CN116284567A - Method for preparing single-layer polymer hollow sphere in one step and prepared single-layer polymer hollow sphere - Google Patents
Method for preparing single-layer polymer hollow sphere in one step and prepared single-layer polymer hollow sphere Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 46
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
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- 239000000203 mixture Substances 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 150000001993 dienes Chemical class 0.000 claims abstract description 23
- 239000000693 micelle Substances 0.000 claims abstract description 19
- 238000012703 microemulsion polymerization Methods 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
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- 238000003756 stirring Methods 0.000 claims abstract description 13
- 239000003999 initiator Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 9
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- -1 sodium triacetoxyborohydride Chemical compound 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
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- HFJRKMMYBMWEAD-UHFFFAOYSA-N dodecanal Chemical compound CCCCCCCCCCCC=O HFJRKMMYBMWEAD-UHFFFAOYSA-N 0.000 claims description 6
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- 239000012265 solid product Substances 0.000 claims description 5
- 229960004050 aminobenzoic acid Drugs 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
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- 239000012321 sodium triacetoxyborohydride Substances 0.000 claims description 4
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- XJPFHIYOQHZAOW-UHFFFAOYSA-N 4-(dodecylamino)benzoic acid Chemical compound CCCCCCCCCCCCNC1=CC=C(C(O)=O)C=C1 XJPFHIYOQHZAOW-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
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- 238000004630 atomic force microscopy Methods 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
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- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
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- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 2
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- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a method for preparing a single-layer polymer hollow sphere in one step and the prepared hollow sphere, wherein the method comprises the following steps: mixing an amphiphilic monomer A, a diene amphiphilic crosslinking agent B, water and alkali, dissolving to form micelles, adding an organic solvent into the mixture after deoxidizing and charging nitrogen, stirring the mixture to form swollen micelles, adding an initiator into the mixture to perform microemulsion polymerization, and purifying the mixture after the reaction is finished to obtain a single-layer polymer hollow sphere; the structural general formula of the amphiphilic monomer A is
The structural general formula of the diene amphiphilic cross-linking agent B is
R 1 ＝‑(CH 2 ) n ‑CH 3 N=9 or 11 or 13;
the preparation method is simple, economical, efficient and environment-friendly, does not need complex post-treatment steps, and the obtained hollow spheres have uniform particle size and complete structure, are monomolecular layers, and have carboxyl and other functional groups on the surfaces.
Description
Technical Field
The invention relates to the technical field of polymer chemistry, in particular to a method for preparing a single-layer polymer hollow sphere by one step and the prepared single-layer polymer hollow sphere.
Background
The polymer hollow sphere is a polymer sphere with a hollow structure, has a particle size of nanometer or micron, can encapsulate micromolecular substances such as water, hydrocarbon and other volatile solvents or other compounds with special functions, has larger specific surface area, smaller density, and special physical properties and application values such as mechanics, light, electricity and the like compared with other block materials, such as nano carriers, nano reactors, optical materials, energy storage, biomedicine, sensors and the like, thereby arousing great interest of scientific researchers and becoming the attractive direction of the material research field.
At present, the preparation methods of the polymer hollow microspheres can be roughly classified into three types, namely a template method, a self-assembly method and a microemulsion polymerization method. The method for preparing the polymer hollow microsphere by using the template method is easy to implement and high in universality, the size of the hollow microsphere can be adjusted by controlling the size of the template, but the template is required to be removed, and the process is complex. The influence factors of the self-assembly process are numerous, so that the block polymer self-assembly method has a severe requirement on experimental conditions. The microemulsion polymerization method has simple reaction conditions, does not need a template, is easy for mass synthesis, but needs to remove a large amount of surfactant after the reaction, and pollutes the environment. The preparation method of the hollow microsphere has many advantages, but most of the preparation methods have many reaction steps and the preparation process is complex.
