains, the performance of the nano particles can be widely adjusted. There is an urgent need to precisely design single-chain Janus composite nanoparticles and develop a new method for batch preparation thereof. Currently, intramolecular cross-linking of macromolecules, especially block macromolecules, is a common method for preparing such composite nanoparticles (s.mavila, o.eivgi, i.berkovich, n.g.lemcof, chem.rev.2016,116, 878-961). However, this method needs to be carried out in a very dilute polymer solution, otherwise intermolecular crosslinking occurs to cause a gel phenomenon. Recently, we propose a new method of intramolecular cross-linking based on electrostatic interaction regulation, enabling the preparation of single-chain nanoparticles in concentrated solution (d.xiang, x.chen, l.tang, b.y.jiang, z.z.yang, CCS chem.2019,1, 407-430). In order to generate the functionality, the nanoparticles are required to be used as a micro reactor for further composite growth. The method has complicated steps, and relates to a multi-step separation process, so that the preparation efficiency is low. In addition, the choice of block polymer structures and compositions is limited, limiting the microstructural design of single-chain Janus composite nanoparticles. Both of these aspects severely limit the wide engineering applications of such materials. Therefore, the design of a novel structure of the single-chain Janus composite nanoparticle and a low-cost and efficient preparation method thereof are problems to be solved at present.
Disclosure of Invention
The invention provides an amphiphilic single-chain Janus composite nanoparticle which comprises an oleophylic high-molecular single chain, a polymer molecular brush, a hydrophilic high-molecular single chain and an inorganic nanoparticle compounded on the polymer molecular brush in situ.
Preferably, the inorganic nanoparticles are growth-complexed in situ through the carboxyl modified ends of the polymer molecular brush. Preferably, the carboxyl modified end of the polymer molecular brush can introduce carboxyl to the polymer molecular brush through thiol-double bond click reaction.
According to an embodiment of the present invention, the lipophilic single-chain polymer is located at one end of the polymer molecular brush, and the hydrophilic single-chain polymer is located at the other end of the polymer molecular brush. Preferably, the number of the hydrophilic macromolecule single chains and the number of the lipophilic macromolecule single chains are both one.
According to an embodiment of the present invention, the polymer molecular brush is obtained by introducing a macromonomer into the single-chain end of the lipophilic macromolecule for polymerization.
Preferably, the macromonomer is polymerized from a monomer X and a monomer Y. For example, the monomer X may be selected from anionic living polymerization monomers, such as at least one selected from 4- (vinylphenyl) -1-butene, isoprene, butadiene and the like. For example, the monomer Y is at least one selected from 4- (chlorodimethylsilyl) styrene, 4-chloromethylstyrene, etc.
According to an embodiment of the present invention, the hydrophilic polymer single-chain polymerized monomer may be at least one of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, oligoethyleneglycolmethylether methacrylate, ethyleneglycol methylether acrylate, N-dimethylacrylamide, N-diethylacrylamide, N-ethylmethacrylamide, N-methacryloyl-N '-methylpiperazine, N-acryloyl-N' -methylpiperazine, dimethylaminoethyl methacrylate, glycidyl methacrylate, ethylene oxide, propylene oxide, butylene oxide, and the like; 2- (2-methoxyethoxy) ethyl 2-methyl-2-acrylate, dimethylaminoethyl methacrylate or glycidyl methacrylate are preferred.
According to an embodiment of the present invention, the lipophilic polymeric single chain monomer may be a styrenic monomer, such as at least one of styrene, p-methylstyrene, α -methylstyrene, and the like, illustratively styrene.
According to an embodiment of the present invention, the degree of polymerization of the hydrophilic polymer single chain is 30 to 1000, such as 35 to 500, further such as 40 to 200, exemplary 35, 50, 80, 100, 120, 150.
According to an embodiment of the invention, the degree of polymerization of said lipophilic polymeric single chains is in the range of 30 to 1000, such as 35 to 500, further such as 40 to 200, exemplary 40, 46, 60, 100.
