CN115784243A - Preparation method for constructing monodisperse hollow-structure silicon oxide microsphere material by using salt as template - Google Patents
Preparation method for constructing monodisperse hollow-structure silicon oxide microsphere material by using salt as template Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 239000004005 microsphere Substances 0.000 title claims abstract description 61
- 150000003839 salts Chemical class 0.000 title claims abstract description 57
- 229910052814 silicon oxide Inorganic materials 0.000 title claims abstract description 52
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000945 filler Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 239000000377 silicon dioxide Substances 0.000 claims description 26
- 239000002243 precursor Substances 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 15
- 239000000084 colloidal system Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 238000004132 cross linking Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 8
- -1 organic acid anion Chemical class 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000001737 promoting effect Effects 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 239000001509 sodium citrate Substances 0.000 claims description 4
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- WPUMTJGUQUYPIV-JIZZDEOASA-L disodium (S)-malate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)CC([O-])=O WPUMTJGUQUYPIV-JIZZDEOASA-L 0.000 claims description 3
- 235000019265 sodium DL-malate Nutrition 0.000 claims description 3
- 239000001394 sodium malate Substances 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FENRSEGZMITUEF-ATTCVCFYSA-E [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].OP(=O)([O-])O[C@@H]1[C@@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H](OP(=O)([O-])[O-])[C@H](OP(=O)(O)[O-])[C@H]1OP(=O)([O-])[O-] FENRSEGZMITUEF-ATTCVCFYSA-E 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 238000001338 self-assembly Methods 0.000 claims description 2
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 2
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 2
- 229960005055 sodium ascorbate Drugs 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 229940083982 sodium phytate Drugs 0.000 claims description 2
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims 1
- 150000001282 organosilanes Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 20
- 239000002244 precipitate Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000004100 electronic packaging Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZUEKXCXHTXJYAR-UHFFFAOYSA-N tetrapropan-2-yl silicate Chemical compound CC(C)O[Si](OC(C)C)(OC(C)C)OC(C)C ZUEKXCXHTXJYAR-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- BCLLLHFGVQKVKL-UHFFFAOYSA-N tetratert-butyl silicate Chemical compound CC(C)(C)O[Si](OC(C)(C)C)(OC(C)(C)C)OC(C)(C)C BCLLLHFGVQKVKL-UHFFFAOYSA-N 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention belongs to the field of silicon oxide microsphere materials, and particularly discloses a preparation method for constructing a silicon oxide microsphere material with a monodisperse hollow structure by using salt as a template. Compared with the prior art, the preparation method has the advantages of simple operation, good repeatability, low cost, easily obtained raw materials, industrial preparation and the like, and the obtained hollow silica microspheres have wider and adjustable size, good monodispersity and uniform granularity and can be used as low dielectric fillers with excellent performance.
Description
Technical Field
The invention belongs to the field of silicon oxide microsphere materials, and particularly discloses a preparation method for constructing a monodisperse hollow-structure silicon oxide microsphere material by using salt as a template.
Background
Due to the special physical and chemical properties (such as high porosity and hollow rate) and the available internal cavity and external shell structure characteristics, the hollow structure nano material has wide application prospects in various fields of electronic information, environmental quality, light weight manufacturing, cosmetics, daily necessities and the like. In the application process, a plurality of structural characteristics of the material itself play a very critical role in performance, such as monodispersity, size, surface state, conductivity and other structural characteristics of material particles, so that higher and higher requirements are provided for the preparation control of the hollow structural material, and the preparation and application of the hollow structural material with high-efficiency and adjustable size and monodispersity are paid more and more attention. Silicon oxide is the most abundant element substance on the earth, efficient utilization of the silicon oxide is an important way for improving resource utilization efficiency, the silicon oxide has good electrical insulation and relatively low dielectric constant, and in recent years, the silicon oxide is more and more concerned in the fields of electronic chip packaging substrates and the like, and can be used as a low dielectric filler to improve the dielectric performance of related devices. Therefore, the development of a simple preparation method of the low-cost high-efficiency size-adjustable monodisperse hollow-structure silica microsphere has very important significance.
Disclosure of Invention
In view of the above situation, the invention discloses a preparation method for constructing a monodisperse hollow structure silicon oxide microsphere material by using salt as a template and the silicon oxide microsphere material obtained by the preparation method, and provides a monodisperse hollow structure silicon oxide microsphere material which is easy to operate, cheap and easily available in raw materials, good in repeatability and capable of being industrially prepared, and a method for preparing the same by using organic-inorganic hybrid salt as a template for deposition assembly.
