CN115141223A - Surface modifier, modified filler, preparation method of modified filler and pouring sealant - Google Patents
Surface modifier, modified filler, preparation method of modified filler and pouring sealant Download PDFInfo
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- CN115141223A CN115141223A CN202110354552.2A CN202110354552A CN115141223A CN 115141223 A CN115141223 A CN 115141223A CN 202110354552 A CN202110354552 A CN 202110354552A CN 115141223 A CN115141223 A CN 115141223A
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- 239000000945 filler Substances 0.000 title claims abstract description 124
- 239000003607 modifier Substances 0.000 title claims abstract description 56
- 239000000565 sealant Substances 0.000 title abstract description 46
- 238000002360 preparation method Methods 0.000 title abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 106
- 238000003756 stirring Methods 0.000 claims description 29
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 238000004382 potting Methods 0.000 claims description 12
- 239000000853 adhesive Substances 0.000 claims description 11
- 230000001070 adhesive effect Effects 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 238000005507 spraying Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 abstract description 7
- 238000000576 coating method Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 description 18
- 230000004048 modification Effects 0.000 description 16
- 238000012986 modification Methods 0.000 description 16
- 125000003545 alkoxy group Chemical group 0.000 description 14
- 239000003292 glue Substances 0.000 description 8
- 239000011231 conductive filler Substances 0.000 description 7
- 229920002545 silicone oil Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- RSKGMYDENCAJEN-UHFFFAOYSA-N hexadecyl(trimethoxy)silane Chemical compound CCCCCCCCCCCCCCCC[Si](OC)(OC)OC RSKGMYDENCAJEN-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 230000009974 thixotropic effect Effects 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000007259 addition reaction Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000009775 high-speed stirring Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/40—Compounds of aluminium
- C09C1/407—Aluminium oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- 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
- C09J183/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Adhesives based on derivatives of such polymers
- C09J183/04—Polysiloxanes
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The application provides a surface modifier, a filler, a preparation method of the filler and a pouring sealant, wherein the surface modifier has a structure shown in a formula I:
wherein R is 1 Is C 1‑4 An alkyl group; r 2 ，R 3 And R 4 Each of which is independently C 1‑20 Alkyl radical, C 1‑10 Cycloalkyl or C 6‑20 An aromatic group. The surface modifier can realize chemical coating of the filler, the filler modified by the surface modifier is not easy to agglomerate, and the viscosity and the thixotropy of the filler are not increased when the surface modifier is applied to pouring sealant.
Description
Technical Field
The application relates to the technical field of pouring sealant, in particular to a surface modifier, a modified filler, a preparation method of the modified filler and the pouring sealant.
Background
The organic silicon pouring sealant has good thermal stability, small stress and low hygroscopicity, is superior to other types of pouring sealant products, and is widely applied to heat dissipation and potting protection of heating sources and power components. The bi-component addition type organic silicon pouring sealant is the most common type of pouring sealant due to excellent performance and convenient use. However, when the addition type organic silicon pouring sealant with high heat conductivity and low viscosity is produced, a lot of fillers and flame retardants need to be filled, so that the viscosity is high, the densities of the fillers are high, and the fillers are easy to settle and agglomerate. Currently, surface modification is commonly used to reduce viscosity, improve settling resistance, and prevent caking. The common surface treating agent is long-carbon-chain trialkoxysilane or various surfactants, but the surfactants are physically adsorbed on the surfaces of filler particles, so that the coating effect is not ideal, and the long-chain trialkoxysilane can realize chemical coating through reaction, but the modified filler particles are agglomerated, the modification effect is influenced, the viscosity of the system is increased, the fluidity is poor, and the system cannot be leveled seriously or even.
Therefore, the related art of the pouring sealant still needs to be improved.
Content of application
The present application is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present application is to provide a surface modifier suitable for modifying a filler, which has a good coating effect on filler particles, and the modified filler does not agglomerate and does not increase thixotropy and viscosity of a system when applied to a potting adhesive.
In one aspect of the present application, a surface modifying agent is provided. According to embodiments of the present application, the surface modifying agent has a structural formula shown in formula I:
wherein R is 1 Is C 1-4 An alkyl group;
R 2 ，R 3 and R 4 Each of which is independently C 1-20 Alkyl radical, C 1-10 Cycloalkyl or C 6-20 An aromatic group.
