CN116218037A - Epoxy plastic package material of modified silicon dioxide grafted epoxy resin and preparation method thereof - Google Patents

Epoxy plastic package material of modified silicon dioxide grafted epoxy resin and preparation method thereof Download PDF

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CN116218037A
CN116218037A CN202111470797.8A CN202111470797A CN116218037A CN 116218037 A CN116218037 A CN 116218037A CN 202111470797 A CN202111470797 A CN 202111470797A CN 116218037 A CN116218037 A CN 116218037A
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epoxy
epoxy resin
silicon dioxide
silica
modified
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Inventor
朱朋莉
艾文季
张梦迪
付可欣
刘明强
刘新
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Shenzhen Institute of Advanced Electronic Materials
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Shenzhen Institute of Advanced Technology of CAS
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Priority to PCT/CN2021/137828 priority patent/WO2023097771A1/en
Publication of CN116218037A publication Critical patent/CN116218037A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • 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
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/001—Macromolecular compounds containing organic and inorganic sequences, e.g. organic polymers grafted onto silica
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • 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
    • C09C1/28—Compounds of silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Abstract

The invention discloses an epoxy plastic packaging material of modified silicon dioxide grafted epoxy resin and a preparation method thereof, wherein the epoxy plastic packaging material comprises (A) epoxy resin; (B) a phenolic resin; (C) an inorganic filler; (D) a silane coupling agent; (E) a release agent; (F) a curing accelerator; (G) a flame retardant; (H) vapor phase silicon; (I) a colorant; wherein the inorganic filler is modified silicon dioxide or a mixture of modified silicon dioxide and unmodified silicon dioxide; the content of the inorganic filler is 60-95 wt% of the total epoxy plastic package material. The modified silicon dioxide is a prepolymer modified silicon dioxide of polyethylene glycol and diisocyanate under the action of a catalyst. According to the invention, after the silicon dioxide is modified, epoxy resin is grafted on the surface of the silicon dioxide through a flexible chain; the epoxy plastic package material obtained by the invention has the characteristics of high temperature resistance and high toughness, and can be used for packaging various electronic materials.

Description

Epoxy plastic package material of modified silicon dioxide grafted epoxy resin and preparation method thereof
Technical Field
The invention relates to an epoxy plastic packaging material of modified silicon dioxide grafted epoxy resin and a preparation method thereof, belonging to the technical field of electronic packaging materials.
Background
The epoxy plastic packaging material has high reliability, simple production process and lower production cost, and is widely applied to the fields of semiconductor devices, integrated circuits, consumer electronics and the like, and almost occupies the whole microelectronic packaging material market. The epoxy resin contains unique epoxy groups, hydroxyl groups, ether bonds and other active groups, so that the epoxy resin has a plurality of excellent performances, and can be combined with a plurality of curing agents, accelerators, modifiers and the like to obtain various epoxy resin curing systems with excellent performances and characteristics, thereby adapting to and meeting the requirements of different service performances and technological performances.
However, since cured epoxy resins have a high crosslinking density and a large internal stress, when filled in packaging materials, there are disadvantages such as brittleness, fatigue resistance, heat resistance, poor impact toughness, and the like, and thus improvement of the properties of epoxy resin materials has been attracting attention. The silicon dioxide material has excellent performances such as high heat resistance, high humidity resistance and the like due to low thermal expansion coefficient, and is widely applied to filling of filler into polymer and resin matrix to improve the performance of the resin composite material.
Aiming at the defect of insufficient toughness of the epoxy packaging material when the silicon dioxide is used as a filling material, the project prepares the high-performance epoxy resin composite packaging material by preparing the surface grafted epoxy resin, toughening and modifying the silicon dioxide material and then using the silicon dioxide material as the filling material.
Disclosure of Invention
Aiming at the technical problems, the invention provides an epoxy plastic package material of modified silicon dioxide grafted epoxy resin, which is used for improving the toughness of silicon dioxide, enabling the silicon dioxide to be used as a filler of the epoxy package material and improving the performance of a composite material of an electronic package material.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the present invention provides a method for modifying the surface of silica, comprising the steps of:
1) Preparing a modified prepolymer:
stirring polyethylene glycol and diisocyanate under the action of a catalyst to react until the isocyanate concentration in a polymerization reaction system is reduced to 40-60% of the initial concentration;
2) Surface modification:
and (2) stirring silicon dioxide and the prepolymer obtained in the step (1) in a solvent for reaction.
