CN115181277B - Preparation method of metal composite polymer single-chain nano particles - Google Patents

Preparation method of metal composite polymer single-chain nano particles Download PDF

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CN115181277B
CN115181277B CN202110360024.8A CN202110360024A CN115181277B CN 115181277 B CN115181277 B CN 115181277B CN 202110360024 A CN202110360024 A CN 202110360024A CN 115181277 B CN115181277 B CN 115181277B
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CN115181277A (en
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邱东
徐薇
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Institute of Chemistry CAS
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Abstract

The invention provides a preparation method of single molecular chain nano particles, which comprises the following steps: a1 A polymer with a crosslinkable active chain segment is synthesized by taking a monomer with at least two crosslinkable active groups as a raw material through active anion polymerization; or A1') taking a monomer which has only one crosslinkable active group but contains other groups which can be converted into at least one crosslinkable active group as a raw material to carry out active anion polymerization, and then converting the groups which can be converted into the crosslinkable active groups to obtain a polymer with crosslinkable active chain segments; a2 A) introducing an electric charge into the resulting polymer; a3 Under the protection of electric charge, adding metal ions to enable the crosslinkable active chain segments in the polymer to carry out intramolecular crosslinking by utilizing the metal ions to obtain single-chain nano particles; a4 Adding a reducing agent, and reducing to obtain the single-chain nano-particles of the metal simple substance composite polymer. The invention provides a method for preparing single molecular chain nano particles with universality in a large scale.

Description

Preparation method of metal composite polymer single-chain nano particles
Technical Field
The invention relates to the technical fields of inorganic, organic and high polymer science and materials, in particular to a mass preparation method of single-chain nano particles, and more particularly relates to a preparation method of metal composite polymer single-chain nano particles.
Background
The history of intramolecular cross-linking polymers can be traced back to 1955, when Kuhn and Majer reported that cross-linking polymers in ultra-dilute polymer solutions and cross-linking between different molecules could be avoided. The polymer single-chain particles can meet the requirements of complex environments due to the unique size and the structure of obvious partition in the space, and have wide application prospects in the fields of physics, chemistry, biology and the like. The single-stranded polymer particles as nano-scale templates can be easily derivatized to other functional complexes. In the last three decades, a great deal of research has begun focusing on single-stranded nanoparticles of polymers, and a great deal of nanoparticles with precisely adjustable microstructures have been prepared. The currently commonly used method for synthesizing single molecular chain nanoparticles is mainly to carry out intramolecular cross-linking on specific segments of block polymers (Mavila, eivgi, berkovich, lemcoff. Chem. Rev. 2016, 116:878-961, gonzalez-Burgos, latorre-Sanchez, pomposo. Chem. Soc. Rev. 2015, 44:6122-6142). However, this is generally only possible in solutions with very low solids (.ltoreq.1%) or else intermolecular crosslinking occurs which leads to gel phenomena, which lead to failure in the preparation of the composite structure. The experimental conditions of dilute solutions greatly limit the mass production of SCNP, thereby limiting its large-scale application, and furthermore, to produce functionality, the composition of nanoparticles needs to be universally adjusted. Therefore, designing single-stranded nanoparticles that can be synthesized in large quantities and universally adjusting their composition are currently a problem to be solved.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of single-molecular-chain nano particles.
The preparation method of the single molecular chain nano-particles provided by the invention comprises the following steps:
a1 A polymer with a crosslinkable active chain segment is synthesized by taking a monomer with at least two crosslinkable active groups as a raw material through active anion polymerization; or (b)
A1') carrying out living anion polymerization by taking a monomer which has only one crosslinkable active group but contains other groups which can be converted into at least one crosslinkable active group as a raw material, and then converting the groups which can be converted into the crosslinkable active groups to obtain a polymer with crosslinkable active chain segments;
a2 A) introducing an electric charge into the resulting polymer;
a3 Under the protection of electric charge, adding metal ions to enable the crosslinkable active chain segments in the polymer to carry out intramolecular crosslinking by utilizing the metal ions to obtain single-chain nano particles;
a4 Adding a reducing agent to reduce metal ions in the single-chain nano particles to obtain the single-chain nano particles of the metal simple substance composite polymer.
