CN116239865A - Polyimide-coated inorganic particle modified epoxy resin and preparation method thereof - Google Patents

Polyimide-coated inorganic particle modified epoxy resin and preparation method thereof Download PDF

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Publication number
CN116239865A
CN116239865A CN202211584976.9A CN202211584976A CN116239865A CN 116239865 A CN116239865 A CN 116239865A CN 202211584976 A CN202211584976 A CN 202211584976A CN 116239865 A CN116239865 A CN 116239865A
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epoxy resin
polyimide
coated inorganic
modified epoxy
inorganic particle
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Inventor
马彦
孟思益
刘永亮
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Aerospace Science and Industry Changsha New Materials Research Institute Co Ltd
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Aerospace Science and Industry Changsha New Materials Research Institute Co Ltd
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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
    • C08K9/10—Encapsulated ingredients
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • 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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds

Abstract

The invention relates to polyimide coated inorganic particle modified epoxy resin and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving diamine in an organic solvent, adding dianhydride for reaction, adding inorganic particles for stirring, adding a catalyst and heating to form turbid liquid; filtering, washing, drying and crushing the turbid liquid to obtain polyimide coated inorganic particles; and adding polyimide coated inorganic particles into epoxy resin, stirring at constant temperature, and then adding a curing agent to carry out curing reaction to obtain polyimide coated inorganic particle modified epoxy resin. The polyimide is amino-terminated, the amino-terminated polyimide wrapped on the surface of the inorganic particles has higher activity, the addition amount and the dispersion degree of the inorganic particles can be improved, the inorganic particles are fully and uniformly dispersed in the epoxy resin, the epoxy resin obtained after curing has higher glass transition temperature, and the heat resistance is superior to that of the modified epoxy resin prepared in the prior art.