In a preferred embodiment, in step 1), the temperature of the stirring reaction is 15 to 55 ℃, for example 15 ℃,20 ℃, 25 ℃,30 ℃, 35 ℃,40 ℃, 45 ℃,50 ℃, 55 ℃ or any temperature therebetween;
preferably, the catalyst is selected from dibutyltin dilaurate or dibutyltin dilaurate;
preferably, the diisocyanate is selected from toluene diisocyanate or diphenylmethane diisocyanate;
preferably, the polyethylene glycol is polyethylene glycol with molecular weight of 400-800;
preferably, in step 1), the mass ratio of the diisocyanate to the polyethylene glycol is 1.5 to 2.5:1, for example 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2.0:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1 or any mass ratio therebetween;
preferably, the mass of the catalyst is 0.05 to 0.5%, such as 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% or any mass percentage therebetween, of the total mass of polyethylene glycol and diisocyanate;
preferably, step 1) is carried out under an inert gas;
in a preferred embodiment, in the step 2), the rotation speed of the stirring reaction is 1000-1500 r/min, for example, 1000r/min, 1100r/min, 1200r/min, 1300r/min, 1400r/min, 1500r/min or any rotation speed between them; the temperature of the stirring reaction is 70-90 ℃, such as 70 ℃, 75 ℃,80 ℃, 85 ℃, 90 ℃ or any temperature between the two; the stirring reaction time is 6-10 h;
preferably, in step 2), the solvent is selected from toluene or toluene cyclohexanone;
preferably, in step 2), the mass ratio of silica to prepolymer is 1:1 to 3, for example 1:1, 1:2, 1:3 or any mass ratio therebetween;
preferably, step 2) is carried out under an inert gas;
silica nanoparticles are readily water-absorbing and typically have silanol groups on their surface. In the technical scheme of the invention, the reaction of the prepolymer and the silicon dioxide is mainly that silanol groups on the surface of the silicon dioxide react with flexible chains of polyethylene glycol prepolymer with isocyanic acid groups so that the flexible chains are grafted to the surface of the silicon dioxide.
The second aspect of the present invention provides a modified silica obtained by the above method.
The third aspect of the invention provides a method for grafting modified silica to epoxy resin, comprising the steps of:
dispersing the modified silicon dioxide and the epoxy resin in a solvent, introducing dimethylamine gas, and stirring for reaction.
As a preferred embodiment, the mass ratio of the modified silica to the epoxy resin is 0.35 to 1.5:1, for example, 0.35:1, 0.40:1, 0.45:1, 0.50:1, 0.55:1, 0.65:1, 0.75:1, 0.85:1, 0.95:1, 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1 or any ratio therebetween.
Preferably, the solvent is a mixed solvent of ethylene glycol butyl ether and absolute ethyl alcohol, and the volume ratio is preferably 1.8-2.2:1;
preferably, the rotation speed of the stirring reaction is 200-400 r/min, the temperature of the stirring reaction is 50-70 ℃, and the time of the stirring reaction is 2-4 hours;
preferably, the preparation method further comprises a post-treatment operation, the post-treatment operation comprising suction filtration, washing and drying.
The fourth aspect of the invention provides an epoxy molding compound of modified silica grafted epoxy resin, which comprises the following components:
(A) An epoxy resin;
(B) A phenolic resin;
(C) An inorganic filler;
(D) A silane coupling agent;
(E) A release agent;
(F) A curing accelerator;
(G) A flame retardant;
(H) Vapor phase silicon;
(I) A colorant;
wherein the inorganic filler (C) is the modified silica or a mixture of the modified silica and unmodified silica; the method comprises the steps of carrying out a first treatment on the surface of the The content of the inorganic filler (C) is 60-95 wt% of the total epoxy plastic package material.
