CN113604005B - Preparation and application of benzoxazine epoxy resin composite material with high thermal stability - Google Patents
Preparation and application of benzoxazine epoxy resin composite material with high thermal stability Download PDFInfo
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- CN113604005B CN113604005B CN202110575206.7A CN202110575206A CN113604005B CN 113604005 B CN113604005 B CN 113604005B CN 202110575206 A CN202110575206 A CN 202110575206A CN 113604005 B CN113604005 B CN 113604005B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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Abstract
The invention provides a preparation method and application of a benzoxazine epoxy resin composite material with high thermal stability. The benzoxazine epoxy resin composite material prepared by the invention has a multiple cross-linking structure of epoxy groups, oxazine rings and double bonds after high-temperature treatment, and is high in thermal stability.
Description
Technical Field
The invention relates to a preparation method of a benzoxazine epoxy resin composite material with high thermal stability, belonging to the technical field of composite material preparation.
Background
Epoxy resin is used as a commonly used electronic packaging material and plays an important role in supporting and protecting an integrated circuit. In recent years, the rapid development of high-frequency and high-speed integrated circuits has put higher demands on packaging techniques and materials. The traditional bisphenol A epoxy resin has large molecular polarity, so that the dielectric constant and the dielectric loss are relatively high; the thermal deformation temperature after curing is lower than 130 ℃, the maximum use temperature is between 200 and 250 ℃, and the requirements of the new generation of semiconductor packaging are difficult to meet. Therefore, the preparation of new epoxy resins or composite materials has become a focus of research.
Compared with the traditional epoxy resin, the molecular structure of the DCPD resin contains benzene rings and also has an alicyclic structure of dicyclopentadiene, so that the DCPD resin has excellent thermal stability, low water absorption, low dielectric constant, high adhesiveness, chemical resistance and other performances, and therefore, the DCPD resin receives more and more attention. The benzoxazine epoxy resin composite material contains an oxazine ring group, an epoxy group and a norbornene structure, forms a multiple crosslinking system under the action of a high temperature and a curing agent, and further improves the thermal stability.
Disclosure of Invention
In order to solve the problems, the invention provides a preparation method of a benzoxazine epoxy resin composite material with high thermal stability, and simultaneously provides an application of the composite material.
The invention is realized by the following technical scheme:
a preparation method of a benzoxazine epoxy resin composite material with high thermal stability is characterized in that DCPD epoxy resin and fluorine-containing benzoxazine epoxy resin in a certain mass ratio are dissolved in a solvent to prepare a mixed solution, a curing agent is added and the mixed solution is uniformly stirred, and the benzoxazine epoxy resin composite material is obtained through high-temperature treatment.
Preferably, in the above method for preparing a composite material of fluorine-containing benzoxazine and epoxy resin, the structural formula of the composite material of fluorine-containing benzoxazine and epoxy resin is:
m1 is any natural number of 15-180, m2 is any natural number of 15-180, and m3 is any natural number of 8-130.
The solvent is one or a mixture of two of acetone, butanone, dichloromethane, toluene, xylene or ethyl acetate.
The curing agent is one of methylimidazole, diaminodiphenylmethane, diaminodiphenyl sulfone, ethylenediamine or 4, 4' -diaminodiphenyl ether.
The mass ratio of the DCPD epoxy resin to the fluorine-containing benzoxazine epoxy resin copolymer is 1: 9-9: 1.
The concentration of the mixed solution is 10-60 wt% (mass fraction of solute).
The stirring time is 3-24 h.
The drying temperature is 30-60 ℃.
The drying time is 6-24 h.
Further, the multi-stage heating mode is a first stage of heating from room temperature to 100-120 ℃, keeping the temperature for 10-60 min, and the heating rate is 5-10 ℃/min; in the second stage, the temperature is continuously raised to 150-180 ℃, the temperature is kept for 30-120 min, and the temperature raising rate is 5-10 ℃/min; the temperature is raised to 210-240 ℃ in the third stage, the temperature is preserved for 60-120 min, the temperature raising rate is 10-20 ℃/min, the temperature is raised to 260-280 ℃ in the fourth stage, the temperature is preserved for 60-120 min, and the temperature raising rate is 10-20 ℃/min.
Furthermore, the benzoxazine epoxy resin composite material has the thickness of 100-200 mu m.
