CN113150728A - Heat-conducting pouring sealant and preparation method thereof - Google Patents

Heat-conducting pouring sealant and preparation method thereof Download PDF

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CN113150728A
CN113150728A CN202110639196.9A CN202110639196A CN113150728A CN 113150728 A CN113150728 A CN 113150728A CN 202110639196 A CN202110639196 A CN 202110639196A CN 113150728 A CN113150728 A CN 113150728A
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component
heat
conducting
agent
filler
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周佩先
岳利
俞国金
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Hunan Chuangjin Technology Research Institute Co ltd
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3236—Heterocylic compounds
    • C08G59/3245—Heterocylic compounds containing only nitrogen as a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C08G59/64—Amino alcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/66—Mercaptans
    • 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
    • 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
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/222—Magnesia, i.e. magnesium oxide
    • 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
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/282—Binary compounds of nitrogen with aluminium

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  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Sealing Material Composition (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a heat-conducting pouring sealant and a preparation method thereof, wherein the heat-conducting pouring sealant comprises a component A and a component B, wherein the component A comprises 10-30 wt% of 1,3, 5-triglycidyl isocyanurate; the component B comprises 95.5 to 99.97 weight percent of curing agent. The preparation method comprises the following steps: mixing 1,3, 5-triglycidyl isocyanurate and a heat-conducting filler by an air flow mixer to obtain a component A; stirring and mixing a curing agent, a dispersing agent, a defoaming agent and a flatting agent to obtain a component B; and extruding the component A and the component B through a heatable single-screw extrusion device to obtain the heat-conducting pouring sealant. The invention uses the resin with self-flame-retardant property and the curing agent as the matrix material, and can reduce the using amount of the flame-retardant filler, thereby reserving the space for increasing the heat-conducting filler by the donor, thereby realizing the purposes of ensuring the resin amount to be unchanged, improving the filling amount of the heat-conducting filler and further improving the heat-conducting property.

Description

Heat-conducting pouring sealant and preparation method thereof
Technical Field
The invention belongs to the field of resin, and relates to a heat-conducting pouring sealant and a preparation method thereof.
Background
With the rapid development of microelectronic integration technology, electronic components and instruments are more and more widely used in the electronic industry. In order to ensure the stability and reliability of electronic devices, the electronic devices have the properties of impact vibration resistance, severe environment resistance, electrical insulation, heat conduction and the like, and the electronic devices are often required to be encapsulated and protected. Typical potting materials have thermal conductivities of only 0.2w (m · k) and poor thermal conductivity. Typical potting materials are poor in flame retardant properties and burn completely once ignited. Therefore, the research has important theoretical significance and application prospect on the heat conduction and flame retardant property of the pouring sealant.
The addition of flame-retardant filler, heat-conducting filler and auxiliary agent into the base material (resin) of pouring sealant is an important means for improving the heat-conducting and flame-retardant properties of pouring sealant. However, the increase of the thermal conductivity depends on the increase of the filling ratio of the thermal conductive filler, and the excessive filling ratio of the thermal conductive filler can negatively affect the adhesive force of the adhesive. Therefore, how to ensure the adhesive force and the mechanical property of the adhesive while enhancing the thermal conductivity and the flame retardance is particularly important. At present, on the basis of the requirements of bonding strength, flame retardance and insulation strength, the requirement on heat-conducting performance is higher and higher, so that the pursuit on the aspects of the filling amount of a heat-conducting filler and high heat-conducting powder is higher and higher. However, as the filling amount of the heat-conducting filler is increased, the flame retardant performance of the heat-conducting filler is improved, the heat-conducting performance of the heat-conducting filler is also improved, but the occupation amount of the resin in a system is reduced, so that the cohesive force and the bonding strength of the heat-conducting filler are reduced, and meanwhile, the viscosity is increased, so that higher requirements are put on a use scene.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and the resin and the curing agent with self-flame retardant property are used as matrix materials, so that the using amount of the flame retardant filler can be reduced, an increased space of the heat-conducting filler is reserved by a donor, the resin amount is ensured to be unchanged, the filling amount of the heat-conducting filler is increased, and the heat-conducting property is further improved.