In the technical scheme of the invention, the average particle size of the unmodified silicon dioxide is 5-8 mu m, and the modified silicon dioxide is prepared by modifying the unmodified silicon dioxide with the average particle size of 5-8 mu m by the method.
As a preferred embodiment, the epoxy molding compound comprises the following components in percentage by weight:
the content of the epoxy resin (A) is 10-40 wt% of the total epoxy plastic package material.
The content of the phenolic resin (B) is 2-6wt% of the total epoxy plastic packaging material;
the silane coupling agent (D) is 0.05-5 wt% of inorganic filler (C);
the release agent (E) accounts for 0.005-2 wt% of the total epoxy plastic packaging material, and is preferably 0.1-2.5 wt%;
the curing accelerator (F) is 0.005-2 wt% of the total epoxy plastic packaging material, and preferably 0.01-0.5 wt%;
the flame retardant (G) is 0.2-0.5 wt% of the whole epoxy plastic packaging material;
the weight of the gas phase silicon (H) is 0.2 to 0.5 percent of the total epoxy plastic package material;
the colorant (I) is 0.05 to 0.3 weight percent of the total epoxy molding compound;
preferably, when the inorganic filler is a mixture of the modified silica and the unmodified silica, the mass ratio of the modified silica to the unmodified silica is 0.15-20:1.
In certain specific embodiments, the mass ratio of the modified silica to the unmodified silica is 0.15:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, or any mass ratio therebetween.
In some specific examples, the epoxy resin as the component (a) is a commonly used encapsulating epoxy resin, and is not particularly limited. Examples thereof include (1) glycidyl ether type epoxy resins such as diglycidyl ethers of bisphenol A, bisphenol F, bisphenol S, cresols, xylenols, resorcinol, catechol, alkyl-substituted or unsubstituted diphenols, and the like; (2) Aldehyde-containing compounds such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde and salicylaldehyde are subjected to self-condensation or co-condensation under an acidic catalyst to obtain phenolic epoxy resin; (3) Glycidyl ester type epoxy resins obtained by reacting a sulfur atom-containing epoxy resin, hydroquinone type epoxy resin, a polybasic acid such as phthalic acid or dimer acid with epichlorohydrin; (4) Glycidylamine type epoxy resin obtained by reacting polyamine such as diaminodiphenylmethane and isocyanic acid with epichlorohydrin; (5) Epoxide of dicyclopentadiene and phenol and/or naphthol co-condensation resin; (6) naphthalene ring-containing epoxy resin; (7) An epoxide of an aralkyl type phenol resin such as a phenol aralkyl resin or a naphthol aralkyl resin; (8) trimethylolpropane type epoxy resin; (9) And an alicyclic epoxy resin, which may be used alone or in combination of 2 or more.
Since the raw materials are easily available and at low cost, bisphenol a type epoxy resins are preferably used, and epoxy resins having the general formula (1) are more preferable.
Figure BDA0003392030380000051
In the formula (I), n is the polymerization degree and is an integer of 0 to 3;
in the general formula (I), the hydrogen atom on C1 to C6 may be substituted with a substituent, which may be a substituted or unsubstituted monovalent hydrocarbon group, which may be saturated or unsaturated; the substituted or unsubstituted monovalent hydrocarbon group may be linear, branched or cyclic, but is particularly preferably methyl or ethyl.
In the present invention, the phenolic resin (B) is used as the curing agent for the epoxy resin (a), and represents monomers, oligomers and polymers having two or more phenolic hydroxyl groups. Examples thereof include novel phenol type phenolic resins represented by the formula (II), cresol novolak type epoxy resins, aralkylphenol resins, triphenolmethane type phenolic resins represented by the formula (III), naphthol novolak resins, aralkylphenol resins and biphenyl novolak resins. The phenolic resins mentioned above may be used alone or in any combination.
In order to protect the semiconductor chip from moisture, it is preferable to use a low hygroscopic phenol resin such as a novel phenol type phenol resin having the formula (II) and a trisphenol methane type phenol resin having the formula (III).