According to an embodiment of the invention, the degree of polymerization of the polymer molecular brush is in the range of 5 to 500, such as 8 to 200, further such as 10 to 150, exemplary 10, 25, 50, 100.
According to an embodiment of the present invention, the inorganic nanoparticles may be selected from at least one of metal, metal compound, and nonmetal compound nanoparticles.
For example, the metal may be selected from at least one of Au, ag, pt, pd, fe, co, ni, sn, in, and alloys thereof; preferably Au, ni, pd, fe or Co.
For example, the metal compound may be selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 、SrTiO 3 At least one of CdS, znS, pbS, cdTe and CdSe; preferably Fe 3 O 4 、TiO 2 Or Al 2 O 3 。
For example, the non-metallic compound is SiO 2 。
According to an embodiment of the invention, the inorganic nanoparticles have an average particle size of 5-30nm, such as 10-25nm, exemplary 10nm, 15nm, 20nm.
According to an exemplary embodiment of the present invention, the amphiphilic single-chain Janus composite nanoparticle may be a polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, a polystyrene-gold-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, a polystyrene-nickel-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, a polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, or a polystyrene-ferroferric oxide-polyglycidyl methacrylate Janus composite nanoparticle.
The invention also provides a preparation method of the amphiphilic single-chain Janus composite nanoparticle, which comprises the following steps: sequentially adding lipophilic monomers, macromonomers and hydrophilic monomers according to an active sequence by using an anion active polymerization method, and carrying out segmented polymerization to obtain a polymer with a polymer molecular brush in the middle, wherein one end of the polymer molecular brush is a hydrophilic chain segment, and the other end of the polymer molecular brush is a lipophilic chain segment structure; and modifying a polymer molecular brush in the polymer, introducing carboxyl, and carrying out in-situ composite growth on inorganic nanoparticles to obtain the amphiphilic single-chain Janus composite nanoparticles.
Preferably, the lipophilic monomer has the same meaning as the above-mentioned polymeric monomer of the lipophilic macromolecule single chain. The hydrophilic monomer has the same meaning as the hydrophilic polymer single-chain polymerized monomer. The macromer and inorganic nanoparticles have the meanings as described above.
According to an embodiment of the present invention, the preparation method comprises the steps of:
step 1), under the action of an initiator, carrying out anion active polymerization on a monomer X, and adding a monomer Y to terminate anion active species to obtain a macromonomer;
the monomer X and the monomer Y have the meanings as described above;
step 2), under the action of an initiator, carrying out anion active polymerization reaction on a polymerized monomer of the oleophylic high-molecular single chain to obtain the oleophylic high-molecular single chain;
step 3), adding the macromonomer obtained in the step 1) into the reaction system obtained in the step 2), and continuously initiating the end of the oleophylic macromolecule single chain to generate a polymer molecular brush;
step 4), adding a hydrophilic polymer single-chain polymerization monomer into the reaction system in the step 3), and continuously initiating the tail end of the polymer molecular brush to generate a hydrophilic polymer single-chain to obtain a polymer with a middle polymer molecular brush, wherein one end of the polymer is a hydrophilic chain segment, and the other end of the polymer is a lipophilic chain segment structure, and the polymer is marked as a polymer C with a lipophilic chain-polymer molecular brush-hydrophilic chain composite structure;
and 5) modifying the polymer molecular brush in the polymer C, introducing carboxyl, and carrying out in-situ composite growth on inorganic nanoparticles to obtain the amphiphilic single-chain Janus composite nanoparticles.
According to an embodiment of the present invention, in step 1) and/or step 2), the initiator is at least one of n-butyllithium, t-butyllithium, and the like.
According to an embodiment of the present invention, in step 1), the concentration of the monomer X in the reaction system of the anionic living polymerization reaction is 1 to 40wt%, preferably 10 to 20wt%, and exemplarily 10wt%, 15wt%, 20wt%, 30wt%.