Since the first report of the synthesis of polymerizable surfactants and their use in 1958 Freedman et al, polymerizable surfactants have not been widely studied until the last 20 years. The polymerizable surfactant contains a polymerizable structural unit in the molecule, so that the polymerizable surfactant not only has the function of the surfactant, but also has the polymerizable reaction activity. In recent years, it has been reported that micro-nano materials with hollow structures are prepared through self-assembly and polymerization reaction of amphiphilic molecules, such as Ji J, wei Z, jian L, et al (Guandidinium-Based Polymerizable Surfactant as a Multifunctional Molecule for Controlled Synthesis of Nanostructured Materials with Tunable Morphologies [ J ]. Acs Applied Materials & interfaces.2017,9 (22)) design and synthesize a guanidyl polymerizable surfactant as a multifunctional molecule, the adjustable self-assembly behavior of the guanidyl group can adjust the filling parameters of the surfactant, and the surfactant can be used as a structure guiding agent to synthesize a series of nano silicon dioxide materials with various forms (spherical, disc-shaped, fibrous and cocoon-shaped), but the materials can obtain hollow structures after calcination; yang L, huimin G, huan Y, et al (Two-dimensional polymers with versatile functionalities via gemini monomers. [ J ]. Science Advances.2019,5 (11)) synthesized a amphiphilic gemini monomer MA-11-2-11-MA (N, N ' -bis (11- (methyo-yloxy) undecyl) -N, N, N ', N ' -tetramethyethane-diaminiumbromide) by in situ free radical polymerization in a bilayer at the solid-liquid interface to produce a bilayer of highly crosslinked independent Two-dimensional network poly (MA-112-11-MA). The monomer takes micro-scale particles as templates to prepare two-dimensional reticular poly (MA-11-2-11-MA) with different microstructures, such as microspheres, micro rods and microplates, but the silicon dioxide particle templates are required to be removed by etching with hydrofluoric acid with stronger corrosiveness, so that the hollow polymer structure can be obtained. At present, no complex post-treatment is needed, and a simple, efficient, economic and environment-friendly polymerization method is adopted to prepare the reported phoenix-like horns of the single-layer polymer hollow sphere.
The Chinese patent application publication No. CN114591457A discloses a method for preparing a two-dimensional polymer by utilizing hydrogen bond action, which comprises the steps of self-assembling amphiphilic monomers containing hydrogen bond donors/acceptors in aqueous solution to form two-dimensional supermolecules, and carrying out free radical polymerization reaction in a limited space of the two-dimensional supermolecules to obtain the two-dimensional polymer; the structure of the amphiphilic monomer is as follows:
the self-assembly of amphiphilic molecules in solution and the principle of free radical polymerization are combined, and groups containing hydrogen bond function are introduced into amphiphilic monomers to prepare a two-dimensional polymer with the thickness of about a few nanometers and the surface hydrophilic groups uniformly arranged. But does not involve polymerizing it as a monomer to produce a monolayer polymeric hollow sphere.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a method for preparing the monolayer polymer hollow sphere in one step, which is simple, economical, efficient and environment-friendly, does not need complex post-treatment steps, and has uniform particle size, complete structure and a monomolecular layer, wherein the surface of the sphere is provided with carboxyl and other functional groups.
The invention solves the technical problems by the following technical means:
a method for preparing a monolayer polymeric hollow sphere in one step comprising the steps of: mixing an amphiphilic monomer A, a diene amphiphilic crosslinking agent B, water and alkali, dissolving to form micelles, adding an organic solvent into the mixture after deoxidizing and charging nitrogen, stirring the mixture to form swollen micelles, adding an initiator into the mixture to perform microemulsion polymerization, and purifying the mixture after the reaction is finished to obtain the monolayer polymer hollow spheres;
the structural general formulas of the amphiphilic monomer A and the diene amphiphilic crosslinking agent B are respectively shown in the following formulas 1 and 2:
wherein R is 1 ＝-(CH 2 ) n -CH 3 n=9 or 11 or 13;
preferably, the structural formula of the amphiphilic monomer A is
One of the following; the structural formula of the diene amphiphilic cross-linking agent B is +.>
Preferably, in the micelle formed after dissolution, the concentration of the amphiphilic monomer A is 20 mg/mL-35 mg/mL, and the diene amphiphilic crosslinking agent B is 1-5% of the molar quantity of the amphiphilic monomer A; the amount of organic solvent is the maximum capacity of the micelle at this concentration.