Figure BDA0003392030380000061
In a preferred embodiment, the ratio of the equivalent weights of the epoxy resin (a) and the phenolic resin (B), that is, the ratio of the number of epoxy groups in the epoxy resin to the number of hydroxyl groups in the phenolic resin, is not particularly limited, and is preferably set in the range of 0.5 to 2, more preferably in the range of 0.6 to 1.3, in order to improve the conversion of the reactants and control the reaction rate. In order to obtain an encapsulating epoxy resin molding compound excellent in moldability and reflow resistance, the molding compound is more preferably set in the range of 0.8 to 1.0.
In certain embodiments, (D) the silane coupling agent has a structure represented by the following general formula (IV),
Figure BDA0003392030380000062
in the formula (II), m is an integer of 1 to 3, n is an integer of 0 to 3, R 1 Selected from the group consisting of
Figure BDA0003392030380000063
Either one of the above-mentioned materials,
wherein, (X) j Any one selected from hydrogen atoms and alkyl groups having 1 to 6 carbon atoms; r is R 2 、R 3 Each independently selected from methyl or ethyl, and at R 2 OR 3 In the case where a plurality of the above-mentioned materials are present, they may be the same or different from each other;
preferably, R 1 Is that
Figure BDA0003392030380000071
The silane coupling agent is mixed into the epoxy molding compound, so that the cohesiveness of the inorganic filler and the resin can be improved, and the bulk performance of the filler can be better exerted. Specific examples thereof include gamma-anilinopropyl trimethoxysilane, gamma-anilinopropyl triethoxysilane, gamma-anilinopropyl methyl dimethoxysilane, gamma-anilinopropyl methyl diethoxysilane, gamma-anilinopropyl ethyl diethoxysilane, and gamma-anilinopropyl ethyl dimethoxysilane.
More preferably, the component (D) silane coupling agent is gamma-anilinopropyl trimethoxysilane.
In certain specific embodiments, the (E) mold release agent is selected from at least one of (alpha) a linear saturated carboxylic acid having a number average molecular weight of 550 to 800, and (beta) an oxidized polyethylene wax.
Specifically, the structure of the linear saturated carboxylic acid with the number average molecular weight of 550-800 is shown as a general formula (V):
Figure BDA0003392030380000072
where n is 32 to 52, but in practice the appropriate number of repetitions n is chosen such that the number average molecular weight reaches 550 to 800. Preferably, the linear saturated carboxylic acid has a number average molecular weight of 600 to 800.
In the technical scheme of the invention, from the viewpoint of the hardenability of the epoxy molding compound, a curing accelerator is further added. The curing accelerator (F) accounts for 0.005 to 2 weight percent of the total epoxy molding compound, and if the dosage of the curing accelerator is less than 0.005 weight percent, the hardening property tends to be poor in a short time; if the curing rate is higher than 2%, the curing rate becomes too high, and it becomes difficult to obtain a molded article having a good shape. In some specific examples, the (F) curing accelerator is a substance generally used in encapsulating epoxy resin molding compounds, and there are no particular restrictions thereon, and (1) a cyclic amidine compound: 1, 8-diaza-bicyclo [5.4.0] undecene-7, 1, 5-diaza-bicyclo [4.3.0] nonene, 5, 6-dibutylamino-1, 8-diaza-bicyclo [5.4.0] undecene-7, and the like; (2) quinone compounds: quinone compounds such as maleic anhydride, 1, 4-benzoquinone, 2, 5-benzoquinone, 2, 3-dimethylbenzoquinone, 2, 6-dimethylbenzoquinone, 2, 3-dimethoxy-5-methyl-1, and the like are added to the cyclic amidine compound; (3) Imidazolines such as 2-methylimidazoline, 2-phenylimidazoline and 2-phenyl-4-methylimidazoline, and derivatives thereof; (4) an organophosphine: tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4-methylphenyl) phosphine, diphenylphosphine, phenylphosphine, etc.; (5) A compound having an intramolecular polarity, which is obtained by adding a pi-bond compound such as maleic anhydride, the quinone compound, phenylazomethane, or phenol resin to the organic phosphine compound.
