CN112480477B - Surface modification method of spherical alumina for high-strength epoxy molding compound - Google Patents
Surface modification method of spherical alumina for high-strength epoxy molding compound Download PDFInfo
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The invention discloses a surface modification method of spherical alumina for a high-strength epoxy molding compound. The method comprises the steps of firstly carrying out hydroxylation treatment on spherical alumina, then carrying out surface treatment on the hydroxylated alumina by using a silane coupling agent, and finally carrying out heat treatment on the surface-modified alumina at the temperature of 250-300 ℃ to obtain the spherical alumina for the epoxy molding compound. The spherical alumina prepared by the invention has excellent compatibility with epoxy resin, and simultaneously has higher Shore hardness, bending strength and good moisture resistance.
Description
Technical Field
The invention belongs to the technical field of preparation of heat-conducting fillers, and relates to a surface modification method of spherical alumina for a high-strength epoxy molding compound.
Background
With the further penetration of 5G, electronic products such as smart phones, tablet computers, wearable devices and the like tend to be more miniaturized, high-frequency, high-speed and highly integrated, and higher requirements are put forward on the performance of epoxy molding compounds. The filler in the epoxy molding compound has a great influence on the performance of the epoxy molding compound. The current requirements for fillers mainly include: 1) the insulativity is good, the reliability is high; 2) low thermal expansion coefficient and high thermal conductivity; 3) good moisture resistance and difficult microcracking.
Conventionally used insulating and heat conducting fillers include alumina, aluminum nitride, boron nitride, and the like. Because aluminum nitride and boron nitride are expensive and boron nitride is low in filling amount, aluminum nitride is easy to deliquesce, and the application of the aluminum nitride and the boron nitride is limited. The alumina has high cost performance and is the insulation heat-conducting filler with the largest use amount at present.
When alumina is used as a filler and is filled into the epoxy resin component containing the phosphorus-containing curing accelerator, the phosphorus-containing curing agent is inactivated, so that the micro-crack phenomenon of the finished epoxy film plastic packaging material is caused, and the Shore hardness and the bending strength of the product are reduced.
Chinese patent application CN106660817A discloses a spherical alumina powder and a resin composition using the same, which is modified by a dry modification method using a ball mill or a mixer and a wet modification method using organic solvent mixing, and the methods improve the thermal conductivity, fluidity and wettability of the filler, but still have the problems of inhibiting the curing action of a phosphorus-containing curing accelerator, deactivating the phosphorus-containing curing agent, and having poor moisture resistance. And the method has longer production flow and production period, higher production cost and is not suitable for batch production.
Disclosure of Invention
The invention aims to provide a surface modification method of spherical alumina for a high-strength epoxy molding compound, which is easy for batch production and can slow down the deactivation of a phosphorus-containing curing accelerator.
The technical scheme for realizing the purpose of the invention is as follows:
the surface modification method of spherical alumina for the high-strength epoxy molding compound comprises the following specific steps:
step (1), hydroxylation of alumina: adding a mixed solution of hydrogen peroxide and water in a mass ratio of 1:1 into spherical alumina, stirring at 60-90 ℃ until the mixture is fully modified, performing suction filtration, crushing and drying to obtain hydroxylated spherical alumina;
step (2), surface modification: adding silane coupling agent solution with boiling point more than 300 ℃ into hydroxylated spherical alumina to modify the surface of alumina powder;
and (3) heat treatment: and carrying out heat treatment on the surface-modified alumina at the temperature of 250-300 ℃ to obtain the spherical alumina for the high-strength epoxy molding compound.
In a specific embodiment of the present invention, in the step (1), the spherical alumina has a particle size of 9 to 11 μm.
In a specific embodiment of the present invention, in the step (1), the mass of the mixed solution of hydrogen peroxide and water is 20% of the mass of the spherical alumina.
Preferably, in the step (1), the stirring time is 2 to 8 hours.
In a specific embodiment of the present invention, in step (2), the silane coupling agent solution is added to the hydroxylated spherical alumina in the form of a spray.
In a specific embodiment of the present invention, in the step (2), the silane coupling agent solution is composed of a silane coupling agent, acetic acid, water and isopropyl alcohol in a mass ratio of 7:0.1:14: 7.