Preferably, in the micelle formed after dissolution, the concentration of the amphiphilic monomer A is 31.25mg/mL, and the diene amphiphilic crosslinking agent B is 1% of the molar quantity of the amphiphilic monomer A.
Preferably, the base is one of 1, 3-tetramethylguanidine, triethylamine, sodium hydroxide, and potassium hydroxide.
Preferably, the organic solvent is one or more of toluene, n-hexane, n-heptane, n-octane, dodecane and hexadecane.
Preferably, the initiator comprises one of a photoinitiator, a thermal initiator, a redox initiation system.
Preferably, the initiator is one or more of photo initiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphate, potassium persulfate and sodium thiosulfate pentahydrate.
Preferably, the pH of the micelles formed by dissolution is 8.
Preferably, the preparation method of the amphiphilic monomer A comprises the following steps:
s1, dissolving 4-aminobenzoic acid in ethanol, placing at 0 ℃ and adding sodium triacetoxyborohydride, dodecanal or 1-decanal for reaction, then continuing the reaction at room temperature, and performing post-treatment after the reaction is finished to obtain a solid product;
s2, mixing and dissolving the solid product in the S1 and N-methylpyrrolidone, placing at 0 ℃, adding acryloyl chloride or methacryloyl chloride to react with the N-methylpyrrolidone mixed solution, then continuing to react at room temperature, adding ice water, and performing aftertreatment to obtain the amphiphilic monomer A.
Preferably, the purification comprises dialysis purification.
Preferably, the dialysis-purified solvent is a mixture of ethanol and water or a mixture of tetrahydrofuran and water.
Preferably, the dialysis purification uses dialysis bags with molecular weight cut-off of 8000-14000, dialysis time of one week, 5 changes of solvent per day.
The invention also provides a single-layer polymer hollow sphere, which is prepared by the method for preparing the single-layer polymer hollow sphere in one step.
The method combines self-assembly of amphiphilic molecules with microemulsion polymerization, assembles the amphiphilic molecules with an organic solvent in a solution through hydrophilic-hydrophobic interaction to form a swelling micelle, and directly obtains the polymer hollow sphere after polymerization and purification. Because the designed amphipathic molecules contain double bonds, the amphipathic polymer can serve as an emulsifier to stabilize emulsion and has reactivity to become a polymer component, meanwhile, the diolefin crosslinking agent can stabilize a hollow structure, and the surface of the prepared polymer sphere contains carboxyl functional groups, so that the method is a simple, economical, efficient and environment-friendly preparation method of the polymer hollow sphere; the hollow sphere prepared by the one-step method has the characteristics of uniform particle size, complete structure and monomolecular layer, the surface of the sphere is provided with carboxyl and other functional groups, and the thickness and mechanical properties of the sphere shell can be regulated and controlled by changing an organic solvent into a polymerizable monomer in the follow-up process, so that the hollow sphere has strong application expansibility. The method has the advantages of low price of raw materials, high yield, simple and convenient preparation process, high repeatability, easy mass preparation of the polymer hollow spheres by taking water as a reaction medium for polymerization, simplicity, economy, high efficiency and environmental protection.