In the embodiment of the present invention, the flame retardant (G) is not particularly limited as long as it is an ester formed from a compound of phosphoric acid and an alcohol or a compound of phosphoric acid and phenol. Examples thereof include trimethyl phosphate, triethyl phosphate, triphenyl phosphate, dihydroxytolyl phosphate, and xylyl phosphate. Among them, from the viewpoint of hydrolysis resistance, an aromatic condensed phosphoric ester having a structure represented by the general formula (VI) is preferably used.
Figure BDA0003392030380000081
In a preferred embodiment, the amount of the flame retardant (G) to be added is preferably 0.2% to 0.5% based on the total mixed components excluding the filler. If the amount is less than 0.2%, the problem of wire sweep, molding cavities, and the like tends to occur. If it exceeds 3%, moldability and moisture resistance are lowered.
In the technical scheme of the invention, the (H) gas phase silicon is gas phase silicon dioxide commonly used in epoxy plastic packaging materials for packaging, and is not particularly limited. Preferably, the fumed silica has an average particle diameter in the range of 5 to 40nm and a specific surface area of 360.+ -.30 m 2 The larger specific surface area and particle size of the silicon dioxide can reduce the toughness of the epoxy molding compound.
The fifth aspect of the present invention provides a method for preparing the epoxy molding compound, comprising the following steps:
(1) Dispersing the surface-modified silicon dioxide and epoxy resin in a solvent, introducing dimethylamine gas, and stirring for reaction;
(2) And (3) mixing the mixed system obtained in the step (1) with other components in proportion, and extruding and mixing to obtain the epoxy molding compound.
In a preferred embodiment, in the step (1), the mass ratio of the modified silicon dioxide to the epoxy resin is 0.35-1.5:1;
preferably, in the step (1), the solvent is a mixed solvent of ethylene glycol butyl ether and absolute ethyl alcohol, and the volume ratio is preferably 1.8-2.2:1;
preferably, in the step (1), the rotation speed of the stirring reaction is 200-400 r/min, the temperature of the stirring reaction is 50-70 ℃, and the time of the stirring reaction is 2-4 hours;
preferably, step (1) further comprises a post-treatment operation, said post-treatment comprising suction filtration, washing and drying.
In a preferred embodiment, the temperature of the extrusion kneading in the step (2) is 80 to 120 ℃.
In the technical scheme of the invention, the flexible chain-extended urea is generated by reacting on the surface of silicon dioxide, and the active end group of the flexible chain-extended urea participates in an epoxy resin network, so that the bonding performance of the interface between particles and a resin matrix is improved. At the same time, the flexible part of the particle surface can improve the plastic deformation capability of the matrix around the particles, and the local plastic deformation is more easy to occur. The fracture toughness value of the epoxy plastic packaging material can be effectively increased, the epoxy resin matrix is toughened, and the mechanical property of the epoxy resin composite material is obviously improved. After the modified silica is mixed with the epoxy resin, the modifier is incorporated into the crosslinked network of the epoxy resin through the reactive end groups of the modified silica, and the flexible chains grafted on the surface of the modified silica filler are capped through dimethylamine, so that the epoxy resin is grafted on the surface of the silica.
The beneficial effects of this application are: compared with the method without adding modified silica filler, the method has the advantages that the modified silica powder with the surface grafted with the epoxy resin is used as the filler, and under the condition that the performance of other parameters is basically unchanged, the fracture toughness value of the plastic package material is increased while high filling is completed, and the toughness of the plastic package material is improved.
Detailed Description
In order that the above-recited objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The invention may be embodied in many other forms other than as described herein and similar modifications may be made by those skilled in the art without departing from the spirit of the invention. Therefore, the invention is not limited by the specific implementations disclosed below.
The epoxy resins used in the following examples and comparative examples are listed below:
bisphenol A type epoxy resin represented by the formula (VII) (epoxy equivalent: 192, melting point: 105 ℃ C., available from Japanese chemical Co., ltd., trade name: RE 410).
Figure BDA0003392030380000101
The phenolic resins used in the following examples and comparative examples are listed below:
phenolic resin 1: new phenolic resins of formula (VIII) (hydroxyl equivalent: 203, softening point: 110 ℃ C. Available from Kelong chemical Co., ltd., brand KPH-F3065)
Figure BDA0003392030380000102
Phenolic resin 2: the triphenolmethane-type phenol resin represented by formula (IX) (hydroxyl equivalent: 110, softening point: 97 ℃, available from Ming He Chemie Co., ltd., trade name: MEH-7500).
