CN114349985B - Silica microsphere and preparation method and application thereof - Google Patents
Silica microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic and inorganic nano hybrid materials, and particularly relates to a silicon dioxide microsphere and a preparation method and application thereof. The preparation method of the silicon dioxide microsphere comprises the following steps: mixing tadpole type conjugated polymer solution with a silicon source to obtain a suspension; volatilizing the solvent in the suspension to obtain the silica microsphere. According to the invention, tadpole type conjugated polymer containing hydrophobic cage-shaped silsesquioxane and rigid conjugated chain segments is used as a soft template for preparing silicon dioxide, and micelle formed by polymer aggregation clusters is larger than the inner core of micelle formed by a common surfactant, so that the preparation of silicon dioxide microspheres with large particle sizes is facilitated.
Description
Technical Field
The invention belongs to the technical field of organic and inorganic nano hybrid materials, and particularly relates to a silicon dioxide microsphere and a preparation method and application thereof.
Background
The silica microspheres synthesized by different methods have attractive characteristics of ordered mesopores, high specific surface area, large pore volume, multi-layer framework structure and the like, and are widely applied to the fields of adsorption, catalysis, biomedicine, energy storage, conversion and the like. Meanwhile, in order to meet the increasing application demands, spherical mesoporous materials with core-shell structures are receiving more and more attention because a plurality of components can be combined into one functional unit, and the spherical mesoporous materials show improved or new physicochemical properties which cannot be obtained from isolated mesoporous materials. In addition, the spherical structure consisting of multiple shells can provide a more active interface and unique separation environment, and is expected to exhibit superior activity to the volumetric congeners in various applications.
In recent years, researchers synthesize monodisperse three-dimensional spherical mesoporous silica with adjustable size through various methods such as a nanoemulsion assembly method, an evaporation induced aggregation assembly method and the like. For example, the preparation method of hollow mesoporous silica microspheres is introduced by using the methods of high-class (high-class, yu Chuanbai, du Linlin, luo Haijiang, li Yiqiu, wei Chun, preparation and research progress [ J ], chemical novel materials, 2019,47 (03)), and the research progress and the advantages and disadvantages of the three preparation methods of a template method, a selective etching method, a spray drying method and the like are reviewed and evaluated, and the application prospect is expected; in another example, wei-Ji (Ji Wei, qin Yue, zhenkun Sun, yonghui Deng, and Dongyuan Zhao. Synthesis of Dual-Mesoporous Silica Using Non-Ionic Diblock Copolymer and Cationic Surfactant as Co-Templates [ J ], angewandte Chemie International Edition,2012,51,6149-6153) was assembled into large-sized mesoporous silica microspheres with a multi-layered structure by evaporation-induced aggregation. As another example, chinese patent application No. 201080055248.8 provides a method for preparing mesoporous silica microspheres, which can regulate the size of the produced nano silica particles by adjusting the crosslinking degree of the polystyrene template, thereby regulating the size of the mesopores produced after the particles are stacked, and having excellent pore diameter adjustable properties. In the related art, a star-shaped hetero-arm hydrophilic polymer is used as a soft template, and a solvent volatilizing method is used for preparing the silicon dioxide microsphere, however, the particle size of the obtained silicon dioxide microsphere is 100-150 nm, the particle size is smaller, the requirements of certain fields cannot be met, and the application of the silicon dioxide microsphere is limited.
Disclosure of Invention
A first object of the present invention is to provide a method for producing silica microspheres, which can increase the particle size of silica microspheres.
A second object of the present invention is to provide a silica microsphere.
It is a further object of the present invention to provide the use of said silica microspheres.
Specifically, the invention relates to the following technical scheme:
a preparation method of silica microspheres comprises the following steps:
mixing tadpole type conjugated polymer solution with a silicon source to obtain a suspension; volatilizing a solvent in the suspension to obtain silica microspheres;
the tadpole type conjugated polymer has a structural general formula shown in the following formula I:
wherein m is more than or equal to 20 and less than or equal to 50; n is more than or equal to 10 and less than or equal to 30.
The tadpole type conjugated polymer containing the hydrophobic cage-shaped silsesquioxane is used as a soft template for preparing the silicon dioxide, and the micelle formed by the polymer aggregation clusters is larger than the inner core of the micelle formed by the common surfactant, so that the preparation of the silicon dioxide microsphere with large particle size is facilitated; meanwhile, the tadpole type conjugated polymer used in the invention contains a rigid conjugated chain segment, so that the micelle formed by polymer aggregation clusters has better stability than the micelle formed by common surfactant, and the preparation of large-particle-size silica microspheres with uniform sizes is facilitated. The tadpole-type conjugated polymer is used as a soft template, and the silicon dioxide microsphere is prepared by a solvent volatilization method, and the internal core of the obtained silicon dioxide microsphere is an inorganic-organic hybrid material of silsesquioxane, and the inorganic-organic hybrid material has good compatibility with an organic solvent and a carbon material, so that after the silicon dioxide microsphere is prepared, the polymer in the silicon dioxide microsphere does not need to be removed, thereby simplifying the synthesis step and increasing the mechanical property and thermodynamic property of the material.
In some examples of the invention, the tadpole-type conjugated polymer has a mass average molecular weight of 30000-70000 Da.
In some examples of the invention, the tadpole-type conjugated polymer solution is a mixed solution of a tadpole-type conjugated polymer and an organic solvent, hydrochloric acid.
The mass ratio of the organic solvent to the tadpole type conjugated polymer is 100-500: 1, preferably 300 to 500:1.
the concentration of the hydrochloric acid is 0.5 to 2mol/L, preferably 0.5 to 1mol/L. The mass ratio of the hydrochloric acid to the tadpole type conjugated polymer is 50-100: 1.
in some examples of the invention, the silicon source comprises white carbon black, silica sol, sodium silicate, having the general structural formula xR 1 -Si-y(O-R 2 ) At least one of the compounds of (1), wherein x+y=4, and y > 0, r 1 、R 2 Independently selected from the group consisting of C1-C20 alkyl, optionally substituted C1-C20 alkyl, C1-C20 alkenyl, and optionally substituted C1-C20 alkenyl. Preferably, the optionally substituted C1-C20 alkyl group comprises an amino-substituted, halogen-substituted, oxygen-containing functional group-substituted C1-C20 alkyl group, and the optionally substituted C1-C20 alkenyl group comprises an amino-substituted, halogen-substituted, oxygen-containing functional group-substituted C1-C20 alkenyl group.
In some examples of the invention, the silicon source comprises at least one of tetraethyl orthosilicate (TEOS), methyl orthosilicate (TMOS), trimethylethoxysilane, hexadecyltrimethoxysilane.
In some examples of the invention, the mass ratio of the silicon source to tadpole-type conjugated polymer is from 1 to 50:1, preferably 5 to 20:1, more preferably 10 to 30:1.
in some examples of the invention, the tadpole-type conjugated polymer solution is mixed with the silicon source and then stirred to form a suspension. The stirring time is 0.5 to 5 hours, preferably 1 to 3 hours. Stirring until no precipitate is formed. The stirring speed is 300-600 r/min. In the stirring process, a mixed system formed by the tadpole type conjugated polymer solution and a silicon source is sealed to avoid premature volatilization of the solvent.