In the above method step A1), the monomer having at least two crosslinkable reactive groups may be: at least one of 1-vinylimidazole, 2-vinylimidazole, 1-vinyl 2-pyrrolidone, acrylonitrile, methacrylonitrile, butadiene, isoprene, methyl acrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate, oligoethylene glycol (meth) acrylate (OEGMA), methyl vinyl ketone, nitroethylene, diethyl methylene malonate, ethyl α -cyanoacrylate, dicyanoethylene, ethyl α -cyano-2, 4-hexadienoate; or a mixture of the above monomers having at least two crosslinkable reactive groups with other reactive anionically polymerizable monomers, wherein the reactive anionically polymerizable monomers may be: at least one of styrene, alpha-methylstyrene, p-methylstyrene, isobutylene;
the monomer having at least two crosslinkable active groups may specifically be: 1-vinyl 2-pyrrolidone, t-butyl acrylate (tBA), mixtures of styrene and t-butyl acrylate (tBA), isoprene or acrylonitrile;
in step A1'), the monomer having only one crosslinkable active group but containing other groups which are convertible to at least one crosslinkable active group may be: alpha-methylstyrene, p-methylstyrene, isobutylene; specifically, p-methylstyrene;
the conversion may be achieved by adding an oxidizing agent, in particular potassium permanganate, to the reacted polymer;
the polymer having a crosslinkable living segment may be a homopolymer or a block copolymer having a crosslinkable living segment;
an initiator can be added in the step A1) or A1') active anionic polymerization, and the initiator can be at least one of metal sodium, metal lithium, n-butyl lithium, tertiary butyl lithium, butyl strontium, butyl calcium, butyl sodium, butyl magnesium chloride, butyl magnesium bromide, amino potassium, sodium methoxide, potassium methoxide, lithium methoxide, triethylamine, pyridine and sodium naphthalene; specifically, n-butyllithium or tert-butyllithium;
the living anionic polymerization may be performed in a solvent, which may be at least one selected from tetrahydrofuran, dioxane, pyridine, diethyl ether, cyclohexane, 1, 2-dimethoxyethane, n-pentane, n-heptane, n-hexane, n-octane, n-decane, m-trimethylbenzene, xylene, ethylbenzene, diethylbenzene, benzene, toluene, naphthalene; in particular tetrahydrofuran or cyclohexane;
the operation of step A2) is as follows: dissolving the polymer in a solvent, adding a charge introducing agent, and reacting to introduce charges into the polymer;
wherein the solid content of the polymer in the solvent can be 0.1-5%, and can be 1%;
the charge introducing agent may be selected from: at least one of chloroethane, bromoethane, iodoethane, chloropropane, bromopropane, iodopropane, chlorobutane, bromobutane, iodobutane, chloropentane, bromopentane, iodopentane, hydrogen chloride, cyanogen bromide, hydrogen iodide, sodium hydroxide, potassium hydroxide and ammonia water, and can be sodium hydroxide or hydrogen iodide;
the reaction time can be 1-30min, and can be specifically 10min;
based on the mole number of the monomer units of the high molecular chain, the charge introducing agent is generally added in an amount of 10-60% mole number, and can be specifically 40%;
in the step A3), the metal ion may be at least one of cobalt ion, silver ion, zinc ion, gold ion, nickel ion, manganese ion, calcium ion and magnesium ion;
specifically, the method can be realized by adding at least one of cobalt trichloride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt carbonate, cobalt nitrate, cobalt sulfate, silver chloride, silver bromide, silver iodide, silver nitrate, silver sulfate, zinc chloride, zinc sulfate, gold perchlorate, chloroauric acid, nickel nitrate, nickel chloride, manganese sulfate, manganese hydroxide, manganese carbonate, calcium chloride, calcium sulfate and magnesium chloride into a reaction system, and specifically can be: nickel nitrate, chloroauric acid or silver nitrate;
the metal ion feeding amount is 1-20% (mole ratio) of the number of the high molecular chain monomer units, and can be specifically 5%;
the intramolecular crosslinking is performed in a solvent, and the solvent can be at least one selected from N, N-dimethylformamide, ethanol, methanol, isopropanol, N-butanol, tetrahydrofuran, water, acetonitrile, acetone, dimethyl sulfoxide, ethyl acetate, dioxane, chloromethane, dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane and dichlorobenzene; specifically, N-Dimethylformamide (DMF);
the temperature of the intramolecular cross-linking may be-50 ℃ to 80 ℃, specifically 10 ℃ to 30 ℃, and the time of the intramolecular cross-linking may be 1 to 120min, specifically 10 to 30min, more specifically 30min;
step A4) the reducing agent may be selected from at least one of sodium borohydride, potassium borohydride, dimethylaminoborane (DMAB), lithium aluminum hydride, carbon monoxide, oxalic acid, ascorbic acid, sodium bisulfate, sodium sulfate, citric acid, tartaric acid, succinic acid, glutaric acid, cuprous naphthalate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chloroethanol, 1, 2-propanediol, cycloheptanol, cyclic ethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycollic acid, ethanethiol, triethylaluminum, triethylboron, N-dimethylaniline; specifically, sodium borohydride, dimethylaminoborane (DMAB);
the molar ratio of the addition amount of the reducing agent to the metal ions is 1:1-4:1;
the temperature of the reduction may be from 0 ℃ to 80 ℃, specifically from 10 ℃ to 40 ℃, more specifically from 20 to 30 ℃;
or A4) does not add a reducing agent, and reduces the metal ions in the single-chain nano particles under ultraviolet irradiation.