Preferably, in step (2), the surface modification temperature is 110. + -. 10 ℃.
Preferably, in the step (2), the silane coupling agent with the boiling point of more than 300 ℃ is selected from one or more of N-phenyl-3-aminopropyltrimethoxysilane (KBM573), Y-glycidoxypropyltriethoxysilane (A1871), methacrylamide silane (A178) and 3-glycidoxypropyltrimethoxysilane (KBE-403).
Preferably, in the step (2), the amount of the silane coupling agent added is 0.01 to 10%, more preferably 0.02 to 2% by mass of the alumina.
Preferably, in step (3), the heat treatment time is 4 to 12 hours, more preferably 4 to 6 hours.
Compared with the prior art, the invention has the following advantages:
(1) the hydroxyl content of the surface of the alumina is increased by hydroxylating the alumina, and meanwhile, the dispersibility of the alumina in the epoxy resin is improved by surface modification, so that the compatibility of the alumina and the epoxy resin is improved;
(2) the heat treatment method is adopted to slow down the inactivation of the phosphorus-containing curing accelerator, control the heat treatment temperature and keep the surface modification effect of the aluminum oxide;
(3) the epoxy molding compound prepared from the alumina modified by the method has the advantages of good product molding, high Shore hardness, large bending strength and good moisture resistance.
Detailed Description
The present invention will be described in more detail with reference to specific examples.
In the following examples and comparative examples, spherical alumina having a particle size of 9 to 11 μm was used, and spherical alumina having a particle size of 9 to 11 μm was prepared by mixing spherical alumina having a particle size of 2 μm, spherical alumina having a particle size of 7 μm, and spherical alumina having a particle size of 20 μm in a ratio of 1:3: 6.
Example 1
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirrer, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 60 ℃, and carrying out suction filtration, crushing and drying to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of hydroxylated alumina was charged into a powder surface modifier, and a mixture of KBM5737g, 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol was added by spraying and mixed in a heat flow field at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was charged into a muffle furnace and heat-treated at 300 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
Example 2
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 60 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(1) Surface modification: 1kg of the hydroxylated alumina of the step (2) was put into a stirred tank, and a mixture of A18717g, 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol was added by spraying and mixed at 110 ℃ for 1 hour.
(1) And (3) heat treatment: 1kg of surface-modified alumina was put into a muffle furnace and heat-treated in a heat flow field at 300 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
Example 3
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 80 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of hydroxylated alumina in the step (2) is put into a stirring kettle, and a mixed solution of diamino A1787 g, 0.1g of acetic acid, 14g of pure water and 7g of isopropanol is added in a spraying manner and mixed for 1 hour at 110 ℃.
(3) And (3) heat treatment: 1kg of surface-modified alumina was put into a muffle furnace and heat-treated in a heat flow field at 300 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
Example 4
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 80 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of the hydroxylated alumina of the step (2) was put into a stirred tank, and a mixture of 7g of 3-glycidoxypropyltrimethoxysilane (KBE-403), 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol was sprayed and mixed at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was put into a muffle furnace and heat-treated in a heat flow field at 300 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
Example 5
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 80 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of the hydroxylated alumina of the step (2) was put into a stirred tank, and a mixture of KBM5737g, 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol was added by spraying and mixed at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was put into a muffle furnace and heat-treated in a heat flow field at 250 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
This example is substantially the same as example 1 except that the heat treatment temperature in step (3) is different, and the heat treatment temperature of this comparative example is 250 ℃.
Comparative example 1
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 60 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of hydroxylated alumina was put into a stirred tank and mixed with a mixture of KBM5737g, 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was put in a muffle furnace and heat-treated in a heat flow field at 200 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
This comparative example is substantially the same as example 1 except that the heat treatment temperature in step (3) is different, and the heat treatment temperature of this comparative example is 200 ℃.
Comparative example 2
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 60 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of the hydroxylated alumina of the step (2) was put into a stirred tank and mixed with a mixture of KBM5737g, 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was charged into a muffle furnace and heat-treated at 400 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
This comparative example is substantially the same as example 1 except that the heat treatment temperature in step (3) is different, and the heat treatment temperature of this comparative example is 400 ℃.
