CN115466488A - Hollow spherical silicon dioxide epoxy resin composite material and preparation method and application thereof - Google Patents
Hollow spherical silicon dioxide epoxy resin composite material and preparation method and application thereof 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 266
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 125
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 104
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 104
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229920006336 epoxy molding compound Polymers 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 26
- 239000000243 solution Substances 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 8
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003607 modifier Substances 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- KOGSPLLRMRSADR-UHFFFAOYSA-N 4-(2-aminopropan-2-yl)-1-methylcyclohexan-1-amine Chemical compound CC(C)(N)C1CCC(C)(N)CC1 KOGSPLLRMRSADR-UHFFFAOYSA-N 0.000 claims description 4
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- YYLGKUPAFFKGRQ-UHFFFAOYSA-N dimethyldiethoxysilane Chemical compound CCO[Si](C)(C)OCC YYLGKUPAFFKGRQ-UHFFFAOYSA-N 0.000 claims description 4
- 238000006073 displacement reaction Methods 0.000 claims description 4
- LDWBQADKOUWRIR-UHFFFAOYSA-N n-trimethoxysilylaniline Chemical compound CO[Si](OC)(OC)NC1=CC=CC=C1 LDWBQADKOUWRIR-UHFFFAOYSA-N 0.000 claims description 4
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 4
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- AHUXYBVKTIBBJW-UHFFFAOYSA-N dimethoxy(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](OC)(OC)C1=CC=CC=C1 AHUXYBVKTIBBJW-UHFFFAOYSA-N 0.000 claims description 2
- TWFQJFPTTMIETC-UHFFFAOYSA-N dodecan-1-amine;hydron;chloride Chemical compound [Cl-].CCCCCCCCCCCC[NH3+] TWFQJFPTTMIETC-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 2
- 235000013824 polyphenols Nutrition 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 28
- 230000009477 glass transition Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
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- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 230000032683 aging Effects 0.000 description 8
- 238000004821 distillation Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
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- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- ZRYCRPNCXLQHPN-UHFFFAOYSA-N 3-hydroxy-2-methylbenzaldehyde Chemical compound CC1=C(O)C=CC=C1C=O ZRYCRPNCXLQHPN-UHFFFAOYSA-N 0.000 description 1
- OECTYKWYRCHAKR-UHFFFAOYSA-N 4-vinylcyclohexene dioxide Chemical compound C1OC1C1CC2OC2CC1 OECTYKWYRCHAKR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Silicon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a preparation method of a hollow spherical silicon dioxide epoxy resin composite material, which comprises the following steps: 1) Synthesizing hollow spherical silicon dioxide by a soft template method; 2) The structure and the strength of the hollow spherical silicon dioxide are regulated and controlled through high-temperature treatment; 3) Modifying the liquid phase surface of the hollow spherical silicon dioxide, and mixing with epoxy resin to obtain hollow spherical silicon dioxide epoxy resin slurry; 4) Mixing with a curing agent, and carrying out curing reaction at 110-180 ℃ to obtain the hollow spherical silicon dioxide epoxy resin composite material. The hollow spherical silicon dioxide epoxy resin composite material prepared by the invention effectively improves the compatibility and the dispersibility of the hollow spherical silicon dioxide in epoxy resin. The cured composite material has higher mechanical strength and glass transition temperature, and can be applied to the fields of circuit boards, substrates, epoxy molding compounds and the like. The method has simple process and low cost, and is suitable for large-scale production.
Description
Technical Field
The invention belongs to the technical field of epoxy plastic packaging material production, and particularly relates to a hollow spherical silicon dioxide epoxy resin composite material and a preparation method and application thereof.
Background
With the rapid development of semiconductors and integrated circuits, the packaging of ceramics, metals, glass, etc. is difficult to meet the requirements of industrialization, and the cost is high. The epoxy plastic packaging material is used as a new generation of non-airtight packaging filler, so that the automation is facilitated, the packaging efficiency is improved, and the cost is reduced. The epoxy molding compound needs inorganic filler with low dielectric constant, low thermal expansion coefficient and high surface strength to meet the development requirement.