The invention comprises the following technical scheme:
a preparation method for constructing a monodisperse hollow structure silicon oxide microsphere material by taking salt as a template comprises the following steps:
s1, adopting salt as a template agent for self-assembly deposition, dissolving the salt in good solvent water, then adding an acid or alkali catalyst capable of effectively promoting hydrolysis and crosslinking of a silicon oxide precursor, and uniformly dispersing under stirring to obtain a clear salt water solution;
preferably, the stirring is mechanical stirring, the stirring power range is 50-500W, and the stirring speed is 0-200rpm.
S2, dropwise adding the solution into a poor solvent organic alcohol of the salt, so that the anions and cations of the salt are assembled in a solution system to form colloid assembly particles with a certain size, and thus obtaining a colloid solution;
s3, adding a silicon oxide precursor into the colloidal solution; promoting the deposition, crosslinking and growth of a silicon oxide precursor on the surfaces of the particles of the colloid assembly by using an acid or alkali catalyst in the system, and aging to obtain a mixed solution of the silicon oxide colloid;
preferably, the volume ratio of the catalyst to the silicon oxide precursor is 1:1-5;
preferably, the salt is an organic-inorganic hybrid salt;
preferably, the molar ratio of the organic alcohol, the water, the organic-inorganic hybrid salt and the silicon oxide precursor is 20-500:1-10:0.01-0.5:1;
preferably, standing and aging for 6-24h to obtain a white silica colloid mixed solution;
preferably, the temperature of the catalytic reaction is 0-40 ℃, and the reaction time is 6-24h;
s4, centrifuging the silica gel mixed solution to collect solid matters, cleaning and removing template agent salt by adopting a good solvent of salt, and drying to obtain a monodisperse hollow structure silica gel microsphere material;
preferably, the good solvent is water;
preferably, the centrifugal speed of the centrifugal separation is 8000-15000rpm, and the centrifugal time is 5-30min;
s5, further calcining the formed silicon oxide microsphere material with the monodisperse hollow structure to obtain a silicon oxide microsphere material with a monodisperse hollow structure;
preferably, the calcination is carried out in a muffle furnace under air atmosphere to obtain the silica microsphere material with adjustable size within the range of 200-800nm, monodispersed shell and compact structure.
Furthermore, the preparation method of the silica microsphere material with the monodisperse hollow structure is constructed by taking salt as a template, wherein the salt is salt which is highly soluble in water and is difficult to dissolve in organic alcohol and contains organic acid anions and alkali metal cations.
Further, the preparation method of the silica microsphere material with the monodisperse hollow structure is constructed by taking salt as a template, wherein the salt is one or any combination of ionic ammonium citrate, sodium citrate, potassium citrate, sodium malate, sodium ascorbate and sodium phytate.
Further, in the preparation method for constructing the silica microsphere material with the monodisperse hollow structure by using the salt as the template, the organic alcohol in the step S2 is a low-carbon organic alcohol containing a short alkyl chain.
Further, in the preparation method for constructing the silicon oxide microsphere material with the monodisperse hollow structure by using the salt as the template, the organic alcohol in the step S2 is one or any combination of methanol, ethanol, n-propanol, isopropanol and n-butanol.
Further, in the preparation method for constructing the silica microsphere material with the monodisperse hollow structure by using the salt as the template, the acid catalyst is one or any combination of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid and acetic acid; the alkali catalyst is one of ammonia water, sodium hydroxide, potassium hydroxide and ethanolamine or any combination thereof.
Further, in the preparation method for constructing the silicon oxide microsphere material with the monodisperse hollow structure by using the salt as the template, the silicon oxide precursor is organic silicate or organic silane coupling agent.
Further, in the preparation method for constructing the silicon oxide microsphere material with the monodisperse hollow structure by using the salt as the template, the silicon oxide precursor is an organic silicon alkoxide precursor which can be hydrolyzed and crosslinked in a mixed solution of water and alcohol, and can be tetraethyl silicate (C) 8 H 20 O 4 Si), tetrapropyl silicate (C) 12 H 28 O 4 Si), tetraisopropyl silicate (C) 12 H 28 O 4 Si), tetrabutyl silicate (C) 16 H 36 O 4 Si), tetra-tert-butyl silicate (C) 16 H 36 O 4 Si), 3-aminopropyltriethoxysilane (C) 9 H 23 O 3 NSi), 3- (2,3-glycidoxy) propyltrimethoxysilane (C) 9 H 20 O 5 Si), methyltriethoxysilane (C) 7 H 18 O 3 Si) or any combination thereof.
