CN112662354A - Silicon dioxide filler, preparation method thereof and epoxy resin composite material - Google Patents
Silicon dioxide filler, preparation method thereof and epoxy resin composite material Download PDFInfo
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- CN112662354A CN112662354A CN202011461976.0A CN202011461976A CN112662354A CN 112662354 A CN112662354 A CN 112662354A CN 202011461976 A CN202011461976 A CN 202011461976A CN 112662354 A CN112662354 A CN 112662354A
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- epoxy resin
- silane coupling
- silica filler
- silica
- filler
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 85
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 75
- 239000000945 filler Substances 0.000 title claims abstract description 75
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 14
- 125000000524 functional group Chemical group 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 23
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 10
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 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 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- NMEPHPOFYLLFTK-UHFFFAOYSA-N trimethoxy(octyl)silane Chemical compound CCCCCCCC[Si](OC)(OC)OC NMEPHPOFYLLFTK-UHFFFAOYSA-N 0.000 claims description 6
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 5
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 claims description 5
- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 5
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 4
- -1 alicyclic acid anhydride Chemical class 0.000 claims description 4
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 4
- WHGNXNCOTZPEEK-UHFFFAOYSA-N dimethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](C)(OC)CCCOCC1CO1 WHGNXNCOTZPEEK-UHFFFAOYSA-N 0.000 claims description 4
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 claims description 4
- GOFSGYGYWCKLTO-UHFFFAOYSA-N dimethoxy-methyl-propylsilane;ethane-1,2-diamine Chemical compound NCCN.CCC[Si](C)(OC)OC GOFSGYGYWCKLTO-UHFFFAOYSA-N 0.000 claims description 4
- VVNATJLDMWFTTM-UHFFFAOYSA-N ethane-1,2-diamine;triethoxy(propyl)silane Chemical compound NCCN.CCC[Si](OCC)(OCC)OCC VVNATJLDMWFTTM-UHFFFAOYSA-N 0.000 claims description 4
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 4
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 claims description 4
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 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
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims 1
- 229920000193 polymethacrylate Polymers 0.000 claims 1
- 238000012986 modification Methods 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000011049 filling Methods 0.000 abstract description 7
- 125000000962 organic group Chemical group 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 238000007605 air drying Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000012876 topography Methods 0.000 description 5
- 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 description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 229910000679 solder Inorganic materials 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 3
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a silica filler, which is silica particles with more than two different organic functional groups grafted on the surface by surface modification of more than two different silane coupling agents. The preparation method of the silica filler comprises the following steps: stirring and dispersing silicon dioxide particles in a silane coupling agent solvent to obtain a mixed reaction solution; wherein the silane coupling agent solvent comprises more than two different silane coupling agents; and (3) carrying out a high-temperature reflux reaction process on the reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the silica particles with more than two different organic functional groups grafted on the surfaces. The surface of the silica filler provided by the invention is grafted with more than two different organic groups, and the silica filler is filled in the epoxy resin composite material, so that the composite material has lower viscosity and excellent viscosity stability when the particle size of the filler is smaller and the filling amount is higher.
Description
Technical Field
The invention belongs to the technical field of polymer composite materials, and particularly relates to a silica filler and a preparation method thereof, and an epoxy resin composite material containing the silica filler.
Background
New forms of electronic products such as bio-micro-electromechanical systems, artificial intelligent micro-robots, wearable electronic devices, 5G communication electronic devices, light and thin notebooks, ultra-thin mobile phones and the like are more and more frequently appeared in daily life of people. The miniaturization, lightness, thinness and high operation speed of electronic devices make the chip develop towards high integration, miniaturization and high reliability. The underfill is a key one of plastic electronic packaging materials, can reduce the mismatch of thermal expansion coefficients between a Chip and a substrate, provides adhesive force, protects a solder Ball and the like, is used for underfill of CSP (Chip Scale Package)/BGA (Ball grid array Package), has the characteristics of good process operability, easy maintenance, good shock resistance, good vibration resistance and the like, greatly improves the reliability of electronic products, and is also expanded to be applied to increase the mechanical strength of the CSP. As the density of mobile electronic products is higher and higher, the underfill technology is gradually improved, and more underfill materials are developed.