Hollow spherical silica is preferred by researchers because of its low dielectric constant and low coefficient of thermal expansion. The shell of the hollow spherical silicon dioxide has a loose porous structure, so that the surface structure of the hollow spherical silicon dioxide is unstable, the strength of the hollow spherical silicon dioxide is insufficient, the hollow spherical silicon dioxide is used as a filler of an epoxy plastic package material, and the improvement of the mechanical strength of the hollow spherical silicon dioxide epoxy resin composite material obtained by adding the hollow spherical silicon dioxide into epoxy resin is limited. In addition, the hollow spherical silicon dioxide has large specific surface area, more surface hydroxyl groups and high reaction activity, and is dispersed unevenly and easily aggregated in an epoxy matrix; these can adversely affect the overall performance of the silica/epoxy composite when applied to epoxy molding compounds.
Disclosure of Invention
The present invention aims to solve the problems raised in the background art described above, and provides a hollow spherical silica epoxy resin composite material; the structural strength of the hollow spherical silicon dioxide is improved through high-temperature treatment; the stably dispersed silicon dioxide/epoxy resin composite slurry is prepared through surface modification.
The invention also provides a preparation method and application of the hollow spherical silicon dioxide epoxy resin composite material.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Synthesizing hollow spherical silicon dioxide by a soft template method: in an alkaline solution, tetraethyl orthosilicate (TEOS), a surfactant and a silane coupling agent are subjected to hydrolysis condensation reaction for 2-8h at the temperature of 20-80 ℃, then the temperature is raised to 110-200 ℃ for hydrothermal reaction for 5-18h to obtain a hollow spherical silicon dioxide solution, and solid-liquid separation, drying and grinding are carried out;
2) High-temperature treatment: treating the product obtained in the step 1) at a high temperature of 400-800 ℃ (preferably 450-600 ℃) for 5-10h to obtain hollow spherical silicon dioxide powder;
3) Surface modification of hollow spherical silica: dispersing the hollow spherical silicon dioxide powder obtained in the step 2) into a displacement solvent, adding a surface modifier, and reacting at 30-80 ℃ for 1-10h to obtain a surface modified hollow spherical silicon dioxide solution;
4) Preparing hollow spherical silicon dioxide epoxy resin slurry: adding epoxy resin into the surface modified hollow spherical silica solution obtained in the step 3), then reacting for 2-8h at 20-60 ℃, and then distilling under reduced pressure until no solvent is distilled off to obtain hollow spherical silica epoxy resin slurry;
5) Preparing a hollow spherical silicon dioxide epoxy resin composite material: mixing the hollow spherical silicon dioxide epoxy resin slurry obtained in the step 4) with a curing agent, and curing and reacting for 2-8h at 110-180 ℃ to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Specifically, in the step 1), the alkaline solution is obtained by dissolving alkali in an ethanol aqueous solution; the alkali is one or two of triethanolamine, diethanolamine and the like.
Specifically, in the step 1), the surfactant is one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), dodecyl ammonium chloride, sodium dodecyl sulfate, cetyl Trimethyl Ammonium Chloride (CTAC), and the like; the mass ratio of the surfactant to tetraethyl orthosilicate may preferably be 1: (2-40).
Specifically, in the step 1), the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane (KH 550), gamma-glycidoxypropyltrimethoxysilane (KH 560), gamma-methacryloxypropyltrimethoxysilane (KH 570), gamma-mercaptopropyltrimethoxysilane (KH 590), dimethyldiethoxysilane, hexamethyldisilazane, and the like; the mass ratio of the silane coupling agent to the TEOS may preferably be 1: (5-50).
Further, in step 3), the substitution solvent may preferably be one or more of ethanol, acetone, methyl ethyl ketone, propylene glycol monomethyl ether, and the like.
Specifically, in the step 3), the surface modifier is one or more of KH560, KH570, dimethyldiethoxysilane, hexamethyldisilazane, phenyltrimethoxysilane, phenylaminotrimethoxysilane, diphenyldimethoxysilane and the like; the addition amount of the surface modifier can be 1-20% of the mass of the hollow spherical silicon dioxide powder.
Specifically, in step 4), the epoxy resin may be one or more of bisphenol a type, bisphenol F type, polyphenol type (e.g., phenol formaldehyde epoxy resin, cresol formaldehyde epoxy resin, etc.), aliphatic (e.g., vinylcyclohexene diepoxide, diisopropadiene diepoxide), etc.; the mass ratio of the epoxy resin to the hollow spherical silica powder may preferably be 20: (1-10).