The benzoxazine epoxy resin composite material has excellent thermal stability, low water absorption and low dielectric constant, and can be used for packaging materials, electronic packaging materials, high glass transition temperature (Tg) laminated boards and the like.
Drawings
FIG. 1 is a process for preparing a benzoxazine epoxy resin composite;
FIG. 2 shows the structure of the copolymer of fluorine-containing benzoxazine epoxy resin.
Advantageous effects
The benzoxazine epoxy resin composite material has excellent thermal stability, the glass transition temperature (Tg) of the benzoxazine epoxy resin composite material is higher than 150 ℃, the initial decomposition temperature (Td 5%) of the benzoxazine epoxy resin composite material is 305-404 ℃, the carbon residue rate (ycd%) at 800 ℃ is higher than 55%, the dielectric constant under 1MHz is 2.68-3.84, the dielectric loss is 0.0038-0.0112, and the water absorption rate is lower than 0.10%.
Detailed Description
The following examples are given for the detailed implementation and specific operation of the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
Preparing a benzoxazine epoxy resin composite material: dissolving 0.9g of DCPD epoxy resin and 0.1g of benzoxazine epoxy resin copolymer in 5g of acetone, adding methylimidazole, stirring for 3h at room temperature, taking a glass plate as a substrate, coating the mixed solution on the substrate through a 1000-micron film scraper, drying for 24h at 30 ℃, transferring to a muffle furnace, heating to 100 ℃ from room temperature at a first stage heating rate of 5 ℃/min, keeping the temperature for 60min, heating to 150 ℃ at a second stage heating rate of 5 ℃/min, keeping the temperature for 120min, heating to 210 ℃ at a third stage heating rate of 120min, heating to 10 ℃/min at a fourth stage heating rate of 10 ℃/min, keeping the temperature for 60min, and naturally cooling to prepare the composite material with the thickness of 100 microns.
The benzoxazine epoxy resin composite material has a glass transition temperature (Tg) of 158 ℃, an initial decomposition temperature (Td 5%) of 352 ℃, a carbon residue rate (ycd%) of 55% at 800 ℃, adjustable dielectric properties, a dielectric constant of 3.84 at 1MHz, a dielectric loss of 0.0038 and a water absorption of 0.09%.
Example 2
Preparing a benzoxazine epoxy resin composite material: dissolving 0.5g of DCPD epoxy resin and 0.5g of benzoxazine epoxy resin copolymer in 3g of acetone/toluene mixed solvent, adding methylimidazole, stirring for 12h at room temperature, taking a glass plate as a substrate, coating the mixed solution on the substrate through a film scraper of 750 mu m, drying for 6h at 60 ℃, and transferring to a muffle furnace, wherein the first-stage heating rate is 10 ℃/min, heating from room temperature to 120 ℃, keeping the temperature for 30min, the second-stage heating rate is 10 ℃/min, continuing to heat to 180 ℃, keeping the temperature for 60min, the third-stage heating rate is 220 ℃, keeping the temperature for 90min, the heating rate is 15 ℃/min, the fourth-stage heating rate is 15 ℃/min, continuing to heat to 260 ℃, keeping the temperature for 120min, and naturally cooling to prepare the composite film with the thickness of 110 mu m.
The benzoxazine epoxy resin composite material has a glass transition temperature (Tg) of 178 ℃, an initial decomposition temperature (Td 5%) of 384 ℃, a carbon residue rate (ycd%) of 61% at 800 ℃, adjustable dielectric properties, a dielectric constant of 3.25 at 1MHz, a dielectric loss of 0.0064 and a water absorption of 0.08%.
Example 3
Preparing a cyclobenzoxazine epoxy resin composite material: dissolving 0.1g of DCPD epoxy resin and 0.9g of benzoxazine epoxy resin copolymer in 2g of ethyl acetate/dichloromethane mixed solvent, adding ethylenediamine, stirring for 24h at room temperature, taking a glass plate as a substrate, coating the mixed solution on the substrate through a 500-micron film scraper, drying for 12h at 45 ℃, transferring to a muffle furnace, heating to 110 ℃ from room temperature at a first stage heating rate of 5 ℃/min, keeping the temperature for 20min, heating to 170 ℃ continuously at a second stage heating rate of 10 ℃/min, keeping the temperature for 60min, heating to 240 ℃ at a third stage heating rate of 60min at a heating rate of 15 ℃/min, heating to 270 ℃ at a fourth stage heating rate of 20 ℃/min, keeping the temperature for 90min, and naturally cooling to obtain a composite film with the thickness of 150 microns.
