CN110643321B

Movatterモバイル変換

Info

Publication number: CN110643321B
Application number: CN201910951744.4A
Authority: CN
Inventors: 彭代信; 宁礼健
Original assignee: Suzhou Yiketai Electronic Material Co ltd
Current assignee: Hunan Kairuisi Microelectronics Materials Technology Co ltd
Priority date: 2019-09-24
Filing date: 2019-09-24
Publication date: 2022-03-29
Anticipated expiration: 2039-09-24
Also published as: CN110643321A

Abstract

Translated fromChinese

本发明公开了一种电子材料胶液及其应用。具体制备为，将2‑烯丙基苯基缩水甘油醚与对苯二甲酸共混在乙腈中，在季铵盐作为催化剂的条件下发生酯化反应，得到含有可逆动态基团的双(3‑(2‑烯丙基苯氧基)‑2‑羟丙基)对苯二甲酸酯；然后将双(3‑(2‑烯丙基苯氧基)‑2‑羟丙基)对苯二甲酸酯与双马来酰亚胺、聚苯醚包覆的介孔二氧化硅、溶剂混合均匀，制得电子材料胶液。本发明制备的电子材料胶液用于制备电子材料不仅具有良好介电性能、耐热性能，而且能在热压条件下实现重塑，具有广阔的应用前景。

The invention discloses an electronic material glue and its application. Specifically prepared as follows: 2-allylphenyl glycidyl ether and terephthalic acid are blended in acetonitrile, and esterification takes place under the condition that a quaternary ammonium salt is used as a catalyst to obtain a bis(3-(3-) containing reversible dynamic group (2-allylphenoxy)-2-hydroxypropyl)terephthalate; then bis(3-(2-allylphenoxy)-2-hydroxypropyl)terephthalate Formate, bismaleimide, polyphenylene ether-coated mesoporous silica, and solvent are mixed uniformly to prepare electronic material glue. The electronic material glue prepared by the invention not only has good dielectric properties and heat resistance properties for preparing electronic materials, but also can realize remodeling under hot pressing conditions, and has broad application prospects.

Description

Electronic material glue solution and application thereof

Technical Field

The invention relates to an electronic material glue solution, a preparation method and application thereof.

Background

Bismaleimide is a thermosetting resin, has excellent mechanical properties and heat resistance, is widely applied to the fields of aerospace and the like, and currently, copper-clad plates based on bismaleimide resin are reported in a lot.

In recent years, new demands have been made on substrates for high-frequency applications, because antennas, base stations, and satellite communications require high signal transmission speeds at high frequencies without distortion, and particularly, signal transmission capabilities under high-frequency and high-temperature and high-humidity conditions are consistent with those under normal conditions.

Disclosure of Invention

Aiming at the defects in the prior art, the invention provides the bismaleimide resin adhesive solution with secondary curing, high heat resistance and high dielectric property and the preparation method thereof, and provides a method for preparing the repairable copper-clad plate.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

an electronic material glue solution, wherein the preparation method of the electronic material glue solution comprises the following steps:

(1) reacting 2-allylphenyl glycidyl ether with terephthalic acid in the presence of quaternary ammonium salt to prepare bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate;

(2) stirring and mixing bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate, bismaleimide, a zinc compound, mesoporous silica coated by polyphenyl ether and a solvent to obtain an electronic material glue solution.

The polyphenylene ether-coated mesoporous silica is an existing material, is obtained from embodiment one of CN109021235A, and can provide good dielectric properties.

In the invention, epoxy chloropropane is added into a mixed solution of 2-allyl phenol, sodium hydroxide, quaternary ammonium salt and tetrahydrofuran to react to prepare 2-allyl phenyl glycidyl ether.

In the technical scheme, in the step (1), the mass ratio of the 2-allyl phenyl glycidyl ether to the terephthalic acid to the quaternary ammonium salt is 120: 40-50: 5-10, the reaction temperature is 65-80 ℃, and the reaction time is 8-12 hours; in the step (2), the mass ratio of the bismaleimide, the bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate, the zinc compound and the polyphenylene oxide coated mesoporous silica is 50: 75-80: 6-6.5: 1.5.

In the technical scheme, in the step (2), the mesoporous silica coated with bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate, bismaleimide, a zinc compound and polyphenyl ether is stirred at 130-135 ℃ for 50-60 min, and then mixed with a solvent to obtain the electronic material glue solution.

In the technical scheme, the quaternary ammonium salt is tetramethyl ammonium bromide and/or tetrabutyl ammonium bromide; the zinc compound is zinc acetylacetonate hydrate; the bismaleimide is one or more of N, N '-4, 4' -diphenylmethane bismaleimide, N '- (1, 4-phenylene) bismaleimide and N, N' -m-phenylene bismaleimide; the solid content of the electronic material glue solution is 60-62%; the solvent is a mixture of N, N-dimethylformamide and butanone.

The bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate and bismaleimide system has good plasticity and can be used for preparing shape memory materials and wear-resistant materials.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention synthesizes a novel diallyl compound containing reversible dynamic groups, which is used for modifying bismaleimide and preparing a novel electronic material glue solution containing reversible covalent bonds.

2. Compared with the traditional thermosetting SMPs, the remodelable shape memory bismaleimide prepared by the glue solution has good shape memory performance and remodeling performance.

3. Compared with the traditional 2, 2' -diallyl bisphenol A, the novel diallyl compound-bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate provided by the invention is synthesized without high-temperature rearrangement, the synthesis process is simple, and the required energy consumption is low; compared with the traditional 2, 2' -diallyl bisphenol A, the bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate synthesized by the method is non-bisphenol A type, so that the risks of carcinogenesis, teratogenicity, influence on fertility and the like of the bisphenol A are avoided.

Drawings

FIG. 1 is a reaction scheme for synthesizing 2-allylphenyl glycidyl ether and bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate prepared according to the present invention.

FIG. 2 shows the NMR spectrum of 2-allylphenyl glycidyl ether prepared in example 1 of the present invention: (¹H-NMR)。

FIG. 3 is a drawing showing bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate prepared in example 1 of the present invention¹H-NMR。

FIG. 4 is a NMR spectrum of bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate prepared in example 1 of the present invention (C¹³C-NMR)。

FIG. 5 is a high resolution mass spectrum of bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate prepared in example 1 of the present invention.

Detailed Description

The technical solution of the present invention is further described with reference to the accompanying drawings and examples.

The preparation method of the electronic material glue solution comprises the following steps:

Synthesis example

Mixing 120g of 2-allylphenol, 140g of sodium hydroxide, 10g of tetrabutylammonium bromide and 230g of tetrahydrofuran by mass, and carrying out heat preservation reaction for 1.5h at 35 ℃ under the stirring condition to obtain a solution A; slowly dropwise adding 270g of epoxy chloropropane into the solution A, and keeping the temperature at 35 ℃ and stirring for reacting for 6 hours; and after the reaction is finished, removing tetrahydrofuran and epichlorohydrin by vacuum rotary evaporation to obtain a crude product. Washing the crude product with saturated ammonium chloride solution (200mL × 2) and deionized water (200mL × 2), and separating and purifying with chromatographic column to obtain yellow transparent liquid, i.e. 2-allyl phenyl glycidyl ether, with yield of about 93%, according to the reaction formula¹H-NMR is shown in the attached figures 1 and 2 respectively. Mixing 120g of 2-allyl phenyl glycidyl ether, 45g of terephthalic acid, 10g of tetrabutylammonium bromide and 230g of acetonitrile by mass, and carrying out heat preservation reaction for 8 hours at 70 ℃ under the stirring condition; after the reaction is finished, removing acetonitrile by vacuum rotary evaporation to obtain a crude product. Washing the crude product with saturated sodium bicarbonate solution (200mL × 2) and deionized water (200mL × 2), and separating and purifying with chromatographic column to obtain yellow transparent viscous liquid, i.e. bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate with yield of 86%, according to the reaction formula,¹H-NMR、¹³C-NMR and high resolution mass spectra are shown in FIGS. 1, 3, 4 and 5, respectively, for the following examples.

Completely dissolving 2g of polyphenylene oxide (vinyl-terminated polyphenylene oxide (PPO. MX9000-111) with the number average molecular weight of 1100) in 25ml of toluene to obtain a polyphenylene oxide solution, then adding 0.6g of mesoporous silica (UC-S-1), stirring and dispersing, adding into 500ml of aqueous solution of sodium dodecyl sulfate surfactant with the mass concentration of 0.15% to form an oil-in-water system, stirring for 4 hours, washing and filtering precipitates, and performing vacuum drying at 120 ℃ for 4 hours to obtain the polyphenylene oxide-coated mesoporous silica, wherein the mass ratio of the polyphenylene oxide to the mesoporous silica is 3.3: 1. Because the polyphenyl ether is insoluble in water, the separated polyphenyl ether can be deposited or adsorbed on the surface of the mesoporous silicon dioxide along with the gradual volatilization of the toluene solvent, and the mesopores are sealed.