Figure BDA0003392030380000103
Unmodified silica used in the following examples and comparative examples: silica powder having an average particle diameter of 5 to 8 mu m.
The silane coupling agents used in the following examples and comparative examples are listed below: gamma-anilinopropyl trimethoxysilane.
The release agents used in the following examples and comparative examples are listed below: CH (CH) 3 -(CH 2 ) n COOH (n=24 average), unicid700 (number average molecular weight: 789) manufactured by beck oil company.
The curing accelerators used in the following examples and comparative examples were: triphenylphosphine.
The flame retardants used in the following examples and comparative examples are: trimethyl phosphate.
The vapor phase silicon used in the following examples and comparative examples was: silica having an average particle diameter of 15nm and a specific surface area of 360m 2 /g。
The colorants used in the following examples and comparative examples were: black organic dye.
Preparation example of modified silica graft epoxy resin:
1.2, 4-Toluene Diisocyanate (TDI) was added to the reaction apparatus and nitrogen was purged for 15 minutes. Polyethylene glycol having a molecular weight of 600 was slowly added at a dropping rate of 0.5 mL/min. After the completion of the dropwise addition, the mixture was heated to 60℃at a heating rate of 5℃per minute at a rotational speed of 1200r/m, and then heated continuously for 4 hours. Dibutyl tin dilaurate was added as a reaction catalyst. Carrying out titration detection on the heated sample to detect the isocyanate content in a reaction system; when the isocyanate concentration was reduced to half of the starting concentration, the heating was stopped.
2. The vacuum dried unmodified silica was dispersed in anhydrous toluene and sonicated for 0.5 hours. Dissolving the toluene diisocyanate and polyethylene glycol prepolymer in anhydrous toluene, uniformly stirring, and mixing with the ultrasonic-treated silicon dioxide. Under the protection of nitrogen, the reaction is mechanically stirred for 8 hours at the temperature of 80 ℃ and the rotating speed of 1200 r/min. Repeatedly washing with anhydrous toluene to remove unreacted polyethylene glycol prepolymer, and vacuum drying the obtained product at 60 ℃ for 12 hours to obtain modified silicon dioxide powder.
3. 10mL of ethylene glycol butyl ether and 5mL of absolute ethanol were mixed, and the modified silica powder was dissolved in epoxy resin and heated to 60 ℃. Dimethylamine gas was introduced under a mechanical stirring condition of 300r/min, and the reaction was carried out for 3 hours. After the reaction is finished, the mixture is filtered, washed and dried in vacuum for 12 hours at the temperature of 60 ℃, and the product is white or light yellow powder, so that the modified silica grafted by the epoxy resin is obtained.
Wherein, in examples 1-9, the mass of diisocyanate, polyethylene glycol, dibutyltin dilaurate in step 1, the amount of unmodified silica used in step 2 and the amount of epoxy resin in step 3 are shown in Table 1.
TABLE 1
Figure BDA0003392030380000111
Figure BDA0003392030380000121
In the step 1, the determination mode of the isocyanate concentration is as follows: about 1g of the sample was weighed, placed in a 100mL Erlenmeyer flask, and 10mL of dioxane was added. After dissolution, the solution is accurately transferred into 10mL of 0.5mol/L dioxane solution of n-butylamine by a pipette, and 3 to 5 drops of methyl red solution are dripped after the solution is placed for 15 minutes. Titration was performed with 0.1mol/L hydrochloric acid standard solution, and the solution was subjected to blank titration from Huang Biangong at the end point.
The calculation formula of the isocyanate concentration is shown as a formula (VIII):
Figure BDA0003392030380000122
in formula (VIII): c is the percentage of isocyanate in the sample;
v is the volume (mL) of hydrochloric acid standard solution consumed in the sample titration;
V 0 is the volume of hydrochloric acid standard solution (mL) consumed in blank titration;
m is the concentration (mol/L) of the hydrochloric acid standard solution;
w is the weight (g) of the sample.