In some examples of the invention, the method of volatilizing the solvent in the suspension is by leaving the suspension to stand. The standing time is 20 to 30 hours. The temperature of the standing is 15-30 ℃, preferably 20-30 ℃, and in actual operation, the standing is carried out at room temperature. During the rest, the suspension was not sealed.
And after standing, removing the upper liquid and yellow floating matters, taking the lower yellow sediment, carrying out vacuum suction filtration, taking the sediment, washing with water, standing to remove the upper liquid, and drying to obtain the silicon dioxide microspheres. Wherein the steps of washing with water and standing to remove the supernatant liquid may be circulated a plurality of times, for example, 2 to 5 times.
In some examples of the invention, the preparation method of the tadpole-type conjugated polymer comprises the following steps:
1) Reacting DL-N-acetylhomocysteine thiolactone (compound 1) with 2-thiopheneethylamine (compound 2) to obtain compound 3; reacting compound 3 with octavinyl cage silsesquioxane (CSQ, compound 4) to give thiophene group-containing octahedral silsesquioxane (CSQ-Th, compound 5);
2) Desulfurizing the poly (N, N-dimethylaminoethyl methacrylate) (PDMA, compound 6) to give Compound 7; reacting the compound 5 with a compound 7 to obtain a silsesquioxane-based star-shaped hybrid polymer containing thiophene active groups (CSQ-PDMA-Th, compound 8);
3) To contain compound 8 and Fe 3+ The aqueous solution of (2) is a water phase, 3, 4-Ethylenedioxythiophene (EDOT)/n-butanol solution is covered on the water phase, and standing is carried out to carry out interface reaction, thus obtaining the tadpole type conjugated polymer shown in the formula I.
The synthesis route of the tadpole type conjugated polymer is as follows:
in some examples of the invention, in step 1), the reaction of compound 1 with compound 2 is performed in the presence of a catalyst comprising at least one of 4-dimethylaminopyridine, tributylphosphine, triphenylphosphine.
In some examples of the invention, the molar ratio of compound 1 to compound 2 is from 1 to 1.5:1, a step of; the molar ratio of the compound 2 to the compound 4 is 1:1 to 1.2.
In some examples of the invention, the reaction of compound 1 with compound 2 is performed in a solvent, and the ratio of DL-N-acetylhomocysteine thiolactone to solvent is 0.01 to 0.02g:1mL. The ratio of the catalyst to the solvent is 0.0005-0.001 g:1mL of the mixture is proportioned. The ratio of the compound 2 to the solvent is 0.005-0.01 g:1mL of the mixture is proportioned.
In some examples of the present invention, the reaction between the compound 3 and the compound 4 is specifically that an organic solution of the compound 4 is added to a mixture containing the compound 3 obtained after the reaction between the compound 1 and the compound 2 is completed, and the reaction is performed. Wherein the organic solution of compound 4 is a solution obtained by dissolving compound 4 in an organic solvent, which is preferably the same as the solvent in the reaction system of compound 1 and compound 2. The concentration of the organic solution of the compound 4 is 0.1 to 0.5mmol/mL, preferably 0.2 to 0.3mmol/mL. The volume ratio of the organic solution of the compound 4 to the solvent for dissolving the compound 1 and the compound 2 is 1:2 to 5.
In some examples of the invention, the reaction of compound 1 with compound 2 and the reaction of compound 3 with compound 4 are both carried out in a protective atmosphere.
In some examples of the invention, the reaction time of compound 1 with compound 2 is from 5 to 24 hours, preferably from 8 to 14 hours. The reaction time of the compound 3 with the compound 4 is 10 to 24 hours, preferably 12 to 20 hours.
The reaction temperatures of compound 1 and compound 2, and the reaction temperatures of compound 3 and compound 4 are independently 30 to 50 ℃, and the temperatures of the two reactions are preferably the same.
In some examples of the present invention, after the reaction of the compound 3 with the compound 4 is completed, the purified target product may be obtained by the steps of vacuum pumping the solvent, washing with water, dissolving with dichloromethane, drying with molecular sieves, concentrating, separating with a chromatographic column, and vacuum drying. Wherein the vacuum drying temperature is 25-30 ℃, and the vacuum drying time is about 20-30 hours.
In some examples of the invention, in step 2), the step of desulfurizing the compound 6 to form a compound 7 is specifically: dissolving the compound 6 in an organic solvent, adding a nucleophilic catalyst and a reducing agent, and reacting to obtain the compound 7. The reaction is carried out under a protective atmosphere.
In some examples of the invention, the nucleophilic catalyst comprises at least one of tributylphosphine, triphenylphosphine. The reducing agent comprises at least one of propylamine, ethylamine and hexylamine.
In some examples of the invention, the compound 6 and the organic solvent are present in a mass to volume ratio of 0.2 to 0.5g:1mL of the mixture is proportioned; the volume ratio of nucleophilic catalyst to organic solvent is 0.5-1.5: 1, proportioning; the volume ratio of the reducing agent to the organic solvent is 0.5-1: 1, proportioning.
In some examples of the invention, after the reaction of the compound 6 with the nucleophilic catalyst and the reducing agent is completed, the organic solvent and the unreacted reducing agent are removed, and then the compound 5/triethylamine/organic solvent is added to perform a reaction, thereby obtaining the star-shaped hybrid polymer shown as the compound 8.
The volume ratio of the compound 5/triethylamine/organic solvent to the organic solvent for dissolving the compound 6 is 0.8-1.2: 1, proportioning. In the compound 5/triethylamine/organic solvent, the mass volume ratio of the compound 5 to the organic solvent is 0.002-0.006 g:1mL, wherein the volume ratio of triethylamine to organic solvent is 0.05-0.1: 1, proportioning.
In some examples of the invention, in step 2), the reaction time for desulphurisation of compound 6 to form compound 7 is 3 to 5 hours. The reaction time of the compound 5 and the compound 7 is 12 to 36 hours. The two-step reaction temperature of the step 2) is independently 30-50 ℃.
In some examples of the invention, in step 3), the compound 8 is mixed with Fe 3+ The ratio of (2) is 1g: 1-2 mmol.
In some examples of the invention, the aqueous phase is formed from a hydrochloric acid solution of compound 8 with Fe 3+ The aqueous solution is mixed.
In some examples of the invention, the hydrochloric acid solution of compound 8 is obtained by dissolving compound 8 in hydrochloric acid, and the concentration of the hydrochloric acid is 0.1 to 5mol/L, preferably 0.5 to 3mol/L, and more preferably 0.5 to 1.5mol/L. The ratio of the compound 8 to the hydrochloric acid is 1g: 10-100 mL, preferably 1g:20 to 80mL, more preferably 1g: 20-50 mL.
In some examples of the invention, the Fe 3+ The concentration of the aqueous solution is 0.05 to 1mol/L, preferably 0.08 to 0.5mol/L, more preferably 0.1 to 0.2mol/L.
In some examples of the invention, the Fe 3+ The volume ratio of the aqueous solution to the hydrochloric acid solution of compound 8 was 1:0.5 to 5: preferably 1:1 to 5, more preferably 1:2 to 3.