According to an embodiment of the present invention, in step 1), the molar ratio of initiator to monomer depends on the degree of polymerization of the macromonomer, as will be appreciated by those skilled in the art. For example, the molar ratio of the monomer X to the initiator is 10 to 50, such as 20 to 40, and is exemplified by 20. The monomer Y is a polymerization terminator, and the molar ratio of the monomer Y to the initiator is 1-10.
According to an embodiment of the invention, the temperature of the anionic living polymerization reaction in step 1) is in the range of-85 to-70 deg.C, such as-80 to-75 deg.C, and is exemplary-78 deg.C.
Wherein the anionic living polymerization reaction time is 10-30min, such as 15-25min, exemplary 20min.
Wherein the anionic living polymerization reaction is carried out under vigorous stirring conditions, for example, at a stirring speed of 400 to 600rpm, preferably 500rpm.
According to an embodiment of the present invention, in step 1), the anionic living polymerization reaction solution is added dropwise to the monomer Y under stirring.
According to an embodiment of the present invention, in step 1), the number average molecular weight of the macromonomer is (2-12). Times.10 3 E.g. (3-10). Times.10 3 Exemplary is 3 × 10 3 ，3.1×10 3 ，5×10 3 ，6×10 3 ，7×10 3 ，7.8×10 3 g/mol，8×10 3 ，9×10 3 ，10×10 3 。
According to an embodiment of the invention, in step 1), the DLS size of the macromer in tetrahydrofuran solvent is 1-8nm, such as 2-6nm, exemplary 2nm, 3nm, 4nm, 5nm, 6nm.
According to an embodiment of the invention, the temperature of the anionic living polymerization reaction in step 2) is in the range of-85 to-70 deg.C, such as-80 to-75 deg.C, and is exemplary-78 deg.C.
Wherein the anionic living polymerization reaction time is 10-30min, such as 15-25min, exemplary 20min.
According to an embodiment of the present invention, in step 2), the concentration of the polymerized monomer of the lipophilic macromolecule single chain in the anionic living polymerization reaction system is 0.5-3wt%, such as 0.8-2wt%, exemplarily 0.8wt%,1wt%,1.2wt%,1.5wt%.
According to an embodiment of the present invention, in step 2), the number average molecular weight of the lipophilic single-chain is (2-6). Times.10 3 E.g. (3-5). Times.10 3 Exemplary is 3 × 10 3 ，4×10 3 ，4.8×10 3 ，5×10 3 ，6×10 3 。
According to an embodiment of the invention, in step 2), the DLS size of the lipophilic polymeric single chain in tetrahydrofuran solvent is 1-5nm, such as 2-4nm, exemplary 2nm, 3nm, 4nm.
According to an embodiment of the invention, in step 3), the concentration of the macromonomer in the anionic living polymerization system is 5 to 20wt%, for example 10 to 15wt%, illustratively 10wt%,12wt%,15wt%.
According to an embodiment of the present invention, in step 3), the temperature of the reaction is the same as the temperature of the reaction system in step 2). Wherein the reaction time is 10-30min, such as 15-25min, exemplary 20min.
According to an embodiment of the present invention, in step 3), the number average molecular weight of the polymer molecular brush is (40 to 110) × 10 3 E.g. (60-100). Times.10 3 Exemplary is 60 × 10 3 ，70×10 3 ，78.2×10 3 ，80×10 3 ，90×10 3 ，95×10 3 ，95.2×10 3 。
According to an embodiment of the invention, in step 3), the DLS size of the polymer molecular brush in tetrahydrofuran solvent is 7-15nm, such as 8-12nm, exemplary 8nm, 9nm, 10nm, 11nm, 12nm, 13nm.
According to an embodiment of the present invention, in step 4), the concentration of the polymerized monomer of the hydrophilic polymer single chain in the anionic living polymerization reaction system is 0.5 to 3wt%, for example, 0.8 to 2wt%, illustratively 0.8wt%,1wt%,1.2wt%,1.5wt%.
According to an embodiment of the present invention, when the polymerized monomer of the hydrophilic polymer single strand is selected from oligoethylene glycol methyl ether methacrylate in step 4), the average number average molecular weight of the oligoethylene glycol methyl ether methacrylate may be selected from 200 to 5000, for example 300, 475, 950 or 4000.