The benzoxazine epoxy resin composite material has the glass transition temperature (Tg) of 173 ℃, the initial decomposition temperature (Td 5%) of 404 ℃, the carbon residue rate (ycd%) of 65% at 800 ℃, adjustable dielectric property, a dielectric constant of 2.68 at 1MHz, dielectric loss of 0.0112 and water absorption of 0.06%.
Claims (8)
1. A preparation method of benzoxazine epoxy resin composite material with high thermal stability is characterized in that DCPD epoxy resin and fluorine-containing benzoxazine epoxy resin in a certain mass ratio are dissolved in a solvent to prepare a mixed solution, a curing agent is added and the mixed solution is uniformly stirred, and the benzoxazine epoxy resin composite material is obtained through high-temperature treatment; the mass ratio of the DCPD epoxy resin to the fluorine-containing benzoxazine epoxy resin is 1: 9-9: 1, and the concentration of the mixed solution is 10-60 wt% of solute mass fraction;
the structural formula of the fluorine-containing benzoxazine epoxy resin is as follows:
R 1 ：
R 2 ：
R 3 ：
m 1 is any natural number of 15-180, m 2 Is any natural number of 15-180, m 3 And is any natural number from 8 to 130.
2. The method for preparing benzoxazine epoxy resin composite according to claim 1, wherein the solvent is one or a mixture of two of acetone, butanone, dichloromethane, toluene, xylene or ethyl acetate.
3. The method of claim 1, wherein the curing agent is one of methylimidazole, diaminodiphenylmethane, diaminodiphenyl sulfone, ethylenediamine or 4, 4' -diaminodiphenyl ether.
4. The preparation method of the benzoxazine epoxy resin composite material according to claim 1, wherein the stirring time is 3-24 h, the drying temperature is 30-60 ℃, the drying time is 6-24 h, and the benzoxazine epoxy resin composite material is obtained by drying under a multi-stage heating mode.
5. The preparation method of benzoxazine epoxy resin composite according to claim 4, wherein the multi-stage heating manner is: in the first stage, the temperature is heated from room temperature to 100-120 ℃, the temperature is kept for 10-60 min, and the heating rate is 5-10 ℃/min; in the second stage, the temperature is continuously increased to 150-180 ℃, the temperature is kept for 30-120 min, and the temperature increasing rate is 5-10 ℃/min; the temperature is raised to 210-240 ℃ in the third stage, the temperature is kept for 60-120 min, the temperature raising rate is 10-20 ℃/min, the temperature is raised to 260-280 ℃ in the fourth stage, the temperature is kept for 60-120 min, and the temperature raising rate is 10-20 ℃/min.
6. The method for preparing the benzoxazine epoxy resin composite according to claim 1, wherein the benzoxazine epoxy resin composite has a glass transition temperature Tg of more than 150 ℃, an initial decomposition temperature Td5% of 305-404 ℃, and a carbon residue rate ycd% of more than 55% at 800 ℃.
7. The preparation method of the benzoxazine epoxy resin composite material according to claim 1, wherein the benzoxazine epoxy resin composite material has adjustable dielectric properties, a dielectric constant of 2.42-3.84 at 1MHz, and a dielectric loss of 0.0038-0.0112.
8. The method of preparing a benzoxazine epoxy composite according to claim 1, wherein the water absorption of the benzoxazine epoxy composite is less than 0.10%.
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| TWI626664B (en) * | 2017-02-07 | 2018-06-11 | 聯茂電子股份有限公司 | Non-halogen epoxy resin composition having low dielectric loss |
| CN108440901B (en) * | 2018-03-26 | 2020-07-14 | 常熟生益科技有限公司 | High-frequency resin composition, and prepreg, interlayer insulating film and laminated board prepared from high-frequency resin composition |
| CN111072980B (en) * | 2019-12-30 | 2021-11-23 | 四川东材科技集团股份有限公司 | Modified hydrocarbon resin prepolymer, modified hydrocarbon-DCPD epoxy composite material copper-clad plate and preparation method |
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