According to an embodiment of the present invention, the method for preparing the single molecular chain nanoparticle comprises the steps of:
step a 1) adding n-butyllithium and p-methylstyrene into tetrahydrofuran, carrying out polymerization reaction to obtain poly-p-methylstyrene (PMS), and oxidizing methyl into carboxyl by using potassium permanganate;
step a 2) reacting PMS with sodium hydroxide to introduce charges into PMS;
step a 3) adding a solution of nickel nitrate in N, N-Dimethylformamide (DMF) to the solution of step a 2) under the condition of charge protection, and carrying out intramolecular crosslinking reaction on the poly (p-methylstyrene) (PMS) chain to obtaincPMS single-stranded nanoparticles;
step a 4) in N, N-Dimethylformamide (DMF) solutioncIntroducing sodium borohydride into the PMS single-chain nano-particles, and reducing to obtain metal nickel composite polymer single-chain nano-particles;
according to an embodiment of the invention, the poly-p-methylstyrene (PMS) in step a 1) has a molecular weight of from 2 k to 300 k, preferably from 10 k to 100 k;
according to an embodiment of the present invention, the temperature of the polymerization reaction of step a 1) may be-90 ℃ to 30 ℃; preferably-80 ℃ to 0 ℃.
According to an embodiment of the invention, the concentration of the methylstyrene of step a 1) is from 1 to 40%, preferably from 10 to 30%.
According to an embodiment of the invention, the concentration of potassium permanganate in step a 1) is 0.01-10%, preferably 1-3%.
According to an embodiment of the invention, the overall solids content of the PMS polymer after the introduction of charge in step a 2) is between 1 and 40%, preferably between 5 and 30%.
According to an embodiment of the invention, the reaction time described in step a 2) may be from 1 to 120 minutes, preferably from 10 to 30 minutes.
According to an embodiment of the present invention, the intramolecular crosslinking reaction temperature in step a 3) may be-50 ℃ to 80 ℃; preferably 10 ℃ to 30 ℃.
According to an embodiment of the invention, the time for the crosslinking reaction described in step a 3) may be from 1 to 120min, preferably from 10 to 30min.
According to an embodiment of the invention, the temperature of the reaction in step a 4) may be from 0 ℃ to 80 ℃, preferably from 10 ℃ to 40 ℃, for example from 20 ℃ to 30 ℃.
According to an embodiment of the invention, the reaction time in step a 4) may be from 1 h to 24 h, preferably from 5 to 10 h.
The single-chain nano-particles or the metal composite polymer single-chain nano-particles prepared by the preparation method also belong to the protection scope of the invention.
According to embodiments of the present invention, the single-molecular-chain nanoparticles comprise a variety of morphologies and compositions, including spherical single-molecular-chain nanoparticles, tadpole-like single-molecular-chain nanoparticles, chain-sphere-chain single-molecular-chain nanoparticles, dumbbell-like single-molecular-chain nanoparticles, and the like; different micro-regions of the single molecular chain nanoparticle carry different functional groups.
The invention also provides a nano material, which comprises the single-molecular-chain nano particles or the metal composite polymer single-chain nano particles.