When the hydrophilic polymeric single-chain monomer is selected from polyethylene glycol methyl ether acrylate, the average molecular weight of the polyethylene glycol methyl ether acrylate may be selected from 400 to 40000, such as 480, 1000, 2000, 4000, 5000, 10000, 20000 or 30000.
According to an embodiment of the present invention, in the step 4), the temperature of the reaction is the same as that of the reaction system of the step 3). Wherein the reaction time is 1-4h, such as 1.5-3h, exemplary 2h.
According to an embodiment of the present invention, in step 4), the number average molecular weight of the polymer C is (60 to 120) × 10 3 E.g., (80-110). Times.10 3 Exemplary is 80 × 10 3 ，84.7×10 3 ，85×10 3 ，90×10 3 ，100×10 3 。
According to an embodiment of the invention, in step 4), the polymer C brush has a DLS size in tetrahydrofuran solvent of 7-18nm, such as 10-15nm, exemplary 10nm, 13nm, 15nm.
According to an embodiment of the present invention, in step 5), the modification is to introduce carboxyl groups to the side chains of the polymer brush by using a thiol-double bond click reaction.
Preferably, the mercapto compound used in the mercapto-double bond click reaction may be selected from thioglycolic acid and/or mercaptopropionic acid.
Preferably, the thiol-double bond click reaction is performed with an initiator, for example a photoinitiator, such as 2, 2-dimethoxy-2-phenylacetophenone.
Preferably, the molar ratio of the mercapto compound to the double bonds contained in polymer C is 1-2, illustratively 1.2.
Preferably, the initiator is present in a molar ratio of 1 to 5%, exemplarily 2%, of the double bonds present in polymer C.
Preferably, the thiol-double bond click reaction is initiated under ultraviolet illumination.
Preferably, the temperature of the thiol-double bond click reaction is 15-40 ℃, such as 20-35 ℃, exemplary 25 ℃,30 ℃.
Preferably, the thiol-double bond click reaction is carried out for a time of 2 to 6h, such as 3 to 5h, exemplary 3h, 4h, 5h.
According to an embodiment of the present invention, in step 5), the in-situ growth of the inorganic nanoparticles may be performed using a method known in the art.
According to an embodiment of the present invention, the reaction system of steps 1) -5) further comprises a reaction solvent, for example, the reaction solvent is an organic solvent, preferably at least one of Tetrahydrofuran (THF), N-Dimethylformamide (DMF).
According to an embodiment of the present invention, the preparation method of the amphiphilic single-chain Janus composite nanoparticle comprises the following steps:
step 1), under the action of an initiator, carrying out anion active polymerization on 4- (vinyl phenyl) -1-butene, and adding 4- (chlorodimethylsilyl) styrene to terminate anion active species to obtain a macromonomer;
step 2), under the action of an initiator, carrying out anion active polymerization reaction on a polymerization monomer of the oleophylic high-molecular single chain to obtain an oleophylic high-molecular single chain;
step 3), adding the macromonomer obtained in the step 1) into the reaction system obtained in the step 2), and continuously initiating at the tail end of the oleophylic macromolecule single chain to generate a polymer molecular brush;
step 4), adding a hydrophilic polymer single-chain polymerization monomer into the reaction system in the step 3), and continuously initiating the tail end of the polymer molecular brush to generate a hydrophilic polymer single-chain to obtain a polymer with a middle polymer molecular brush, wherein one end of the polymer is a hydrophilic chain segment, and the other end of the polymer is a lipophilic chain segment structure, and the polymer is marked as a polymer C with a lipophilic chain-polymer molecular brush-hydrophilic chain composite structure;
and 5) modifying the polymer molecular brush in the polymer C by using a sulfydryl-double bond click reaction to introduce carboxyl, and carrying out in-situ composite growth on inorganic nanoparticles to obtain the amphiphilic single-chain Janus composite nanoparticles.
The invention also provides the amphiphilic single-chain Janus composite nanoparticle prepared by the method.