In some examples of the invention, the concentration of the 3, 4-ethylenedioxythiophene/n-butanol solution is from 0.005 to 0.5mol/L, preferably from 0.01 to 0.1mol/L, more preferably from 0.01 to 0.03mol/L. In actual operation, 3, 4-ethylenedioxythiophene and n-butanol can be mixed according to the mass volume ratio of 0.001-0.005 g:1mL, preferably 0.002 to 0.003g:1mL of the mixture is proportioned.
In some examples of the invention, the volume ratio of the aqueous phase to the 3, 4-ethylenedioxythiophene/n-butanol solution is from 0.1 to 0.5:1, preferably 0.3 to 0.4:1.
in some examples of the invention, the ratio of compound 8 to n-butanol is from 0.01 to 0.015g:1mL.
In some examples of the invention, the interfacial reaction is performed under light-protected conditions.
In some examples of the invention, the temperature of the interfacial reaction is 10 to 50 ℃, preferably 20 to 30 ℃. The interfacial reaction time is 10 to 40 hours, preferably 24 to 36 hours.
In some examples of the invention, after the interfacial reaction is complete, further comprising a step of purification comprising: taking a lower water phase after interface reaction is finished, and centrifuging; taking supernatant after centrifugation; mixing the supernatant with NaHCO 3 Mixing the THF mixed solution, stirring until no bubbles overflow, and standing; concentrating the supernatant after standing, precipitating in ice petroleum ether after concentrating, and taking out the precipitate; and drying the precipitate to obtain the star-type soluble conjugated polymer.
Wherein NaHCO 3 The THF mixture was NaHCO 3 Mixed solution of aqueous solution and tetrahydrofuran。NaHCO 3 The concentration of the aqueous solution is 0.1 to 2mol/L, preferably 0.5 to 1.5mol/L. NaHCO (NaHCO) 3 The volume ratio of the aqueous solution to the tetrahydrofuran is 1:1 to 5, preferably 1:2 to 4.NaHCO (NaHCO) 3 The volume ratio of the THF mixed solution to the 3, 4-ethylenedioxythiophene/n-butanol solution is 1-2: 1, preferably 1.2 to 1.6:1. the volume ratio of petroleum ether to 3, 4-ethylenedioxythiophene/n-butanol solution is 5-30: 1, preferably 10 to 20:1.
step 3) of the invention in Fe 3+ Poly 3, 4-Ethylenedioxythiophene (EDOT) chain segments grow from the thiophene-terminated group of the compound 8 under catalysis to form tadpole-type conjugated polymers, the reaction monomers can be reduced to crosslink different conjugated chains together in the synthesis process, the envisaged molecular structure can be successfully obtained, the solubility of the product is maintained, and the molecular weight distribution of the product can be effectively controlled.
In some examples of the invention, the method of preparation of compound 6 is: under the action of an initiator, N-dimethylaminoethyl methacrylate (DMA, a compound A) and S-dodecyl-S ' - (R, R ' -dimethyl-R ' -acetic acid) trithiocarbonate (DTTC, a compound B) are reacted to obtain the N, N-dimethylaminoethyl methacrylate (PDMA, a compound 6).
The synthetic route for compound 6 is as follows:
in some examples of the invention, the reaction temperature of compound a and compound B is 65-75 ℃ and the reaction time is 0.5-2 hours.
In some examples of the invention, the molar ratio of compound a to compound B is 80 to 120:1. in practice, the compound a and the compound B may be dissolved in an organic solvent and then reacted. The mass volume ratio of the compound B to the organic solvent is 0.03-0.05 g:1mL of the mixture is proportioned; the mass volume ratio of the compound A to the organic solvent is 1.2-1.8 g:1mL of the mixture is proportioned; the mass volume ratio of the initiator to the organic solvent is 0.0014-0.0018 g:1mL of the mixture is proportioned.
In some examples of the invention, after the desired reaction of the compound A and the compound B is achieved, the reaction system is cooled (to-78 ℃ C. To 0 ℃ C.) to quench the reaction, then the reaction solution is dripped into ice petroleum ether to precipitate, and the precipitate is dried to obtain the target product. Petroleum ether and organic solvent according to the volume ratio of 10-20: 1, proportioning.
In some examples of the present invention, the initiator is not particularly limited, and an initiator for polymerization commonly used in the art, such as Azobisisobutyronitrile (AIBN), may be used.
In some examples of the present invention, the organic solvent involved in each step is not particularly limited, and any organic solvent capable of dissolving the reactants and not participating in the reaction may be used. As an example, the organic solvent used in the step of the present invention independently includes at least one of dioxane, tetrahydrofuran, toluene.
A silica microsphere is prepared by the preparation method. The silicon dioxide microsphere has a spherical morphology and the particle size is 2-10 mu m.
The application of the silica microsphere is applied to the preparation of antistatic coating materials. The large-particle-size silica microspheres are not easy to agglomerate, can be applied to preparing antistatic coating materials, and improve the antistatic performance of the materials.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the tadpole type conjugated polymer is used as a soft template for preparing the silica microsphere, the molecular weight of a flexible part chain segment of the tadpole type conjugated polymer can be regulated by controlling the polymerization time, and the prepared tadpole type conjugated polymer has the characteristics of controllable structure, controllable molecular weight, narrow molecular weight distribution and the like. The space size of the obtained tadpole-type conjugated polymer soft template is uniform, so that the size of the obtained silica microsphere is uniform.
(2) The method can accurately adjust the space ratio of the hydrophilic segment and the hydrophobic segment in the polymer by changing the polymerization time of the flexible segment to control the size of micelle cores, thereby controlling the particle size of the prepared silica microsphere and further obtaining the uniform silica microsphere.
(3) The tadpole type conjugated polymer used in the invention contains hydrophobic cage-shaped silsesquioxane, and the micelle formed by the polymer aggregation cluster is larger than the inner core of the micelle formed by the common surfactant, thus being more beneficial to preparing the silica microsphere with large particle size.
(4) The tadpole type conjugated polymer used in the invention contains a rigid conjugated chain segment, and the micelle formed by the polymer aggregation cluster has better stability than the micelle formed by the common surfactant, thereby being more beneficial to preparing large-particle-diameter silica microspheres with uniform size.
(5) The silica microsphere prepared by the invention has the internal core of the inorganic-organic hybrid material of silsesquioxane, and has good compatibility with organic solvents and carbon materials, so that after the silica microsphere is prepared, the internal polymer does not need to be removed, thereby simplifying the synthesis steps and increasing the mechanical property and thermodynamic property of the material.
(6) Compared with the star-shaped hetero-arm block polymer in the prior art, the tadpole-shaped conjugated polymer provided by the invention has the advantages that the connecting chain segments of CSQ are changed, the number of hydrophilic chain segments are increased, the hydrophobic part in the polymer molecule occupies smaller specific gravity of the whole polymer molecule, and the specific gravity of the hydrophilic part is larger, so that the polymer micelle formed in the aqueous solution has larger particle size, and the particle size of the silicon dioxide microsphere is increased.