Further, in the step 5), the curing agent may be one or more of Diethylenetriamine (DETA), m-xylylenediamine (MDA), menthane Diamine (MDA), diethyl toluene diamine (DETDA), methyl hexahydrophthalic anhydride, etc.; the mass ratio of the epoxy resin to the curing agent may preferably be 10: (1-9).
The invention provides a hollow spherical silicon dioxide epoxy resin composite material prepared by the preparation method.
The invention also provides the application of the hollow spherical silicon dioxide epoxy resin composite material as an epoxy plastic package material.
The invention adopts liquid phase preparation, modification and mixing technology, and synthesizes hollow spherical silicon dioxide by a soft template method; high-strength modified hollow spherical silicon dioxide is obtained through high-temperature treatment and surface modification; obtaining stably dispersed hollow spherical silicon dioxide epoxy resin slurry through solvent replacement and reduced pressure distillation; the hollow spherical silicon dioxide epoxy resin composite material is obtained by introducing a curing agent and carrying out curing reaction. The surface-modified hollow spherical silicon dioxide has better interface compatibility with epoxy resin, improves the comprehensive performance of the hollow spherical silicon dioxide epoxy resin composite material, and is an ideal resin composite material of epoxy molding compound.
The hollow spherical silicon dioxide epoxy resin composite material prepared by the invention effectively improves the compatibility and the dispersibility of the hollow spherical silicon dioxide in epoxy resin; the cured composite material has higher mechanical strength and glass transition temperature, and can be applied to the fields of circuit boards, substrates, epoxy molding compounds and the like. Compared with the prior art, the invention has the following beneficial effects:
1) According to the invention, high-temperature treatment is adopted to obtain the hollow spherical silicon dioxide with high surface strength, so that the defect that the shell of the hollow spherical silicon dioxide is loose and has a porous structure is overcome, and the surface hydroxyl reaction activity is reduced;
2) The hollow spherical silicon dioxide prepared by the invention has good dispersion stability in epoxy resin through surface modification;
3) The hollow spherical silicon dioxide epoxy resin composite slurry prepared by the invention has a stable system, can realize high filling, and has easy adjustment of filler content;
4) Compared with pure epoxy resin, the hollow spherical silicon dioxide epoxy resin composite material prepared by the invention has higher mechanical strength;
5) The preparation method provided by the invention has the characteristics of simple process and low cost, and is suitable for large-scale production.
Drawings
FIG. 1 shows 50nm hollow spherical silica epoxy resin paste (a), a photograph (b) of dispersion in butanone, a laser particle size chart (c), and a TEM image (d) in example 1;
FIG. 2 shows a 100nm hollow spherical silica epoxy resin paste (a), a photograph (b) of dispersion in butanone, a laser particle size chart (c), and a TEM image (d) in example 4;
FIG. 3 is a sectional profile of a 50nm hollow spherical silica epoxy composite (a) in example 1 and a 100nm hollow spherical silica epoxy composite (b) in example 4, respectively;
FIG. 4 is a graph of tensile strength and elongation at break of a 100nm hollow spherical silica epoxy resin composite material under different hollow spherical silica addition amounts (based on epoxy resin).
Detailed Description
The following description of the present patent refers to the field of 'electric digital data processing'.
