CN115181277A - 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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CN115181277A
CN115181277A CN202110360024.8A CN202110360024A CN115181277A CN 115181277 A CN115181277 A CN 115181277A CN 202110360024 A CN202110360024 A CN 202110360024A CN 115181277 A CN115181277 A CN 115181277A
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CN115181277B (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 Taking a monomer with at least two crosslinkable active groups as a raw material, and synthesizing a polymer with a crosslinkable active chain segment by active anionic polymerization; or A1') living anionic polymerization of monomers having only one crosslinkable anchor group, but whose other groups are convertible into at least one crosslinkable anchor group, and conversion of the groups which are convertible into crosslinkable anchor groups to give polymers having crosslinkable anchor segments; a2 Introducing a charge into the resulting polymer; a3 Under the protection of electric charge, adding metal ions to ensure that the crosslinkable active chain segment in the polymer is subjected to 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 field of inorganic, organic and polymer science and materials, in particular to a mass preparation method of single-chain nanoparticles, and more particularly relates to a preparation method of metal composite polymer single-chain nanoparticles.
Background
The history of intramolecular cross-linking of polymers dates back to 1955, when Kuhn and Majer reported cross-linking polymers in ultra-dilute polymer solutions and cross-linking between different molecules could be avoided. Due to the unique size and the structure of obvious partition in space, the polymer single-chain particle can meet the requirements of complex environment, and has wide application prospect in the fields of physics, chemistry, biology and the like. The polymer single-chain particles used as the nano-scale template can easily derive other functional complexes. In recent thirty years, a great deal of scientific research begins to focus on polymer single-chain nanoparticles, and a great deal of nanoparticles with precisely adjustable microstructures have been prepared. The synthetic single-chain nanoparticles currently in widespread use are mainly produced by intramolecular cross-linking of specific segments of block polymers (Mavila, eivgi, berkovich, lemcoff. Chem. Rev.2016, 116. However, this is usually only possible in solutions with very low solids content (< 1%), since otherwise intermolecular crosslinking occurs leading to gelling, which leads to failure of the composite structure. The experimental conditions of dilute solutions greatly limit the large-scale preparation of SCNPs, thus limiting their large-scale application, and furthermore, the composition of nanoparticles needs to be universally adjusted in order to generate functionality. Therefore, designing single-stranded nanoparticles that can be synthesized in large quantities and adjusting their composition universally is a current challenge.
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 Taking a monomer with at least two crosslinkable active groups as a raw material, and synthesizing a polymer with a crosslinkable active chain segment by living anion polymerization; or
A1') living anionic polymerization of monomers having only one crosslinkable anchor group, but whose other groups are convertible into at least one crosslinkable anchor group, and conversion of the groups which are convertible into crosslinkable anchor groups to give polymers having crosslinkable anchor segments;
a2 Introducing a charge into the resulting polymer;
a3 Under the protection of electric charge, adding metal ions to ensure that the crosslinkable active chain segment in the polymer is subjected to intramolecular crosslinking by using 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 metal simple substance composite polymer single-chain nano particles.