Epoxy resin composites are a common underfill, generally composed of an epoxy resin, a curing agent, and a silica filler. With the miniaturization trend of electronic products, the pitch of the CSP also becomes smaller and smaller, and the pitch of the solder ball also becomes smaller and smaller, which puts higher requirements on the underfill: the spherical silica filler of the underfill has a reduced particle size and a high sphericity. Underfill requires a low coefficient of thermal expansion after curing and therefore a large loading of silica filler. For better filling of chips with low solder ball height and narrow solder ball pitch, spherical silica with small particle size is required to be used as the filler of the underfill, but the reduction of the particle size of the spherical silica filler increases the contact area of the spherical silica filler and the resin matrix in the epoxy resin, the volume fraction of the interface item increases, the smaller particle size at higher filling amount causes the composite material to have high viscosity, the high-viscosity underfill causes the operation difficulty of the packaging process to increase and the viscosity stability during room-temperature storage is also poor, which is not favorable for storage.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a silica filler and a preparation method thereof, which aim to solve the problem that the viscosity of the composite material is too high when the conventional silica filler has a small particle size and a high filling amount.
In order to achieve the above object, one aspect of the present invention provides a silica filler, which is silica particles surface-modified with two or more different silane coupling agents to graft two or more different organic functional groups on the surface.
Preferably, the silicon dioxide particles are spherical silicon dioxide particles, and the particle size of the silicon dioxide particles is 90 nm-110 nm.
Preferably, the two or more different silane coupling agents are selected from two of aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, hexadecyltrimethoxysilane and octadecyltrimethoxysilane, which are not reactive with each other The above.
The invention provides a method for preparing the silica filler, which comprises the following steps:
stirring and dispersing silicon dioxide particles in a silane coupling agent solvent to obtain a mixed reaction solution; wherein the silane coupling agent solvent comprises more than two different silane coupling agents;
and (3) carrying out a high-temperature reflux reaction process on the reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the silica particles with more than two different organic functional groups grafted on the surfaces.
Preferably, the mass ratio of the silica particles to the silane coupling agent solvent is 1: (1-5).
Preferably, the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 90-140 ℃, and the reaction time is 3-24 h.
Preferably, the detergent used in the centrifugal washing process is absolute ethyl alcohol; the temperature of the drying process is 100-300 ℃, and the time is 3-24 h.
Another aspect of the present invention is to provide an epoxy resin composite material, comprising an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises an epoxy resin and a curing agent, and the filler is a silica filler as described above.
Preferably, the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin and alicyclic epoxy resin, and the curing agent is alicyclic acid anhydride curing agent or amine curing agent.
Preferably, in the epoxy resin matrix, the mass ratio of the epoxy resin to the curing agent is 10: (1-5); the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-7).
The silica filler provided by the embodiment of the invention is specifically silica particles with more than two different silane coupling agents subjected to surface modification and more than two different organic functional groups grafted on the surface, and the compatibility and the dispersibility of the silica filler in a resin base material are improved by grafting more than two different organic functional groups on the surface, so that the composite material has lower viscosity and excellent viscosity stability when the particle size of the filler is smaller and the filling amount is higher.
The preparation method of the silicon dioxide filler provided by the embodiment of the invention has the advantages of simple process flow and easy realization of process conditions, and is beneficial to large-scale industrial application.
Drawings
FIG. 1 is an SEM photograph of unmodified silica particles in example 1 of the present invention;
FIG. 2 is an SEM image of a silica filler prepared according to example 1 of the present invention;
FIG. 3 shows that the shear rate of the epoxy resin composite material prepared in example 1 of the present invention is 0-100S-1Viscosity profile under conditions;
FIG. 4 is an SEM image of a silica filler prepared according to example 2 of the present invention;
FIG. 5 is an SEM image of a silica filler prepared according to example 3 of the present invention;
FIG. 6 is an SEM image of a silica filler prepared according to example 4 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments.
It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
The embodiment of the invention firstly provides a silica filler, which is silica particles with more than two different organic functional groups grafted on the surface by surface modification of more than two different silane coupling agents.