Comparative example 3
(1) Spherical alumina hydroxylation: putting 1kg of spherical alumina with the particle size of 9-11 mu m into a stirring kettle, adding a mixed solution of 100g of hydrogen peroxide and 100g of pure water, stirring for 4 hours at the temperature of 60 ℃, filtering, drying and crushing to obtain 1kg of hydroxylated alumina.
(2) Surface modification: 1kg of the hydroxylated alumina of the step (2) was put into a stirred tank, and a mixture of 7g of vinyltrimethoxysilane (A171) (boiling point < 300 ℃ C.), 0.1g of acetic acid, 14g of pure water and 7g of isopropyl alcohol was mixed at 110 ℃ for 1 hour.
(3) And (3) heat treatment: 1kg of surface-modified alumina was charged into a muffle furnace and heat-treated at 300 ℃ for 6 hours to obtain 1kg of surface-heat-treated alumina.
This comparative example is essentially the same as example 1 except that in step (2) the coupling agent is of a different type, vinyl trimethoxysilane (A171) having a boiling point < 300 ℃.
The results of performing a viscosity test using examples 1, 2, 3, 4, 5, 1, 2, and 3 at 60 ℃ in a heat flow field, selecting 96 parts of a filler and 64 parts of an epoxy resin to prepare a resin mixture, stirring the mixture in a stirrer for 0.5 hour, evacuating the mixture for 1 hour, and measuring the viscosity using a Boehler rotary viscometer:
TABLE 1 viscosity of modified alumina and epoxy resin compounded mixtures of examples and comparative examples
From table 1, the viscosity of the heat treated example is reduced significantly compared to the untreated spherical alumina, while the viscosity of the samples of comparative example 1 (lower than the heat treatment temperature of the example) and comparative example 2 (higher than the heat treatment temperature of the example) is reduced slowly, which indicates that the heat treatment temperature between 250 ℃ and 300 ℃ increases the powder flowability, while exceeding the temperature range decreases the powder flowability. From the fact that the boiling point of the coupling agent used in comparative example 3 was lower than 300 ℃, the viscosity of the modified sample was close to that of the untreated spherical alumina sample, indicating that the kind of the coupling agent has a large influence on the powder flowability.
The above examples and comparative examples were used to test hardness, and an epoxy resin composition was prepared by mixing 6 parts of an epoxy resin, 5 parts of a phenol resin, 88 parts of modified alumina, 0.3 part of carbon black, 0.5 part of a coupling agent, 0.1 part of a curing agent (manufactured by EDL-CR320 Guangdong Zhihui Kaishi), 0.2 part of a phenyl phosphate as a curing agent accelerator, 1.2 parts of sulfamic acid as a release agent, and 0.3 part of antimony trioxide as an additive into a roll kneader. The resulting mixture was molded in a mold, and the hardness of the composition was measured by a Vickers hardness tester. The results are shown in Table 2.
TABLE 2 Shore hardness of modified epoxy resin compositions of examples and comparative examples
As can be seen from table 2, the shore hardness of the heat treated examples is greatly improved compared to that of the untreated spherical alumina, and the shore hardness of example 4 is preferably improved by 73.6%. The Shore hardness of the samples of comparative example 1 (lower than the heat treatment temperature of the example) and comparative example 2 (higher than the heat treatment temperature of the example) are lower than those of examples 1-5, which shows that setting the heat treatment temperature at 250 ℃ and 300 ℃ increases the Shore hardness of the EMC product, the obtained alumina has good application performance, and the heat treatment temperature exceeding the range reduces the hardness of the EMC product. The lower Shore hardness of the comparative example 3 (coupling agent boiling point < 300 ℃) sample indicates that the type of coupling agent also affects the Shore hardness of the EMC article.
The untreated spherical alumina and the treated spherical alumina of the above examples and comparative examples were applied to the formulation of an EMC product, the filling rate of the spherical alumina was 90%, and the obtained flexural strength and flexural modulus were as shown in table 3.