Description

Polyimide-coated inorganic particle modified epoxy resin and preparation method thereof
Technical Field
The invention relates to the technical field of epoxy resin preparation, in particular to polyimide coated inorganic particle modified epoxy resin and a preparation method thereof.
Background
Because of the characteristics of high mechanical property, excellent adhesive property and the like, the epoxy resin is widely applied to the fields of electronics, chemical industry, aerospace and the like. However, general epoxy resins have problems of poor wet heat stability, poor high temperature resistance and the like, and are difficult to meet application requirements in high-temperature and high-humidity environments, particularly in the field of semiconductor packaging, high glass transition temperature (Tg) is required for epoxy resins, the Tg of the existing epoxy resins is usually about 120 ℃, and even if some existing technologies modify epoxy resin systems, the Tg of the existing epoxy resins is generally only about 160 ℃.
Therefore, the glass transition temperature of the epoxy resin material is still to be further raised to meet the application requirements in some high-temperature and high-humidity environments.
Disclosure of Invention
In order to make up the defects of the prior art, the invention provides polyimide-coated inorganic particle modified epoxy resin and a preparation method thereof, wherein the epoxy resin has higher glass transition temperature and can meet the application requirements in high-temperature and high-humidity environments.
In order to achieve the technical purpose, the invention adopts the following technical scheme: a preparation method of polyimide-coated inorganic particle modified epoxy resin comprises the following steps:
s1, dissolving diamine in an organic solvent, adding dianhydride for reaction, adding inorganic particles for stirring, adding a catalyst, and heating to form turbid liquid; filtering, washing, drying and crushing the turbid liquid to obtain polyimide coated inorganic particles;
s2, adding the polyimide coated inorganic particles into epoxy resin, stirring at constant temperature, and then adding a curing agent to carry out curing reaction to obtain polyimide coated inorganic particle modified epoxy resin.
Further, the diamine in the step S1 includes one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine and biphenyl diamine.
The organic solvent for dissolving diamine can be one or more of dimethylacetamide (DMAc), N-Dimethylformamide (DMF) and N-methylpyrrolidone (NMP); the mass of the organic solvent is preferably 4 to 6 times the total mass of the diamine and the dianhydride.
Further, the dianhydride in the step S1 includes one or more of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride and 4,4' -biphenyl ether dianhydride.
Preferably, the catalyst in the step S1 is triethylamine, and the mass of the catalyst is 2% -30% of the total mass of diamine and dianhydride.
Further, the inorganic particles in the step S1 include one or two of carbon black and white carbon black.
Preferably, the ratio of the total mass of diamine and dianhydride to the mass of inorganic particles in step S1 is 5: (1-3) the molar ratio of dianhydride to diamine is 1 (1.1-1.4), wherein the dianhydride needs to be added in at least three batches.
Further, the mass ratio of the polyimide coated inorganic particles to the epoxy resin in the step S2 is (1-3): 10.
Further, the curing agent in the step S2 is an amine curing agent, specifically at least one of ethylenediamine, hexamethylenediamine and m-phenylenediamine.
Further, the heating temperature in the step S1 is 130-180 ℃.
Further, the temperature of constant temperature stirring in the step S2 is 50-80 ℃ and the time is 2-5 hours.
The invention also provides polyimide coated inorganic particle modified epoxy resin, which is prepared by the preparation method of the polyimide coated inorganic particle modified epoxy resin.
Compared with the prior art, the invention has the following beneficial effects:
in the process of synthesizing polyimide, diamine is excessive, polyimide formed is amino-terminated, amino-terminated polyimide wrapped on the surfaces of inorganic particles has higher activity, the addition amount and the dispersion degree of the inorganic particles can be improved, the inorganic particles are fully and uniformly dispersed in epoxy resin, the epoxy resin obtained after curing has higher glass transition temperature, and the heat resistance is superior to that of modified epoxy resin prepared by the prior art.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
26g of 4,4 '-diaminodiphenyl ether was dissolved in 300g of DMAc at normal temperature, 34g of 4,4' -biphenyl ether dianhydride was added in three portions, 18g of carbon black was then added with stirring, 3g of triethylamine was then added, and the temperature was raised to 180℃with stirring and kept for 10 hours. Filtering, cooling to room temperature, adding 200mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 10g of polyimide-coated inorganic particles, stirring for 2 hours at the constant temperature of 70 ℃, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 2
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
26g of 4,4 '-diaminodiphenyl ether is dissolved in 290g of NMP at normal temperature, 32g of 4,4' -diphenyl ether dianhydride is added in three batches, 25.4g of white carbon black is added under stirring, 2.9g of triethylamine is added, and the temperature is raised to 150 ℃, stirred and kept for 10 hours. Filtering, cooling to room temperature, adding 200mL of acetone for washing, drying in an oven at 120 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 20g of polyimide-coated inorganic particles, stirring at a constant temperature of 65 ℃ for 3 hours, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 3
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
25g of biphenyldiamine was dissolved in 320g of DMAc at normal temperature, 28g of 3,3', 4' -biphenyltetracarboxylic dianhydride was added in three portions, followed by stirring, 28g of carbon black, 2.5g of triethylamine was added, and the temperature was raised to 130℃and kept at the same time for 10 hours. Filtering, cooling to room temperature, adding 300mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 30g of polyimide-coated inorganic particles, stirring at a constant temperature of 60 ℃ for 5 hours, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 4
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
26g of 4,4' -diaminodiphenyl ether is dissolved in 320g of DMF at normal temperature, 24g of pyromellitic dianhydride is added in three batches, 15g of white carbon black is added under stirring, 2.3g of triethylamine is added, and the temperature is raised to 130 ℃, stirred and kept for 10 hours. Filtering, cooling to room temperature, adding 300mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 15g of polyimide-coated inorganic particles, stirring at a constant temperature of 65 ℃ for 5 hours, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 5
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
27g of p-phenylenediamine was dissolved in 300g of DMAc at room temperature, 41g of pyromellitic dianhydride was added in three portions, followed by stirring, 28g of carbon black, 2.5g of triethylamine was added thereto, and the temperature was raised to 130℃and kept at the same time for 10 hours. Filtering, cooling to room temperature, adding 300mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 24g of polyimide-coated inorganic particles, stirring at a constant temperature of 70 ℃ for 4 hours, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 6
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
26g of 4,4 '-diaminodiphenyl ether was dissolved in 300g of DMAc at normal temperature, 52g of 4,4' -biphenyl ether dianhydride was added in three portions, 23.4g of carbon black was then added with stirring, 3g of triethylamine was then added, and the temperature was raised to 180℃with stirring and kept for 10 hours. Filtering, cooling to room temperature, adding 200mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 30g of polyimide-coated inorganic particles, stirring for 2 hours at the constant temperature of 70 ℃, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Example 7
The preparation method of the polyimide coated inorganic particle modified epoxy resin comprises the following steps:
26g of 4,4 '-diaminodiphenyl ether was dissolved in 300g of DMAc at normal temperature, 34g of 4,4' -biphenyl ether dianhydride was added in three portions, 18g of carbon black was then added with stirring, 3g of triethylamine was then added, and the temperature was raised to 180℃with stirring and kept for 10 hours. Filtering, cooling to room temperature, adding 200mL of acetone for washing, drying in a drying oven at 100 ℃ for 4 hours, and crushing to obtain polyimide coated inorganic particles;
and adding 100g of epoxy resin into 45g of polyimide-coated inorganic particles, stirring for 5 hours at a constant temperature of 70 ℃, and finally adding ethylenediamine for crosslinking and curing to obtain the polyimide-coated inorganic particle modified epoxy resin.
Comparative example 1
A preparation method of inorganic particle modified epoxy resin comprises the following steps:
25g of carbon black is added into 100g of epoxy resin, stirred for 5 hours at a constant temperature of 70 ℃, and finally ethylenediamine is added for crosslinking and curing.
The epoxy resins prepared in examples 1 to 7 and comparative example 1 were subjected to performance test, and the results are shown in Table 1;
testing the glass transition temperature by adopting a differential scanning calorimetry;
bending strength testing was performed according to GB/T9341-2008;
tensile strength testing is carried out according to GB/T1040.2-2006;
TABLE 1 epoxy resin Performance test of examples 1-7 and comparative examples 1-3
Figure BDA0003991306080000061
As can be seen from Table 1, the polyimide prepared in example 6, which is not amino-terminated, has a low activity and hardly has an improvement in mechanical properties although improving the glass transition temperature of the resin, and thus the molar ratio of dianhydride to diamine is preferably 1 (1.1-1.4). Example 7 modification of epoxy resin with an excessive amount of polyimide-coated inorganic particles is effective in raising the glass transition temperature, but the tensile strength of the resin is slightly lowered, so that the mass ratio of polyimide-coated inorganic particles to epoxy resin is preferably (1-3): 10. Comparative example 1 in which carbon black was directly added to an epoxy resin, the effect of improving the glass transition temperature was limited due to its poor dispersibility, and the mechanical properties of the resin were seriously affected, resulting in deterioration of the mechanical properties.
In summary, the polyimide is wrapped on the surfaces of the inorganic particles, and the polyimide is dispersed in the epoxy resin, so that the glass transition temperature of the resin can be remarkably improved, and meanwhile, the mechanical properties of the resin can be further improved by selecting the amino-terminated polyimide or controlling the dosage proportion among materials, so that the modified epoxy resin is suitable for high-temperature and high-humidity environments.