Drawings
FIG. 1 is a chart showing the nuclear magnetic resonance hydrogen spectrum of 4-dodecylaminobenzoic acid, an intermediate prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of an amphiphilic monomer A1 prepared in example 1 of the present invention;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the diene amphiphilic crosslinking agent B1 prepared in example 1 of the present invention;
FIG. 4 is a graph showing the change of the surface tension of the aqueous solution of the amphiphilic monomer A1 prepared in example 1 according to the present invention with the concentration;
FIG. 5 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the reaction mixture before and after polymerization of the monomer prepared in example 1 of the present invention;
FIG. 6 is an infrared spectrum of the amphiphilic monomer A1 prepared in example 1 before and after polymerization;
FIG. 7 is a scanning electron microscope image of a polymer solution after microemulsion polymerization dialysis according to example 1 of the present invention;
FIG. 8 is a transmission electron microscope image of a polymer solution after microemulsion polymerization dialysis according to example 1 of the present invention;
FIG. 9 is an atomic force microscope image a and Origin-treated cross-sectional analysis images b, c of a polymer solution after microemulsion polymerization dialysis according to example 1 of the present invention;
FIG. 10 is a simulation of the amphiphilic monomer A1 of example 1 of the present invention under the lowest energy state via Chem 3D;
FIG. 11 is a scanning electron microscope image of a polymer solution after emulsion polymerization dialysis according to comparative example 1 of the present invention;
FIG. 12 is a transmission electron microscope image of a polymer solution after emulsion polymerization dialysis according to comparative example 1 of the present invention;
FIG. 13 is a transmission electron microscope image of a polymer solution after microemulsion polymerization dialysis according to example 2 of the present invention;
FIG. 14 is a nuclear magnetic resonance hydrogen spectrum of the diene amphiphilic crosslinking agent B2 prepared in example 3 of the present invention;
FIG. 15 is a transmission electron micrograph of a polymer solution after microemulsion polymerization dialysis in accordance with example 3 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described in the following in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Those of skill in the art, without any particular mention of the techniques or conditions, may follow the techniques or conditions described in the literature in this field or follow the product specifications.
Example 1
A method for preparing a single-layer polymer hollow sphere in one step, which comprises the following steps:
1. the preparation method of the amphiphilic monomer A1 specifically comprises the following two steps:
(1) Intermediate synthesis: 4-aminobenzoic acid (3.0 g,21.9 mmol) was dissolved in ethanol (70 mL), placed in an ice bath at 0deg.C, sodium triacetoxyborohydride (6.95 g,32.8 mmol) and dodecanal (4.9 mL,21.9 mmol) were added to the solution, and after 1 hour the ice bath was removed and the reaction was continued at room temperature for 12 hours. After the reaction is finished, adding a dilute hydrochloric acid solution for acidification, collecting precipitated solid through filtration, washing with water, recrystallizing with ethanol, carrying out suction filtration, and drying to obtain white solid. Yield: 88%. As shown in fig. 1, intermediate 4-dodecylaminobenzoic acid was characterized by nuclear magnetic resonance hydrogen spectroscopy.
The synthesis reaction formula of the intermediate is shown as follows:
(2) A1 synthesis: 4-dodecylaminobenzoic acid (1.5262 g,5.0 mmol) was weighed, N-methylpyrrolidone (10 mL) was added thereto to dissolve the mixture to obtain a reaction solution, the reaction solution was placed in an ice bath at 0℃and a mixture of acryloyl chloride (610. Mu.L, 7.5 mmol) and N-methylpyrrolidone (5 mL) was dropped into the reaction solution, the ice bath was removed after 1 hour, and the reaction was carried out at room temperature for 12 hours. Adding ice water, precipitating, and suction filtering to obtain yellowish crude product. Dissolving the crude product in ethanol, dripping water with the volume of 2 times of the ethanol, precipitating white precipitate, repeating for 3 times, filtering, drying and collecting the white product. Yield: 70%. As shown in fig. 2, the amphiphilic monomer A1 was characterized by nuclear magnetic resonance hydrogen spectroscopy.