In step A1) of the above method, 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 methylenemalonate, ethyl alpha-cyanoacrylate, vinylidene, ethyl alpha-cyano-2, 4-hexadienoate; or a mixture of the above monomer having at least two crosslinkable reactive groups with other living anionic polymerizable monomers, wherein the living anionic polymerizable monomers may be: at least one of styrene, alpha-methyl styrene, p-methyl styrene and isobutene;
the monomer having at least two crosslinkable reactive groups may specifically be: 1-vinyl-2-pyrrolidone, tert-butyl acrylate (tBA), a mixture of styrene and tert-butyl acrylate (tBA), isoprene or acrylonitrile;
in step A1'), the monomer having only one crosslinkable reactive group, but whose other groups can be converted into at least one crosslinkable reactive group, can be: alpha-methylstyrene, p-methylstyrene, isobutylene; specifically p-methylstyrene;
the conversion can be realized by adding an oxidant into the reacted polymer, wherein the oxidant can be potassium permanganate;
the polymer having a crosslinkable active segment may be a homopolymer or a block copolymer having a crosslinkable active segment;
step A1) or A1') of living anion polymerization, wherein an initiator can be added, and the initiator can be selected from at least one of metal sodium, metal lithium, n-butyl lithium, tert-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 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; in particular tetrahydrofuran or cyclohexane;
the operation of the step A2) is as follows: dissolving the polymer in a solvent, adding a charge-introducing agent, and reacting to introduce a charge into the polymer;
wherein the solid content of the polymer in the solvent can be 0.1-5%, specifically 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 specifically can be sodium hydroxide or hydrogen iodide;
the reaction time can be 1-30min, specifically 10min;
the charge-introducing agent is generally added in a molar amount of 10 to 60%, specifically 40%, based on the number of moles of the polymer chain monomer units;
in the step A3), the metal ions can be at least one of cobalt ions, silver ions, zinc ions, gold ions, nickel ions, manganese ions, calcium ions and magnesium ions;
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 comprises the following steps: nickel nitrate, chloroauric acid or silver nitrate;
the feeding amount of the metal ions is 1 to 20 percent (mol ratio) of the number of the high molecular chain monomer units, and can be 5 percent;
the intramolecular cross-linking is carried out in a solvent, which may be at least one selected from the group consisting of N, N-dimethylformamide, ethanol, methanol, isopropanol, N-butanol, tetrahydrofuran, water, acetonitrile, acetone, dimethyl sulfoxide, ethyl acetate, dioxane, methyl chloride, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, dichlorobenzene; specifically, N-Dimethylformamide (DMF);
the temperature of the intramolecular cross-linking can be-50 ℃ to 80 ℃, specifically 10 ℃ to 30 ℃, and the time of the intramolecular cross-linking can be 1 min to 120min, specifically 10min to 30min, more specifically 30min;
the reducing agent of step A4) 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 naphthoate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chlorohydrin, 1, 2-propanediol, cycloheptanol, cycloethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycolic acid, ethanethiol, triethylaluminum, triethylboron, N-dimethylaniline; specifically, sodium borohydride and dimethylamino borane (DMAB);
the molar ratio of the addition amount of the reducing agent to the metal ions is 1;
the temperature of the reduction can be 0-80 ℃, specifically 10-40 ℃, more specifically 20-30 ℃;
or A4) reducing metal ions in the single-chain nano particles under ultraviolet irradiation without adding a reducing agent.
According to an embodiment of the present invention, the method for preparing single-molecular-chain nanoparticles comprises the following steps:
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 an N, N-Dimethylformamide (DMF) solution of nickel nitrate into the solution obtained in the step a 2) under the charge protection condition, and carrying out intramolecular crosslinking reaction on a poly-p-methylstyrene (PMS) chain to obtain a cPMS single-chain nano particle;
step a 4) introducing sodium borohydride into the cPMS single-chain nano-particles in a N, N-Dimethylformamide (DMF) solution, and reducing to obtain metal nickel composite polymer single-chain nano-particles;
according to an embodiment of the invention, the molecular weight of the poly-p-methylstyrene (PMS) in step a 1) is between 2k and 300k, preferably between 10k and 100k;
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 methylstyrene in 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 between 0.01 and 10%, preferably between 1 and 3%.
According to an embodiment of the invention, the total solids content of said charge-introduced PMS polymer in step a 2) is between 1 and 40%, preferably between 5 and 30%.
According to an embodiment of the present invention, the reaction time of step a 2) may be 1 to 120min, preferably 10 to 30min.
According to an embodiment of the present invention, the intramolecular cross-linking reaction temperature of step a 3) may be-50 ℃ to 80 ℃; preferably from 10 ℃ to 30 ℃.
According to an embodiment of the present invention, the time of the crosslinking reaction in step a 3) may be 1 to 120min, preferably 10 to 30min.