The application of the single-molecular-chain nano-particles or the metal composite polymer single-chain nano-particles or the nano-materials in catalysis, oil-water separation, environmental response, drug controlled release and catalyst carriers also belongs to the protection scope of the invention.
The invention provides a large-scale preparation method of metal composite polymer single-chain nano particles, which has the advantages of simple reaction and abundant and easily obtained raw materials. The polymer with functional blocks can be obtained through living anion polymerization reaction, and single molecular chain nano particles with universality can be prepared in large quantities. The prepared single-molecular-chain nano-particles are further modified and metal loaded to obtain the metal composite polymer single-chain nano-material, which has important significance in the fields of composite material high performance, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carrier and the like.
The invention discloses a method for preparing single molecular chain nano particles with universality in a large scale. The single molecular chain nanoparticle is prepared by using living anion polymerization, and then modifying the polymer chain with a monovalent agent to form a charged group along a crosslinkable segment, thereby achieving a more effective protection over a long period of time, and ensuring the following intramolecular crosslinking by using a polyvalent agent as a crosslinking agent in a solution of higher concentration. The polymerization activity of the single molecular chain nano-particles is controllable, and the nano-particles with different sizes and shapes, such as sphere, tadpole, chain-sphere-chain, dumbbell, and the like, can be obtained, so that the shape of the nano-particles is universally adjusted. And (3) carrying out intramolecular crosslinking on the polymer chain by utilizing metal ions to obtain single-chain nano particles with metal, and continuously reducing by using a reducing agent to obtain single-chain nano particles of the metal simple substance composite polymer, thereby endowing the polymer composite nano particles with the characteristics of magnetic response, light, electricity, catalysis and the like. The conversion rate of the polymerization reaction in each step is complete, no interference is caused to the subsequent steps, the separation of the product is simple and rapid, the process is simple, the large-scale operation can be realized, and the universal adjustable single molecular chain nano particles and the composite material thereof can be prepared.
Drawings
FIG. 1 is a block diagram of the present invention prepared in example 1cPMS@Ni magnetic compositeAnd (3) combining transmission electron microscopy images of the single-chain nano particles.
FIG. 2 is a schematic illustration of the process of example 2cTransmission electron microscopy of paa@ni magnetic composite single-stranded nanoparticles.
FIG. 3 shows the PS-stage of example 4 of the present inventionb-cTransmission electron microscope image of paa@ag composite single-stranded nanoparticles.
Detailed Description
The present invention will be described with reference to the following specific examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
The invention provides a preparation method of single molecular chain nano particles, which comprises the following steps:
a1 A polymer with a crosslinkable active chain segment is synthesized by taking a monomer with at least two crosslinkable active groups as a raw material through active anion polymerization;
a1') carrying out living anion polymerization by taking a monomer which has only one crosslinkable active group but contains other groups which can be converted into at least one crosslinkable active group as a raw material, and then converting the groups which can be converted into the crosslinkable active groups to obtain a polymer with crosslinkable active chain segments; or (b)
A2 Introducing a charge to the crosslinkable active segment in the resulting polymer;
a3 Under the effect of charge protection, adding metal ions to enable the crosslinkable active chain segments in the polymer to carry out intramolecular crosslinking by utilizing the metal ions to obtain single-chain nano particles;
a4 Adding a reducing agent to reduce metal ions in the single-chain nano particles to obtain the single-chain nano particles of the metal simple substance composite polymer.