Claims (10)

1. The preparation method of the polyimide coated inorganic particle modified epoxy resin is characterized by comprising the following steps:
s1, dissolving diamine in an organic solvent, adding dianhydride for reaction, adding inorganic particles for stirring, adding a catalyst, and heating to form turbid liquid; filtering, washing, drying and crushing the turbid liquid to obtain polyimide coated inorganic particles;
s2, adding the polyimide coated inorganic particles into epoxy resin, stirring at constant temperature, and then adding a curing agent to carry out curing reaction to obtain polyimide coated inorganic particle modified epoxy resin.
2. The method for preparing polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the diamine in the step S1 comprises one or more of 4,4' -diaminodiphenyl ether, p-phenylenediamine, biphenyl diamine.
3. The method for preparing polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the dianhydride in the step S1 comprises one or more of pyromellitic dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, 3', 4' -benzophenone tetracarboxylic dianhydride, and 4,4' -biphenyl ether dianhydride.
4. The method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the inorganic particles in the step S1 comprise one or both of carbon black and white carbon black.
5. The method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein in the step S1, the ratio of the total mass of diamine and dianhydride to the mass of inorganic particles is 5: (1-3), the molar ratio of dianhydride to diamine is 1 (1.1-1.4).
6. The method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the mass ratio of the polyimide-coated inorganic particles to the epoxy resin in the step S2 is (1-3): 10.
7. The method for preparing polyimide-coated inorganic particle modified epoxy resin according to claim 1, wherein in the step S2, the curing agent is an amine curing agent, specifically at least one of ethylenediamine, hexamethylenediamine and m-phenylenediamine.
8. The method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the heating temperature in the step S1 is 130 to 180 ℃.
9. The method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to claim 1, wherein the temperature of the constant-temperature stirring in the step S2 is 50-80 ℃ for 2-5 hours.
10. A polyimide-coated inorganic particle-modified epoxy resin, characterized by being prepared by the method for preparing the polyimide-coated inorganic particle-modified epoxy resin according to any one of claims 1 to 9.
CN202211584976.9A 2022-12-09 2022-12-09 Polyimide-coated inorganic particle modified epoxy resin and preparation method thereof Pending CN116239865A (en)

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