EXAMPLE A preparation of an electronic Material glue solution

Mixing 50g of N, N '-4, 4' -diphenylmethane bismaleimide, 76.17g of bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate, 6.29g (22.3mmol) of zinc acetylacetonate hydrate and 1.5g of polyphenylene oxide-coated mesoporous silica, stirring at 130 ℃, carrying out prepolymerization for 60min to obtain a prepolymer, and sampling and testing DSC (10 ℃/min, the maximum reaction exothermic peak is 242.8 ℃); and cooling the prepolymer to room temperature, adding the cooled prepolymer into a mixture of N, N-dimethylformamide and butanone in a mass ratio of 2: 8, and stirring at room temperature for 2 hours to obtain an electronic material glue solution, wherein the solid content of the electronic material glue solution is 60%.

Preparation of copper-clad plate

Using 1080 fiber glass cloth (Shanghai macrosum) to dip the resin liquid to obtain a prepreg, and then drying (160 ℃ for 40 seconds) to remove the solvent to obtain a prepreg; and (3) overlapping 8 prepregs, covering copper foils (1 ounce) on two sides of the prepregs, and performing high-temperature hot-pressing curing in a press to prepare the electronic material glue solution.

The high-temperature hot-pressing curing process comprises the following steps: 150 ℃/1h/0.5MPa +180 ℃/2h/1MPa +200 ℃/1h/1MPa +220 ℃/1h/2 MPa; and naturally cooling and demoulding to obtain the copper-clad plate.

Preparation of electronic insulating material

And (3) overlapping 8 semi-cured sheets of the embodiments, pressing and covering conventional release films on two sides of the semi-cured sheets, and performing high-temperature hot-pressing curing in a press to prepare the electronic material glue solution. The high-temperature hot-pressing curing process comprises the following steps: 150 ℃/1h/0.5MPa +180 ℃/2h/1MPa +200 ℃/1h/1MPa +220 ℃/1h/2 MPa; and naturally cooling and demoulding to obtain the electronic insulating material.

Comparative example 1

50g of N, N '-4, 4' -diphenylmethane bismaleimide, 76.17g of bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate and 6.29g of zinc acetylacetonate hydrate were mixed, and stirred at 130 ℃ to perform prepolymerization for 60min, thereby obtaining a prepolymer. And replacing the prepolymer in the first embodiment with the prepolymer in the second embodiment, keeping the rest unchanged to obtain a comparison electronic material glue solution, and preparing a comparison copper-clad plate and a comparison insulating material by the same method.

Comparative example No. two

A comparative electronic material glue solution was obtained by replacing bis (3- (2-allylphenoxy) -2-hydroxypropyl) terephthalate of example one with 73.41g (139.5mmol) of bis (3- (2-allylphenoxy) -2-hydroxypropyl) adipate, and the remainder was unchanged, and a comparative copper clad laminate and a comparative insulating material were prepared in the same manner.

Performance testing

Secondary curing capability. A bending strength test plate (process for preparing an electronic insulating material) is prepared according to IPC-TM-6502.4.4, one electronic insulating material is equally divided into four blocks, any two blocks are used for initial bending strength test, the remaining two blocks are dropped by a 5512 impact instrument to the extent that a resin layer has cracks and glass cloth is not damaged, then the two dropped plates are hot-pressed for 5 hours under the conditions that the temperature is 270 ℃ and the pressure is 30MPa, and demoulding is carried out after natural cooling to obtain a secondary cured plate, wherein the appearance of the secondary cured plate has no cracks and is almost the same as the initial one. The flexural strength is measured according to the standard (three averages in N/mm)²) The initial values are 493 (warp direction) and 457 (weft direction), and the secondary values are 486 (warp direction) and 450 (weft direction) after secondary curing. In the same method, if the diallyl bisphenol A modified bismaleimide resin is adopted to prepare the plate (with a conventional formula), secondary curing cannot be performed, the plate is hot-pressed for 5 hours at the temperature of 270 ℃ and the pressure of 30MPa, and the plate is demoulded after natural cooling, and the drop hammer is still fuzzy and has cracks.

Table 1 copper-clad plate prepared by embodiment and comparative example

Wherein, T_gThe glass transition temperature is obtained by DMA test (1Hz, 3 ℃/min, 20-350 ℃, three-point bending); the dielectric constant and dielectric loss of the panels at room temperature were tested using a Novocontrol Concept 80 dielectric tester, Germany.

Table 1 shows the above examples and the performance tests related to the comparative examples, and it can be seen that the glue solution prepared by using the polyphenylene oxide-coated mesoporous silica and bismaleimide together can ensure the heat resistance and simultaneously show excellent dielectric properties when used for preparing the copper-clad plate.