In the above method step A1), the monomer having at least two crosslinkable reactive groups may be: at least one of 1-vinylimidazole, 2-vinylimidazole, 1-vinyl 2-pyrrolidone, acrylonitrile, methacrylonitrile, butadiene, isoprene, methyl acrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate, oligoethylene glycol (meth) acrylate (OEGMA), methyl vinyl ketone, nitroethylene, diethyl methylene malonate, ethyl α -cyanoacrylate, dicyanoethylene, ethyl α -cyano-2, 4-hexadienoate; or a mixture of the above monomers having at least two crosslinkable reactive groups with other reactive anionically polymerizable monomers, wherein the reactive anionically polymerizable monomers can be: at least one of styrene, alpha-methylstyrene, p-methylstyrene, isobutylene;
the monomer having at least two crosslinkable active groups may specifically be: 1-vinyl 2-pyrrolidone, t-butyl acrylate (tBA), mixtures of styrene and t-butyl acrylate (tBA), isoprene or acrylonitrile;
in step A1'), the monomer having only one crosslinkable active group but containing other groups which are convertible to at least one crosslinkable active group may be: alpha-methylstyrene, p-methylstyrene, isobutylene; specifically, p-methylstyrene;
the conversion may be achieved by adding an oxidizing agent, in particular potassium permanganate, to the reacted polymer;
the polymer having a crosslinkable living segment may be selected from homopolymers or block copolymers having a crosslinkable living segment;
an initiator can be added in the living anion polymerization in the step A1), and the initiator can be at least one of metal sodium, metal lithium, n-butyl lithium, tertiary butyl lithium, butyl strontium, butyl calcium, butyl sodium, butyl magnesium chloride, butyl magnesium bromide, amino potassium, sodium methoxide, potassium methoxide, lithium methoxide, triethylamine, pyridine and sodium naphthalene; specifically, n-butyllithium or tert-butyllithium;
the charge introducing manner in the step A2) may be that at least one of chloroethane, bromoethane, iodoethane, chloropropane, bromopropane, iodopropane, chlorobutane, bromobutane, iodobutane, chloropentane, bromopentane, iodopentane, hydrogen chloride, cyanogen bromide, hydrogen iodide, sodium hydroxide, potassium hydroxide and ammonia water is added into the reaction system, and specifically sodium hydroxide or hydrogen iodide is added;
in the step A3), the metal ion may be cobalt ion, silver ion, zinc ion, gold ion, nickel ion, manganese ion, calcium ion or magnesium ion;
specifically, cobalt trichloride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt carbonate, cobalt nitrate, cobalt sulfate, silver chloride, silver bromide, silver iodide, silver nitrate, silver sulfate, zinc chloride, zinc sulfate, gold perchlorate, chloroauric acid, nickel nitrate, nickel chloride, manganese sulfate, manganese hydroxide, manganese carbonate, calcium chloride, calcium sulfate and magnesium chloride are added into a reaction system, and specifically: nickel nitrate, chloroauric acid or silver nitrate;
the intramolecular crosslinking is performed in a solvent, and the solvent can be at least one selected from N, N-dimethylformamide, ethanol, methanol, isopropanol, N-butanol, tetrahydrofuran, water, acetonitrile, acetone, dimethyl sulfoxide, ethyl acetate, dioxane, chloromethane, dichloromethane, trichloromethane, chloroethane, 1, 2-dichloroethane and dichlorobenzene; specifically, N-Dimethylformamide (DMF);
the temperature of the intramolecular cross-linking may be-50 ℃ to 80 ℃, specifically 10 ℃ to 30 ℃, and the time of the intramolecular cross-linking may be 1 to 120min, specifically 10 to 30min, more specifically 30min;
step A4) the reducing agent may be selected from at least one of sodium borohydride, potassium borohydride, dimethylaminoborane (DMAB), lithium aluminum hydride, carbon monoxide, oxalic acid, ascorbic acid, sodium bisulfate, sodium sulfate, citric acid, tartaric acid, succinic acid, glutaric acid, cuprous naphthalate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chloroethanol, 1, 2-propanediol, cycloheptanol, cyclic ethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycollic acid, ethanethiol, triethylaluminum, triethylboron, N-dimethylaniline; specifically, sodium borohydride, dimethylaminoborane (DMAB);
the molar ratio of the addition amount of the reducing agent to the metal ions is 1:1-4:1;
the temperature of the reduction may be from 0 ℃ to 80 ℃, specifically from 10 ℃ to 40 ℃, more specifically from 20 to 30 ℃;
or A4) does not add a reducing agent, and reduces the metal ions in the single-chain nano particles under ultraviolet irradiation.
The invention provides a large-scale preparation method of metal composite polymer single-chain nano particles, which has the advantages of simple reaction and abundant and easily obtained raw materials. The polymer with functional blocks can be obtained through living anion polymerization reaction, and single molecular chain nano particles with universality can be prepared in large quantities. The prepared single-molecular-chain nano-particles are further modified and metal loaded to obtain the metal composite polymer single-chain nano-material, which has important significance in the fields of composite material high performance, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carrier and the like.