Example 1:
a preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 2g of CTAB, 25g of triethanolamine, 18g of ethanol, 120g of pure water and 8g of KH550, adding the CTAB, the triethanolamine, the ethanol, the pure water and the KH550 into a 500ml reaction kettle, stirring at 30 ℃, adding 40g of TEOS, reacting at constant temperature for 2 hours, heating to 120 ℃, reacting at constant temperature for 16 hours, finishing the reaction, performing suction filtration, drying and grinding to obtain 12g of 50nm hollow spherical silicon dioxide;
2) Reacting the sample obtained in the step 1) at the high temperature of 550 ℃ for 5 hours to obtain 10g of hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 100g of ethanol as a substitution solvent, adding 1g of KH560, and reacting at 30 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 20g of bisphenol A epoxy resin 828 (Jining Macro Ming chemical reagent Co., ltd.) into the solution obtained in the step 3), reacting for 2h at 60 ℃, and distilling under reduced pressure until no solvent is distilled off to obtain hollow spherical silica epoxy resin slurry (see a in FIG. 1);
5) And (3) adding 2g of methyl hexahydrophthalic anhydride into the slurry obtained in the step (4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 150 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
FIG. 1 shows a photograph a) of a 50nm hollow spherical silica epoxy resin paste obtained in step 4) of this example, a photograph b) of a hollow spherical silica epoxy resin composite material obtained by preparation dispersed in methyl ethyl ketone, and a laser particle size image c) and a TEM image d) of the hollow spherical silica epoxy resin composite material. The results of fig. 1 show that: the 50nm hollow spherical silica epoxy resin slurry is dispersed into a blue solution in butanone (the concentration is 10%), the dispersed particle size in butanone is D50=59nm, and a TEM image shows that the 50nm hollow spherical silica has good monodispersity.
Example 2
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 1.5g of CTAC, 20g of diethanolamine, 18g of ethanol, 120g of pure water and 6g of KH590, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 40g of TEOS, reacting for 2 hours at constant temperature, heating to 130 ℃, reacting for 15 hours at constant temperature, filtering, drying and grinding after the reaction is finished;
2) Reacting the sample obtained in the step 1) at 550 ℃ for 5 hours to obtain 10g of 50nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 100g of replacement solvent methyl ethyl ketone, adding 1g of phenyltrimethoxysilane, and reacting for 2h at 30 ℃ to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 25g of phenol formaldehyde epoxy resin F-44 (tin-free resin factory) into the solution obtained in the step 3), reacting for 2 hours at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silica epoxy resin slurry;
5) And (3) adding 5g of diethylenetriamine into the slurry obtained in the step (4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 150 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Example 3
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 3g of sodium dodecyl sulfate, 30g of diethanolamine, 18g of ethanol, 120g of pure water and 6g of KH550, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 60g of TEOS, reacting at constant temperature for 2h, heating to 160 ℃, reacting at constant temperature for 10h, filtering after the reaction is finished, drying and grinding;
2) Reacting the sample obtained in the step 1) at 500 ℃ for 6 hours to obtain 15g of 50nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 150g of replacement solvent ethanol, adding 1.5g of phenylamino trimethoxy silane, and reacting at 30 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 50g of bisphenol F type epoxy resin 370 (Shanghai friendship resin Co., ltd.) into the solution obtained in the step 3), reacting for 2 hours at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) Adding 25g DETDA into the slurry obtained in the step 4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 170 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Example 4
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 6g of CTAC, 30g of diethanolamine, 28g of ethanol, 130g of pure water and 6g of KH590, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 50g of TEOS, reacting at constant temperature for 2h, heating to 160 ℃, reacting at constant temperature for 10h, filtering after the reaction is finished, drying and grinding;
2) Reacting the sample obtained in the step 1) at 600 ℃ for 4h to obtain 13g of 100nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 130g of displacement solvent ethanol, adding 1.3g of KH570, and reacting at 30 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 130g of bisphenol F type epoxy resin 370 (Shanghai friendship resin Co., ltd.) into the solution in the step 3), reacting for 2h at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) Adding 25g DETDA into the slurry obtained in the step 4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 170 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Fig. 2 shows a photograph a) of the 100nm hollow spherical silica epoxy resin paste obtained in step 4) of this example, a photograph b) of the hollow spherical silica epoxy resin composite material obtained by preparation dispersed in butanone, and a laser particle size view c) and a TEM view d) of the hollow spherical silica epoxy resin composite material. The results of fig. 2 show that: the epoxy resin slurry of the 100nm hollow spherical silica is dispersed into a white solution in butanone (the concentration is 10%), the dispersed particle diameter D50 in butanone is =110nm, and a TEM image shows that the monodispersity of the 100nm hollow spherical silica is good.
FIG. 3 shows the profile of 50nm hollow spherical silica epoxy resin composite (a) prepared in example 1 and 100nm hollow spherical silica epoxy resin composite (b) prepared in example 4. The results of fig. 3 show that: the hollow spherical silica with the particle size of 50nm and 100nm has good dispersibility and compatibility in epoxy resin and has no agglomeration.