In order to solve the technical problems, the invention provides a heat-conducting pouring sealant which comprises a component A and a component B, wherein the component A comprises 10-30 wt% of 1,3, 5-triglycidyl isocyanurate; the 1,3, 5-triglycidyl groupThe isocyanurate has the formula
Figure 873695DEST_PATH_IMAGE001
The structural formula (II) is as follows:
Figure 287359DEST_PATH_IMAGE002
（
Figure 46367DEST_PATH_IMAGE001
）；
the component B comprises 95.5 to 99.97 weight percent of curing agent; the curing agent is 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -sulfenyl ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate;
the-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene]The tri-2, 1-ethanediol ester has the following formula
Figure 661019DEST_PATH_IMAGE003
Structural formula (II)
Figure 364533DEST_PATH_IMAGE004
（
Figure 316309DEST_PATH_IMAGE003
）；
The 1,3, 5-tris (2-hydroxyethyl) isocyanurate has the formula
Figure 428359DEST_PATH_IMAGE005
The structural formula (II) is as follows:
Figure 807388DEST_PATH_IMAGE006
（
Figure 263777DEST_PATH_IMAGE005
）。
the heat-conducting pouring sealant further comprises the component A, wherein the component A comprises 10-30 wt% of 1,3, 5-triglycidyl isocyanurate and 70-90 wt% of filler;
the component B comprises 95.5 to 99.97 weight percent of curing agent, 0.01 to 1 weight percent of defoaming agent and 0.01 to 2 weight percent of flatting agent.
The heat-conducting pouring sealant further comprises the component A, wherein the component A comprises 20wt% of 1,3, 5-triglycidyl isocyanurate and 80wt% of filler;
the component B comprises 96wt% of curing agent, 1wt% of dispersing agent, 1wt% of defoaming agent and 2wt% of flatting agent.
Further, the filler includes one or more of aluminum nitride, zinc oxide, and silicon carbide.
Further, the filler is a mixture of aluminum nitride, magnesium oxide and silicon carbide, and the aluminum nitride, the magnesium oxide and the silicon carbide are proportioned according to the particle size as follows: 30-50 μm: 10-20 μm: 100 nm-2 μm = (50 wt% -70 wt%): 10wt% -20 wt%: 2wt% -15 wt%.
Further, the dispersant is one or more of Additol VXW6208-60, TEGO Dispers 760W and BYK-220S.
Further, the defoaming agent is one or more of polyether modified polysiloxane, polyether defoaming agent and organic silicon defoaming agent.
Further, the leveling agent is one or more of BYK306, BYK-331, BYK-345 and BYK-349.
Based on a general technical concept, the invention also provides a preparation method of the heat-conducting pouring sealant, and the preparation method of the heat-conducting pouring sealant comprises the following steps:
s1, mixing the resin containing the isocyanurate structure and the epoxy group and the heat-conducting filler through an air flow mixer to obtain a component A;
s2, stirring and mixing the curing agent, the dispersing agent, the defoaming agent and the flatting agent to obtain a component B;
and S3, extruding the component A and the component B through a heatable single-screw extrusion device to obtain the heat-conducting pouring sealant.
In the preparation method, the charging volume coefficient of the air flow mixer in S1 is 0.3-0.8, and the treatment lasts for 5-120 min.
In the preparation method above, further, the S2 is: stirring dispersing agent, defoaming agent and flatting agent for 5-120 min at the speed of 0.3-1.3 m/s, adding curing agent, and treating in a double-planet stirring kettle at the shearing and dispersing linear speed of 3-10 m/s and the stirring linear speed of 0.3-0.8 m/s for 30-80 min to obtain the component B.
In the preparation method, in S3, the mass ratio of the component A to the component B is 10: 1-10: 7; the heating temperature of the heating single-screw extrusion device is 80-120 ℃.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a heat-conducting pouring sealant which comprises a component A and a component B, wherein the component A comprises 1,3, 5-triglycidyl isocyanurate; the component B comprises 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -sulfenyl ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate. 1,3, 5-triglycidyl isocyanurate is a resin with a self-flame-retardant structure, and has the following advantages compared with the conventional epoxy resin:
the powder is powder at normal temperature, which is different from other traditional liquid resin, so that the advantage that the phenomenon of filler sedimentation can be prevented after the liquid resin is placed for a long time, and the use is more convenient.