Example 1
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred and cooled to-78 o C. To this was slowly added dropwise p-methylstyrene 1.0. 1.0 ML (MS), and after 30 minutes of reaction, methanol was added to terminate the reaction. PMS polymer chains are obtained.
10.0. 10.0 mg Poly (p-methylstyrene) (PMS) was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content: 1%), potassium permanganate (1% aqueous solution, 50. Mu.L) was added, sodium hydroxide (38 mmol, mole ratio: 0.4) was added, and the reaction was carried out at room temperature for 10 minutes to introduce charges into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of a 10.0. 10.0 mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, sodium borohydride (100. Mu.L of a 1% aqueous solution) was added, and after the completion of the reduction reaction, the system was freeze-dried to obtaincThe transmission electron microscope image of the PMS@Ni magnetic composite single-chain nano particle is shown in figure 1.
As can be seen from fig. 1:cthe PMS@Ni magnetic composite single-chain nano particles are uniform spherical particles with the diameter of about 5 nm.
Example 2
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred and cooled to-78 o C. To this, t-butyl acrylate 0.8. 0.8 mL (tBA) was slowly added dropwise, and after 30 minutes of reaction, methanol was added to terminate the reaction. PtBA polymer chains were obtained.
10.0 mg PtBA was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content 1%), trifluoroacetic acid (3.8. Mu.L) was added to hydrolyze PtBA into PAA, sodium hydroxide (38 mmol, mole ratio 0.4) was added, and the reaction was carried out at room temperature for 10 minutes, to introduce a charge into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of a 10.0. 10.0 mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, sodium borohydride (100. Mu.L of a 1% aqueous solution) was added, and after the completion of the reduction reaction, the system was freeze-dried to obtaincThe PAA@Ni magnetic composite single-chain nano particle has a transmission electron microscope image shown in fig. 2.
As can be seen from fig. 2: the morphology is spherical particles with uniform size and the diameter is about 3 nm.
Example 3
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred and cooled to-78 o C. Styrene 1.0 mL (St) was slowly added dropwise thereto, and after 10 minutes, tert-butyl acrylate 0.8 mL (tBA) was added, and after 30 minutes of reaction, methanol was added to terminate the reaction. Obtaining PS-bPtBA polymer chain.
10.0 mg of PS-bPtBA polymer chain was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content: 1%), and PtBA was hydrolyzed to PAA by adding trifluoroacetic acid (3.8. Mu.L) to give PS-portb-PAA polymer chains; sodium hydroxide (38 mmol, mole ratio 0.4) was added and reacted at room temperature for 10min to introduce charge into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of chloroauric acid solution (10.0. 10.0 mg/mL) was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, dimethylaminoborane (DMAB) (100. Mu.L of a 1% aqueous solution) was added thereto, and the system was lyophilized after the completion of the reduction reaction to give PS-b-paa@au complex single-stranded nanoparticles.
Example 4
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred andcooled to-78 o C. Styrene 1.0 mL (St) was slowly added dropwise thereto, t-butyl acrylate 1.0 mL (tBA) was added after 10 minutes, and methanol was added after 30 minutes of reaction to terminate the reaction. Obtaining PS-bPtBA polymer chain.
10.0 mg of PS-bPtBA polymer chain was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content: 1%), and PtBA was hydrolyzed to PAA by adding trifluoroacetic acid (3.8. Mu.L) to give PS-portb-PAA polymer chains; sodium hydroxide (38 mmol, mole ratio 0.4) was added and reacted at room temperature for 10min to introduce charge into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of a 10.0. 10.0 mg/mL silver nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, dimethylaminoborane (DMAB) (100. Mu.L of a 1% aqueous solution) was added, and after the completion of the reduction reaction, the system was freeze-dried to give PS-b-paa@ag composite single-stranded nanoparticles whose transmission electron microscopy is shown in fig. 3.
As can be seen from fig. 3: PS-bThe PAA@Ag is observed to be a tadpole-shaped nanoparticle under a transmission electron microscope, the part with higher contrast is a PAA crosslinking area compounded with the Ag nanoparticle, and the part with lower contrast is a PS chain.
Example 5
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred and cooled to-78 o C. Isoprene 1.0. 1.0 mL was slowly added dropwise thereto, and after 30 minutes of reaction, methanol was added to terminate the reaction. PI polymer chains are obtained.