The surface modifier only contains one alkoxy group, when filler particles are modified, after the alkoxy group is combined with hydroxyl on the surfaces of the filler particles, no surplus alkoxy group exists, and therefore the modified filler particles cannot agglomerate due to reaction between the surplus alkoxy groups or reaction between the alkoxy groups and active groups on the surfaces of the filler particles; and R in the surface modifier molecule 2 ，R 3 And R 4 The groups are not long-chain groups, and cannot be twisted with each other or with silicone oil molecules in the pouring sealant, so that the thixotropy of the pouring sealant cannot be increased; in addition, the surface modifier has larger molecular sectional area, thereby having good surface modification effect on filler particles.
In another aspect of the present application, a modified filler is provided. According to an embodiment of the application, the modified filler comprises: a filler particle body; the surface modifying agent as described previously, bonded to the outer surface of the filler particle body. The surface modifier and the filler particle body in the filler are connected (namely bonded) through chemical bonds, the modification effect is good, the filler basically cannot agglomerate, the thixotropy of a pouring sealant system cannot be changed when the filler is applied to pouring sealant, the viscosity of the pouring sealant system is increased, the viscosity of the pouring sealant adopting the filler is appropriate, the fluidity is good, the sedimentation resistance and the caking resistance are good, and the using effect is good.
In yet another aspect of the present application, there is provided a method of making the modified filler described above. According to an embodiment of the application, the method comprises: and mixing the surface modifier with the filler particle body, and reacting active groups in the surface modifier with the filler particle body to obtain the modified filler.
In yet another aspect of the present application, a potting adhesive is provided. According to the embodiment of the application, the pouring sealant comprises the modified filler. The pouring sealant has good service performance, proper viscosity and fluidity and convenient processing.
Detailed Description
Embodiments of the present application are described in detail below. The following embodiments are described as illustrative only and are not to be construed as limiting the present application. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
The present application has been completed based on the following findings and recognition by the inventors:
the bi-component addition type organic silicon pouring sealant is cured by addition reaction of Si-H bonds of hydrogen-containing silicone oil to C = C bonds of vinyl silicone oil under the catalysis of a platinum catalyst, no micromolecular substance is generated in the curing process, no air bubbles are generated, the electrical performance is good, and meanwhile, the curing rate can be adjusted by changing the curing temperature. When the addition type organic silicon pouring sealant product with high heat conductivity and low viscosity is produced, a large amount of filler and flame retardant are required to be filled, the viscosity is often high, the density of the filler is high, the filler is easy to settle and agglomerate, once the filler agglomerates, the pouring sealant is difficult to stir uniformly, and the using effect is seriously influenced. It is therefore often necessary to surface modify the filler to reduce viscosity, increase settling resistance and prevent caking. However, the inventors have found that the conventional surfactant is physically adsorbed on the surface of the filler particles to modify the surface of the filler particles, so that the coating effect is not ideal, and the filler particles modified by the long carbon chain trialkoxysilane (such as hexadecyl trimethoxy silane) surface treatment agent capable of realizing chemical coating are easy to agglomerate. In view of the above problems, the inventors have conducted intensive studies and found that the filler particles are prone to particle agglomeration mainly because one silane molecule of long carbon chain trialkoxysilane contains multiple alkoxy groups, which often results in that after the silane molecule is combined with the filler particles, there are excess alkoxy groups, and these excess alkoxy groups are hydrolyzed to generate silicon hydroxyl groups, which can generate condensation reaction, so that the modified filler particles are agglomerated and the modification effect is affected; furthermore, when the silicon hydroxide is applied to the pouring sealant, the silicon hydroxide can form a hydrogen bond with an active group in a pouring sealant system to generate thixotropy, so that the viscosity of the pouring sealant system is increased; in addition, long carbon chains of the silane molecules are intertwined with each other or with molecular chains of silicone oil in the pouring sealant, so that the thixotropy of the pouring sealant is increased, the fluidity of the pouring sealant is influenced, and the pouring sealant cannot be leveled even seriously and cannot be used for pouring. Based on the above, the inventor provides a surface modifier with only one alkoxy group in the molecule, and the problems that filler particles are easy to agglomerate, the viscosity and the thixotropy of the pouring sealant are changed, and the like are well solved.
In view of the above, in one aspect of the present application, there is provided a surface modifier. According to embodiments of the present application, the surface modifying agent has a structural formula shown in formula I:
wherein R is 1 Is C 1-4 An alkyl group;
R 2 ，R 3 and R 4 Each of which is independently C 1-20 Alkyl radical, C 1-10 Cycloalkyl or C 6-20 An aromatic group.