Secondly, the resin can be melted quickly at about 90 ℃, has good fluidity after being melted, can be well infiltrated and coated with the filler, and ensures the bonding function of the resin.
Thirdly, due to the isocyanurate structure, the isocyanurate structure has the characteristic of flame retardance, so that the addition of flame-retardant filler is greatly saved, the saved flame-retardant filler can be replaced by heat-conducting filler, and the heat conductivity is greatly improved.
(2) The invention provides a heat-conducting pouring sealant, which adopts 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -sulfenyl ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate as a curing agent. On one hand, the two curing agents have flame-retardant structures, and flame-retardant fillers do not need to be additionally added, so that the physical and heat-conducting properties of the heat-conducting pouring sealant are improved. On the other hand, 1,3, 5-triglycidyl isocyanurate and 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate can be subjected to curing reaction, and the 1,3, 5-triglycidyl isocyanurate can be subjected to toughening modification while being cured, wherein the tensile property is obviously improved.
(3) The invention provides a heat-conducting pouring sealant, wherein a heat-conducting filler is added into a component A, and the heat-conducting property of the heat-conducting filler is generally much higher than that of a polymer body. When the content of the heat-conducting filler is less, the fillers are not mutually contacted and acted, and the effect of improving the heat conductivity coefficient is not great; when the content of the filler reaches and exceeds a certain critical value, a heat conduction path similar to a net structure is formed in the composite material. The fillers have different particle sizes, different mass ratios to the maximum stacking degree, and different final electric and thermal conduction effects. The invention mixes the aluminum nitride, the magnesium oxide and the silicon carbide according to the grain diameter: 30-50 μm: 10-20 μm: 100 nm-2 μm = (50-70%): 10-20%): 2-15%, so that an effective heat conduction network chain is formed in the high polymer material, and the heat conduction performance of the heat conduction pouring sealant is remarkably improved. This is because aluminum nitride having a large particle size is dispersed in the resin matrix, and a large void exists, which is not favorable for the formation of a heat conduction channel; after the substances with different particle sizes are mixed, the particles with smaller particle sizes can fill the gaps, so that a heat conduction passage similar to a net structure is formed, and the heat conduction performance of the composite material is obviously improved.
(4) The invention provides a preparation method of a heat-conducting pouring sealant, which is simple in preparation process and easy for industrial production.
Detailed Description
The invention is further described below with reference to specific preferred embodiments, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available. Wherein 1,3, 5-triglycidyl isocyanurate (TGIC) is available from HBC chemical company, USA; aluminum nitride, magnesium oxide, and silicon carbide were purchased from Anhui Shitong materials science and technology, Inc.; 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tris-2, 1-ethanediol ester, CAS: 36196-44-8, available from Nanjing Nippon Chemicals, Inc.; additol VXW6208-60, TEGO Dispers 760W (a non-ionic wetting dispersant, an aqueous solution of a high pigment affinity group-containing polymer and a surface active material), BYK-220S (a low molecular weight unsaturated acidic polycarboxylic polyester solution containing a polysiloxane copolymer) was purchased in the United states; 1520. FG10, Dow Corning DSP antifoam, AFE1520 antifoam, FS-80, BYK-3455, BYK-346 available from Dow Corning; FOAMEX 810 and FOAMEX822 are available from Digao.
Example 1
The heat-conducting pouring sealant comprises a component A and a component B,
the component A comprises 30wt% of 1,3, 5-triglycidyl isocyanurate (TGIC) and 70wt% of heat-conducting filler. The heat conducting filler is 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 200nm silicon carbide = 70: 15%.
The component B comprises 96wt% of 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tri-2, 1-glycol ester (CAS: 36196-44-8), 1wt% of Additol VXW6208-60, 1wt% of Dow Corning FS-80 and 2wt% of BYK 306.
The preparation method of the heat-conducting pouring sealant comprises the following steps:
(1) preparing a component A: mixing 30-50 μm of aluminum nitride: 10-20 μm zinc oxide: and mixing 200nm silicon carbide according to the mass ratio of 70: 15 to obtain the heat conducting filler. And mixing the TGIC and the heat-conducting filler by an air flow mixer to obtain the component A, wherein the condition is that the charging volume coefficient is 0.6, and treating for 20min to obtain the component A.