10.0. 10.0 mg Polyisoprene (PI) was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content 1%), thioglycollic acid and Azobisisobutyronitrile (AIBN) (10%) were added, sodium hydroxide (38 mmol, mole ratio 0.4) was added, and the reaction was carried out at room temperature for 10 minutes, to introduce charges into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of a 10.0. 10.0 mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, sodium borohydride (100. Mu.L, 1% aqueous solution) was added, and after the completion of the reduction reaction, the system was freeze-dried to obtaincPI@Ni magnetic composite single-stranded nanoparticles.
Example 6
15.0 mu.L of n-butyllithium was added to 10.0. 10.0 mL ultra-dry tetrahydrofuran, stirred and cooled to-78 o C. To this was slowly added acrylonitrile 1.0 mL (AN) dropwise, and after 30 minutes of reaction, methanol was added to terminate the reaction. PMS polymer chains are obtained.
10.0. 10.0 mg Polyacrylonitrile (PAN) was sufficiently dissolved in 1.0 mL of N, N-Dimethylformamide (DMF) (solid content 1%), hydrogen iodide (38 mmol, mole ratio 0.4) was added, and reacted at room temperature for 10 minutes, to introduce charges into the polymer. Under the action of charge protection, 300. Mu.L (19 mmol, mole ratio 0.2) of a 10.0. 10.0 mg/mL silver nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the completion of the reaction, sodium borohydride (100. Mu.L of a 1% aqueous solution) was added, and after the completion of the reduction reaction, the system was freeze-dried to obtaincPAN@Ag magnetic composite single-stranded nanoparticles.

Claims (9)

1. A method for preparing single molecular chain nano-particles, comprising the following steps:
a1 A polymer with a crosslinkable active chain segment is synthesized by taking a monomer with at least two crosslinkable active groups as a raw material through active anion polymerization; or (b)
A1') carrying out living anion polymerization by taking a monomer which has only one crosslinkable active group but contains other groups which can be converted into at least one crosslinkable active group as a raw material, and then converting the groups which can be converted into the crosslinkable active groups to obtain a polymer with crosslinkable active chain segments;
a2 A) introducing an electric charge into the resulting polymer;
a3 Under the protection of electric charge, adding metal ions to enable the crosslinkable active chain segments in the polymer to carry out intramolecular crosslinking by utilizing the metal ions to obtain single-chain nano particles;
a4 Adding a reducing agent to reduce metal ions in the single-chain nano particles to obtain single-chain nano particles of the metal simple substance composite polymer;
in step A1), the monomers having at least two crosslinkable reactive groups are: at least one of 1-vinylimidazole, 2-vinylimidazole, 1-vinyl 2-pyrrolidone, acrylonitrile, methacrylonitrile, butadiene, isoprene, methyl acrylate, methyl methacrylate, t-butyl acrylate, t-butyl methacrylate, oligoethylene glycol (meth) acrylate, methyl vinyl ketone, nitroethylene, diethyl methylene malonate, ethyl alpha-cyanoacrylate, dicyanoethylene, ethyl alpha-cyano-2, 4-hexadienoate; or a mixture of the above monomer having at least two crosslinkable reactive groups with other reactive anionically polymerizable monomers, wherein the reactive anionically polymerizable monomers are: at least one of styrene, alpha-methylstyrene, p-methylstyrene, isobutylene;
in step A1'), the monomers having only one crosslinkable active group but containing other groups which are convertible to at least one crosslinkable active group are: alpha-methylstyrene, p-methylstyrene, isobutylene;
in step A1'), the conversion is effected by adding an oxidizing agent to the polymer after the reaction;
the operation of step A2) is as follows: dissolving the polymer in a solvent, adding a charge introducing agent, and reacting;
wherein the solid content of the polymer in the solvent is 0.1-5%;
the charge introducing agent is selected from: at least one of hydrogen chloride, hydrogen bromide, hydrogen iodide, sodium hydroxide, potassium hydroxide and ammonia water;
the charge introducing agent is 10-60% mole number based on mole number of high molecular chain monomer unit number;
in the step A3), the metal ions are at least one of cobalt ions, silver ions, zinc ions, gold ions, nickel ions, manganese ions, calcium ions and magnesium ions;
step A4) the reducing agent is selected from: at least one of sodium borohydride, potassium borohydride, dimethylaminoborane, lithium aluminum hydride, carbon monoxide, oxalic acid, ascorbic acid, sodium bisulfate, sodium sulfate, citric acid, tartaric acid, succinic acid, glutaric acid, cuprous naphthalate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chloroethanol, 1, 2-propanediol, cycloheptanol, cyclic ethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycolic acid, ethanethiol, triethylaluminum, triethylboron, N-dimethylaniline;
the temperature of the reduction is 0-80 ℃.