In a specific scheme, the silicon dioxide particles are spherical silicon dioxide particles, and the particle size of the silicon dioxide particles is 90 nm-110 nm.
In a specific embodiment, the two or more different silane coupling agents are selected from the group consisting of aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, octyltrimethoxysilane, glycidoxypropyltrimethoxysilane, glycid, Any two or more of hexadecyltrimethoxysilane and octadecyltrimethoxysilane do not react with each other.
According to the silica filler, two or more silane coupling agents are selected to modify silica simultaneously, so that two or more different organic groups are grafted on the surface of silica particles, each organic functional group plays a different role, and the silica filler is filled in an epoxy resin composite material, so that the compatibility and the dispersibility of the silica filler in a resin base material are improved, and the composite material has low viscosity and excellent viscosity stability when the particle size of the filler is small and the filling amount is high.
The embodiment of the invention also provides a preparation method of the silica filler, which comprises the following steps:
step S10, stirring and dispersing silicon dioxide particles in a silane coupling agent solvent to obtain a mixed reaction solution; wherein the silane coupling agent solvent contains more than two different silane coupling agents.
In a preferable scheme, the mass ratio of the silicon dioxide particles to the silane coupling agent solvent is selected to be 1 (1-5).
In a preferred embodiment, the two or more different silane coupling agents are selected from the group consisting of aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropyl, Two or more of propyltrimethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, hexadecyltrimethoxysilane and octadecyltrimethoxysilane which do not react with each other.
In a more preferred embodiment, two or more different silane coupling agents are mixed in an equal volume ratio in the silane coupling agent solvent. Wherein, one or more silane coupling agents of phenyl trimethoxy silane, octyl trimethoxy silane, methyl trimethoxy silane, hexadecyl trimethoxy silane, octadecyl trimethoxy silane, diphenyl dimethoxy silane, phenyl triethoxy silane and propyl trimethoxy silane are used, and one coupling agent of (3-mercaptopropyl) trimethoxy silane, 3- (methacryloyloxy) propyl trimethoxy silane, 3-glycidyloxypropyl trimethoxy silane, 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane, methacryloxypropyl trimethoxy silane, phenylaminomethyl triethoxy silane and vinyl trimethoxy silane is used at the same time, so that the silane coupling agents can be ensured not to react.
In a preferred embodiment, a magnetic stirrer is added to the mixed reaction solution for magnetic stirring.
And step S20, carrying out a high-temperature reflux reaction process on the reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain silica particles with more than two different organic functional groups grafted on the surfaces.
In a preferred scheme, the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 90-140 ℃, and the reaction time is 3-24 h.
In a preferred embodiment, the detergent used in the centrifugal washing process is absolute ethyl alcohol; the temperature of the drying process is 100-300 ℃, and the time is 3-24 h.
The preparation method of the silica filler has the advantages of simple process flow and easy realization of process conditions, and is beneficial to large-scale industrial application.
In addition, according to the preparation method of the silica filler, in the process of surface modification of the silica particles, the silane coupling agent is directly used as a solvent, the silica is added into the excessive silane coupling agent solvent, heating is carried out at a certain temperature, and condensation reflux is carried out for a certain time, so that the silane coupling agent successfully modifies the silica particles, and other organic matters or solvents are not added.
The embodiment of the invention also provides an epoxy resin composite material, which comprises an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises epoxy resin and a curing agent, and the filler is the silica filler described in the embodiment of the invention.
In a preferred embodiment, the epoxy resin is one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin, and the curing agent is an alicyclic acid anhydride curing agent or an amine curing agent.
In a preferred embodiment, in the epoxy resin matrix, the mass ratio of the epoxy resin to the curing agent is 10: (1-5); the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-7).
The preparation process of the epoxy resin composite material comprises the following steps:
(1) and mixing the epoxy resin and the curing agent according to a mass ratio of 10: and (1) mixing the raw materials according to the proportion of (1) to (5), and fully and uniformly mixing the raw materials by using a planetary mixer to obtain the epoxy resin matrix.