The resulting modified silica surface grafted with epoxy resin was used in the following examples:
example 1
94.44g of modified silica grafted with epoxy resin (38.6 g of epoxy resin and 19.3g of silica), 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed at an extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy plastic package is obtained.
Example 2
89.44g of modified silica grafted with epoxy resin, wherein 35.6g of epoxy resin, 17.8g of silica, 5g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition of extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy molding compound is obtained.
Example 3
84.44g of modified silica grafted with epoxy resin, wherein 32.6g of epoxy resin, 16.3g of silica, 10g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition that the extrusion temperature is 100 ℃, cooled and finely crushed, and finally the epoxy plastic package is obtained.
Example 4
74.44g of modified silica grafted with epoxy resin, 29.6g of epoxy resin, 14.8g of silica, 20g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition that the extrusion temperature is 100 ℃, cooled and finely crushed, and finally the epoxy plastic package is obtained.
Example 5
64.44g of modified silica grafted with epoxy resin, wherein 26.6g of epoxy resin, 13.3g of silica, 30g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition that the extrusion temperature is 100 ℃, cooled and finely crushed, and finally the epoxy plastic package is obtained.
Example 6
54.44g of modified silica grafted with epoxy resin, 23.6g of epoxy resin, 11.8g of silica, 40g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition that the extrusion temperature is 100 ℃, cooled and finely crushed, and finally the epoxy plastic package is obtained.
Example 7
44.44g of modified silica grafted with epoxy resin, wherein 20.6g of epoxy resin, 10.3g of silica, 50g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition of extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy molding compound is obtained.
Example 8
34.44g of modified silica grafted with epoxy resin, 17.6g of epoxy resin, 8.8g of silica, 60g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition of extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy molding compound is obtained.
Example 9
24.44g of modified silica grafted with epoxy resin, wherein 14.6g of epoxy resin, 7.3g of silica, 80g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition of extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy molding compound is obtained.
Comparative example 1
94.44g of unmodified silica, 2.78g of phenolic resin 1,1.19g of phenolic resin 2,0.28g of curing accelerator, 0.41g of flame retardant, 0.15g of silane coupling agent, 0.25g of release agent, 0.3g of gas-phase silicon and 0.2g of colorant are mixed, kneaded and mixed under the condition of extrusion temperature of 100 ℃, cooled and finely crushed, and finally the epoxy molding compound is obtained.
The content of each component of the above examples, i.e., the performance test, is shown in tables 2-1 and 2-2:
TABLE 2-1
Figure BDA0003392030380000141
Figure BDA0003392030380000151
TABLE 2-2
Figure BDA0003392030380000152
/>
Figure BDA0003392030380000161
As can be seen from tables 2-1 and 2-2, the epoxy molding compound with the modified silica added in examples 1-9 has better adhesion to the resin, less brittle fracture, increased fracture toughness value and increased toughness while maintaining other parameters substantially unchanged, as compared with comparative example 1 without the modified silica added.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent modifications made by the teachings of the present invention, or direct or indirect application in other related arts, are included in the scope of the present invention.

Claims (10)

1. A method for modifying the surface of silica, comprising the steps of:
1) Preparing a modified prepolymer:
stirring polyethylene glycol and diisocyanate under the action of a catalyst to react until the isocyanate concentration in a polymerization reaction system is reduced to 40-60% of the initial concentration;
2) Surface modification:
and (2) stirring silicon dioxide and the prepolymer obtained in the step (1) in a solvent for reaction.
2. The method for surface modification of silica according to claim 1, wherein in step 1), the temperature of the stirring reaction is 15 to 55 ℃;
preferably, the catalyst is selected from dibutyltin dilaurate or dibutyltin dilaurate;
preferably, the diisocyanate is selected from toluene diisocyanate or diphenylmethane diisocyanate;
preferably, the polyethylene glycol is polyethylene glycol with molecular weight of 400-800;
preferably, in the step 1), the mass ratio of the diisocyanate to the polyethylene glycol is 1.5-2.5:1;
preferably, the mass of the catalyst is 0.05-0.5% of the total mass of the polyethylene glycol and the diisocyanate;
preferably, step 1) is carried out under an inert gas.