Further, the monodisperse hollow-structure silica microsphere material prepared by the preparation method is provided.
Furthermore, the monodisperse hollow-structure silicon oxide microsphere material prepared by the preparation method has a hollow spherical appearance, the diameter of the whole microsphere is 200-800nm, the size of an internal cavity is 100-500nm, the outer shell has a compact structure and has a small pore structure, the thickness of the outer shell ranges from 50nm to 300nm, and the specific surface area of the microsphere is 5-20m 2 Per g, pore volume of 0.2-0.7cm 3 /g。
Furthermore, the monodisperse hollow-structure silica microsphere material is applied to low dielectric fillers, and is particularly used for processing and manufacturing electronic packaging substrates.
According to the invention, ionic salt composed of organic acid anions and alkali metals can realize good ionization dispersion in water generally, but after the ionic salt is added into poor solvent organic alcohol, the ions can be assembled to form spherical colloid particles, so that colloidal solution of uniformly dispersed salt ion particles is formed, then oligomer obtained by hydrolysis of a silicon oxide precursor can be deposited and assembled on the surface of the salt colloid particles, then a cross-linking growth process is carried out, an acid or alkali catalyst capable of effectively adjusting the hydrolysis cross-linking speed of the silicon oxide precursor is added in the process, the hydrolysis cross-linking speed of the silicon oxide precursor in a mixed solvent can be effectively adjusted, so that core-shell structure colloid microspheres with the inside being salt colloid particles and the outside being silicon oxide are obtained, then the internal ionic salt template agent can be dissolved and removed by water through repeated cleaning of organic alcohol and water, and after proper drying and calcining treatment, the silicon oxide microsphere material with the adjustable monodisperse mesoporous structure in a large range is obtained, and the compact silicon oxide of the shell layer has no participation of pore-forming agents such as surfactants and the like in the assembly growth process.
The invention has the following beneficial effects:
compared with the prior art, the invention can well dissolve and disperse the organic-inorganic hybrid ionic salt in water, the organic-inorganic hybrid ionic salt can be self-assembled and aggregated into uniformly dispersed colloidal salt ion particles in a poor solvent organic alcohol, and simultaneously, the acid or alkali catalyst capable of effectively regulating the hydrolysis and crosslinking of the silicon oxide precursor is introduced, after the silicon oxide precursor is added into a system, the deposition growth process of the silicon oxide precursor is generated on the surface of the salt colloidal particles, the hydrolysis crosslinking speed of the silicon oxide precursor in a mixed solvent of water and organic alcohol and the aggregation degree among the particles are regulated, so that the uniformly monodisperse core-shell structure composite colloidal microspheres are obtained, the organic-inorganic hybrid salt template agent can be dissolved and removed in the subsequent cleaning process by adopting organic alcohol and water, so that the material has an obvious hollow structure, and the monodisperse hollow structure silicon oxide microsphere material is obtained after drying and calcining treatment.
Compared with the traditional synthetic method, the method has the advantages of strong controllability, simple process, good repeatability, convenient operation and low cost, and does not need corrosive substances to remove the template agent. The obtained hollow silica microspheres have wider and adjustable diameter size (200-800 nm), spherical appearance, good monodispersity and uniform granularity, and because the silica on the outer layer does not participate in pore-forming agents such as surfactants and the like in the assembling and growing process, the silica on the shell layer has a compact structure and less pore structures, and can be used as low dielectric filler with excellent performance and used for processing and manufacturing electronic packaging substrates.
Drawings
FIG. 1: a characteristic scanning electron microscope (TEM) image of the monodisperse hollow silica microsphere material prepared in example 1;
FIG. 2: a nitrogen adsorption and desorption curve diagram of the monodisperse hollow carbon mesoporous microsphere material prepared in example 1.
Detailed Description
The following embodiments of the present invention are provided by way of specific examples, and other advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure herein. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention.
It is to be understood that the processing equipment or apparatus not specifically identified in the following examples is conventional in the art.