The invention also provides application of the amphiphilic single-chain Janus composite nano-particle in the fields of catalysis, drug controlled release, enzyme immobilization, product separation, pollutant treatment and the like.
The invention has the beneficial effects that:
the invention provides an amphiphilic single-chain Janus composite nanoparticle and a preparation method thereof, which realize the mass preparation of the amphiphilic single-chain Janus composite nanoparticle, combine the excellent performances of an oleophylic and hydrophilic high-molecular single chain and a nanomaterial to ensure that the composite material has high performance, and the composite nanoparticle has important application value in the fields of catalysis, drug controlled release, enzyme fixation, product separation, pollutant treatment and the like.
Drawings
Fig. 1 is a TEM topography of the composite nanoparticle prepared in example 2.
Fig. 2 is a TEM topography of the composite nanoparticle prepared in example 4.
Fig. 3 is a schematic diagram of the preparation of composite nanoparticles of example 1.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1 polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles
1) 10mL of THF and 1mL of n-BuLi were added in this order, and 1mL of VSt monomer was added at-78 ℃ under vigorous stirring at 500rpm and reacted for 20min. Dropwise adding an anionic active species into the VSt monomer polymerization system under stirring: 1mL CDMSS monomer and 1mL THF mixture. And purifying the crude product obtained by polymerization in absolute ethyl alcohol for 3 times, and drying in vacuum to obtain the macromonomer. The number average molecular weight of the macromer was 7.8k, and the DLS size was 3nm (tetrahydrofuran as solvent).
2) 10mL THF and 0.1mL styrene are added in turn, 6.7 μ L initiator n-BuLi (0.01 mmol) is added under-78 deg.C condition, reaction is carried out for 20min, and polystyrene, i.e. lipophilic macromolecule single chain, is obtained. The number average molecular weight of polystyrene is 4.8k, the DLS size is 2nm (tetrahydrofuran is used as a solvent), and the polymerization degree of the oleophylic macromolecule single chain is 46.
3) Adding 1g of the macromolecular monomer into the system obtained in the step 2), reacting for 20min, and continuously initiating at the tail end of the oleophylic macromolecular single chain to generate the polymer molecular brush. The number average molecular weight of the polymer molecular brush was 78.2k, the dls size was 11nm (tetrahydrofuran as a solvent), and the polymerization degree of the polymer molecular brush was 10.
4) Adding 0.1mL of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester (MEO) into the system in the step 3) 2 MA) and reacting for 2h, and continuously initiating to generate a hydrophilic macromolecule single chain at the tail end of the polymer molecular brush to obtain a polymer C with a lipophilic chain-polymer molecular brush-hydrophilic chain composite structure. The molecular weight of polymer C was 84.7k, the DLS size was 13nm (tetrahydrofuran), and the degree of polymerization of the hydrophilic polymer single chain was 35.
5) 2, 2-dimethoxy-2-phenylacetophenone is taken as a photoinitiator, and the 3-mercaptopropionic acid and the double bonds of the polymer molecular brush side chains of the polymer C are subjected to click reaction:
adding 5mL of N, N-dimethylformamide, 50 mu L of 3-mercaptoacetic acid and 3mg of 2, 2-dimethoxy-2-phenylacetophenone into a single-mouth bottle in sequence, introducing nitrogen for 30min to remove oxygen, initiating a reaction under the irradiation of a 365nm ultraviolet lamp, slowly dropwise adding a 1mLDMF solution of 100mg of polymer C (containing 0.57mmol of double bonds), and reacting at room temperature for 4h. The crude product was purified 3 times in anhydrous ethanol and dried under vacuum to obtain a carboxyl group-introduced polymer.
0.3g of the polymer to which a carboxyl group was introduced was dissolved in 300mL of N, N-dimethylformamide, stirred at room temperature and purged with nitrogen for 1 hour. 87.6mg of ferrous sulfate heptahydrate and 170.1mg of ferric chloride hexahydrate in a molar ratio of 1. And then heating the reaction to 83 ℃ by using an oil bath, adding 26.25mL of ammonia water into the reaction system in batches, and rapidly stirring for about 1h to obtain the polystyrene-ferroferric oxide-poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nano particles.