It should be noted that the description "C" is used herein 1-4 "means that the number of carbon atoms is 1 to 4 (i.e., the number of carbon atoms is 1, 2, 3 or 4)," C 1-4 The alkyl group refers to an alkyl group having 1 to 4 carbon atoms, specifically methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl, and other similar descriptions are the same and will not be described in detail herein.
According to some embodiments of the application, R 2 ，R 3 And R 4 Each of which may be independently C 1-8 Alkyl radical, C 1-8 Cycloalkyl or optionally substituted phenyl.
It is to be noted that the description "optionally substituted phenyl" as used herein refers to unsubstituted phenyl or phenyl substituted with one or more substituents.
According to some embodiments of the application, R 1 Can be methyl, ethyl, propyl or isopropyl; (ii) a R 2 ，R 3 And R 4 Each of which may be independently methyl, ethyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, -C (CH) 3 ) 2 (C 2 H 5 )、-C(CH 3 )(C 2 H 5 ) 2 、-C(C 2 H 5 ) 3 Or a phenyl group.
According to some embodiments of the application, R 2 ，R 3 And R 4 At least one of which is cycloalkyl, aryl or-C (R) 5 ) 3 Wherein R is 5 Is an alkyl group. Therefore, the surface modifier has larger molecular sectional area, can cover more surfaces of the filler particles, further improves the surface modification effect of the filler particles, and can also obviously improve the anti-settling performance of the modified filler.
According to some embodiments of the present application, the surface modifier has a structural formula represented by any one of formulae (1) to (17):
the surface modifier only contains one alkoxy group, when filler particles are modified, after the alkoxy group is combined with hydroxyl on the surfaces of the filler particles, surplus alkoxy groups are basically avoided, so that the modified filler particles cannot agglomerate due to the reaction between the surplus alkoxy groups or the reaction between the alkoxy groups and active groups on the surfaces of the filler particles; and R in the surface modifier molecule 2 、R 3 And R 4 All of the groups areThe surface modified filler is a long-chain group, more of the surface modified filler is spread on the surface of filler particles, and the filler does not extend into the air to cause the filler particles to be intertwined with each other or with silicone oil molecules in the pouring sealant, so that the pouring sealant has lower viscosity and thixotropy while ensuring the heat conductivity; in addition, the surface modifier has larger molecular sectional area, and can cover more surfaces of filler particles, thereby having good surface modification effect on the filler particles.
In another aspect of the present application, a modified filler is provided. According to an embodiment of the application, the modified filler comprises: a filler particle body; the surface modifying agent as described previously, bonded to the outer surface of the filler particle body. The surface modifier and the filler particle body in the filler are connected (namely bonded) through chemical bonds, the modification effect is good, the filler basically cannot agglomerate, and when the filler is applied to pouring sealants, the thixotropic property and the viscosity of a pouring sealant system are lower while the same heat conductivity is achieved, so that the pouring sealant adopting the filler is good in fluidity, good in sedimentation resistance and caking resistance and good in using effect.
According to the embodiment of the present application, the specific kind of the filler particle body is not particularly limited, and can be flexibly selected according to actual needs. In some embodiments, the filler particles may be heat conductive filler particles for potting adhesive, and in particular, the filler particle body may be at least one of alumina particles, silica micropowder particles, boron nitride particles, aluminum nitride particles, magnesium oxide particles, zinc oxide particles, and aluminum hydroxide particles. Therefore, the modification effect is good, the heat conduction performance of the pouring sealant can be effectively improved when the modified resin is used for the pouring sealant, and the viscosity and the thixotropy of the pouring sealant cannot be increased.
According to the embodiments of the present application, the shape of the filler particle body is not particularly limited and may be selected according to the use needs. In some embodiments, the filler particle bodies can be at least one of platelet, triangular, spheroidal, and spherical in shape.
According to embodiments herein, the filler particle bodies may have a D50 particle size of 0.01 microns to 100 microns, such as 0.01 microns, 0.1 microns, 1 micron, 10 microns, 20 microns, 30 microns, 40 microns, 50 microns, 60 microns, 70 microns, 80 microns, 90 microns, 100 microns, and the like. Within the range of the particle size, the particles are slow to settle and good in storage performance, and the viscosity is larger when the particle size is too large and the particle size is too small.
According to embodiments herein, the surface modifier may be used in an amount of 0.01% to 2%, specifically such as 0.01%, 0.05%, 0.1%, 0.5%, 1%, 1.5%, 2%, etc., by weight of the bulk of the filler particles. Within the dosage range, the surface modifier can well coat the filler particle body, and if the dosage is too large, the surface modifier remains too much, so that the heat conduction is influenced; and too little affects the surface modification effect of the filler particle body.