Claims

Translated fromChinese

1.一种电子材料胶液，其特征在于，所述电子材料胶液的制备方法包含如下步骤：（1）在季铵盐存在下，将2-烯丙基苯基缩水甘油醚与对苯二甲酸反应，制备双（3-（2-烯丙基苯氧基）-2-羟丙基）对苯二甲酸酯；将环氧氯丙烷加入2-烯丙基苯酚、氢氧化钠、季铵盐与四氢呋喃的混合液中，反应制备2-烯丙基苯基缩水甘油醚；2-烯丙基苯基缩水甘油醚、对苯二甲酸、季铵盐的质量比为120∶40～50∶5～10，反应的温度为65～80℃，时间为8～12h；（2）将双（3-（2-烯丙基苯氧基）-2-羟丙基）对苯二甲酸酯、双马来酰亚胺、锌化合物、聚苯醚包覆的介孔二氧化硅、溶剂搅拌混合，得到电子材料胶液；双马来酰亚胺、双（3-（2-烯丙基苯氧基）-2-羟丙基）对苯二甲酸酯、锌化合物、聚苯醚包覆的介孔二氧化硅的质量比为50∶75～80∶6～6.5∶1.5。1. An electronic material glue, characterized in that the preparation method of the electronic material glue comprises the following steps: (1) in the presence of a quaternary ammonium salt, mixing 2-allylphenyl glycidyl ether with p-benzene Dicarboxylic acid reaction to prepare bis(3-(2-allylphenoxy)-2-hydroxypropyl) terephthalate; add epichlorohydrin to 2-allylphenol, sodium hydroxide, In the mixed solution of quaternary ammonium salt and tetrahydrofuran, 2-allylphenyl glycidyl ether is prepared by reaction; the mass ratio of 2-allylphenyl glycidyl ether, terephthalic acid and quaternary ammonium salt is 120:40～ 50:5～10, the temperature of the reaction is 65～80℃, and the time is 8～12h; (2) bis(3-(2-allylphenoxy)-2-hydroxypropyl)terephthalene Acid ester, bismaleimide, zinc compound, polyphenylene ether-coated mesoporous silica, and solvent are stirred and mixed to obtain electronic material glue; bismaleimide, bis(3-(2-ene) The mass ratio of propylphenoxy)-2-hydroxypropyl) terephthalate, zinc compound, and polyphenylene ether-coated mesoporous silica is 50:75-80:6-6.5:1.5.

2.根据权利要求1所述电子材料胶液，其特征在于，所述季铵盐为四甲基溴化铵和/或四丁基溴化铵；锌化合物为乙酰丙酮锌水合物。2 . The electronic material glue solution according to claim 1 , wherein the quaternary ammonium salt is tetramethylammonium bromide and/or tetrabutylammonium bromide; and the zinc compound is zinc acetylacetonate hydrate. 3 .

3.根据权利要求1所述电子材料胶液，其特征在于，步骤（2）中，将双（3-（2-烯丙基苯氧基）-2-羟丙基）对苯二甲酸酯、双马来酰亚胺、锌化合物、聚苯醚包覆的介孔二氧化硅于130～135℃搅拌50～60min，然后与溶剂混合，得到电子材料胶液。3 . The electronic material glue solution according to claim 1 , wherein in step (2), bis(3-(2-allylphenoxy)-2-hydroxypropyl) terephthalic acid is added to The ester, bismaleimide, zinc compound, and polyphenylene ether-coated mesoporous silica are stirred at 130 to 135° C. for 50 to 60 minutes, and then mixed with a solvent to obtain an electronic material glue.

4.根据权利要求3所述电子材料胶液，其特征在于，电子材料胶液的固含量为60%～62%；溶剂为N,N-二甲基甲酰胺与丁酮的混合物。4 . The electronic material glue solution according to claim 3 , wherein the solid content of the electronic material glue solution is 60% to 62%; and the solvent is a mixture of N,N-dimethylformamide and butanone. 5 .

5.根据权利要求4所述电子材料胶液，其特征在于，N,N-二甲基甲酰胺与丁酮的质量比为2∶8。5 . The electronic material glue solution according to claim 4 , wherein the mass ratio of N,N-dimethylformamide and butanone is 2:8. 6 .

6.根据权利要求1所述电子材料胶液，其特征在于，所述双马来酰亚胺为N,N’-4,4’-二苯甲烷双马来酰亚胺、N,N’-（1,4-亚苯基）双马来酰亚胺、N,N’-间苯撑双马来酰亚胺的一种或几种。6. electronic material glue solution according to claim 1 is characterized in that, described bismaleimide is N,N'-4,4'-diphenylmethane bismaleimide, N,N' One or more of -(1,4-phenylene)bismaleimide and N,N'-m-phenylene bismaleimide.

7.权利要求1所述电子材料胶液在制备电路传输材料中的应用。7. Application of the electronic material glue according to claim 1 in the preparation of circuit transmission materials.