The preparation process of this example is shown in FIG. 3. The structure with a plurality of branched chains is a polymer molecular brush, one end of the polymer molecular brush is connected with a lipophilic single chain, and the other end of the polymer molecular brush is connected with a hydrophilic single chain. Ferroferric oxide is compounded on the polymer molecular brush in situ.
Example 2 polystyrene-gold-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles
Steps 1) -4) are the same as in example 1. The carboxyl group-introduced polymer (10 mg) obtained in step 5) of example 1 was dissolved in 10mL of DMF, and HAuCl was added 4 ·3H 2 O, COOH and HAuCl in a polymer having carboxyl groups introduced therein 4 ·3H 2 The molar ratio of O is 1. The mixture was stirred at room temperature overnight to allow the gold chlorate ions to be adsorbed sufficiently by COOH. And dialyzing the mixture with water to remove unadsorbed gold chlorate ions, dissolving the mixture in DMF again after freeze-drying, and reducing the mixture for 12 hours under the irradiation of an ultraviolet lamp with the wavelength of 303nm to obtain the polystyrene-gold-poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles.
TEM shows the existence of about 10nm nano particles, and proves that the polymer molecular brush is partially made of the successfully-compounded alloy nano particles (see figure 1).
Example 3 polystyrene-Nickel-Poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles
Steps 1) -4) are the same as in example 1. The carboxyl group-introduced polymer (2 mg) obtained in step 5) of example 1 was dissolved in 4.0mL of DMF, and nickel nitrate (Ni (NO) was added 3 ) 2 ·6H 2 O) in DMF (0.01mL, 50.0 mg/mL), and stirred overnight at room temperature to allow Ni to settle 2+ Sufficiently adsorb to the micro-regions where the nanoparticles are cross-linked. Dialysis to remove free Ni (NO) 3 ) 2 Thereafter, the polymer was redispersed in DMF and NaBH was added 4 In DMF (100. Mu.L, 5.0 mg/mL), and reduced at room temperature for 24h. Collecting the product with a magnet and washing with water for multiple times to obtain the polystyrene-nickel-poly (2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nano particles。
Example 4 polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles
1) 10mL of THF and 2mL of n-BuLi were added in this order, and 1mL of VSt monomer was added at-78 ℃ under vigorous stirring at 500rpm and reacted for 20min. Dropwise adding an anionic active species into the VSt monomer polymerization system under stirring: a mixture of 2mL CDMSS monomer and 2mL THF. And purifying the crude product obtained by polymerization in absolute ethyl alcohol for 3 times, and drying in vacuum to obtain the macromonomer. The number average molecular weight of the macromer was 3.1k and the DLS size was 2nm (tetrahydrofuran as solvent).
Subsequent steps were performed in the same manner as in steps 2) to 5) of example 1 to obtain polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticles. Transmission Electron Microscope (TEM) shows that about 15nm of nano particles exist, and proves that the polymer molecular brush part successfully compounds Fe 3 O 4 (see FIG. 2).
Example 5 polystyrene-ferroferric oxide-polyglycidyl methacrylate Janus composite nanoparticles
A polystyrene-polymer molecular brush was obtained in the same manner as in steps 1) to 3) of example 1.
In the step 4), 0.1mL of glycidyl methacrylate is added into the reaction system in the step 3) and reacted for 2h to obtain a polymer C. The number average molecular weight of the polymer C was 95.2k, the DLS size was 13nm (tetrahydrofuran as a solvent), and the degree of polymerization of the hydrophilic polymer single chain was 120.
The subsequent steps are to prepare the polystyrene-ferroferric oxide-polyglycidyl methacrylate Janus composite nano particles by the same method as the step 5) in the embodiment 1.