Drawings
FIG. 1 shows CSQ-Th synthesized in example 1 1 H-NMR spectrum;
FIG. 2 is a schematic diagram of CSQ-PDMA-PEDOT synthesized in example 1 1 H-NMR spectrum;
FIG. 3 is a micelle distribution of CSQ-PDMA-PEDOT synthesized in example 1 in an acidic aqueous solution;
FIG. 4 is a scanning electron microscope image of silica microspheres prepared in example 1.
Detailed Description
The invention provides a preparation method of silicon dioxide microspheres, which comprises the following steps of:
octavinyl Cage Silsesquioxane (CSQ) having the structural formula:
an octahedral silsesquioxane (CSQ-Th) containing thiophene groups, the structure of which is:
the silsesquioxane-based star-shaped hybrid polymer (CSQ-PDMA-Th) containing thiophene active groups has the structural formula:
wherein, m is more than or equal to 20 and less than or equal to 50.
The structural formula of the tadpole type conjugated polymer (CSQ-PDMA-PEDOT) containing the conjugated chain segment by silsesquioxane is as follows:
wherein m is more than or equal to 20 and less than or equal to 50; n is more than or equal to 10 and less than or equal to 30.
In some examples, the method of preparing the silica microspheres comprises the steps of:
(1) Synthesis of thiophene group-containing octahedral silsesquioxane (CSQ-Th):
DL-N-acetylhomocysteine thiolactone and 4-dimethylaminopyridine are dissolved in dioxane, transferred into a Schlenk flask and protected by nitrogen. Adding 2-thiopheneethylamine, freezing and degassing the reaction liquid, and placing the reaction liquid in an oil bath reactor for reaction.
The degassed CSQ/dioxane solution was then injected into the reactor flask and the reaction was continued in the oil bath reactor. The solvent was then pumped away under reduced pressure and the dope was washed with a large amount of deionized water. The aqueous solution was discarded, and dichloromethane was added to dissolve the dope, and 4A molecular sieve was added to dry the solution. Filtering, concentrating, separating with chromatographic column, and vacuum drying to obtain the final product.
Wherein, the mass volume ratio of DL-N-acetylhomocysteine thiolactone to dioxane is 0.01-0.02: 1 (g/mL) for proportioning; the mass volume ratio of the 4-dimethylaminopyridine to the dioxane is 0.0005-0.001: 1 (g/mL) for proportioning; the mass volume ratio of the 2-thiopheneethylamine to the dioxane is 0.005-0.01: 1 (g/mL) for proportioning; the volume ratio of the CSQ/dioxane solution to the dioxane is 0.2-0.5: 1 (mL/mL).
In the step (1), the reaction time of DL-N-acetylhomocysteine thiolactone, 4-dimethylaminopyridine and 2-thiopheneethylamine is 5-24 hours, preferably 8-14 hours. The reaction is continued for 10 to 24 hours, preferably 12 to 20 hours, after the addition of the CSQ/dioxane solution. The reaction temperature of each step of the step (1) is 30-50 ℃. The vacuum drying temperature is 25-30 ℃ and the drying time is about 24 hours.
(2) Synthesis of Poly (N, N-dimethylaminoethyl methacrylate) (PDMA):
n, N-Dimethylaminoethyl Methacrylate (DMA), S-dodecyl-S ' - (R, R ' -dimethyl-R ' -acetic acid) trithiocarbonate (DTTC) and Azobisisobutyronitrile (AIBN) were dissolved in dioxane, transferred into a Schlenk reactor, rapidly stirred uniformly, and subjected to 3 freeze degassing cycles. The reaction is carried out in an oil bath pot. Quenching the reaction with liquid nitrogen, melting the frozen reaction bottle in warm water, dripping the reaction liquid into ice petroleum ether for precipitation, rapidly stirring, standing and pouring out the upper liquid. And (5) drying the precipitate in vacuum to obtain a target product.
Wherein, the mass volume ratio of the S-dodecyl-S '- (R, R-dimethyl-R' -acetic acid) trithiocarbonate to the dioxane is 0.03-0.05: 1 (g/mL) for proportioning; the mass volume ratio of the methacrylic acid N, N-dimethyl amino ethyl ester to the dioxane is 1.2-1.8: 1 (g/mL) for proportioning; the mass volume ratio of the azodiisobutyronitrile to the dioxane is 0.0014-0.0018: 1 (g/mL) for proportioning; the volume ratio of petroleum ether to dioxane is 10-20: 1 (mL/mL).
The reaction time of the step (2) is 0.5-2 hours, and the reaction temperature is 65-75 ℃.
The stirring speed is 300-600 r/min. The vacuum drying temperature is 25-30 ℃ and the drying time is about 24 hours. S-dodecyl-S '- (R, R' -dimethyl-R "-acetic acid) trithiocarbonate (DTTC) is prepared from Macromolecules (2002), volume 35.Issue 18,pages 6754-6756.
(3) Synthesis of silsesquioxane based Star hybrid Polymer containing thiophene active groups (CSQ-PDMA-Th):
PDMA was dissolved in dioxane, transferred into Schlenk flask, and then rapidly subjected to 3 freeze-degassing cycles. Tributylphosphine and propylamine were injected under argon protection and a freeze degassing cycle was performed 3 more times. And (5) heating and reacting in an oil bath. Then the solvent and unreacted propylamine are removed under reduced pressure, the degassed dioxane is injected, and the solvent is removed under reduced pressure after dissolution. Then, under the protection of argon atmosphere, CSQ-Th/triethylamine/dioxane solution is injected, and then the reactor is placed in an oil bath for reaction. The solvent was then removed under reduced pressure, the viscous material was dissolved in dichloromethane, and petroleum ether was slowly added dropwise. And (5) drying the precipitate in vacuum to obtain a target product.
Wherein, the mass volume ratio of the PDMA to the dioxane is 0.2-0.5: 1 (g/mL) for proportioning; the volume ratio of the tributylphosphine to the dioxane is 0.5-1.5: 1 (mL/mL) for proportioning; the volume ratio of the propylamine to the dioxane is 0.5-1: 1 (mL/mL) for proportioning; the volume ratio of CSQ-Th/triethylamine/dioxane solution to dioxane is 0.8-1.2: 1 (mL/mL) for proportioning; the mass volume ratio of the CSQ-Th to the dioxane is 0.002-0.006: 1 (g/mL) for proportioning; the volume ratio of the triethylamine to the dioxane is 0.05-0.1 (mL/mL).
In the step (3), the reaction time of PDMA, tributylphosphine and propylamine is 3-5 hours, and after CSQ-Th/triethylamine/dioxane solution is added, the reaction is continued for 12-36 hours. The temperature of each reaction in the step (3) is independently 30-50 ℃.
The stirring speed is 300-600 r/min. The vacuum drying temperature is 25-30 ℃ and the drying time is about 24 hours.