According to an embodiment of the invention, the temperature of the reaction in step a 4) may be between 0 ℃ and 80 ℃, preferably between 10 ℃ and 40 ℃, for example between 20 ℃ and 30 ℃.
According to an embodiment of the present invention, the reaction time in step a 4) may be between 1h and 24h, preferably between 5 and 10h.
The single-molecular-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-shaped single-molecular-chain nanoparticles, chain-sphere-chain single-molecular-chain nanoparticles, dumbbell-shaped single-molecular-chain nanoparticles, and the like; different micro-regions of the single molecular chain nano-particles are provided with 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 mass preparation method of metal composite polymer single-chain nano particles, which has simple reaction and abundant and easily-obtained raw materials. The polymer with functional blocks can be obtained through living anionic polymerization, and single molecular chain nano-particles with universality can be prepared in large batch. The prepared single-chain nano-particles are further modified and metal-loaded to obtain the metal composite polymer single-chain nano-material, and the metal composite polymer single-chain nano-material has important significance in the fields of composite material high-performance, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carriers 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 nanoparticles are prepared by using living anionic polymerization to prepare a polymer chain, and then modifying the polymer chain with a monovalent reagent to form a charged group along a crosslinkable chain segment, so that long-term more effective protection is realized, and the following intramolecular crosslinking is ensured by using a multivalent reagent as a crosslinking agent in a solution with higher concentration. The polymerization activity of the single molecular chain nano-particles is controllable, and different sizes and shapes such as a ball shape, a tadpole shape, a chain-ball-chain shape, a dumbbell shape and the like can be obtained, so that the shapes of the nano-particles can be universally adjusted. The polymer chain is subjected to intramolecular crosslinking by utilizing metal ions to obtain single-chain nano particles with metal, and the single-chain nano particles are reduced by using a reducing agent to obtain single-metal compound polymer single-chain nano particles, so that the polymer compound nano particles are endowed with the characteristics of magnetic response, light, electricity, catalysis and the like. The polymerization reaction in each step has complete conversion rate, no interference to subsequent steps, simple and fast product separation, simple process and large-scale operation, and can prepare and form universally adjustable single molecular chain nano particles and composite materials thereof.
Drawings
FIG. 1 is a transmission electron microscope image of cPMS @ Ni magnetic composite single-chain nanoparticles prepared in example 1 of the present invention.
FIG. 2 is a transmission electron microscope image of cPAA@ Ni magnetic composite single-chain nanoparticles prepared in example 2 of the present invention.
FIG. 3 is a transmission electron microscope image of the PS-b-cPAA @ Ag composite single-chain nanoparticle prepared in example 4 of the present invention.
Detailed Description
The present invention will be described below with reference to 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; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
The invention provides a preparation method of single molecular chain nano particles, which comprises the following steps:
a1 Taking a monomer with at least two crosslinkable active groups as a raw material, and synthesizing a polymer with a crosslinkable active chain segment by active anionic polymerization;
a1') living anionic polymerization of monomers having only one crosslinkable anchor group, but whose other groups are convertible into at least one crosslinkable anchor group, and conversion of the groups which are convertible into crosslinkable anchor groups to give polymers having crosslinkable anchor segments; or
A2 Introducing a charge to the crosslinkable living segment in the resulting polymer;
a3 Under the action of charge protection, adding metal ions to ensure that a crosslinkable active chain segment in the polymer is subjected to intramolecular crosslinking by using 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 metal simple substance composite polymer single-chain nano particles.