Particularly, the invention belongs to the pioneering invention, and the amphiphilic single-chain Janus composite nanoparticles which are most easily applied to the industry are exemplarily described in the examples, but from the mechanism and illustration described in the description of the invention, those skilled in the art can foresee that the inventive idea can be easily applied to the preparation of other amphiphilic single-chain Janus composite nanoparticles, and the application of the prepared amphiphilic single-chain Janus composite nanoparticles to the fields of catalysis, drug controlled release, enzyme immobilization and product separation, pollutant treatment, and the like.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (18)
1. A preparation method of an amphiphilic single-chain Janus composite nanoparticle is characterized by comprising the following steps: sequentially adding lipophilic monomers, macromonomers and hydrophilic monomers according to the active sequence by using an anion active polymerization method, and carrying out sectional polymerization to obtain a polymer with a polymer molecular brush in the middle, wherein one end of the polymer molecular brush is a hydrophilic chain segment, and the other end of the polymer molecular brush is a lipophilic chain segment structure; modifying a polymer molecular brush in the polymer, introducing carboxyl, and carrying out in-situ composite growth on inorganic nanoparticles to obtain the amphiphilic single-chain Janus composite nanoparticles;
the hydrophilic monomer is at least one of 2-methyl-2-acrylic acid-2- (2-methoxyethoxy) ethyl ester, oligoethylene glycol monomethyl ether methacrylate, ethylene glycol methyl ether acrylate, N-dimethylacrylamide, N-diethylacrylamide, N-ethyl methacrylamide, N-methacryl-N '-methylpiperazine, N-acryl-N' -methylpiperazine, dimethylaminoethyl methacrylate, ethylene oxide, propylene oxide and butylene oxide;
the oleophylic monomer is at least one of styrene, p-methylstyrene and alpha-methylstyrene;
the macromonomer is prepared by the following method: under the action of an initiator, carrying out anion active polymerization reaction on the monomer X, and adding the monomer Y to terminate the anion active species to obtain a macromonomer; the monomer X is selected from at least one of 4- (vinyl phenyl) -1-butylene, isoprene and butadiene, and the monomer Y is selected from at least one of 4- (chloro dimethyl silyl) styrene and 4-chloromethyl styrene;
the inorganic nanoparticles are at least one selected from metal, metal compound and nonmetal compound nanoparticles;
the amphiphilic single-chain Janus composite nanoparticle comprises an oleophylic high-molecular single chain, a polymer molecular brush, a hydrophilic high-molecular single chain and an inorganic nanoparticle compounded on the polymer molecular brush in situ.
2. The method according to claim 1, wherein the number of the hydrophilic polymer single chains and the number of the lipophilic polymer single chains are both one.
3. The method for preparing composite nanoparticles according to claim 1, wherein the degree of polymerization of the hydrophilic polymer single chains is 30 to 1000;
and/or the polymerization degree of the oleophylic macromolecule single chain is 30-1000;
and/or the degree of polymerization of the polymer molecular brush is 5-500;
and/or, the metal is selected from at least one of Au, ag, pt, pd, fe, co, ni, sn, in and alloy thereof;
and/or, the metal compound is selected from Fe 3 O 4 、TiO 2 、Al 2 O 3 、BaTiO 3 、SrTiO 3 At least one of CdS, znS, pbS, cdTe and CdSe;
and/or, the non-metallic compound is SiO 2 ；
And/or the inorganic nanoparticles have an average particle size of 5-30nm.
4. The method of any one of claims 1-3, wherein the amphiphilic single-chain Janus composite nanoparticle is a polystyrene-ferroferric oxide-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, a polystyrene-gold-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle, or a polystyrene-nickel-poly (2-methyl-2-propenoic acid-2- (2-methoxyethoxy) ethyl ester) Janus composite nanoparticle.