Example 5
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 8g of CTAB, 25g of triethanolamine, 38g of ethanol, 130g of pure water and 7g of KH590, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 70g of TEOS, reacting at constant temperature for 2h, heating to 160 ℃, reacting at constant temperature for 10h, filtering, drying and grinding after the reaction is finished;
2) Reacting the sample obtained in the step 1) at 600 ℃ for 4h to obtain 14g of 100nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 130g of replacement solvent propylene glycol monomethyl ether, adding 1.4g of phenyl trimethoxy silane, and reacting at 30 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 70g of bisphenol A epoxy resin 828 (Jining Hongming chemical reagent, inc.) into the solution obtained in the step 3), reacting for 2h at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) And (3) adding 30g of methyl hexahydrophthalic anhydride into the slurry obtained in the step (4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 170 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Example 6
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 8g of CTAB, 30g of triethanolamine, 28g of ethanol, 140g of pure water and 7g of hexamethyldisilazane, adding the CTAB, the triethanolamine, the ethanol, the pure water and the pure water into a 500ml reaction kettle, adding 80g of TEOS under stirring at 30 ℃, reacting at constant temperature for 2 hours, heating to 160 ℃, reacting at constant temperature for 10 hours, filtering after the reaction is finished, drying and grinding;
2) Reacting the sample obtained in the step 1) at 600 ℃ for 4h to obtain 15g of 100nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 150g of ethanol as a replacement solvent, adding 2g of KH570, and reacting at 30 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 50g of bisphenol F type epoxy resin 370 (Shanghai Huayi resin Co., ltd.) into the solution obtained in the step 3), reacting for 2 hours at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) And (3) adding 40g of DETDA into the slurry obtained in the step 4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 180 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Example 7
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 10g of CTAC, 35g of triethanolamine, 18g of ethanol, 100g of pure water and 7g of KH590, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 40g of TEOS, reacting at constant temperature for 2h, heating to 160 ℃, reacting at constant temperature for 10h, filtering, drying and grinding after the reaction is finished;
2) Reacting the sample obtained in the step 1) at 600 ℃ for 4h to obtain 8g of 200nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 90g of ethanol serving as a displacement solvent, adding 1.5g of KH560, and reacting at 30 ℃ for 2h to obtain a hollow spherical silicon dioxide solution with a modified surface;
4) Adding 30g of bisphenol A epoxy resin 828 (Jining Hongming chemical reagent, inc.) into the solution obtained in the step 3), reacting for 2 hours at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) And (3) adding 10g of methyl hexahydrophthalic anhydride into the slurry obtained in the step (4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 2h at 180 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Example 8
A preparation method of a hollow spherical silicon dioxide epoxy resin composite material comprises the following steps:
1) Weighing 12g of CTAB, 40g of diethanolamine, 18g of ethanol, 110g of pure water and 5g of KH550, adding into a 500ml reaction kettle, stirring at 30 ℃, adding 50g of TEOS, reacting at constant temperature for 2h, heating to 160 ℃, reacting at constant temperature for 10h, filtering after the reaction is finished, drying and grinding;
2) Reacting the sample obtained in the step 1) for 5 hours at 500 ℃ to obtain 12g of 300nm hollow spherical silicon dioxide powder with high surface strength;
3) Dispersing the product obtained in the step 2) in 110g of replacement solvent propylene glycol monomethyl ether, adding 1g of phenylamino trimethoxy silane, and reacting at 50 ℃ for 2h to obtain a surface-modified hollow spherical silicon dioxide solution;
4) Adding 50g of bisphenol F type epoxy resin 370 (Shanghai friendship resin Co., ltd.) into the solution obtained in the step 3), reacting for 2 hours at 60 ℃, and then carrying out reduced pressure distillation until no solvent is distilled off to obtain hollow spherical silicon dioxide epoxy resin slurry;
5) And (3) adding 20g of methyl hexahydrophthalic anhydride into the slurry obtained in the step (4), transferring the slurry into a homogenizer for defoaming and mixing treatment (at room temperature for 2 min), and carrying out curing reaction for 3h at 170 ℃ in an aging oven to obtain the hollow spherical silicon dioxide epoxy resin composite material.