(2) And (2) mixing the epoxy resin matrix and the silicon dioxide filler according to the mass ratio of 10: and (3) uniformly mixing the components in the ratio of (3) to (7) by using a high-speed planetary mixer to obtain the epoxy resin composite material.
Example 1
Silica filler and preparation process thereof
Adding 50g of phenyltrimethoxysilane and 50g of 3-glycidyloxypropyltrimethoxysilane into a single-neck flask of a reaction device, adding 50g of silicon dioxide with the particle size of 100nm into the single-neck flask, adding a magnetic stirring rotor, heating to 120 ℃, stirring at the rotating speed of 800rpm, and carrying out condensation reflux reaction for 12 hours.
And placing the liquid mixture obtained after the reaction in a centrifugal bottle, centrifuging for 10 minutes at the rotation speed of 8000rpm in a high-speed centrifuge, separating the powder from the silane coupling agent liquid, recovering and collecting the silane coupling agent liquid for recycling, ultrasonically cleaning and centrifuging the powder by using absolute ethyl alcohol, repeating for 3 times to remove the physical adsorption silane on the surface of the silicon dioxide, placing the obtained powder in a 110 ℃ forced air drying box for forced air drying for 6 hours, and further promoting the chemical grafting of the silane coupling agent and the surface of the silicon dioxide to obtain the modified silicon dioxide filler.
The SEM topography of the unmodified silica is shown in fig. 1, and the SEM topography of the silica filler obtained after modification in this example is shown in fig. 2.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and curing agent diethyl toluene diamine are prepared into a uniform epoxy resin matrix according to the mass ratio of 10:2.7, and are uniformly mixed in a planetary mixer. The epoxy resin matrix and the silica filler prepared in the embodiment are mixed according to the mass ratio of 10:4, and are uniformly mixed in a vacuum state through a high-speed planetary mixer, bubbles are removed, and the epoxy resin composite material is prepared.
Viscosity test of epoxy resin composite material
The liquid epoxy resin composite material prepared in this example was subjected to viscosity measurement with a parallel plate rheometer. During testing, the distance between the two plates of the flat-plate rheometer is 0.2mm, and the shear rate is 0-100S-1The test temperature was 25 ℃. FIG. 3 shows that the shear rate of the epoxy resin composite material prepared in this embodiment is 0-100S-1Viscosity curve under conditions of whichIn 50S-1The viscosity was 12.7 pas.
Referring to the graph of fig. 3, the epoxy resin composite material prepared in this example has a low viscosity and excellent viscosity stability.
Example 2
Silica filler and preparation process thereof
50g of methyltrimethoxysilane and 50g of aminopropyltriethoxysilane are added into a single-neck flask of a reaction device, 100g of silicon dioxide with the particle size of 100nm is added into the single-neck flask, a magnetic stirring rotor is added, the mixture is heated to 140 ℃, stirred at the rotating speed of 800rpm, and condensed reflux reaction is carried out for 3 hours.
And placing the liquid mixture obtained after the reaction in a centrifugal bottle, centrifuging for 10 minutes at the rotation speed of 8000rpm in a high-speed centrifuge, separating the powder from the silane coupling agent liquid, recovering and collecting the silane coupling agent liquid for recycling, ultrasonically cleaning and centrifuging the powder by using absolute ethyl alcohol, repeating for 3 times to remove the physical adsorption silane on the surface of the silicon dioxide, placing the obtained powder in a 110 ℃ forced air drying box for forced air drying for 6 hours, and further promoting the chemical grafting of the silane coupling agent and the surface of the silicon dioxide to obtain the modified silicon dioxide filler.
The SEM topography of the modified silica filler of this example is shown in FIG. 4.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and curing agent diethyl toluene diamine are prepared into a uniform epoxy resin matrix according to the mass ratio of 10:2.7, and are uniformly mixed in a planetary mixer. The epoxy resin matrix and the silica filler prepared in the embodiment are mixed according to the mass ratio of 10:5, and are uniformly mixed in a vacuum state through a high-speed planetary mixer, bubbles are removed, and the epoxy resin composite material is prepared.
The epoxy resin composite material prepared in this example was subjected to a viscosity test in the manner as described in example 1. The shear rate of the epoxy resin composite material of the embodiment is 50S-1The viscosity was 19.0 pas.