(4) Synthesis of tadpole-type conjugated polymer (CSQ-PDMA-PEDOT) with silsesquioxane containing conjugated segment:
CSQ-PDMA-th is dissolved in hydrochloric acid solution, and ferric chloride solution is added. The mixture was transferred into a serum bottle so as to avoid touching the inner wall as much as possible. The EDOT/n-butanol solution was then slowly overlaid onto the aqueous phase along the inner wall of the bottle. And (3) after the reaction is kept stand at room temperature in a dark place, taking out a lower blue water phase, centrifuging at a high speed, and taking out an upper blue clear liquid. Dripping the clear liquid into NaHCO 3 The mixture of the aqueous solution and the tetrahydrofuran is stirred rapidly. When no bubbles overflow, the mixture is left to stand. And removing the upper brown clear liquid, concentrating, precipitating in ice petroleum ether, taking out the precipitate, and drying in vacuum to obtain the target product.
Wherein, the mass volume ratio of CSQ-PDMA-Th to n-butanol is 0.01-0.015: 1 (g/mL) for proportioning; the volume ratio of the hydrochloric acid aqueous solution to the n-butanol is 0.3-0.4: 1 (mL/mL) for proportioning; 3, 4-ethylenedioxythiophene and n-butanol with mass volume ratio of 0.002-0.003: 1 (g/mL) for proportioning; naHCO (NaHCO) 3 The volume ratio of the THF solution to the n-butanol is 1.2-1.6: 1 (mL/mL) for proportioning; the volume ratio of petroleum ether to n-butanol is 10-20: 1 (mL/mL).
The reaction time in the step (4) is 24-36 hours, and the reaction temperature is 20-30 ℃. The aqueous hydrochloric acid solution was 1mol/L. The concentration of the aqueous solution of ferric trichloride is preferably 0.1mol/L. NaHCO (NaHCO) 3 THF solution 1mol/LNaHCO 3 Aqueous solution and tetrahydrofuran mixed solution, naHCO 3 The volume ratio of the aqueous solution to the tetrahydrofuran is 1:3 (mL/mL). The vacuum drying temperature is 25-30 ℃ and the drying time is about 24 hours.
(5) Synthesis of silica microspheres:
CSQ-PDMA-PEDOT is dissolved in tetrahydrofuran, hydrochloric acid is added, and the mixture is stirred uniformly until the mixture is clear. Slowly dropwise adding Tetraethoxysilane (TEOS), sealing and rapidly stirring. The bottle cap was opened and the solvent was slowly evaporated by standing at room temperature. Standing, removing upper liquid, taking lower sediment, vacuum filtering, taking sediment, adding water, ultrasonic washing, and standing to remove upper liquid. After the above washing-standing cycle for 3 times, the precipitate was dried in vacuo at room temperature to obtain the objective product.
Wherein, the mass ratio of TEOS to CSQ-PDMA-PEDOT is 1-50: 1, proportioning; tetrahydrofuran and CSQ-PDMA-PEDOT are mixed according to the mass ratio of 100-500: 1, proportioning; the concentration of the hydrochloric acid is 0.5-1 mol/L, and the mass ratio of the hydrochloric acid to the CSQ-PDMA-PEDOT is 50-100: 1, proportioning.
The stirring speed is 300-600 r/min.
The technical scheme of the invention is further described below with reference to specific examples. The starting materials used in the examples below, unless otherwise specified, are all commercially available from conventional sources; the processes used, unless otherwise specified, are all conventional in the art. The room temperature or the normal temperature refers to 25+/-5 ℃ unless otherwise specified.
Example 1
(1) Synthesis of thiophene group-containing octahedral silsesquioxane (CSQ-Th):
DL-N-acetylhomocysteine thiolactone (1.2 mmol) and 4-dimethylaminopyridine (0.1 mmol) were dissolved in 18mL dioxane, transferred into a 50mL Schlenk flask, and purged with nitrogen for 30 minutes. 2-thiopheneethylamine (1 mmol) was added thereto, and the reaction mixture was subjected to three freeze-degassing cycles, and reacted in an oil bath reactor at 40℃for 8 hours.
The degassed CSQ/dioxane solution (5 mL,0.2 mmol/mL) was then injected into the flask and reacted in a 40℃oil bath reactor for a further 14 hours. The solvent was then pumped off under reduced pressure and the dope was washed 3 times with a large amount of deionized water. The aqueous solution was discarded, and then 20mL of methylene chloride was added to dissolve the viscous material, and the solution was dried by adding 4A molecular sieve. The filtrate was filtered and concentrated, and then separated by chromatography (petroleum ether/ethyl acetate=4:4), and dried under vacuum at room temperature for 24 hours to obtain a pale yellow viscous liquid.
(2) Synthesis of Poly (N, N-dimethylaminoethyl methacrylate) (PDMA):
DMA (15.7 g,0.1 mol), DTTC (0.264 g,1 mmol) and AIBN (0.0164 g,0.1 mmol) were dissolved in 10mL dioxane, transferred into a 50mL Schlenk flask, and after rapid stirring, 3 freeze degassing cycles were performed. The reaction was carried out in an oil bath at 65℃for 0.5 hour. Quenching the reaction with liquid nitrogen, melting the frozen reaction flask in warm water, dropping the reaction solution into 220mL of ice petroleum ether for precipitation, rapidly stirring, standing, and pouring out the upper liquid. The precipitate was dried in vacuo for 24 hours to give a yellow solid.
(3) Synthesis of silsesquioxane based Star hybrid Polymer containing thiophene active groups (CSQ-PDMA-Th):
PDMA (7.5 g) was dissolved in 36mL dioxane, transferred into Schlenk flask, and then subjected to 3 freeze-degassing cycles rapidly. Tributylphosphine (1.04 mL,5 mmol) and propylamine (0.411 mL,5 mmol) were injected under argon and a freeze degassing cycle was performed 3 more times. The reaction was heated in an oil bath at 40℃and stirred continuously for 4 hours. Next, the solvent and unreacted propylamine were removed under reduced pressure, 20mL of degassed dioxane was injected, and after dissolution, the solvent was removed under reduced pressure.
Next, CSQ-Th/triethylamine/dioxane solution (1.310 g/0.505mL/30 mL) was injected under argon atmosphere, and then the reactor was placed in an oil bath at a reaction temperature of 30deg.C with stirring for 12 hours. The solvent was then removed under reduced pressure, the viscous material was dissolved in 10mL of dichloromethane, and 180mL of petroleum ether was slowly dropped into the solution, and the solution was dried under vacuum to obtain a pale yellow solid. The mass average molecular weight of the obtained polymer is 32662Da, M w /M n ＝1.42。
(4) Synthesis of tadpole-type conjugated polymer (CSQ-PDMA-PEDOT) with silsesquioxane containing conjugated segment:
CSQ-PDMA-Th (0.1 g) was dissolved in 3.5mL of hydrochloric acid solution (1 mol/L), 1.5mL of ferric trichloride solution (0.1 mol/L) was added, and then 0.5mL of tetrahydrofuran was added. The mixture was transferred to a 30mL serum bottle, and the inner wall was kept as small as possible. Then 10mL of EDOT/n-butanol solution (0.02 mol/L) was slowly overlaid on the aqueous phase along the inner wall of the bottle.
