阅读说明：本技术 一种具有高热稳定性的苯并恶嗪环氧树脂复合材料的制备及应用 (Preparation and application of benzoxazine epoxy resin composite material with high thermal stability ) 是由 李辉 燕晴 宗传永 倪西强 吕虎 郭品玺 袁靓 于 2021-05-26 设计创作，主要内容包括：本发明提供一种具有高热稳定性的苯并恶嗪环氧树脂复合材料的制备及应用,将一定质量的DCPD环氧树脂与苯并恶嗪环氧树脂共聚物溶于溶剂中制备混合溶液,再加入固化剂并搅拌均匀,通过刮涂方法涂覆到基材上烘干,并经高温处理得到环氧树脂复合薄膜。本发明制备苯并恶嗪环氧树脂复合材料经高温处理后存在环氧基团、恶嗪环和双键的多重交联结构,热稳定性高,此外采用刮涂方法的的优点在于操作简单,易于获得厚度均匀,表面平整的复合膜,制备的复合薄膜具有更加优异的热稳定性和较低的介电常数。(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.)

1. 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 composite material with 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.

2. The preparation method of the benzoxazine epoxy resin composite material according to claim 1, wherein the structural formula of the fluorine-containing benzoxazine resin is shown in formula 1:

m₁is any natural number of 15-180, m₂Is any natural number of 15-180, m₃And is any natural number from 8 to 130.

3. 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.

4. The method of claim 1, wherein the curing agent is one of methylimidazole, diaminodiphenylmethane, diaminodiphenyl sulfone, ethylenediamine and 4, 4' -diaminodiphenyl ether.

5. The preparation method according to claim 1, wherein 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, stirring time is 3-24 h, drying temperature is 30-60 ℃, drying time is 6-24 h, and drying is carried out in a multi-stage heating manner to obtain the benzoxazine epoxy resin composite material.

6. The multi-stage heating method according to claim 4, wherein the first stage is heating from room temperature to 100-120 ℃, the temperature is maintained for 10-60 min, and the temperature rise 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; and in the third stage, heating to 210-240 ℃, keeping the temperature for 60-120 min, wherein the heating rate is 10-20 ℃/min, heating to 260-280 ℃ in the fourth stage, keeping the temperature for 60-120 min, and the heating rate is 10-20 ℃/min.

7. The method according to claim 1, wherein a thickness of a scraped film of a scraper is 250 to 1000 μm, and the thickness of the epoxy resin composite film is 100 to 200 μm.

8. The benzoxazine epoxy resin composite according to claim 1, having a glass transition temperature (Tg) of more than 150 ℃, an initial decomposition temperature (Td 5%) of 305-404 ℃, and a char yield (ycd%) of more than 55% at 800 ℃.

9. The benzoxazine epoxy resin composite material of claim 1, which has adjustable dielectric properties, a dielectric constant of 2.42-3.84 at 1MHz, and a dielectric loss of 0.0038-0.0112.

10. The benzoxazine epoxy resin composite of claim 1 having a water absorption of less than 0.10%.

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 200-250 ℃, 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, the invention also 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 composite material with 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 preparation method of the fluorine-containing benzoxazine epoxy resin composite material.

The structural formula of the fluorine-containing benzoxazine epoxy resin composite material is shown in the specification

m₁Is any natural number of 15-180, m₂Is any natural number of 15-180, m₃And is any natural number from 8 to 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 and 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 increased to 150-180 ℃, the temperature is kept for 30-120 min, and the temperature increasing rate is 5-10 ℃/min; and in the third stage, heating to 210-240 ℃, keeping the temperature for 60-120 min, wherein the heating rate is 10-20 ℃/min, heating to 260-280 ℃ in the fourth stage, keeping the temperature for 60-120 min, and the heating rate is 10-20 ℃/min.

Furthermore, the benzoxazine epoxy resin composite material has a thickness of 100-200 μm.

The benzoxazine epoxy resin composite material has excellent thermal stability, low water absorption rate 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 preparation process of benzoxazine epoxy resin composite material, and FIG. 2 is a fluorine-containing benzoxazine epoxy resin copolymer structure

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 ℃, and the initial decomposition temperature (T)_d5％) The carbon residue rate (y) is 305-404 ℃ and 800 DEG C_cd％) Higher than 55 percent, the dielectric constant under 1MHz is 2.68-3.84, the dielectric loss is 0.0038-0.0112, and the water absorption is lower than 0.10 percent.

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 glass transition temperature (Tg) of the benzoxazine epoxy resin composite material is 158 ℃, and the initial decomposition temperature (T)_d5％) The carbon residue rate (y) was 352 ℃ and 800 DEG C_cd％) 55 percent, adjustable dielectric property, a dielectric constant of 3.84 under 1MHz, dielectric loss of 0.0038 and water absorption of 0.09 percent.

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 ℃ and 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 the thickness of the prepared composite film after natural cooling is 110 mu m.

The glass transition temperature (Tg) of the benzoxazine epoxy resin composite material is 178 ℃, and the initial decomposition temperature (T)_d5％) The carbon residue ratio (y) was 384 ℃ at 800 ℃_cd％) 61 percent, adjustable dielectric property, a dielectric constant of 3.25 under 1MHz, a dielectric loss of 0.0064 and a water absorption of 0.08 percent.

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 ℃, and transferring to a muffle furnace, wherein the first-stage heating rate is 5 ℃/min, heating from room temperature to 110 ℃, keeping the temperature for 20min, the second-stage heating rate is 10 ℃/min, continuing to heat to 170 ℃, keeping the temperature for 60min, the third-stage heating rate is 240 ℃, keeping the temperature for 60min, the heating rate is 15 ℃/min, the fourth-stage heating rate is 20 ℃/min, continuing to heat to 270 ℃, keeping the temperature for 90min, and the thickness of the prepared composite film after natural cooling is 150 microns.

The glass transition temperature (Tg) of the benzoxazine epoxy resin composite material is 173 ℃, and the initial decomposition temperature (T)_d5％) The carbon residue rate (y) was 404 ℃ and 800 DEG C_cd％) 65 percent, adjustable dielectric property and a dielectric constant of 1MHz2.68, dielectric loss of 0.0112 and water absorption of 0.06%.