Example 3
Silica filler and preparation process thereof
100g of octyl trimethoxy silane and 50g of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane are added into a single-neck flask of a reaction device, 50g of silicon dioxide with the particle size of 100nm is added into the single-neck flask, a magnetic stirring rotor is added, the mixture is heated to 90 ℃, stirred at the rotating speed of 800rpm, and condensed and refluxed for reaction for 24 hours.
And placing the liquid mixture obtained after the reaction in a centrifugal bottle, centrifuging for 10 minutes at the rotation speed of 8000rpm in a high-speed centrifuge, separating the powder from the silane coupling agent liquid, recovering and collecting the silane coupling agent liquid for recycling, ultrasonically cleaning and centrifuging the powder by using absolute ethyl alcohol, repeating for 3 times to remove the physical adsorption silane on the surface of the silicon dioxide, placing the obtained powder in a 110 ℃ forced air drying box for forced air drying for 6 hours, and further promoting the chemical grafting of the silane coupling agent and the surface of the silicon dioxide to obtain the modified silicon dioxide filler.
The SEM topography of the silica filler obtained after modification in this example is shown in fig. 5.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and curing agent diethyl toluene diamine are prepared into a uniform epoxy resin matrix according to the mass ratio of 10:2.7, and are uniformly mixed in a planetary mixer. The epoxy resin matrix and the silica filler prepared in the embodiment are mixed according to the mass ratio of 10:7, and are uniformly mixed in a vacuum state through a high-speed planetary mixer, bubbles are removed, and the epoxy resin composite material is prepared.
The epoxy resin composite material prepared in this example was subjected to a viscosity test in the manner as described in example 1. The shear rate of the epoxy resin composite material of the embodiment is 50S-1The viscosity was 21.0 pas.
Example 4
Silica filler and preparation process thereof
Adding 100g of phenyltriethoxysilane, 100g of phenylaminomethyltriethoxysilane and 50g of propyltrimethoxysilane into a single-neck flask of a reaction device, adding 50g of silicon dioxide with the particle size of 100nm into the single-neck flask, adding a magnetic stirring rotor, heating to 100 ℃, stirring at the rotating speed of 800rpm, and carrying out condensation reflux reaction for 18 hours.
And placing the liquid mixture obtained after the reaction in a centrifugal bottle, centrifuging for 10 minutes at the rotation speed of 8000rpm in a high-speed centrifuge, separating the powder from the silane coupling agent liquid, recovering and collecting the silane coupling agent liquid for recycling, ultrasonically cleaning and centrifuging the powder by using absolute ethyl alcohol, repeating for 3 times to remove the physical adsorption silane on the surface of the silicon dioxide, placing the obtained powder in a 110 ℃ forced air drying box for forced air drying for 6 hours, and further promoting the chemical grafting of the silane coupling agent and the surface of the silicon dioxide to obtain the modified silicon dioxide filler.
The SEM topography of the silica filler obtained after modification in this example is shown in fig. 6.
Second, epoxy resin composite material and preparation process thereof
Bisphenol F epoxy resin and curing agent diethyl toluene diamine are prepared into a uniform epoxy resin matrix according to the mass ratio of 10:2.7, and are uniformly mixed in a planetary mixer. The epoxy resin matrix and the silica filler prepared in the embodiment are mixed according to the mass ratio of 10:4, and are uniformly mixed in a vacuum state through a high-speed planetary mixer, bubbles are removed, and the epoxy resin composite material is prepared.
The epoxy resin composite material prepared in this example was subjected to a viscosity test in the manner as described in example 1. The shear rate of the epoxy resin composite material of the embodiment is 50S-1The viscosity was 16.1 pas.
In summary, the surface of the silica filler provided in the embodiment of the present invention is grafted with two or more different organic groups, and the silica filler is filled in the epoxy resin composite material, so that the compatibility and the dispersibility of the silica filler in the resin base material are improved, and the composite material has a lower viscosity and excellent viscosity stability when the particle size of the filler is smaller and the filling amount is higher.