Furthermore, it is to be understood that one or more method steps mentioned in the present invention does not exclude that other method steps may also be present before or after the combined steps or that other method steps may also be inserted between these explicitly mentioned steps, unless otherwise indicated; it is also to be understood that a combined connection between one or more devices/apparatus as referred to in the present application does not exclude that further devices/apparatus may be present before or after the combined device/apparatus or that further devices/apparatus may be interposed between two devices/apparatus explicitly referred to, unless otherwise indicated. Moreover, unless otherwise indicated, the numbering of the method steps is only a convenient tool for identifying each method step, and is not intended to limit the order of the method steps or the scope of the invention, and changes or modifications in the relative relationship thereof may be regarded as the scope of the invention without substantial change in the technical content.
Example 1
(1) Dissolving 0.3g sodium citrate with 12mL water under stirring, adding 6mL ammonia water
Continuously mechanically stirring the mixture as a polymerization catalyst for 5min, quickly introducing 300mL of ethanol into the mixed solution, continuously stirring the mixture for 5min, adding 10mL of TEOS (tetraethoxysilane) into the mixture, stirring the mixture to dissolve the tetraethoxysilane, continuously stirring the mixture for 5min, standing the mixture for ageing reaction for 12h to obtain a white gel mixed solution, and controlling the whole polymerization reaction process to be at the room temperature of 25 ℃.
(2) And centrifuging the obtained white gel mixed solution at 10000rpm for 10min to separate a white gel precipitate product, then washing the white gel precipitate product with ethanol for three times, then washing the white gel precipitate product with water for three times, and drying the obtained white precipitate in air at 60 ℃ for 12h to obtain the monodisperse hollow structure microspheres with the diameter size of 350 nm.
(3) Then calcining for 4h at 700 ℃ in the air atmosphere to obtain the monodisperse hollow silicon oxide microspheres with the diameter size of 300 nm. The morphology and characteristics are shown in FIGS. 1-2; as shown in the attached figure 1, the prepared silicon oxide microsphere material has a hollow structure with spherical morphology, and the diameter size of the microsphere is about 300nm; the thickness of the shell layer is about 40-50nm. The spherical material has an obvious cavity structure composition, the outer shell layer has a compact structure, and the monodispersion coefficient can reach 0.17 through dynamic light scattering measurement; as shown in FIG. 2, it has a value as high as 17g/m as measured by nitrogen adsorption and desorption 2 The specific surface area of (2).
Example 2
(1) 0.3g of sodium citrate was dissolved in 10mL of water under stirring, and after dissolution, 5mL of aqueous ammonia was added and the solution was dissolved by continuing mechanical stirring. Stirring for 5min, quickly introducing the mixed solution into 300mL of ethanol mixed solution, continuously stirring for 5min, adding 10mL of TEOS, stirring for dissolving, continuously stirring for 5min, standing, aging and reacting for 12h, wherein the temperature of the whole reaction process is controlled at 20 ℃.
(2) And centrifuging the obtained white gel mixed solution at 10000rpm for 10min to separate a white gel precipitate product, then washing the white gel product with ethanol for three times, then washing the white gel product with water for three times, and drying the obtained white gel in the air at 60 ℃ for 12h to obtain the monodisperse hollow-structure mesoporous high polymer microspheres with the diameter size of 350 nm.
(3) Then calcining for 4h at 700 ℃ in air atmosphere to obtain the monodisperse hollow silicon oxide microspheres with the diameter size of 300nm, wherein the shell layer is thickened by 10nm compared with example 1.
Example 3
0.6g of sodium malate was dissolved in 15mL of water under stirring, and after dissolution, 8mL of ammonia water was added, and the solution was dissolved by continuous mechanical stirring. Stirring for 5min, quickly introducing the mixed solution into 300mL of ethanol mixed solution, continuously stirring for 5min, adding 10mL of TEOS, stirring to disperse, continuously stirring for 5min, standing, aging and reacting for 12h, wherein the temperature in the whole reaction process is controlled at 30 ℃. And centrifuging the obtained white gel mixed solution at 10000rpm for 10min to obtain a white gel precipitate product, washing with ethanol for three times, washing with water for three times, and drying the obtained white precipitate in air at 60 ℃ for 12h to obtain the monodisperse hollow silica gel microspheres with the diameter of 700 nm. Then calcining for 4h at 800 ℃ in the air atmosphere to obtain the monodisperse hollow silicon oxide microspheres with the diameter size of 650 nm.