5. The method for preparing composite nanoparticles according to claim 1, characterized in that it comprises the following steps:
step 1), under the action of an initiator, carrying out anion living polymerization on a monomer X, and adding a monomer Y to terminate an anion living species to obtain a macromonomer;
step 2), under the action of an initiator, carrying out anion active polymerization reaction on a polymerized monomer of the oleophylic high-molecular single chain to obtain the oleophylic high-molecular single chain;
step 3), adding the macromonomer obtained in the step 1) into the reaction system obtained in the step 2), and continuously initiating the end of the oleophylic macromolecule single chain to generate a polymer molecular brush;
step 4), adding a hydrophilic polymer single-chain polymerization monomer into the reaction system in the step 3), and continuously initiating the tail end of the polymer molecular brush to generate a hydrophilic polymer single-chain to obtain a polymer with a middle polymer molecular brush, wherein one end of the polymer is a hydrophilic chain segment, and the other end of the polymer is a lipophilic chain segment structure, and the polymer is marked as a polymer C with a lipophilic chain-polymer molecular brush-hydrophilic chain composite structure;
and 5) modifying the polymer molecular brush in the polymer C, introducing carboxyl, and carrying out in-situ composite growth on inorganic nanoparticles to obtain the amphiphilic single-chain Janus composite nanoparticles.
6. The method for preparing composite nanoparticles according to claim 5, wherein in the step 1), the concentration of the monomer X in the reaction system of the anionic living polymerization reaction is 1-40wt%;
and/or the molar ratio of the monomer Y to the initiator is 1 to 10;
and/or the molar ratio of the monomer X to the initiator is 10-50;
and/or the number average molecular weight of the macromonomer is (2-12). Times.10 3 。
7. The method for preparing composite nanoparticles according to claim 5, wherein in the step 2), the concentration of the lipophilic macromolecule single-chain polymerization monomer in the anionic living polymerization reaction system is 0.5-3wt%;
the number average molecular weight of the oleophylic macromolecule single chain is (2-6) multiplied by 10 3 ；
And/or in the steps 1), 2) and 3), the temperature of the anionic active polymerization reaction is-85 to-70 ℃; the time of the anionic living polymerization reaction is 10-30min.
8. The method for preparing composite nanoparticles according to claim 5, wherein in the step 3), the concentration of the macromonomer in the anionic living polymerization reaction system is 5 to 20wt%;
and/or the number average molecular weight of the polymer molecular brush is (40-110) multiplied by 10 3 ；
And/or, in the step 4), the concentration of the hydrophilic macromolecule single-chain polymerization monomer in the anion living polymerization reaction system is 0.5-3wt%;
and/or the reaction temperature in the step 4) is the same as that in the reaction system in the step 3), and the reaction time is 1-4h;
and/or the number average molecular weight of the polymer C is (60-120) multiplied by 10 3 。
9. The method of claim 5, wherein the modification step 5) is a thiol-double bond click reaction to introduce carboxyl groups into the side chains of the polymer brush.
10. The method for preparing composite nanoparticles according to claim 9, wherein the thiol compound used in the thiol-double bond click reaction is selected from thioglycolic acid and/or mercaptopropionic acid.
11. The method of claim 9 or 10, wherein the thiol-double bond click reaction is performed with an initiator.
12. The method of claim 11, wherein the initiator is a photoinitiator.
13. The method of claim 12, wherein the initiator is 2, 2-dimethoxy-2-phenylacetophenone.
14. The method for preparing composite nanoparticles according to claim 10, wherein the molar ratio of the mercapto compound to the double bonds contained in the polymer C is 1-2.
15. The method of claim 11, wherein the initiator is present in an amount of 1 to 5% by mole relative to the double bonds of the polymer C.
16. The method of claim 9, wherein the thiol-double bond click reaction is initiated under ultraviolet light;
and/or the temperature of the sulfydryl-double bond click reaction is 15-40 ℃;
and/or the time of the sulfydryl-double bond click reaction is 2-6h.
17. The method of claim 5, wherein the reaction system of steps 1) -5) further comprises a reaction solvent.
18. The use of the amphiphilic single-chain Janus composite nanoparticles prepared by the method of any one of claims 1 to 17 in the fields of catalysis, enzyme immobilization, product separation or contaminant treatment.
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| CN106317415A (en) * | 2015-06-23 | 2017-01-11 | 中国科学院化学研究所 | Janus nano-particles based on block copolymer and preparation method thereof |
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