In step A1) of the above method, 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 methylenemalonate, ethyl alpha-cyanoacrylate, vinylidene, ethyl alpha-cyano-2, 4-hexadienoate; or a mixture of the above monomer having at least two crosslinkable reactive groups with other living anion polymerizable monomers, wherein the living anion polymerizable monomers may be: at least one of styrene, alpha-methyl styrene, p-methyl styrene and isobutene;
the monomer having at least two crosslinkable reactive groups may specifically be: 1-vinyl-2-pyrrolidone, t-butyl acrylate (tBA), a mixture of styrene and t-butyl acrylate (tBA), isoprene or acrylonitrile;
in step A1'), the monomer having only one crosslinkable reactive group but other groups contained therein which can be converted into at least one crosslinkable reactive group may be: alpha-methylstyrene, para-methylstyrene, isobutylene; specifically p-methylstyrene;
the conversion can be realized by adding an oxidant into the reacted polymer, wherein the oxidant can be potassium permanganate;
the polymer having a crosslinkable living segment may be selected from a homopolymer or a block copolymer having a crosslinkable living segment;
an initiator can be added in the active anion polymerization in the step A1), and the initiator can be at least one selected from metallic sodium, metallic lithium, n-butyllithium, tert-butyllithium, 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 t-butyllithium;
the manner of introducing the charge in the step A2) may be adding at least one of ethyl chloride, ethyl bromide, ethyl iodide, chloropropane, bromopropane, iodopropane, chlorobutane, bromobutane, iodobutane, chloropentane, bromopentane, iodopentane, hydrogen chloride, cyanogen bromide, hydrogen iodide, sodium hydroxide, potassium hydroxide and ammonia water into the reaction system, and specifically may be adding sodium hydroxide or hydrogen iodide;
in the step A3), the metal ions can be cobalt ions, silver ions, zinc ions, gold ions, nickel ions, manganese ions, calcium ions or magnesium ions;
the method specifically comprises the following steps of adding 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 comprises the following steps: nickel nitrate, chloroauric acid or silver nitrate;
the intramolecular cross-linking is carried out in a solvent, and the solvent can be 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, trichloromethane, ethyl chloride, 1, 2-dichloroethane and dichlorobenzene; specifically, N-Dimethylformamide (DMF);
the temperature of the intramolecular cross-linking can be-50-80 ℃, specifically 10-30 ℃, and the time of the intramolecular cross-linking can be 1-120min, specifically 10-30min, more specifically 30min;
the reducing agent of step A4) 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 naphthoate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chlorohydrin, 1, 2-propanediol, cycloheptanol, cycloethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycolic acid, ethanethiol, triethylaluminum, triethylboron, N-dimethylaniline; specifically, sodium borohydride and dimethylamino borane (DMAB);
the molar ratio of the addition amount of the reducing agent to the metal ions is 1;
the temperature of the reduction can be 0 ℃ to 80 ℃, specifically 10 ℃ to 40 ℃, and more specifically 20 ℃ to 30 ℃;
or A4) reducing metal ions in the single-chain nano particles under ultraviolet irradiation without adding a reducing agent.
The invention provides a mass preparation method of metal composite polymer single-chain nano particles, which has simple reaction and abundant and easily-obtained raw materials. The polymer with functional blocks can be obtained through living anionic polymerization, and single molecular chain nano-particles with universality can be prepared in large batch. The prepared single-chain nano-particles are further modified and metal loaded to obtain the metal composite polymer single-chain nano-material, and the metal composite polymer single-chain nano-material has important significance in the fields of composite material high performance, catalysis, oil-water separation, environmental response, drug controlled release, catalyst carriers and the like.
Example 1
mu.L of n-butyllithium were added to 10.0mL of super-dry tetrahydrofuran, stirred and cooled to-78 ℃. To this, 1.0ML (MS) of p-methylstyrene was slowly added dropwise, and after 30min of reaction, methanol was added to terminate the reaction. To obtain PMS polymer chain.
10.0mg of poly (p-methylstyrene) (PMS) was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), potassium permanganate (1% aqueous solution, 50. Mu.L) was added, sodium hydroxide (38mmol, mole ratio: 0.4) was added, and the reaction was carried out at room temperature for 10min to introduce electric charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction is finished, adding sodium borohydride (100 mu L of 1% aqueous solution), and after the reduction reaction is finished, freezing and drying the system to obtain the cpms @ Ni magnetic composite single-chain nanoparticle, wherein a transmission electron micrograph of the cpms @ Ni magnetic composite single-chain nanoparticle is shown in figure 1.