After a reaction was allowed to stand at room temperature for 36 hours at a dark place, the lower blue aqueous phase was removed and centrifuged at high speed for 5 minutes (12400 rad/min) to obtain the upper blue supernatant. Dripping the clear liquid into NaHCO 3 In an aqueous/tetrahydrofuran mixture (15 mL 1mol/L/45mL THF) was stirred rapidly. When no bubbles overflowed, stirring was continued for 0.5 hours, and then allowed to stand for 2 hours. The upper brown clear liquid was removed, concentrated and precipitated in ice petroleum ether, and the precipitate was dried under vacuum for 24 hours to give a brown solid.
(5) Synthesis of silica microspheres:
CSQ-PDMA-PEDOT (0.1 g) was dissolved in tetrahydrofuran (40 g), 1mol/L HCl (5 g) was added and stirred well until clear. TEOS (1 g) was slowly added dropwise, and the mixture was sealed and stirred rapidly for 2 hours without precipitate formation. The bottle cap was opened and the solvent was slowly evaporated by standing at room temperature. After 24 hours of standing, the upper liquid and yellow floats were removed, the lower yellow precipitate was removed, vacuum filtered, the precipitate was taken, 10mL of water was added to wash with ultrasound for 30 seconds, and the upper liquid was removed by standing. After the above washing-standing cycle was performed 3 times, the precipitate was dried in vacuo at room temperature for 24 hours to give a white powdery solid.
FIGS. 1 and 2 are the products obtained in step (1) and step (4), respectively 1 H-NMR spectra, from which it can be seen that CSQ-Th and CSQ-PDMA-PEDOT were successfully synthesized by the method of example 1.
Different amounts of CSQ-PDMA-PEDOT were dissolved in an acidic aqueous solution (hydrochloric acid solution having pH 1) to give CSQ-PDMA-PEDOT solutions of different concentrations (0.001 g/mL, 0.002g/mL, 0.003 g/mL) and the particle size distribution of micelles formed by CSQ-PDMA-PEDOT in the solutions is shown in FIG. 3. From the figure, it can be seen that the CSQ-PDMA-PEDOT micelle has better uniformity in the aqueous solution, and the size of the micelle increases with the increase of the concentration.
The scanning electron microscope image of the silica microsphere prepared in the step (5) is shown in fig. 4, and it can be seen from the image that the spherical silica microsphere is successfully prepared in the embodiment, and has larger particle size, is distributed in 3-8 μm, has an average particle size of 4.4 μm, and is obviously larger than the particle size of the microsphere obtained by taking the star-shaped heteroarm hydrophilic polymer as a soft template in the prior art. Meanwhile, fig. 4 shows that the particle size distribution range of the silica microspheres is wide, probably due to: although the conjugated segments in the polymer CSQ-PDMA-PEDOT help to increase the aggregation capability between polymer molecules and promote the monodispersity of the particle size of the polymer micelle, the hydrophilic portion with a larger specific gravity also leads to poor stability of the micelle, resulting in formation of microspheres of different sizes during the process of stacking and balling of the polymer/silica oligomer complex after hydrolysis, and also reducing the size uniformity of the silica microspheres.
Example 2
(1) Synthesis of thiophene group-containing octahedral silsesquioxane (CSQ-Th):
DL-N-acetylhomocysteine thiolactone (1.2 mmol) and 4-dimethylaminopyridine (0.1 mmol) were dissolved in 18mL dioxane, transferred into a 50mL Schlenk flask, and purged with nitrogen for 30 minutes. 2-thiopheneethylamine (1 mmol) was added thereto, and the reaction mixture was subjected to three freeze-degassing cycles, and reacted in an oil bath reactor at 35℃for 8 hours.
The degassed CSQ/dioxane solution (5 mL,0.2 mmol/mL) was then injected into the flask and reacted in a 40℃oil bath reactor for 16 hours. The solvent was then pumped off under reduced pressure and the dope was washed 3 times with a large amount of deionized water. The aqueous solution was discarded, and then 20mL of methylene chloride was added to dissolve the viscous material, and the solution was dried by adding 4A molecular sieve. The filtrate was filtered and concentrated, and then separated by chromatography (petroleum ether/ethyl acetate=4:4), and dried under vacuum at room temperature for 24 hours to obtain a pale yellow viscous liquid.
(2) Synthesis of Poly (N, N-dimethylaminoethyl methacrylate) (PDMA):
DMA (15.7 g,0.1 mol), DTTC (0.264 g,1 mmol) and AIBN (0.0164 g,0.1 mmol) were dissolved in 10mL dioxane, transferred into a 50mL Schlenk flask, and after rapid stirring, 3 freeze degassing cycles were performed. The reaction was carried out in an oil bath at 70℃for 1 hour. Quenching the reaction with liquid nitrogen, melting the frozen reaction flask in warm water, dropping the reaction solution into 220mL of ice petroleum ether for precipitation, rapidly stirring, standing, and pouring out the upper liquid. The precipitate was dried in vacuo for 24 hours to give a yellow solid.
(3) Synthesis of silsesquioxane based Star hybrid Polymer containing thiophene active groups (CSQ-PDMA-Th):
PDMA (7.5 g) was dissolved in 36mL dioxane, transferred into Schlenk flask, and then subjected to 3 freeze-degassing cycles rapidly. Tributylphosphine (1.04 mL,5 mmol) and propylamine (0.411 mL,5 mmol) were injected under argon and a freeze degassing cycle was performed 3 more times. The reaction was heated in an oil bath at 35℃and stirred continuously for 4 hours. Next, the solvent and unreacted propylamine were removed under reduced pressure, 20mL of degassed dioxane was injected, and after dissolution, the solvent was removed under reduced pressure.
Next, CSQ-Th/triethylamine/dioxane solution (1.310 g/0.505mL/30 mL) was injected under argon atmosphere, and then the reactor was placed in an oil bath at 35℃with stirring for 12 hours. The solvent was then removed under reduced pressure, the viscous material was dissolved in 10mL of dichloromethane, and 180mL of petroleum ether was slowly dropped into the solution, and the solution was dried under vacuum to obtain a pale yellow solid.
(4) Synthesis of tadpole-type conjugated polymer (CSQ-PDMA-PEDOT) with silsesquioxane containing conjugated segment:
CSQ-PDMA-Th (0.1 g) was dissolved in 3.5mL of hydrochloric acid solution (1 mol/L), 1.5mL of ferric trichloride solution (0.1 mol/L) was added, and then 0.5mL of tetrahydrofuran was added. The mixture was transferred to a 30mL serum bottle, and the inner wall was kept as small as possible. Then 10mL of EDOT/n-butanol solution (0.02 mol/L) was slowly overlaid on the aqueous phase along the inner wall of the bottle.