2. The method according to claim 1, characterized in that:
in the step A1) or A1'), the polymer with the crosslinkable active segment is a homopolymer or a block copolymer with the crosslinkable active segment;
adding an initiator into the living anion polymerization in the step A1) or A1'), wherein the initiator is at least one selected from metal sodium, metal lithium, n-butyl lithium, tertiary butyl lithium, butyl strontium, butyl calcium, butyl sodium, butyl magnesium chloride, butyl magnesium bromide, amino potassium, sodium methoxide, potassium methoxide, lithium methoxide, triethylamine, pyridine and sodium naphthalene;
the living anionic polymerization is carried out in a solvent selected from at least one of tetrahydrofuran, dioxane, pyridine, diethyl ether, cyclohexane, 1, 2-dimethoxyethane, n-pentane, n-heptane, n-hexane, n-octane, n-decane, m-trimethylbenzene, xylene, ethylbenzene, diethylbenzene, benzene, toluene, naphthalene.
3. The method according to claim 1 or 2, characterized in that: in the operation of step A2), the reaction time is 1-30min.
4. The method according to claim 1, characterized in that: the addition of the metal ions in the step A3) is achieved by adding at least one of cobalt trichloride, cobalt chloride, cobalt bromide, cobalt iodide, cobalt carbonate, cobalt nitrate, cobalt sulfate, silver chloride, silver bromide, silver iodide, silver nitrate, silver sulfate, zinc chloride, zinc sulfate, gold perchlorate, chloroauric acid, nickel nitrate, nickel chloride, manganese sulfate, manganese hydroxide, manganese carbonate, calcium chloride, calcium sulfate and magnesium chloride to the reaction system.
5. The method according to claim 1, characterized in that: the temperature of the intramolecular crosslinking is between 50 ℃ below zero and 80 ℃, and the intramolecular crosslinking time is between 1 and 120 minutes;
the intramolecular crosslinking is performed in a solvent selected from at least one of N, N-dimethylformamide, ethanol, methanol, isopropanol, N-butanol, tetrahydrofuran, water, acetonitrile, acetone, dimethyl sulfoxide, ethyl acetate, dioxane, methyl chloride, dichloromethane, chloroform, ethyl chloride, 1, 2-dichloroethane, dichlorobenzene.
6. The method according to claim 1, characterized in that: the preparation method of the single molecular chain nanoparticle comprises the following steps:
step a 1) adding n-butyllithium and p-methylstyrene into tetrahydrofuran, carrying out polymerization reaction to obtain poly-p-methylstyrene, and oxidizing methyl into carboxyl by using potassium permanganate;
step a 2) reacting PMS with sodium hydroxide to introduce charges into PMS;
step a 3) adding an N, N-dimethylformamide solution of nickel nitrate into the solution of the step a 2) under the condition of charge protection, and carrying out intramolecular crosslinking reaction on the poly (p-methylstyrene) chain to obtaincPMS single-stranded nanoparticles;
step a 4) in N, N-dimethylformamide solutioncAnd introducing sodium borohydride into the PMS single-chain nano-particles, and reducing to obtain the metal nickel composite polymer single-chain nano-particles.
7. A single-stranded nanoparticle of a metal elemental composite polymer prepared by the method of any one of claims 1-6.
8. The single-stranded nanoparticle of elemental metal composite polymer according to claim 7, wherein: the metal simple substance composite polymer single-chain nano-particles comprise various morphologies and compositions, including spherical single-molecular-chain nano-particles, tadpole-shaped single-molecular-chain nano-particles, chain-sphere-chain-shaped single-molecular-chain nano-particles or dumbbell-shaped single-molecular-chain nano-particles; different micro-regions of the metal simple substance composite polymer single-chain nano-particles are provided with different functional groups.
9. A nanomaterial comprising the elemental metal composite polymer single-stranded nanoparticle of claim 7 or 8.
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