In yet another aspect of the present application, there is provided a method of making the modified filler described above. According to an embodiment of the application, the method comprises: and mixing the surface modifier with the filler particle body, and reacting active groups in the surface modifier with the filler particle body to obtain the modified filler. The method has simple and convenient steps, is beneficial to large-scale production, and the obtained filler has good modification effect.
According to an embodiment of the application, the method may comprise: carrying out first stirring on the filler particle body to obtain a stirred filler particle body; performing second stirring on the first stirred filler particle body, adding a surface modifier into the first stirred filler particle body in a spraying or dropping mode, and performing third stirring on the obtained mixture to obtain a raw material mixture, wherein the rotating speed of the second stirring is less than that of the third stirring; heating the raw material mixture for 1-2 hours at the temperature of 80-100 ℃.
According to an embodiment of the present disclosure, the first stirring may be performed in a high speed stirrer, the stirring speed may be 100rpm to 1500rpm (e.g., 100rpm, 300rpm, 500rpm, 800rpm, 1000rpm, 1200rpm, 1500rpm, etc.), and the specific stirring time may be 5 minutes to 30 minutes, specifically 5 minutes, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, etc.
According to an embodiment of the present disclosure, after the first stirring, the filler particle body subjected to the first stirring may be subjected to low-speed stirring (i.e., second stirring), and the surface modifier may be sprayed or dropped into the filler particle body subjected to the low-speed stirring, and then stirred at a high speed (i.e., third stirring), specifically, the low-speed stirring may be performed at a speed of 300rpm to 600rpm (e.g., 300rpm, 400rpm, 500rpm, 600rpm, etc.), the time may be 10min to 20min (e.g., 10min, 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min, 19min, 20min, etc.), the high-speed stirring may be performed at a speed of 800rpm to 1500rpm (e.g., 800rpm, 900rpm, 1000rpm, 1100rpm, 1200rpm, 1300rpm, 1400rpm, 1500rpm, etc.), and the time may be 5min to 10min (e.g., 5min, 6min, 7min, 8min, 9min, 10min, etc.). Thereby, a good coating can be achieved.
According to the embodiment of the present application, the raw materials may be mixed and heated to react the surface modifier with the bulk of the filler particles, and specifically, the raw material mixture may be heated to 80 ℃, 85 ℃, 90 ℃, 95 ℃, or 100 ℃ and then held for 1 hour, 1.5 hours, or 2 hours. Under the condition, the surface modifier and the filler particle body can fully react, the cost is improved and the efficiency is reduced due to no overlong time consumption, and the modified filler with better modification effect can be obtained.
In yet another aspect of the present application, a potting adhesive is provided. According to the embodiment of the application, the pouring sealant comprises the modified filler. The pouring sealant has better service performance, lower viscosity and better fluidity, lower thixotropy and convenient processing.
According to the embodiments of the present application, the type of the potting adhesive is not particularly limited, and may be a two-component addition type silicone potting adhesive. Therefore, on the premise of ensuring the service performance of the pouring sealant, the problem of viscosity and thixotropy increase caused by filler agglomeration can be greatly improved, and the using effect of the pouring sealant is better.
It can be understood that the modified filler described above may further include necessary components of a conventional potting adhesive, and taking a two-component addition type silicone potting adhesive as an example, the two-component addition type silicone potting adhesive may further include components such as hydrogen-containing silicone oil and vinyl silicone oil, which may be specifically performed with reference to the prior art, and thus, details thereof are not repeated herein.
Embodiments of the present application are described in detail below.
Example 1
The surface modifier shown in formula (1) is used for modifying the heat-conducting filler alpha-alumina particles (D50 particle size is 5 microns), and the specific method is as follows:
adding 200kg of alpha-alumina particles into a high-speed stirrer, starting stirring at the rotating speed of 300rpm, then adding 400g of a surface modifier shown in the formula (1) in a spraying manner within 20-30 min, then stirring at the high speed (the rotating speed of 1500 rpm) for 10min, then discharging to obtain a raw material mixture, then heating at 80 ℃ for 1h to enable active groups on the surfaces of the alpha-alumina particles to fully react with the surface modifier to complete surface modification treatment, and then cooling to obtain the modified heat-conducting filler TCF-05.