As can be seen from fig. 1: the cpMS @ Ni magnetic composite single-chain nano-particles are uniform spherical particles with the diameter of about 5nm.
Example 2
mu.L of n-butyllithium was added to 10.0mL of ultra-dry tetrahydrofuran, stirred and cooled to-78 ℃. To this was slowly added dropwise 0.8mL (tBA) of t-butyl acrylate, and after 30min of reaction, methanol was added to terminate the reaction. A PtBA polymer chain is obtained.
10.0mg of PtBA was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), ptBA was hydrolyzed to PAA by adding trifluoroacetic acid (3.8. Mu.L), sodium hydroxide (38mmol, mole ratio 0.4) was added, and reacted at room temperature for 10min to introduce electric charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction, sodium borohydride (100 μ L of 1% aqueous solution) was added, and after the reduction reaction, the system was freeze-dried to obtain cpaa @ ni magnetic composite single-chain nanoparticles, whose transmission electron microscopy images are shown in fig. 2.
As can be seen from fig. 2: the morphology is spherical particles with uniform size, and the diameter is about 3nm.
Example 3
mu.L of n-butyllithium was added to 10.0mL of ultra-dry tetrahydrofuran, stirred and cooled to-78 ℃. 1.0mL (St) of styrene was slowly added dropwise thereto, 0.8mL (tBA) of t-butyl acrylate was added after 10min, and the reaction was terminated by adding methanol after 30min of reaction. To obtain a PS-b-PtBA polymer chain.
10.0mg of the PS-b-PtBA polymer chain was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), and trifluoroacetic acid (3.8. Mu.L) was added to hydrolyze PtBA into PAA, to give a PS-b-PAA polymer chain; sodium hydroxide (38mmol, mole ratio 0.4) was added and reacted at room temperature for 10min to introduce charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL chloroauric acid solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction, dimethylamino borane (DMAB) (100 mu L of 1% aqueous solution) is added, and after the reduction reaction is finished, the system is frozen and dried to obtain the PS-b-PAA @ Au composite single-chain nano-particles.
Example 4
mu.L of n-butyllithium were added to 10.0mL of super-dry tetrahydrofuran, stirred and cooled to-78 ℃. 1.0mL (St) of styrene was slowly added dropwise thereto, 1.0mL (tBA) of t-butyl acrylate was added after 10min, and the reaction was terminated by adding methanol after 30min of reaction. To obtain a PS-b-PtBA polymer chain.
10.0mg of the PS-b-PtBA polymer chain was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), and trifluoroacetic acid (3.8. Mu.L) was added to hydrolyze PtBA to PAA, to give a PS-b-PAA polymer chain; sodium hydroxide (38mmol, mole ratio 0.4) was added and reacted at room temperature for 10min to introduce charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL silver nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction, dimethylamino borane (DMAB) (100. Mu.L of 1% aqueous solution) was added, and after the reduction reaction, the system was freeze-dried to obtain PS-b-PAA @ Ag composite single-chain nanoparticles, whose transmission electron microscope is shown in FIG. 3.
As can be seen from fig. 3: the PS-b-PAA @ Ag is observed as tadpole-shaped nano particles under a transmission electron microscope, the part with higher contrast is a PAA cross-linking area compounded with the Ag nano particles, and the part with lower contrast is a PS chain.
Example 5
mu.L of n-butyllithium were added to 10.0mL of super-dry tetrahydrofuran, stirred and cooled to-78 ℃. 1.0mL of isoprene was slowly added dropwise thereto, and after reacting for 30min, methanol was added to terminate the reaction. A PI polymer chain is obtained.
10.0mg of Polyisoprene (PI) was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), thioglycolic acid and Azobisisobutyronitrile (AIBN) (10%) were added, sodium hydroxide (38mmol, mole ratio 0.4) was added, and reacted at room temperature for 10min to introduce electric charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL nickel nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction is finished, adding sodium borohydride (100 mu L of 1% aqueous solution), and after the reduction reaction is finished, freezing and drying the system to obtain the cPI @ Ni magnetic composite single-chain nano-particles.