3. The method for modifying the surface of silica according to claim 1, wherein in the step 2), the rotation speed of the stirring reaction is 1000 to 1500r/min; the temperature of the stirring reaction is 70-90 ℃, and the time of the stirring reaction is 6-10 hours;
preferably, the solvent is selected from any one of toluene and toluene cyclohexanone;
preferably, the mass ratio of the silicon dioxide to the prepolymer is 1:1-3;
preferably, step 2) is carried out under an inert gas.
4. A modified silica obtainable by the process according to any one of claims 1 to 3.
5. The method for grafting the modified silicon dioxide on the epoxy resin is characterized by comprising the following steps:
the modified silica according to claim 4 and an epoxy resin are dispersed in a solvent, and dimethylamine gas is introduced and stirred for reaction.
6. The method of claim 5, wherein the mass ratio of the modified silica to the epoxy resin is 0.35-1.5:1;
preferably, the solvent is a mixed solvent of ethylene glycol butyl ether and absolute ethyl alcohol, and the volume ratio is preferably 1.8-2.2:1;
preferably, the rotation speed of the stirring reaction is 200-400 r/min, the temperature of the stirring reaction is 50-70 ℃, and the time of the stirring reaction is 2-4 hours;
preferably, the preparation method further comprises a post-treatment operation, the post-treatment operation comprising suction filtration, washing and drying.
7. The modified silicon dioxide branch-connected epoxy resin epoxy plastic packaging material is characterized by comprising the following components in percentage by weight:
(A) An epoxy resin;
(B) A phenolic resin;
(C) An inorganic filler;
(D) A silane coupling agent;
(E) A release agent;
(F) A curing accelerator;
(G) A flame retardant;
(H) Vapor phase silicon;
(I) A colorant;
wherein the (C) inorganic filler is the modified silica of claim 4 or a mixture of the modified silica and unmodified silica of claim 4; the content of the inorganic filler (C) is 60-95 wt% of the total epoxy plastic package material.
8. The epoxy molding compound according to claim 7, wherein the epoxy molding compound comprises the following components:
the content of the epoxy resin (A) is 10-40 wt% of the total epoxy plastic packaging material;
the content of the phenolic resin (B) is 2-6wt% of the total epoxy plastic packaging material;
the silane coupling agent (D) is 0.05-5 wt% of inorganic filler (C);
the release agent (E) accounts for 0.005-2 wt% of the total epoxy plastic packaging material, and is preferably 0.1-2.5 wt%;
the curing accelerator (F) is 0.005-2 wt% of the total epoxy plastic packaging material, and preferably 0.01-0.5 wt%;
the flame retardant (G) is 0.2-0.5 wt% of the whole epoxy plastic packaging material;
the weight of the gas-phase silicon (H) is 0.2-0.5% of the total epoxy plastic package material;
the colorant (I) is 0.05 to 0.3 weight percent of the total epoxy molding compound;
preferably, when the inorganic filler is a mixture of the modified silica and the unmodified silica according to claim 4, the mass ratio of the modified silica to the unmodified silica is 0.15 to 20:1.
9. The method for preparing the epoxy molding compound according to any one of claims 6 to 7, which is characterized by comprising the following steps:
(1) Dispersing the modified silicon dioxide and epoxy resin in a solvent, introducing dimethylamine gas, and stirring for reaction;
(2) And (3) mixing the mixed system obtained in the step (1) with other components in proportion, and extruding and mixing to obtain the epoxy molding compound.
10. The method according to claim 9, wherein in the step (1), the mass ratio of the modified silica to the epoxy resin is 0.35 to 1.5:1;
preferably, in the step (1), the solvent is a mixed solvent of ethylene glycol butyl ether and absolute ethyl alcohol, and the volume ratio is preferably 1.8-2.2:1;
preferably, in the step (1), the rotation speed of the stirring reaction is 200-400 r/min, the temperature of the stirring reaction is 50-70 ℃, and the time of the stirring reaction is 2-4 hours;
preferably, step (1) further comprises a post-treatment operation comprising suction filtration, washing and drying;
preferably, the temperature of the extrusion kneading in step (2) is 80 to 120 ℃.
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