The synthesis reaction formula is as follows:
2. the preparation method of the diene amphiphilic cross-linking agent B1 specifically comprises the following steps:
into a 250mL pear-shaped bottle were added 3, 5-diaminobenzoic acid (0.4425 g,2.9 mmol) and ethyl acetate (35 mL), and an aqueous solution (35 mL) of potassium carbonate (8.0162 g,58.0 mmol) was further added, followed by dropwise addition of acryloyl chloride (0.95 mL,11.6 mmol) after stirring at 0℃for 20 minutes, and the mixture was allowed to react at room temperature for 2 hours. After the reaction was completed, the organic layer was removed, and the ph=4 of the mixed system was adjusted with dilute hydrochloric acid to produce a precipitate. The solid product is extracted by ethyl acetate, the organic phase is dried by magnesium sulfate, the solid obtained by spin drying after filtration is washed by deionized water, and then the solid is dried in an oven to obtain gray purple solid, the yield is: 92%. B1 was characterized by nuclear magnetic resonance hydrogen spectroscopy as shown in FIG. 3.
The synthetic reaction formula of the diene amphiphilic crosslinking agent B1 is shown as follows:
3. critical micelle concentration determination: the surface tension of the surfactant monomer A1 was measured by KRUSS DSA25 standard contact angle measurement using built-in pendant drop method, as shown in fig. 4, and the surface tension of the liquid was significantly reduced with the increase of the concentration of the surfactant monomer. Turning occurs at a concentration of 0.41239g/L, which is the Critical Micelle Concentration (CMC) of A1, and when CMC is reached, the surfactant molecules associate in the solvent to form micelles, which provides a basis for the selection of the subsequent polymerization concentration.
4. Microemulsion (microemulsion)Polymerization: amphiphilic monomer A1 (0.5 g,1.3918 mmol) and diene amphiphilic crosslinking agent B1 (0.0036 g,0.01398 mmol) were weighed into water (16 g) and tetramethyl guanidine (176. Mu.L, 1.4058 mmol) was added and heated to 65℃with stirring to dissolve completely. Freezing, vacuumizing, charging nitrogen, dripping weighed toluene (0.3 g,3.2559 mmol) dropwise to form semitransparent microemulsion, and adding a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphate salt
(0.0021 g,0.0069 mmol) to give a reaction solution, and illuminating for 10 minutes with stirring at 500 r/min. After polymerization, the polymer solution is transferred into a dialysis bag with a molecular weight cut-off of 8000 for dialysis for one week, and the dialysis solvent is ethanol: water = 1:5 (volume ratio), changing the solvent 5 times a day, and removing unreacted monomer and toluene in the polymer solution.
When the surfactant concentration is greater than cmc= 0.41239mg/mL, micelles are assembled in solution, and in conventional microemulsion polymerization systems, the surfactant acts to reduce the surface tension to stabilize the emulsion droplets, so that a large amount of surfactant is often required for the formation of the microemulsion. However, in this system, the surfactant may act as a monomer in addition to the above two functions because it has an olefinic double bond that can be a carbon source by radical polymerization, but a large amount of surfactant may generate chemical gel during polymerization. The optimal concentration of the monomer A1 is 31.25mg/mL, which is far greater than CMC because a large amount of surfactant can stabilize liquid drops and load more organic solvent, but gel is generated in the polymerization process when the concentration is greater than 35mg/mL, the consumption of the cross-linking agent B1 is 1% of the mole fraction of the A1 for polymerization, and the polymerization solution in a reaction bottle is directly taken to be D after polymerization 2 In O, the nuclear magnetic resonance spectrum characterization is carried out, as shown in FIG. 5, a is the nuclear magnetic resonance spectrum of the reaction liquid before polymerization, b is the nuclear magnetic resonance spectrum of the reaction liquid after polymerization, and the double bond peaks at 5.5ppm,5.9ppm and 6.1ppm are completely disappeared in comparison with the nuclear magnetic resonance spectrum of the reaction liquid before polymerization, which indicates that the monomers are completely polymerized. In addition, 3066cm in the IR spectrum of FIG. 6 -1 C-H stretching vibration peak and 959, 973cm -1 The c=c stretching vibration peak disappeared, also provedSuccessful polymerization was achieved. The polymer solution after dialysis was subjected to morphological characterization. The polymer obtained by the microemulsion polymerization is in a round sphere outline, the size of which is about 300nm, and is evenly spread on a silicon wafer, as can be seen from a Scanning Electron Microscope (SEM) figure 7. Transmission Electron Microscopy (TEM) figure 8, a continuous arrangement of hollow particles of uniform size was also observed. Flat circular profile nanoparticles can also be observed by Atomic Force Microscopy (AFM) fig. 9a, and AFM further demonstrates the hollow structure of the spheres as well as the single layer polymer structure, and cross-sectional analysis by Origin treatment shows that the spheres are about 3.6nm in height and chem3d simulates the thickness of the amphiphilic monomer A1 molecule at the lowest energy state to be about 1.8nm as in fig. 10, thus AFM data is about two monolayers thick, which is positive to demonstrate the flexibility of the monolayer polymer and collapse of the hollow spheres after removal of the organic solvent molecules, strongly demonstrating the success of one-step synthesis of single layer polymer hollow spheres.