After 24 hours of reaction at room temperature in a dark place, the lower blue aqueous phase was removed and centrifuged at high speed for 5 minutes (12400 rad/min) to obtain the upper blue supernatant. Dripping the clear liquid into NaHCO 3 In an aqueous/tetrahydrofuran mixture (15 mL 1mol/L/45mL THF) was stirred rapidly. When no bubbles overflowed, stirring was continued for 0.5 hours, and then allowed to stand for 2 hours. The upper brown clear liquid was removed, concentrated and precipitated in ice petroleum ether, and the precipitate was dried under vacuum for 24 hours to give a brown solid. The mass average molecular weight of the obtained polymer is 47328Da, M w /M n ＝1.48。
(5) Synthesis of silica microspheres:
CSQ-PDMA-PEDOT (0.1 g) was dissolved in tetrahydrofuran (30 g), 1mol/L HCl (10 g) was added and stirred well until clear. TEOS (2 g) was slowly added dropwise, and the mixture was sealed and rapidly stirred for 2 hours without precipitate formation. The bottle cap was opened and the solvent was slowly evaporated by standing at room temperature. After 24 hours of standing, the upper liquid and yellow floats were removed, the lower yellow precipitate was removed, vacuum filtered, the precipitate was taken, 10mL of water was added to wash with ultrasound for 30 seconds, and the upper liquid was removed by standing. After the above washing-standing cycle was performed 3 times, the precipitate was dried in vacuo at room temperature for 24 hours to give a white powdery solid.
The silica microspheres obtained in this example have a spherical morphology, a particle size of 3 to 10 μm and an average particle size of 5.5 μm.
Example 3
(1) Synthesis of thiophene group-containing octahedral silsesquioxane (CSQ-Th):
DL-N-acetylhomocysteine thiolactone (1.1 mmol) and 4-dimethylaminopyridine (0.1 mmol) were dissolved in 18mL dioxane, transferred into a 50mL Schlenk flask, and purged with nitrogen for 30 minutes. 2-thiopheneethylamine (1 mmol) was added thereto, and the reaction mixture was subjected to three freeze-degassing cycles, and reacted in an oil bath reactor at 40℃for 14 hours.
The degassed CSQ/dioxane solution (5 mL,0.2 mmol/mL) was then injected into the flask and reacted in a 40℃oil bath reactor for a further 14 hours. The solvent was then pumped off under reduced pressure and the dope was washed 3 times with a large amount of deionized water. The aqueous solution was discarded, and then 20mL of methylene chloride was added to dissolve the viscous material, and the solution was dried by adding 4A molecular sieve. The filtrate was filtered and concentrated, and then separated by chromatography (petroleum ether/ethyl acetate=4:4), and dried under vacuum at room temperature for 24 hours to obtain a pale yellow viscous liquid.
(2) Synthesis of Poly (N, N-dimethylaminoethyl methacrylate) (PDMA):
DMA (15.7 g,0.1 mol), DTTC (0.264 g,1 mmol) and AIBN (0.0164 g,0.1 mmol) were dissolved in 10mL dioxane, transferred into a 50mL Schlenk flask, and after rapid stirring, 3 freeze degassing cycles were performed. The reaction was carried out in an oil bath at 70℃for 0.5 hour. Quenching the reaction with liquid nitrogen, melting the frozen reaction flask in warm water, dropping the reaction solution into 220mL of ice petroleum ether for precipitation, rapidly stirring, standing, and pouring out the upper liquid. The precipitate was dried in vacuo for 24 hours to give a yellow solid.
(3) Synthesis of silsesquioxane based Star hybrid Polymer containing thiophene active groups (CSQ-PDMA-Th):
PDMA (7.5 g) was dissolved in 36mL dioxane, transferred into Schlenk flask, and then subjected to 3 freeze-degassing cycles rapidly. Tributylphosphine (1.04 mL,5 mmol) and propylamine (0.411 mL,5 mmol) were injected under argon and a freeze degassing cycle was performed 3 more times. The reaction was heated in an oil bath at 40℃and stirred for 5 hours. Next, the solvent and unreacted propylamine were removed under reduced pressure, 20mL of degassed dioxane was injected, and after dissolution, the solvent was removed under reduced pressure.
Next, CSQ-Th/triethylamine/dioxane solution (1.310 g/0.505mL/30 mL) was injected under argon atmosphere, and then the reactor was placed in an oil bath at a reaction temperature of 30deg.C with stirring for 12 hours. The solvent was then removed under reduced pressure, the viscous material was dissolved in 10mL of dichloromethane, and 180mL of petroleum ether was slowly dropped into the solution, and the solution was dried under vacuum to obtain a pale yellow solid.
(4) Synthesis of tadpole-type conjugated polymer (CSQ-PDMA-PEDOT) with silsesquioxane containing conjugated segment:
CSQ-PDMA-Th (0.1 g) was dissolved in 3.5mL of hydrochloric acid solution (1 mol/L), 1.5mL of ferric trichloride solution (0.1 mol/L) was added, and then 0.5mL of tetrahydrofuran was added. The mixture was transferred to a 30mL serum bottle, and the inner wall was kept as small as possible. Then 10mL of EDOT/n-butanol solution (0.02 mol/L) was slowly overlaid on the aqueous phase along the inner wall of the bottle.
After a reaction was allowed to stand at room temperature for 30 hours in the absence of light, the lower blue aqueous phase was removed and centrifuged at high speed for 5 minutes (12400 rad/min) to obtain the upper blue supernatant. Dripping the clear liquid into NaHCO 3 In an aqueous/tetrahydrofuran mixture (15 mL 1mol/L/45mL THF) was stirred rapidly. When no bubbles overflowed, stirring was continued for 0.5 hours, and then allowed to stand for 2 hours. The upper brown clear liquid was removed, concentrated and precipitated in ice petroleum ether, and the precipitate was dried under vacuum for 24 hours to give a brown solid. The mass average molecular weight of the obtained polymer is 438 Da, M w /M n ＝1.36。
(5) Synthesis of silica microspheres:
CSQ-PDMA-PEDOT (0.1 g) was dissolved in tetrahydrofuran (40 g), 0.5mol/L HCl (5 g) was added and stirred well until clear. TEOS (1.5 g) was slowly added dropwise, and the mixture was stirred rapidly under sealed conditions for 2 hours without precipitate formation. The bottle cap was opened and the solvent was slowly evaporated by standing at room temperature. After 24 hours of standing, the upper liquid and yellow floats were removed, the lower yellow precipitate was removed, vacuum filtered, the precipitate was taken, 10mL of water was added to wash with ultrasound for 30 seconds, and the upper liquid was removed by standing. After the above washing-standing cycle was performed 3 times, the precipitate was dried in vacuo at room temperature for 24 hours to give a white powdery solid.
The silica microspheres obtained in this example have a spherical morphology, a particle size of 2 to 10 μm and an average particle size of 4.8. Mu.m.
Example 4
(1) Synthesis of thiophene group-containing octahedral silsesquioxane (CSQ-Th):
DL-N-acetylhomocysteine thiolactone (1.2 mmol) and 4-dimethylaminopyridine (0.1 mmol) were dissolved in 18mL dioxane, transferred into a 50mL Schlenk flask, and purged with nitrogen for 30 minutes. 2-thiopheneethylamine (1 mmol) was added thereto, and the reaction mixture was subjected to three freeze-degassing cycles, and reacted in an oil bath reactor at 40℃for 12 hours.
The degassed CSQ/dioxane solution (5 mL,0.2 mmol/mL) was then injected into the flask and reacted in a 40℃oil bath reactor for 18 hours. The solvent was then pumped off under reduced pressure and the dope was washed 3 times with a large amount of deionized water. The aqueous solution was discarded, and then 20mL of methylene chloride was added to dissolve the viscous material, and the solution was dried by adding 4A molecular sieve. The filtrate was filtered and concentrated, and then separated by chromatography (petroleum ether/ethyl acetate=4:4), and dried under vacuum at room temperature for 24 hours to obtain a pale yellow viscous liquid.