Example 4
0.7g of sodium quininate was dissolved with 12mL of water under stirring, and after dissolution, 6mL of ammonia water was added and the dissolution was continued with mechanical stirring. Stirring for 5min, quickly introducing the mixed solution into 300mL of ethanol mixed solution, continuously stirring for 5min, adding 10mL of TEOS, stirring to disperse, continuously stirring for 5min, standing, aging and reacting for 12h, wherein the temperature in the whole reaction process is controlled at 30 ℃. And centrifuging the obtained white gel mixed solution at 10000rpm for 10min to separate a white gel precipitate product, then washing the white gel precipitate product with ethanol for three times, then washing the white gel precipitate product with water for three times, and drying the obtained white precipitate product in air at 60 ℃ for 12h to obtain the monodisperse hollow-structure mesoporous high polymer microsphere with the diameter size of 850 nm. Then calcining for 4 hours at 600 ℃ under the nitrogen protection atmosphere to obtain the monodisperse hollow silicon oxide microspheres with the diameter size of 800 nm.
Example 5
0.3g ammonium citrate was dissolved in 10mL water under stirring, and after dissolution, 5mL ammonia was added, and mechanical stirring was continued. Stirring for 5min, quickly introducing the mixed solution into 300mL of ethanol mixed solution, continuously stirring for 5min, adding 10mL of TEOS, stirring to disperse, continuously stirring for 5min, standing, aging and reacting for 12h, wherein the whole reaction process is controlled at room temperature of 25 ℃. And centrifuging the obtained white gel mixed solution at 10000rpm for 10min to separate a white gel precipitate product, then washing the white gel precipitate product with ethanol for three times, then washing the white gel precipitate product with water for three times, and drying the obtained white precipitate product in air at 60 ℃ for 12h to obtain the monodisperse hollow structure mesoporous silica microspheres with the diameter size of 750 nm. Then calcining for 4 hours at 600 ℃ in the air atmosphere to obtain the monodisperse hollow silicon oxide microspheres with the diameter size of 700 nm.
The morphology and characteristics of the monodisperse carbon mesoporous microspheres prepared in examples 2-5 are similar to those of example 1, and are not repeated.
From the above examples 1-5, it can be seen that, according to the present invention, by well dissolving and dispersing an organic-inorganic hybrid ionic salt in water, the organic-inorganic hybrid ionic salt can self-assemble and aggregate in a poor solvent organic alcohol to form uniformly dispersed colloidal salt ionic particles, and simultaneously introducing an acid or base catalyst capable of effectively adjusting hydrolysis and crosslinking of a silica precursor, after the silica precursor is added into a system, a deposition growth process of the silica precursor occurs on the surface of the salt colloidal particles, and the rate of hydrolytic crosslinking of the silica precursor in a mixed solvent of water and organic alcohol and the degree of aggregation between particles are adjusted, so as to obtain uniformly monodisperse core-shell structure composite colloidal microspheres, and then the organic-inorganic hybrid salt template agent can be dissolved and removed by adopting a cleaning process of organic alcohol and water, so that the material has an obvious hollow structure, and then the monodisperse hollow structure silica microsphere material is obtained after drying and calcining.
The above-mentioned embodiments only represent a limited number of preferred embodiments of the present invention, and the description is specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. A preparation method for constructing a monodisperse hollow structure silicon oxide microsphere material by taking salt as a template is characterized by comprising the following steps:
s1, adopting salt as a template agent for self-assembly deposition, dissolving the salt in good solvent water, then adding an acid or alkali catalyst capable of effectively promoting hydrolysis and crosslinking of a silicon oxide precursor, and uniformly dispersing under stirring to obtain a clear salt water solution;
s2, dropwise adding the solution into a poor solvent organic alcohol of the salt, so that the anions and cations of the salt are assembled in a solution system to form colloid assembly particles with a certain size, and thus obtaining a colloid solution;
s3, adding a silicon oxide precursor into the colloidal solution; promoting the deposition, crosslinking and growth of a silicon oxide precursor on the surfaces of the particles of the colloid assembly by using an acid or alkali catalyst in the system, and aging to obtain a mixed solution of the silicon oxide colloid;
s4, centrifuging the silica gel mixed solution to collect solid matters, cleaning and removing template agent salt by adopting a good solvent of salt, and drying to obtain a monodisperse hollow structure silica gel microsphere material;
and S5, further calcining the formed silicon oxide microsphere material with the monodisperse hollow structure to obtain the silicon oxide microsphere material with the monodisperse hollow structure.