Application test:
FIG. 4 is a graph showing the tensile strength and elongation at break of the 100nm hollow spherical silica epoxy resin composite material prepared in example 5 (based on epoxy resin, under the condition of different amounts of hollow spherical silica added).
The results of fig. 4 show that: when the amount of the hollow spherical silica added is 20%, the tensile strength (66.49 Mpa) and the elongation at break (6.38%) of the hollow spherical silica epoxy resin composite material prepared in example 5 reach maximum values, which are respectively improved by 20.21% and 42.41% compared with pure epoxy resin.
To sum up, the following steps are carried out: the hollow spherical silicon dioxide epoxy resin composite material effectively improves the compatibility and the dispersibility of the hollow spherical silicon dioxide in epoxy resin; and has higher mechanical strength (tensile strength and elongation at break), and is suitable for being used as epoxy molding compound.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above examples, and any other modifications without departing from the scope of the present invention should be replaced by equivalents, and all such modifications are included in the scope of the present invention.
Claims (10)
1. The preparation method of the hollow spherical silicon dioxide epoxy resin composite material is characterized by comprising the following steps:
1) In an alkaline solution, tetraethyl orthosilicate, a surfactant and a silane coupling agent are subjected to hydrolysis condensation reaction at the temperature of 20-80 ℃ for 2-8h, then the temperature is raised to 110-200 ℃ for hydrothermal reaction for 5-18h to obtain a hollow spherical silicon dioxide solution, and solid-liquid separation, drying and grinding are carried out;
2) Treating the product obtained in the step 1) at a high temperature of 400-800 ℃ for 5-10h to obtain hollow spherical silicon dioxide powder;
3) Dispersing the hollow spherical silicon dioxide powder obtained in the step 2) into a displacement solvent, adding a surface modifier, and reacting at 30-80 ℃ for 1-10h to obtain a surface modified hollow spherical silicon dioxide solution;
4) Adding epoxy resin into the surface modified hollow spherical silica solution obtained in the step 3), then reacting for 2-8h at 20-60 ℃, and then distilling under reduced pressure until no solvent is distilled off to obtain hollow spherical silica epoxy resin slurry;
5) Mixing the hollow spherical silicon dioxide epoxy resin slurry obtained in the step 4) with a curing agent, and curing and reacting for 2-8h at 110-180 ℃ to obtain the hollow spherical silicon dioxide epoxy resin composite material.
2. The method for preparing a hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 1), the alkaline solution is obtained by dissolving an alkali in an ethanol aqueous solution; the alkali is one or two of triethanolamine and diethanolamine.
3. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 1), the surfactant is one or more of cetyl trimethyl ammonium bromide, dodecyl ammonium chloride, sodium dodecyl sulfate and cetyl trimethyl ammonium chloride; the mass ratio of the surfactant to the tetraethyl orthosilicate is 1: (2-40).
4. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 1), the silane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-methacryloxypropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, dimethyldiethoxysilane, and hexamethyldisilazane; the mass ratio of the silane coupling agent to the TEOS is 1: (5-50).
5. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 3), the substitution solvent is one or more of ethanol, acetone, methyl ethyl ketone and propylene glycol monomethyl ether.
6. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 3), the surface modifier is one or more of KH560, KH570, dimethyldiethoxysilane, hexamethyldisilazane, phenyltrimethoxysilane, phenylaminotrimethoxysilane, diphenyldimethoxysilane; the addition amount of the surface modifier is 1-20% of the mass of the hollow spherical silicon dioxide powder.
7. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 1, wherein in the step 4), the epoxy resin is one or more of bisphenol A type, bisphenol F type, polyphenol type and aliphatic; the mass ratio of the epoxy resin to the hollow spherical silicon dioxide powder is 20: (1-10).
8. The method for preparing the hollow spherical silica epoxy resin composite material according to claim 7, wherein in the step 5), the curing agent is one or more of diethylenetriamine, m-xylylenediamine, menthane diamine, diethyltoluene diamine and methyl hexahydrophthalic anhydride; the mass ratio of the epoxy resin to the curing agent is 10: (1-9).
9. The hollow spherical silica epoxy resin composite material prepared by the preparation method of any one of claims 1 to 8.
10. Use of the hollow spherical silica epoxy composite of claim 9 as an epoxy molding compound.
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