Example 6
mu.L of n-butyllithium was added to 10.0mL of ultra-dry tetrahydrofuran, stirred and cooled to-78 ℃. 1.0mL (AN) of acrylonitrile was slowly added dropwise thereto, and after reacting for 30min, methanol was added to terminate the reaction. To obtain PMS polymer chain.
10.0mg of Polyacrylonitrile (PAN) was sufficiently dissolved in 1.0mL of N, N-Dimethylformamide (DMF) (solid content: 1%), and hydrogen iodide (38mmol, mole ratio: 0.4) was added and reacted at room temperature for 10min to introduce electric charge to the polymer. Under the charge protection, 300. Mu.L (19mmol, mole ratio 0.2) of 10.0mg/mL silver nitrate solution was added with vigorous stirring, and the reaction was continued at room temperature for 30min. After the reaction is finished, adding sodium borohydride (100 mu L of 1% aqueous solution), and after the reduction reaction is finished, freezing and drying the system to obtain the cPAN @ Ag magnetic composite single-chain nano-particles.

Claims (10)

1. A preparation method of single molecular chain nano-particles comprises the following steps:
a1 Taking a monomer with at least two crosslinkable active groups as a raw material, and synthesizing a polymer with a crosslinkable active chain segment by active anionic polymerization; or
A1') living anionic polymerization of monomers having only one crosslinkable anchor group, but whose other groups are convertible into at least one crosslinkable anchor group, and conversion of the groups which are convertible into crosslinkable anchor groups to give polymers having crosslinkable anchor segments;
a2 Introducing a charge into the resulting polymer;
a3 Under the protection of electric charge, adding metal ions to ensure that the crosslinkable active chain segment in the polymer is subjected to 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 metal simple substance composite polymer single-chain nano particles.
2. The method of claim 1, wherein: in step A1), the monomer having at least two crosslinkable reactive groups is: 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 methylenemalonate, ethyl alpha-cyanoacrylate, dicyanoethylene, ethyl alpha-cyano-2, 4-hexadienoate; or a mixture of the above monomer having at least two crosslinkable reactive groups and other living anion polymerizable monomers, wherein the living anion polymerizable monomers are: at least one of styrene, alpha-methyl styrene, p-methyl styrene and isobutene;
in step A1'), the monomers which have only one crosslinkable reactive group but whose other groups are convertible into at least one crosslinkable reactive group are: alpha-methylstyrene, para-methylstyrene, isobutylene;
in step A1'), said conversion is achieved by adding an oxidizing agent to the reacted polymer;
in step A1) or A1'), the polymer having a crosslinkable active segment is a homopolymer or a block copolymer having a crosslinkable active segment;
step A1) or A1') adding an initiator in living anion polymerization, wherein the initiator is selected from at least one of metal sodium, metal lithium, n-butyl lithium, tert-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:
the operation of the 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 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;
the reaction time is 1-30min.
4. The method according to any one of claims 1-3, wherein: 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;
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 any one of claims 1-4, wherein: the temperature of the intramolecular cross-linking is-50 ℃ to 80 ℃, and the time of the intramolecular cross-linking is 1 min to 120min;
the intramolecular cross-linking is carried out 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, methylene chloride, chloroform, ethyl chloride, 1, 2-dichloroethane, dichlorobenzene.
6. The method according to any one of claims 1-5, wherein: 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 naphthoate, 1-propanol, glycerol, ethylene glycol, isobutanol, ethanol, chloroethanol, 1, 2-propanediol, cycloheptanol, cycloethanol, cyclopentanol, malic acid, lactic acid, thiourea, thioacetamide, thioglycolic acid, ethanethiol, triethylaluminum, triethylboron, and N-dimethylaniline;
the temperature of the reduction is 0-80 ℃.