TABLE 3 flexural Strength of modified products of examples and comparative examples
As can be seen from Table 3, the flexural strength of examples 1-5 was improved by 32.5%, 33.5%, 44.3%, 44.8%, 32.5%, and 5% relative to untreated spherical alumina. While the bending strength of comparative examples 1-3 was improved by only 20.7%, 20.2%, 16.3% relative to untreated spherical alumina. The heat treatment temperature can affect the bending strength of the applied product, and the bending strength of the product with the heat treatment temperature of 250-300 ℃ is greatly improved.
The addition of the spherical alumina can greatly increase the bending strength of the composite material, when the composite material is acted by external force, the external force can be effectively transmitted to the reinforcement body from the matrix through the hydrogen bond of the coating structure, and because the silane coupling agent has extremely outstanding mechanical property and can fully absorb energy, the composite material can better resist external stress, simultaneously, under the action of stress, a large number of microcracks and cavities are generated around the material, partial impact energy is consumed, stress concentration is effectively prevented, the three-dimensional tension for limiting the plastic deformation of the matrix is also relaxed due to the existence of the cavities, the stress field around the reinforcement body is not simply superposed but has strong interaction, and the whole matrix is subjected to plastic deformation. Particularly, when the temperature is proper, a plurality of new cross-linking points are formed at the interface of the reinforcing body and the matrix, the process from silver veins to cracks to fracture of the material is inhibited, and the bending strength and the bending modulus of the material are increased. In conclusion, the bending strength and the Shore hardness of the product can be remarkably enhanced by controlling the type of the coupling agent, adopting the coupling agent with the boiling point of more than 300 ℃ and regulating the heat treatment temperature to be 250-300 ℃.
Claims (11)
1. The surface modification method of spherical alumina for the high-strength epoxy molding compound is characterized by comprising the following specific steps of:
step (1), hydroxylation of alumina: adding a mixed solution of hydrogen peroxide and water in a mass ratio of 1:1 into spherical alumina, stirring at 60-90 ℃ until the mixture is fully modified, performing suction filtration, crushing and drying to obtain hydroxylated spherical alumina; the particle size of the spherical alumina is 9-11 mu m, and the spherical alumina is prepared by mixing spherical alumina with the particle size of 2 mu m, spherical alumina with the particle size of 7 mu m and spherical alumina with the particle size of 20 mu m according to the ratio of 1:3: 6;
step (2), surface modification: adding silane coupling agent solution with boiling point more than 300 ℃ into hydroxylated spherical alumina to modify the surface of alumina powder;
and (3) heat treatment: and carrying out heat treatment on the surface-modified alumina at the temperature of 250-300 ℃ to obtain the spherical alumina for the high-strength epoxy molding compound.
2. The surface modification method according to claim 1, wherein the surface modification temperature in the step (2) is 110 ± 10 ℃.
3. The surface modification method according to claim 1, wherein in the step (1), the mass of the mixed solution of hydrogen peroxide and water is 20% of the mass of the spherical alumina.
4. The method for modifying a surface according to claim 1, wherein the stirring time in the step (1) is 2 to 8 hours.
5. The surface modification method according to claim 1, wherein in the step (2), the silane coupling agent solution is added to the hydroxylated spherical alumina in the form of a spray.
6. The surface modification method according to claim 1, wherein in the step (2), the silane coupling agent solution is composed of a silane coupling agent, acetic acid, water and isopropyl alcohol in a mass ratio of 7:0.1:14: 7.
7. The surface modification method according to claim 1, wherein in step (2), the silane coupling agent with a boiling point of more than 300 ℃ is selected from one or more of N-phenyl-3-aminopropyltrimethoxysilane, Y-glycidoxypropyltriethoxysilane, methacrylamidosilane and 3-glycidoxypropyltrimethoxysilane.
8. The surface modification method according to claim 1, wherein in the step (2), the silane coupling agent is added in an amount of 0.01 to 10% by mass based on the mass of the alumina.
9. The surface modification method according to claim 1, wherein in the step (2), the silane coupling agent is added in an amount of 0.02 to 2% by mass based on the mass of the alumina.
10. The surface modification method according to claim 1, wherein in the step (3), the heat treatment time is 4 to 12 hours.
11. The surface modification method according to claim 1, wherein in the step (3), the heat treatment time is 4 to 6 hours.
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