(2) Preparing a component B: firstly adding a dispersant, a defoaming agent and a flatting agent, stirring for 30min at a stirring linear speed of 0.8m/s, then adding a curing agent (3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tri-2, 1-glycol ester), and processing for 50min in a double-planet stirring kettle at a shearing and dispersing linear speed of 5m/s and a stirring linear speed of 0.5m/s to obtain the component B.
(3) Mixing the component A and the component B according to the mass ratio of 10: 5, and extruding the mixture by a heatable single-screw extrusion device for direct use; the heating temperature was 100 ℃.
Example 2
The heat-conducting pouring sealant comprises a component A and a component B.
The component A comprises 30wt% of 1,3, 5-triglycidyl isocyanurate (TGIC) and 70wt% of heat-conducting filler. The heat conductive filler is 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 200nm silicon carbide = 70: 15%.
The component B comprises 96wt% of 1,3, 5-tri (2-hydroxyethyl) isocyanurate (CAS No.: 839-90-7), 1wt% of Additol VXW6208-60, 1wt% of Dow Corning FS-80 and 2wt% of BYK 306.
The preparation method of the heat-conducting pouring sealant comprises the following steps:
(1) preparing a component A: mixing 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 200nm silicon carbide according to a mass ratio of 70: 15 to obtain the heat-conducting filler. And mixing the TGIC and the heat-conducting filler by an air flow mixer to obtain the component A, wherein the condition is that the charging volume coefficient is 0.6, and treating for 20min to obtain the component A.
(2) Preparing a component B: firstly adding a dispersing agent, a defoaming agent and a flatting agent, stirring for 30min at a stirring linear speed of 0.8m/s, then adding a curing agent (1, 3, 5-tris (2-hydroxyethyl) isocyanurate), and processing for 50min in a double-planet stirring kettle at a shearing and dispersing linear speed of 5m/s and a stirring linear speed of 0.5m/s to obtain a component B.
(3) Respectively mixing the component A and the component B according to the mass ratio of 10: 5, and extruding the mixture by a heatable single-screw extrusion device for direct use; the heating temperature was 100 ℃.
Comparative example 1
The component A is as follows: 30% by weight of 1,3, 5-triglycidyl isocyanurate, 70% by weight of silica.
The component B is as follows: polypropylene oxide glycol, 1wt% Additol VXW6208-60, 1wt% Dow Corning FS-80, and 2wt% BYK 306.
The preparation process was identical to example 1.
Comparative example 2
The component A is as follows: 30wt% of isophorone diisocyanate, 70wt% of silica.
The component B is as follows: 96wt% 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tris-2, 1-ethanediol ester (CAS: 36196-44-8), 1wt% Additol VXW6208-60, 1wt% Dow Corning FS-80, 2wt% BYK 306.
The preparation process was identical to example 1.
Comparative example 3
The component A is as follows: 30wt% of isophorone diisocyanate, 70wt% of silica.
The component B is as follows: polypropylene oxide glycol, 1wt% Additol VXW6208-60, 1wt% Dow Corning FS-80, and 2wt% BYK 306.
The preparation process was identical to example 1.
The heat conductive potting adhesives of examples 1 and 2 and comparative examples 1 and 2 were tested for hardness, Al/Al lap shear strength, thermal conductivity, dielectric strength, dielectric constant, flame retardancy, and other parameters.
(1) Viscosity: the test was carried out according to ASTM D1084-2016 Standard test method for adhesive viscosity, viscometer DVnext RV5, speed 60RPM, temperature 25 ℃.
(2) Coefficient of thermal conductivity: the test was carried out according to the test standard for thermal conductivity ASTM D5470.
(3) Lap shear strength: the test was carried out according to ASTM D1002-10 tensile shear Strength test, Al/Al substrates.
(4) Breakdown voltage: the detection is carried out according to the GB/T7752-1987 power frequency breakdown strength test method of the insulating adhesive tape, 500 v/min.
(5) Volume resistivity: testing was performed according to ASTM D257-07 DC resistance and conductivity test methods for insulation materials.
(6) Flame retardant property: the test was carried out according to the UL94 flame resistance test rating.