Comparative example 1
Emulsion polymerization: amphiphilic monomer A1 (0.5 g,1.3918 mmol) and diene amphiphilic crosslinking agent B1 (0.0036 g,0.01398 mmol) in example 1 were weighed into water (16 g) and tetramethyl guanidine (176. Mu.L, 1.4058 mmol) was added and heated with stirring to 65℃for complete dissolution. The mixture was frozen, vacuum-pumped and nitrogen-filled, then, the weighed toluene (4 g,43.4122 mmol) was dropwise added to form an emulsion, and a photoinitiator phenyl (2, 4, 6-trimethylbenzoyl) sodium phosphate salt (0.0021 g,0.0069 mmol) was added to obtain a reaction solution, and the reaction solution was irradiated with light for 10 minutes under stirring at a rotation speed of 500 r/min. After polymerization, the polymer solution is transferred into a dialysis bag with a molecular weight cut-off of 8000 for dialysis for one week, and the dialysis solvent is ethanol: water = 1:5 (volume ratio), changing the solvent 5 times a day, and removing unreacted monomer and toluene in the polymer solution.
The increase in the amount of organic solvent in the comparative example compared to example 1 forms an opaque emulsion. SEM fig. 11 shows that nanoparticles with uneven size distribution and a three-dimensional effect can be observed, which is in sharp contrast to the flat and uniformly aligned nanoparticles on a silicon wafer in example 1. TEM FIG. 12 shows a clear contrast between the interior and the periphery of the sphere, indicating that the nanoparticles formed by emulsion polymerization are hollow structures, but do not give a monolayer hollow sphere like microemulsion polymerization. This is because the amount of organic solvent is excessive, and a part of the surfactant molecules are dissolved in the organic phase, so that hollow spheres with a multi-layer structure are formed after polymerization, and the walls of the spheres are stronger, and even if the organic phase is completely removed, the spheres do not collapse into a flat structure, but have a three-dimensional effect. This also means that the microemulsion polymerization method is an effective method for obtaining hollow spheres having a single-layer structure and a uniform particle diameter.
Example 2
A method for preparing a single-layer polymer hollow sphere in one step, which comprises the following steps:
microemulsion polymerization: amphiphilic monomer A1 (0.3 g,0.8351 mmol) and diene amphiphilic crosslinking agent B1 (0.0022 g,0.0084 mmol) of example 1 were weighed into water (10 g) and tetramethyl guanidine (106. Mu.L, 0.8435 mmol) was added and heated with stirring to 65℃for complete dissolution. The mixture was frozen, evacuated and filled with nitrogen, then weighed toluene (0.2 g,2.1706 mmol) was dropped dropwise to form a translucent microemulsion, and potassium persulfate (0.0113 g,0.0418 mmol) and sodium thiosulfate pentahydrate (0.0086 g,0.0348 mmol) were added as initiators and polymerized for 12 hours under stirring at 40℃and a rotational speed of 500 r/min. After polymerization, the polymer solution is transferred into a dialysis bag with a molecular weight cut-off of 8000 for dialysis for one week, and the dialysis solvent is ethanol: water = 1:5 (volume ratio), changing the solvent 5 times a day, and removing unreacted monomer and toluene in the polymer solution. TEM characterization of the dialyzed polymer solution revealed that hollow spheres having a particle size of about 200nm were observed as shown in FIG. 13.