7. The method according to any one of claims 1-6, wherein: the preparation method of the single molecular chain nano-particles comprises the following steps:
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 an N, N-dimethylformamide solution of nickel nitrate into the solution obtained in the step a 2) under the charge protection condition, and carrying out intramolecular crosslinking reaction on a poly (p-methylstyrene) chain to obtain a cPMS single-chain nanoparticle;
and a 4) introducing sodium borohydride into the cPMS single-chain nano particles in an N, N-dimethylformamide solution, and reducing to obtain the metal nickel composite polymer single-chain nano particles.
8. Single-chain nanoparticles or metal composite polymer single-chain nanoparticles prepared by the method of any one of claims 1 to 7.
9. The single-chain nanoparticle or metal composite polymer single-chain nanoparticle of claim 8, wherein: the single-molecular-chain nano-particles comprise various shapes and compositions, and comprise spherical single-molecular-chain nano-particles, tadpole-shaped single-molecular-chain nano-particles, chain-sphere-chain single-molecular-chain nano-particles or dumbbell-shaped single-molecular-chain nano-particles; different micro-regions of the single molecular chain nano-particles are provided with different functional groups.
10. A nanomaterial comprising the single-molecular-chain nanoparticle or metal composite polymer single-chain nanoparticle of claim 8 or 9.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313305A (en) * 2002-03-06 2003-11-06 Internatl Business Mach Corp <Ibm> Manufacture of crosslinked particle from polymer having crosslinkable group capable of being activated
CN106414529A (en) * 2014-05-16 2017-02-15 科腾聚合物美国有限责任公司 Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom
CN106459328A (en) * 2014-04-02 2017-02-22 科腾聚合物美国有限责任公司 Block copolymers containing a copolymer myrcene block
CN106715501A (en) * 2014-05-16 2017-05-24 科腾聚合物美国有限责任公司 Branched broad mwd conjugated diene polymer
CN106832358A (en) * 2017-03-06 2017-06-13 中国科学院化学研究所 A kind of acrylic polymer nano particle and preparation method thereof
CN108064253A (en) * 2015-07-02 2018-05-22 生命技术公司 Polymer matrices formed from carboxy-functional acrylamides
CN108530582A (en) * 2017-03-03 2018-09-14 中国科学院化学研究所 Multi-component Janus composite nano materials and preparation method thereof
CN111849111A (en) * 2019-04-26 2020-10-30 中国科学院化学研究所 Two-dimensional Janus nano material and preparation method thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003313305A (en) * 2002-03-06 2003-11-06 Internatl Business Mach Corp <Ibm> Manufacture of crosslinked particle from polymer having crosslinkable group capable of being activated
CN106459328A (en) * 2014-04-02 2017-02-22 科腾聚合物美国有限责任公司 Block copolymers containing a copolymer myrcene block
CN106414529A (en) * 2014-05-16 2017-02-15 科腾聚合物美国有限责任公司 Polyalkenyl coupling agent and conjugated diene polymers prepared therefrom
CN106715501A (en) * 2014-05-16 2017-05-24 科腾聚合物美国有限责任公司 Branched broad mwd conjugated diene polymer
CN108064253A (en) * 2015-07-02 2018-05-22 生命技术公司 Polymer matrices formed from carboxy-functional acrylamides
CN108530582A (en) * 2017-03-03 2018-09-14 中国科学院化学研究所 Multi-component Janus composite nano materials and preparation method thereof
CN106832358A (en) * 2017-03-06 2017-06-13 中国科学院化学研究所 A kind of acrylic polymer nano particle and preparation method thereof
CN111849111A (en) * 2019-04-26 2020-10-30 中国科学院化学研究所 Two-dimensional Janus nano material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZHENZHONG YANG ET AL.: "Progress in polymer single-chain based hybrid nanoparticles", 《PROGRESS IN POLYMER SCIENCE》 *
胡爱娟;崔玉双;鲁在君;: "基于PAA-b-PAN嵌段共聚物胶束制备磁性碳纳米粒子", 中国科学:化学, no. 05 *

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