The results of the tests are listed in table 1:
table 1: performance test result table of heat-conducting pouring sealant of each embodiment
Figure 629030DEST_PATH_IMAGE008
From the results of table 1, it can be seen that: the performances of the heat conductivity coefficient, the flame retardant performance, the shear strength and the like of the embodiment 1 and the embodiment 2 are obvious because the comparative examples 1, 2 and 3 prove that the heat conductivity coefficient, the flame retardant performance, the shear strength and the like of the heat conduction pouring sealant are greatly improved by matching 1,3, 5-triglycidyl isocyanurate with 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate, so that the heat conductivity and the flame retardant performance of the heat conduction pouring sealant can be improved, and the curing reaction is carried out on the 1,3, 5-tri (2-hydroxyethyl) isocyanurate.
Example 4
According to the method of the embodiment 1, different heat-conducting fillers are designed, and the influence of the different heat-conducting fillers on the heat-conducting property of the flame-retardant pouring sealant is examined.
Heat conductive filler 1: 1-3 mu m zinc oxide
Heat conductive filler 2: 30-50 μm aluminum nitride
Heat conductive filler 3: 10-20 mu m zinc oxide
Heat conductive filler 4: magnesium oxide of 5-10 μm
Heat conductive filler 5: 1-3 μm silicon carbide
Heat conductive filler 6: 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 1-3 μm silicon carbide = 60%: 25%: 15%
Heat conductive filler 7: 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 200nm silicon carbide = 70: 15%.
Heat conductive filler 8: 30-50 μm aluminum nitride: 10-20 μm zinc oxide: 30nm silicon carbide = 55: 25: 20%.
The influence of the conductive filler on the performance of the heat-conducting potting adhesive is inspected, and the detection results are listed in table 2.
Table 2: result table of influence of heat-conducting filler on performance of heat-conducting potting adhesive
Figure 956106DEST_PATH_IMAGE010
From the results of table 2, it can be seen that: compared with single heat-conducting filler, the heat-conducting fillers 6, 7 and 8 have better electric conductivity and larger heat conductivity coefficient. In which the thermal conductivity of the thermally conductive filler 7 is the highest. The thermal conductivity of the thermal conductive filler 8 is inferior, and the nano particle size thereof is too small because agglomeration thereof is difficult to avoid. Followed by a thermally conductive filler 6.
Meanwhile, as the particle size of the filler is smaller, the conductivity coefficient is higher, the viscosity is higher, and the influence on the tensile property of the filler is larger. However, after the fillers with different particle sizes are mixed, the conductivity coefficient is greatly improved, but the viscosity is not obviously enhanced.
Example 5:
and (5) investigating the influence of the mixture ratio of different components on the performance of the heat-conducting potting adhesive. According to the method of example 1, different proportions of component A and component B were prepared, and the specific proportions are shown in Table 3.
Table 3: influence of different proportions on performance of heat-conducting potting adhesive
Figure DEST_PATH_IMAGE011
From the results in table 3, it can be seen that: with the increase of the content of the heat-conducting filler, the heat-conducting property is obviously improved, but the heat-conducting coefficient is increased and reduced with the increase of the heat-conducting addition. The main reasons for this are: when the content of the heat-conducting filler is low, the filler particles cannot be in direct contact with each other, and the resin layer is a main obstacle for heat flow to pass through at the moment, so that the heat-conducting property of the filler cannot be sufficiently transferred, and the effect of improving the heat-conducting coefficient is not great. When the filler content reaches 70%, a heat conduction path similar to a net structure is formed in the composite material, so that the heat conduction performance of the composite material is obviously improved; meanwhile, the heat-conducting filler can be uniformly dispersed in the resin, plays a role of a physical cross-linking point and plays a role in reinforcing the mechanical property of a cured product.
However, if the content of the thermally conductive filler is too large, the viscosity of the epoxy resin may increase. In addition, if the filler is locally aggregated, cracks are easily formed due to excessive local stress under the action of external force, so that the strength is reduced, and the tensile property of a cured product of the filler is greatly influenced.