Example 3
A method for preparing a single-layer polymer hollow sphere in one step, which comprises the following steps:
the preparation method of the diene amphiphilic cross-linking agent B2 specifically comprises the following steps:
3, 5-dihydroxybenzoic acid (3.08 g,20.0 mmol) was weighed into a 250mL pear-shaped bottle, and an aqueous solution (100 mL) containing 2.35g sodium hydroxide was added, and deoxygenated under dry nitrogen bubbling for 30 minutes. After stirring at 5℃for 20 minutes, acryloyl chloride (6.5 mL,80.0 mmol) was added dropwise, and the mixture was allowed to react at room temperature for 6 hours after completion of the addition. After the reaction, dilute hydrochloric acid was acidified to ph=4, a precipitate was produced, filtered off with suction and rinsed with deionized water. And (5) drying in an oven to obtain white solid. Yield: 92%. As shown in fig. 14, B2 was characterized by nuclear magnetic resonance hydrogen spectroscopy.
The synthetic reaction formula of the diene amphiphilic crosslinking agent B2 is shown as follows:
microemulsion polymerization: amphiphilic monomer A1 (0.25 g,0.6958 mmol) and diene amphiphilic crosslinker B2 (0.0072 g,0.02747 mmol) from example 1 were weighed into water (8 g) and tetramethyl guanidine (91. Mu.L, 0.7233 mmol) was added and heated with stirring to 65℃for complete dissolution. The mixture was frozen, evacuated and filled with nitrogen, then weighed toluene (0.15 g,1.6279 mmol) was dropped dropwise to form a translucent microemulsion, and potassium persulfate (0.0019 g,0.0072 mmol) as an initiator was added thereto, and the mixture was heated to 70℃and polymerized under stirring at a rotation speed of 500r/min for 12 hours. After polymerization, the polymer solution is quenched in an ice-water bath, and then the solution is poured into a dialysis bag with a molecular weight cut-off of 8000 for dialysis for one week, and the dialysis solvent is ethanol: water = 1:5 (volume ratio), changing the solvent 5 times a day, and removing unreacted monomer and toluene in the polymer solution. The polymer solution after dialysis was subjected to TEM characterization as shown in fig. 15.
Example 4
A method for preparing a single-layer polymer hollow sphere in one step, which comprises the following steps:
the preparation method of the amphiphilic monomer A2 comprises the following steps:
4-dodecylaminobenzoic acid was first synthesized according to the method of example 1, and N-methylpyrrolidone (10 mL) was added thereto to dissolve (1.5262 g,5.0 mmol) to obtain a reaction solution, and the reaction solution was placed in an ice bath at 0℃to drop a mixture of methacryloyl chloride (775. Mu.L, 8.0 mmol) and N-methylpyrrolidone (5 mL) into the reaction solution, and after 1 hour, the ice bath was removed and reacted at room temperature for 12 hours. Adding ice water, precipitating, and suction filtering to obtain yellowish crude product. Dissolving the crude product in ethanol, dripping water with the volume of 2 times of the ethanol, precipitating white precipitate, repeating for 3 times, filtering, drying and collecting the white product. Yield: 79%. The synthesis reaction formula is as follows:
microemulsion polymerization: the balance was unchanged by changing A1 in example 1 to an equimolar amount of A2.