Example 2
The surface modifier shown in formula (4) is adopted to modify the heat-conducting filler alpha-alumina particles (D50 particle size is 40-50 microns), and the specific method is as follows:
adding 400kg of alpha-alumina particles into a high-speed stirrer, starting stirring at the rotating speed of 300rpm, then adding 400g of the surface modifier shown in the formula (4) within 20-30 min in a spraying manner, then stirring at the high speed (the rotating speed of 1500 rpm) for 10min, then discharging to obtain a raw material mixture, heating at 80 ℃ for 1 hour to fully react active groups on the surfaces of the alpha-alumina particles with the surface modifier, finishing surface modification treatment, and then cooling to obtain the modified heat-conducting filler TCF-040.
Example 3
The surface modifier shown in formula (4) is used for modifying alpha-alumina particles with D50 particle size of 40-50 microns and 5 microns and aluminum hydroxide particles with D50 particle size of 5 microns, and the specific method is as follows:
240kg of alpha-alumina particles with the D50 particle size of 40 to 50 microns, 160kg of alpha-alumina particles with the D50 particle size of 5 microns and 100kg of aluminum hydroxide particles with the D50 particle size of 5 microns are added into a high-speed stirrer, and stirring is started at the rotating speed of 300rpm for 10min; then stirring is kept, and 500g of surface modifier shown in the formula (4) is added in 20-30 min in a spraying way; and then stirring at a high speed (the rotating speed is 1500 rpm) for 10min, discharging to obtain a mixture, heating at 80 ℃ for 1 hour to fully react active groups on the surfaces of the filler particles with the surface modifier to complete surface modification treatment, and then cooling to obtain the modified thermal conductive filler TCF-4055.
Example 4
The same as in example 1 except that the surface modifier was the surface modifier represented by the formula (11), the modified thermally conductive filler TCF-406 was obtained.
Example 5
The same as in example 1 except that the surface modifier was a surface modifier represented by the formula (16), modified thermally conductive filler TCF-407 was obtained.
Comparative example 1
The same as example 1 except that hexadecyl trimethoxy silane was used as the surface modifier, the modified thermally conductive filler TCF-05D was obtained.
Comparative example 2
The same as example 2 except that hexadecyl trimethoxy silane was used as the surface modifier, the modified thermally conductive filler TCF-040D was obtained.
Comparative example 3
The same as example 3, except that hexadecyltrimethoxysilane was used as the surface modifier, the modified thermally conductive filler TCF-4055D was obtained.
And (4) performance testing:
when the modified heat-conducting fillers obtained in the above examples and comparative examples were left for 6 months, the powder of TCF-05, TCF-040, TCF-4055, TCF-406, and TCF-407 did not cake, while the powder of TCF-05D, TCF-040D, and TCF-4055D did cake and were broken and dispersed again before use.
Weighing the materials according to the following table, stirring at 800rpm for 30min, making a raw material mixture, and testing the viscosity and the anti-settling property of the raw material mixture, wherein the viscosity is measured by a rotational viscometer at 25 ℃, and the test results are shown in the following table 2.
TABLE 2
Preparing a pouring sealant with a thermal conductivity coefficient of about 2.0W/m.k according to the following table 3, and testing the performance of the pouring sealant, specifically, weighing raw materials according to the proportion in the table 3, mixing the raw materials at 1000rpm for 40min to respectively obtain an A1 glue, a B1 glue, an A2 glue and a B2 glue, then mixing the A1 glue and the B1 glue, vacuumizing for 5min, heating and curing (120 ℃ and 1 h), mixing the A2 glue and the B2 glue, vacuumizing for 5min, heating and curing (120 ℃ and 1 h) to obtain a test sample, and then testing the performance of the test sample. Wherein the tensile strength and elongation at break are measured with reference to GB/T528-92, and the hardness is measured with reference to GB/T531-1999.
TABLE 3
As can be seen from the data in Table 2 above, the viscosity and thixotropic index of the raw material mixture of examples 6-10 are significantly lower than those of comparative examples 4-6, which shows that the surface modifier of the present application can effectively improve the viscosity and thixotropy of the potting adhesive. It can be seen from the data in table 3 that the pouring sealant in example 11 has lower viscosity and thixotropic index while ensuring larger thermal conductivity, mechanical properties, hardness and flame retardant property compared to comparative example 7.
In the description of the present application, it is to be understood that the terms "first", "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present application, "a plurality" means two or more unless specifically limited otherwise.