Example 6
According to the formula of the embodiment 1, the influence of the parameters on the performance of the heat-conducting pouring sealant in the preparation method of the heat-conducting pouring sealant is examined:
considering the first step, the component A is obtained by mixing the resin containing the isocyanurate structure and the epoxy group and the silicon oxide through an air flow mixer, and treating for 20min under the condition that the charging volume coefficient is 0.6. Firstly adding a dispersing agent, a defoaming agent and a flatting agent, stirring for 30min at a stirring linear speed of 0.8m/s, then adding a curing agent, and processing for 50min in a double-planet stirring kettle at a shearing and dispersing linear speed of 3,5, 8 and 10m/s respectively at a stirring linear speed of 0.5m/s to obtain a component B. Mixing the component A and the component B according to the mass ratio of 10: 5, and extruding the mixture by a heatable single-screw extrusion device for direct use; the heating temperature was 100 ℃.
The results show that: the dispersion efficiency is higher along with the increase of the stirring speed, and the heat conductivity coefficient of the material is further improved, when the dispersion speed is 5m/s, the heat conductivity coefficient reaches 1.8W/(m.k), and the heat conductivity coefficient is kept stable along with the increase of the dispersion speed, but excessive bubbles are introduced, so that the toughness of the heat-conducting pouring sealant is reduced, and finally, the bubble removal treatment is needed, so that the difficulty of the process is increased.
And secondly, mixing the resin containing the isocyanurate structure and the epoxy group and silicon oxide by an air flow mixer to obtain the component A, wherein the component A is obtained by treating for 20min under the condition that the charging volume coefficient is 0.6. Firstly adding a dispersing agent, a defoaming agent and a flatting agent, stirring for 30min at a stirring linear speed of 0.8m/s, then adding a curing agent, and processing for 50min in a double-planet stirring kettle at a shearing and dispersing linear speed of 5m/s and a stirring linear speed of 0.5m/s respectively to obtain a component B. Mixing component A and component B at a mass ratio of 10:1, 10:3, 10: 5, and 10:7, respectively, and extruding with a single screw extruder capable of heating for direct use; the heating temperature was 100 ℃.
The results show that: when the mass ratio of the component A to the component B is 10:3, the comprehensive performance is optimal, and the curing time is 39 min; if the curing agent is increased, the curing speed becomes too fast, and if the curing agent is too little, the curing cannot be completely cured.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (10)

1. The heat-conducting pouring sealant is characterized by comprising a component A and a component B, wherein the component A comprises 10-30 wt% of 1,3, 5-triglycidyl isocyanurate; the 1,3, 5-triglycidyl isocyanurate has the formula
Figure DEST_PATH_IMAGE002
The structural formula (II) is as follows:
Figure DEST_PATH_IMAGE004
（
Figure 210507DEST_PATH_IMAGE002
）；
the component B comprises 95.5 to 99.97 weight percent of curing agent; the curing agent is 3-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -sulfenyl ] tri-2, 1-glycol ester or 1,3, 5-tri (2-hydroxyethyl) isocyanurate;
the-mercaptopropionic acid- [2,4, 6-trioxo-1, 3, 5-triazine-1, 3,5(2H,4H,6H) -ylidene]The tri-2, 1-ethanediol ester has the following formula
Figure DEST_PATH_IMAGE006
Structural formula (II)
Figure DEST_PATH_IMAGE008
（
Figure 189964DEST_PATH_IMAGE006
）；
The 1,3, 5-tris (2-hydroxyethyl) isocyanurate has the formula
Figure DEST_PATH_IMAGE010
The structural formula (II) is as follows:
Figure DEST_PATH_IMAGE012
（
Figure 376226DEST_PATH_IMAGE010
）。
2. the heat-conducting pouring sealant as claimed in claim 1, wherein the component A comprises 10wt% to 30wt% of 1,3, 5-triglycidyl isocyanurate and 70wt% to 90wt% of filler;
the component B comprises 95.5 to 99.97 weight percent of curing agent, 0.01 to 1 weight percent of dispersant, 0.01 to 1 weight percent of defoaming agent and 0.01 to 2 weight percent of flatting agent.
3. The heat conductive pouring sealant of claim 1, wherein the component a comprises 20wt% of 1,3, 5-triglycidyl isocyanurate, 80wt% of filler;
the component B comprises 96wt% of curing agent, 1wt% of dispersing agent, 1wt% of defoaming agent and 2wt% of flatting agent.
4. The heat conducting potting adhesive of any of claims 1 to 3, wherein the filler comprises one or more of aluminum nitride, magnesium oxide, and silicon carbide.