Example 5
A method for preparing a single-layer polymer hollow sphere in one step, which comprises the following steps:
the preparation method of the amphiphilic monomer A3 specifically comprises the following two steps:
(1) Intermediate synthesis: 4-aminobenzoic acid (3.0 g,21.9 mmol) was dissolved in ethanol (70 mL), placed in an ice bath at 0deg.C, sodium triacetoxyborohydride (6.95 g,32.8 mmol) and 1-decanal (4.12 mL,21.9 mmol) were added to the solution, and after 1 hour the ice bath was removed, the reaction was continued at room temperature for 12 hours. After the reaction is finished, adding a dilute hydrochloric acid solution for acidification, collecting precipitated solid through filtration, washing with water, recrystallizing with ethanol, carrying out suction filtration, and drying to obtain white solid. Yield: 82%. The synthesis reaction formula of the intermediate is shown as follows:
(2) A3, synthesizing: the above-mentioned product (2.7720 g,10.0 mmol) was weighed and dissolved in N-methylpyrrolidone (20 mL) to obtain a reaction solution, which was placed in an ice bath at 0℃to drop a mixture of acryloyl chloride (1.22 mL,15.0 mmol) and N-methylpyrrolidone (8 mL) into the reaction solution, after 1 hour the ice bath was removed and reacted at room temperature for 12 hours. Adding ice water, precipitating, and suction filtering to obtain yellowish crude product. Dissolving the crude product in ethanol, dripping water with the volume of 2 times of the ethanol, precipitating white precipitate, repeating for 3 times, filtering, drying and collecting the white product. Yield: 69%. The reaction formula is as follows:
microemulsion polymerization: the balance was unchanged by changing A1 in example 1 to an equimolar amount of A3.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for preparing a single-layer polymer hollow sphere in one step, which is characterized in that: the method comprises the following steps: mixing an amphiphilic monomer A, a diene amphiphilic crosslinking agent B, water and alkali, dissolving to form micelles, adding an organic solvent into the mixture after deoxidizing and charging nitrogen, stirring the mixture to form swollen micelles, adding an initiator into the mixture to perform microemulsion polymerization, and purifying the mixture after the reaction is finished to obtain the monolayer polymer hollow spheres;
the structural general formulas of the amphiphilic monomer A and the diene amphiphilic crosslinking agent B are respectively shown in the following formulas 1 and 2:
wherein R is 1 ＝-(CH 2 ) n -CH 3 n=9 or 11 or 13;
R 2 ＝
R 3 ＝/>
2. according toThe one-step method for preparing a monolayer polymeric hollow sphere as recited in claim 1, wherein: the structural formula of the amphipathic monomer A is
One of the following; the structural formula of the diene amphiphilic cross-linking agent B is +.>
3. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: in the micelle formed after dissolution, the concentration of the amphiphilic monomer A is 20 mg/mL-35 mg/mL, and the diene amphiphilic crosslinking agent B is 1-5% of the molar quantity of the amphiphilic monomer A; the amount of organic solvent is the maximum capacity of the micelle at this concentration.
4. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: in the micelle formed after dissolution, the concentration of the amphiphilic monomer A is 31.25mg/mL, and the diene amphiphilic crosslinking agent B is 1% of the molar quantity of the amphiphilic monomer A.
5. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: the alkali is one of 1, 3-tetramethyl guanidine, triethylamine, sodium hydroxide and potassium hydroxide.
6. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: the organic solvent is one or more of toluene, n-hexane, n-heptane, n-octane, dodecane and hexadecane.
7. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: the initiator comprises one of a photoinitiator, a thermal initiator and a redox initiation system.
8. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 1, wherein: the pH of the micelle formed by dissolution was 8.
9. The one-step method for preparing a monolayer polymeric hollow sphere according to claim 2, wherein: the preparation method of the amphiphilic monomer A comprises the following steps:
s1, dissolving 4-aminobenzoic acid in ethanol, placing at 0 ℃ and adding sodium triacetoxyborohydride, dodecanal or 1-decanal for reaction, then continuing the reaction at room temperature, and performing post-treatment after the reaction is finished to obtain a solid product;
s2, mixing and dissolving the solid product in the S1 and N-methylpyrrolidone, placing at 0 ℃, adding acryloyl chloride or methacryloyl chloride to react with the N-methylpyrrolidone mixed solution, then continuing to react at room temperature, adding ice water, and performing aftertreatment to obtain the amphiphilic monomer A.
10. A single layer polymer hollow sphere prepared by the one-step method of preparing a single layer polymer hollow sphere according to any one of claims 1 to 9.
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