In the description of the present specification, reference to the description of "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present application. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present application have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present application, and that variations, modifications, substitutions and alterations may be made to the above embodiments by those of ordinary skill in the art within the scope of the present application.
Claims (11)
1. A surface modifying agent having a structural formula represented by formula I:
wherein R is 1 Is C 1-4 An alkyl group;
R 2 ，R 3 and R 4 Each of which is independently C 1-20 Alkyl radical, C 1-10 Cycloalkyl or C 6-20 An aromatic group.
2. The surface modifier of claim 1, wherein R is 2 ，R 3 And R 4 Each of which is independently C 1-8 Alkyl radical, C 1-8 Cycloalkyl or optionally substituted phenyl.
3. The surface-modifying agent according to claim 1,
R 1 is methyl, ethyl, propyl or isopropyl;
R 2 ，R 3 and R 4 Each of which is independently methyl, ethyl, t-butyl, cyclobutyl, cyclopentyl, cyclohexyl, -C (CH) 3 ) 2 (C 2 H 5 )、-C(CH 3 )(C 2 H 5 ) 2 、-C(C 2 H 5 ) 3 Or a phenyl group.
4. The surface modifier of claim 1, wherein R is 2 ，R 3 And R 4 At least one of which is cycloalkyl, a radical or-C (R) 5 ) 3 Wherein R is 5 Is an alkyl group.
5. The surface modifier according to claim 1, having a structural formula represented by any one of formulae (1) to (17):
6. a modified filler, characterized by comprising:
a filler particle body;
the surface modifying agent of any one of claims 1 to 5, which is bonded to the surface of the bulk of the filler particles.
7. The filler according to claim 6, characterized in that the filler particle body fulfils at least one of the following conditions:
the filler particle body is at least one of alumina particles, silica micropowder particles, boron nitride particles, aluminum nitride particles, magnesium oxide particles, zinc oxide particles and aluminum hydroxide particles;
the filler particle body is at least one of flaky, triangular, spheroidal and spherical;
the D50 particle size of the filler particle body is 0.01-100 microns.
8. The filler according to claim 6, wherein the surface modifier is present in an amount of 0.01 to 2% by weight of the bulk filler particles.
9. A method for preparing a modified filler according to any one of claims 6 to 8, characterized in that it comprises:
mixing a surface modifier with a filler particle body, and reacting active groups in the surface modifier with the filler particle body to obtain the modified filler.
10. The method of claim 9, comprising:
carrying out first stirring on the filler particle body to obtain a first stirred filler particle body;
performing second stirring on the first stirred filler particle body, adding a surface modifier into the first stirred filler particle body in a spraying or dropping mode, and performing third stirring on the obtained mixture to obtain a raw material mixture, wherein the rotating speed of the second stirring is less than that of the third stirring;
heating the raw material mixture for 1-2 hours at the temperature of 80-100 ℃.
11. A potting adhesive comprising the modified filler of any one of claims 6 to 8.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892898A (en) * | 2017-11-09 | 2018-04-10 | 南京科孚纳米技术有限公司 | A kind of preparation method of high heat conduction low-gravity flame-proof organosilicon casting glue |
| CN108410416A (en) * | 2018-03-30 | 2018-08-17 | 深圳天鼎新材料有限公司 | A kind of embedding silica gel and its preparation method and application |
| CN110938406A (en) * | 2019-11-04 | 2020-03-31 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Bi-component organic silicon pouring sealant and preparation method thereof |
-
2021
- 2021-03-31 CN CN202110354552.2A patent/CN115141223A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107892898A (en) * | 2017-11-09 | 2018-04-10 | 南京科孚纳米技术有限公司 | A kind of preparation method of high heat conduction low-gravity flame-proof organosilicon casting glue |
| CN108410416A (en) * | 2018-03-30 | 2018-08-17 | 深圳天鼎新材料有限公司 | A kind of embedding silica gel and its preparation method and application |
| CN110938406A (en) * | 2019-11-04 | 2020-03-31 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Bi-component organic silicon pouring sealant and preparation method thereof |
Non-Patent Citations (11)
| Title |
|---|
| "CAS:113591-63-2", STN-REGISTRY 数据库, 26 March 1988 (1988-03-26) * |
| "CAS:17348-65-1", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:17348-66-2", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:1825-59-8", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:1825-62-3", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:54731-56-5", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:55549-79-6", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:597-67-1", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:66548-21-8", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:68260-85-5", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
| "CAS:84960-80-5", STN-REGISTRY 数据库, 16 November 1984 (1984-11-16) * |
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