5. The heat-conducting pouring sealant as claimed in claim 4, wherein the filler is a mixture of aluminum nitride, magnesium oxide and silicon carbide, and the mixture ratio of the aluminum nitride, the magnesium oxide and the silicon carbide according to the particle size is as follows: 30-50 μm: 10-20 μm: 100 nm-2 μm = (50 wt% -70 wt%): 10wt% -20 wt%: 2wt% -15 wt%.
6. The heat-conducting pouring sealant as claimed in any one of claims 1 to 3, wherein the dispersant is one or more of Additol VXW6208-60, TEGO Dispers 760W, BYK-220S;
the defoaming agent is one or more of polyether modified polysiloxane, polyether defoaming agent and organic silicon defoaming agent;
the leveling agent is one or more of BYK306, BYK-331, BYK-345 and BYK-349.
7. A method for preparing the heat conducting pouring sealant as claimed in any one of claims 1 to 7, comprising the following steps:
s1, mixing the resin containing the isocyanurate structure and the epoxy group and the heat-conducting filler through an air flow mixer to obtain a component A;
s2, stirring and mixing the curing agent, the dispersing agent, the defoaming agent and the flatting agent to obtain a component B;
and S3, extruding the component A and the component B through a heatable single-screw extrusion device to obtain the heat-conducting pouring sealant.
8. The method as recited in claim 7, wherein the gas flow mixer in S1 has a charge volume factor of 0.6 and is processed for 20 min.
9. The method according to claim 7, wherein S2 is: stirring the dispersing agent, the defoaming agent and the flatting agent for 30min at the speed of 0.3-1.3 m/s, adding the curing agent, and treating for 30-80 min in a double-planet stirring kettle at the shearing and dispersing linear speed of 3-10 m/s and the stirring linear speed of 0.3-0.8 m/s to obtain the component B.
10. The preparation method according to claim 7, wherein in the S3, the mass ratio of the component A to the component B is 10: 1-10: 7; the heating temperature of the heating single-screw extrusion device is 80-120 ℃.
CN202110639196.9A 2021-06-08 2021-06-08 Heat-conducting pouring sealant and preparation method thereof Pending CN113150728A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113429796A (en) * 2021-07-27 2021-09-24 湖南创瑾技术研究院有限公司 Single-component high-thermal-conductivity silicone gel and preparation method thereof
CN116445115A (en) * 2023-04-20 2023-07-18 广东省固特尔新材料有限公司 Low-density high-heat-conductivity pouring sealant and processing technology thereof

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CN102719099A (en) * 2012-06-08 2012-10-10 金发科技股份有限公司 Thermal conductive molding compound and preparation method thereof
TW201305245A (en) * 2011-07-22 2013-02-01 Elite Material Co Ltd Resin composition and substrate using the same
JP2016222865A (en) * 2015-06-03 2016-12-28 株式会社ダイセル Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device
CN112778501A (en) * 2020-12-24 2021-05-11 艾勒可新材料(佛山)有限公司 Solid mercaptan curing agent, powder coating and preparation method thereof

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GB1169465A (en) * 1966-06-16 1969-11-05 Ciba Ltd Modified Triazine Epoxy Resins.
TW201305245A (en) * 2011-07-22 2013-02-01 Elite Material Co Ltd Resin composition and substrate using the same
CN102634314A (en) * 2012-04-25 2012-08-15 嘉兴荣泰高分子新材料研究所 Heat-conducting epoxy dipped adhesive and preparation method
CN102719099A (en) * 2012-06-08 2012-10-10 金发科技股份有限公司 Thermal conductive molding compound and preparation method thereof
JP2016222865A (en) * 2015-06-03 2016-12-28 株式会社ダイセル Curable epoxy resin composition for white reflector and cured article thereof, substrate for mounting optical semiconductor element and optical semiconductor device
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* Cited by examiner, † Cited by third party
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CN113429796A (en) * 2021-07-27 2021-09-24 湖南创瑾技术研究院有限公司 Single-component high-thermal-conductivity silicone gel and preparation method thereof
CN116445115A (en) * 2023-04-20 2023-07-18 广东省固特尔新材料有限公司 Low-density high-heat-conductivity pouring sealant and processing technology thereof

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Application publication date: 20210723