(2) Synthesis of Poly (N, N-dimethylaminoethyl methacrylate) (PDMA):
DMA (15.7 g,0.1 mol), DTTC (0.264 g,1 mmol) and AIBN (0.0164 g,0.1 mmol) were dissolved in 10mL dioxane, transferred into a 50mL Schlenk flask, and after rapid stirring, 3 freeze degassing cycles were performed. The reaction was carried out in an oil bath at 70℃for 2 hours. Quenching the reaction with liquid nitrogen, melting the frozen reaction flask in warm water, dropping the reaction solution into 220mL of ice petroleum ether for precipitation, rapidly stirring, standing, and pouring out the upper liquid. The precipitate was dried in vacuo for 24 hours to give a yellow solid.
(3) Synthesis of silsesquioxane based Star hybrid Polymer containing thiophene active groups (CSQ-PDMA-Th):
PDMA (7.5 g) was dissolved in 36mL dioxane, transferred into Schlenk flask, and then subjected to 3 freeze-degassing cycles rapidly. Tributylphosphine (1.04 mL,5 mmol) and propylamine (0.411 mL,5 mmol) were injected under argon and a freeze degassing cycle was performed 3 more times. The reaction was heated in an oil bath at 40℃and stirred continuously for 4 hours. Next, the solvent and unreacted propylamine were removed under reduced pressure, 20mL of degassed dioxane was injected, and after dissolution, the solvent was removed under reduced pressure.
Next, CSQ-Th/triethylamine/dioxane solution (1.310 g/0.505mL/30 mL) was injected under argon atmosphere, and then the reactor was placed in an oil bath at 40℃with stirring for 12 hours. The solvent was then removed under reduced pressure, the viscous material was dissolved in 10mL of dichloromethane, and 180mL of petroleum ether was slowly dropped into the solution, and the solution was dried under vacuum to obtain a pale yellow solid.
(4) Synthesis of tadpole-type conjugated polymer (CSQ-PDMA-PEDOT) with silsesquioxane containing conjugated segment:
CSQ-PDMA-Th (0.1 g) was dissolved in 3.5mL of hydrochloric acid solution (1 mol/L), 1.5mL of ferric trichloride solution (0.1 mol/L) was added, and then 0.5mL of tetrahydrofuran was added. The mixture was transferred to a 30mL serum bottle, and the inner wall was kept as small as possible. Then 10mL of EDOT/n-butanol solution (0.02 mol/L) was slowly overlaid on the aqueous phase along the inner wall of the bottle.
After 24 hours of reaction at room temperature in a dark place, the lower blue aqueous phase was removed and centrifuged at high speed for 5 minutes (12400 rad/min) to obtain the upper blue supernatant. Dripping the clear liquid into NaHCO 3 In an aqueous/tetrahydrofuran mixture (15 mL 1mol/L/45mL THF) was stirred rapidly. When no bubbles overflowed, stirring was continued for 0.5 hours, and then allowed to stand for 2 hours. The upper brown clear liquid was removed, concentrated and precipitated in ice petroleum ether, and the precipitate was dried under vacuum for 24 hours to give a brown solid. The mass average molecular weight of the obtained polymer is 67846Da, M w /M n ＝1.62。
(5) Synthesis of silica microspheres:
CSQ-PDMA-PEDOT (0.1 g) was dissolved in tetrahydrofuran (50 g), 0.5mol/L HCl (10 g) was added and stirred well until clear. TEOS (3 g) was slowly added dropwise, and the mixture was sealed and rapidly stirred for 2 hours without precipitate formation. The bottle cap was opened and the solvent was slowly evaporated by standing at room temperature. After 24 hours of standing, the upper liquid and yellow floats were removed, the lower yellow precipitate was removed, vacuum filtered, the precipitate was taken, 10mL of water was added to wash with ultrasound for 30 seconds, and the upper liquid was removed by standing. After the above washing-standing cycle was performed 3 times, the precipitate was dried in vacuo at room temperature for 24 hours to give a white powdery solid.
The silica microspheres obtained in this example have a spherical morphology, a particle size of 2 to 10 μm and an average particle size of 6.2. Mu.m.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (10)
1. A preparation method of silica microspheres is characterized in that: the method comprises the following steps:
mixing tadpole type conjugated polymer solution with a silicon source to obtain a suspension; volatilizing a solvent in the suspension to obtain silica microspheres;
the tadpole type conjugated polymer has a structural general formula shown in the following formula I:
wherein m is more than or equal to 20 and less than or equal to 50; n is more than or equal to 10 and less than or equal to 30.
2. The method of manufacture of claim 1, wherein: the mass average molecular weight of the tadpole type conjugated polymer is 30000-70000 Da.
3. The method of manufacture of claim 1, wherein: the tadpole type conjugated polymer solution is a mixed solution of the tadpole type conjugated polymer, an organic solvent and hydrochloric acid.
4. A method of preparation according to claim 3, characterized in that: the mass ratio of the organic solvent to the tadpole type conjugated polymer is 100-500: 1.
5. A method of preparation according to claim 3, characterized in that: the concentration of the hydrochloric acid is 0.5-2 mol/L.
6. The method of manufacture of claim 1, wherein: the silicon source comprises white carbon black, silica sol, sodium silicate and a knotThe structural formula is xR 1 -Si-y(O-R 2 ) At least one of the compounds of (1), wherein x+y=4, and y > 0, r 1 、R 2 Independently selected from the group consisting of C1-C20 alkyl, optionally substituted C1-C20 alkyl, C1-C20 alkenyl, and optionally substituted C1-C20 alkenyl.
7. The method of manufacture of claim 1, wherein: the mass ratio of the silicon source to the tadpole type conjugated polymer is 1-50: 1.
8. a silica microsphere characterized by: the process according to any one of claims 1 to 7.
9. The silica microsphere according to claim 8, wherein: the silicon dioxide microsphere has a spherical morphology and the particle size is 2-10 mu m.
10. Use of the silica according to claim 8 or 9, characterized in that: the method is applied to the preparation of antistatic coating materials.
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| CN107565149A (en) * | 2017-08-14 | 2018-01-09 | 西北工业大学 | The PEM and preparation method of the tadpole type sulfonation Polymer Synthesizing of hydridization containing POSS |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107565149A (en) * | 2017-08-14 | 2018-01-09 | 西北工业大学 | The PEM and preparation method of the tadpole type sulfonation Polymer Synthesizing of hydridization containing POSS |
| CN109399648A (en) * | 2018-11-10 | 2019-03-01 | 天津大学 | Micron size porous silica microballoon and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| Yangyang Han.Polyhedral oligomeric silsesquioxane grafted silica-based core-shell microspheres for reversed-phase high-performance liquid chromatography.Microchimica Acta.2019,第186卷(第6期),第1-9页. * |
| 胡小勇等.可溶性笼形倍半硅氧烷基共轭聚合物 作为一种高效的单壁碳纳米管分散剂.《广东化工》.2020,第47卷(第412期),第1-3、10页. * |
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