The foregoing is directed to embodiments of the present application and it is noted that numerous modifications and adaptations may be made by those skilled in the art without departing from the principles of the present application and are intended to be within the scope of the present application.
Claims (10)
1. A silica filler characterized by being silica particles surface-modified with two or more different silane coupling agents and having two or more different organic functional groups grafted to the surface.
2. The silica filler according to claim 1, characterized in that the silica particles are spherical silica particles having a particle size of 90-110 nm.
3. The silica filler according to claim 1, wherein the two or more different silane coupling agents are selected from the group consisting of aminopropyltriethoxysilane, glycidoxypropyltrimethoxysilane, methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, mercaptopropyltrimethoxysilane, mercaptopropyltriethoxysilane, ethylenediamine propyltriethoxysilane, ethylenediamine propylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldimethoxysilane, 3- (2, 3-epoxypropoxy) propylmethyldiethoxysilane, phenyltrimethoxysilane, diphenyldimethoxysilane, methylphenyldimethoxysilane, methyldimethoxysilane, poly (meth) acrylates, two or more of methyltriethoxysilane, octyltrimethoxysilane, hexadecyltrimethoxysilane, and octadecyltrimethoxysilane which do not react with each other.
4. A process for the preparation of a silica filler according to any one of claims 1 to 3, comprising:
stirring and dispersing silicon dioxide particles in a silane coupling agent solvent to obtain a mixed reaction solution; wherein the silane coupling agent solvent comprises more than two different silane coupling agents;
and (3) carrying out a high-temperature reflux reaction process on the reaction solution, cooling, and then sequentially carrying out centrifugal washing process and drying process treatment to obtain the silica particles with more than two different organic functional groups grafted on the surfaces.
5. The method of producing a silica filler according to claim 4, characterized in that the mass ratio of the silica particles to the silane coupling agent solvent is 1: (1-5).
6. The preparation method of the silica filler according to claim 5, wherein the high-temperature reflux reaction process is carried out in a condensation reflux device, the reaction temperature is 90-140 ℃, and the reaction time is 3-24 h.
7. The method for preparing a silica filler according to claim 5, wherein the detergent used in the centrifugal washing process is absolute ethanol; the temperature of the drying process is 100-300 ℃, and the time is 3-24 h.
8. An epoxy resin composite comprising an epoxy resin matrix and a filler, wherein the epoxy resin matrix comprises an epoxy resin and a curing agent, and the filler is the silica filler of any one of claims 1 to 3.
9. The epoxy resin composite material according to claim 8, wherein the epoxy resin is one or more of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and an alicyclic epoxy resin, and the curing agent is an alicyclic acid anhydride type curing agent or an amine type curing agent.
10. The epoxy resin composite according to claim 8 or 9, wherein the mass ratio of the epoxy resin to the curing agent in the epoxy resin matrix is 10: (1-5); the mass ratio of the epoxy resin matrix to the silica filler is 10: (3-7).
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| CN202011461976.0A CN112662354A (en) | 2020-12-09 | 2020-12-09 | Silicon dioxide filler, preparation method thereof and epoxy resin composite material |
| PCT/CN2020/136552 WO2022120900A1 (en) | 2020-12-09 | 2020-12-15 | Silica filler and preparation method therefor, and epoxy resin composite material |
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| CN113308021A (en) * | 2021-05-28 | 2021-08-27 | 江苏联瑞新材料股份有限公司 | Preparation method of silicon micropowder for epoxy resin system |
| CN113321912A (en) * | 2021-06-08 | 2021-08-31 | 广东工业大学 | High-temperature-resistant 3D printing photosensitive resin and preparation method and application thereof |
| CN113604073A (en) * | 2021-06-29 | 2021-11-05 | 中国科学院深圳先进技术研究院 | Modified silicon dioxide filler and preparation method thereof |
| CN114262528A (en) * | 2021-12-07 | 2022-04-01 | 中国科学院深圳先进技术研究院 | Surface modification method and application of silicon dioxide |
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| CN113308021A (en) * | 2021-05-28 | 2021-08-27 | 江苏联瑞新材料股份有限公司 | Preparation method of silicon micropowder for epoxy resin system |
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Application publication date: 20210416 |