2. The method for preparing a silica microsphere material with a monodisperse hollow structure by using a salt as a template according to claim 1, wherein the organic salt is a salt containing an organic acid anion and an alkali metal cation, which is highly soluble in water and hardly soluble in an organic alcohol.
3. The method for preparing the silica microsphere material with the monodisperse hollow structure by using the salt as the template according to claim 1, wherein the salt is one or more of ionic ammonium citrate, sodium citrate, potassium citrate, sodium malate, sodium ascorbate and sodium phytate in any combination.
4. The method as claimed in claim 1, wherein the organic alcohol in step S2 is a low-carbon organic alcohol having a short alkyl chain.
5. The method for preparing the silica microsphere material with the monodisperse hollow structure by using the salt as the template as claimed in claim 1, wherein the organic alcohol in the step S2 is one or any combination of methanol, ethanol, n-propanol, isopropanol and n-butanol.
6. The method for preparing the silica microsphere material with the monodisperse hollow structure constructed by taking the salt as the template according to claim 1, wherein the acid catalyst is one or any combination of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid and acetic acid; the alkali catalyst is one of ammonia water, sodium hydroxide, potassium hydroxide and ethanolamine or any combination thereof.
7. The method for preparing the silica microsphere material with the monodisperse hollow structure constructed by using the salt as the template according to claim 1, wherein the silica precursor is organosilicate or an organosilane coupling agent.
8. A monodisperse hollow silica microsphere material prepared by the method of any one of claims 1 to 7.
9. The monodisperse hollow structure silica microsphere material of claim 8, wherein the material has a hollow spherical appearance, the diameter of the whole microsphere is 200-800nm, the size of the inner cavity is 100-500nm, the outer shell has a dense structure and has a less porous structure, the thickness of the outer shell ranges from 50-300nm, and the specific surface area of the microsphere ranges from 5-20m 2 Per g, pore volume of 0.2-0.7cm 3 /g。
10. The use of a monodisperse hollow silica microsphere material according to claim 8 in low dielectric fillers.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800684A (en) * | 2016-04-05 | 2016-07-27 | 复旦大学 | Monodispersive porous crystal titanium oxide nanosphere with size smaller than 100 nm and preparation method thereof |
| CN109675506A (en) * | 2018-12-27 | 2019-04-26 | 上海元颉新材料科技有限公司 | The structure mesoporous silicon oxide microsphere material of monodisperse hollow and its Dual Surfactants induce process for assembly preparing |
| CN110508222A (en) * | 2019-08-02 | 2019-11-29 | 复旦大学 | Monodisperse core-shell particles and preparation method thereof with mesoporous silicon oxide shell |
| CN113086963A (en) * | 2019-12-23 | 2021-07-09 | 中国科学院青岛生物能源与过程研究所 | Monodisperse hollow-structure carbon mesoporous microsphere material and preparation method by taking organic-inorganic hybrid salt as template for induced assembly |
-
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800684A (en) * | 2016-04-05 | 2016-07-27 | 复旦大学 | Monodispersive porous crystal titanium oxide nanosphere with size smaller than 100 nm and preparation method thereof |
| CN109675506A (en) * | 2018-12-27 | 2019-04-26 | 上海元颉新材料科技有限公司 | The structure mesoporous silicon oxide microsphere material of monodisperse hollow and its Dual Surfactants induce process for assembly preparing |
| CN110508222A (en) * | 2019-08-02 | 2019-11-29 | 复旦大学 | Monodisperse core-shell particles and preparation method thereof with mesoporous silicon oxide shell |
| CN113086963A (en) * | 2019-12-23 | 2021-07-09 | 中国科学院青岛生物能源与过程研究所 | Monodisperse hollow-structure carbon mesoporous microsphere material and preparation method by taking organic-inorganic hybrid salt as template for induced assembly |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117550615A (en) * | 2024-01-11 | 2024-02-13 | 络合高新材料(上海)有限公司 | Amination hollow nano silicon dioxide and epoxy resin composition thereof |
| CN117550615B (en) * | 2024-01-11 | 2024-04-12 | 络合高新材料(上海)有限公司 | Amination hollow nano silicon dioxide and epoxy resin composition thereof |
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