CN117050460A - BN micropowder reinforced phenolic resin for copper-clad plate and preparation method thereof - Google Patents

BN micropowder reinforced phenolic resin for copper-clad plate and preparation method thereof Download PDF

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CN117050460A
CN117050460A CN202311175312.1A CN202311175312A CN117050460A CN 117050460 A CN117050460 A CN 117050460A CN 202311175312 A CN202311175312 A CN 202311175312A CN 117050460 A CN117050460 A CN 117050460A
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phenolic resin
copper
micro powder
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CN117050460B (en
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朱利明
陈应峰
谢谏诤
王小龙
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Jiangsu Yaohong Electronics Co ltd
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Abstract

The invention relates to the field of copper-clad plates, in particular to BN micro powder reinforced phenolic resin for a copper-clad plate and a preparation method thereof. The BN micro powder reinforced phenolic resin comprises the following components in parts by weight: 110-130 parts of modified phenolic resin, 50-70 parts of epoxy resin, 15-30 parts of flame retardant, 10-20 parts of curing agent, 0.2-1.0 part of curing accelerator, 20-40 parts of modified BN micro powder, 10-20 parts of nano organic montmorillonite, 120-200 parts of isopropanol and 80-120 parts of propylene glycol. The modified BN micropowder and the nano organic montmorillonite are added into the modified phenolic resin and the epoxy resin, and the synergistic effect of various auxiliary agents and solvents is combined to prepare the BN micropowder reinforced phenolic resin. The high-heat-conductivity copper-clad plate is applied to the preparation process of the copper-clad plate, so that the high-heat-conductivity copper-clad plate has high heat conductivity, and simultaneously has excellent peel strength and oxidation resistance.

Description

BN micropowder reinforced phenolic resin for copper-clad plate and preparation method thereof
Technical Field
The invention relates to the field of copper-clad plates, in particular to BN micro powder reinforced phenolic resin for a copper-clad plate and a preparation method thereof.
Background
With the rapid development of the electronic field and the increasing demand for high-performance electronic devices, the copper-clad plate plays a crucial role as a commonly used electronic substrate material. However, the conventional copper-clad plate has limitations in terms of heat conductivity and peel strength, and cannot meet the current urgent demands for higher performance and reliability. In order to solve the problem, a new background technology, namely a preparation technology of BN (boron nitride) micropowder reinforced phenolic resin for copper-clad plates, has been developed.
The technology aims to improve the heat-conducting property and the peeling strength of the copper-clad plate by compounding BN micro powder with excellent heat-conducting property with phenolic resin, thereby meeting the electronic application requirement of higher requirements. When BN micropowder is used as a unique inorganic filler, the BN micropowder has excellent heat conduction performance, high-temperature stability and mechanical hardness, and can play a role in enhancing and increasing a heat conduction path in a resin matrix. When BN micropowder interacts with phenolic resin, the BN micropowder can effectively conduct heat and improve the thermal conductivity of the material, and simultaneously provide higher peel strength. However, BN micropowder is poorly dispersible, having a high specific surface area and surface energy, and tends to form aggregates and lumps, failing to achieve uniform dispersion when mixed with phenolic resin, poor dispersibility may lead to local aggregation, thereby affecting the thermal conductivity and peel strength of the material. Meanwhile, BN micro powder may undergo thermal oxidation reaction or chemical reaction with phenolic resin under high temperature condition, which affects the thermal stability and long-term reliability of the copper-clad plate.
Therefore, we propose a BN micro powder reinforced phenolic resin for copper-clad plates and a preparation method thereof.
Disclosure of Invention
The invention aims to provide BN micro powder reinforced phenolic resin for a copper-clad plate and a preparation method thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
s1: uniformly mixing phenol and formaldehyde solution, heating to 70-80 ℃, dropwise adding sodium hydroxide solution until the pH value is 9-10, stopping dropwise adding, heating to 85-95 ℃, carrying out reflux reaction for 1-2h, adding phenylboronic acid, continuously carrying out reaction for 1-2h, and cooling to room temperature to obtain modified phenolic resin;
s2: uniformly mixing the modified phenolic resin prepared in the step S1 with epoxy resin, heating to 40-60 ℃, adding a flame retardant, a curing agent, a curing accelerator, modified BN micro powder, nano montmorillonite, isopropanol and propylene glycol, uniformly mixing, and reacting for 3-5 hours to prepare the halogen-free heat-resistant phenolic resin glue solution.
Further, in the step S1, the mass ratio of the phenol to the formaldehyde solution is 1: (1.2-1.5).
Further, the concentration of the formaldehyde solution in the step S1 is 37-40wt%.
Further, the concentration of the sodium hydroxide solution in the step S1 is 10-20wt%.
Further, the mass of phenylboronic acid in the step S1 is 10-20% of the mass of phenol.
Further, the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing BN micro powder and sucrose, ball milling, washing, ultrasonic treatment, centrifuging, and vacuum drying at 70-80 ℃ for 24-48 hours to obtain hydroxylated modified BN;
step (2): dispersing the hydroxylation modified BN in a mixed solution of ethanol and Tris buffer solution, carrying out ultrasonic treatment for 30-40min, adding dopamine hydrochloride, heating to 20-30 ℃, and stirring at the speed of 450-550r/min for 4-6h to obtain polydopamine grafted BN;
step (3): mixing 4- (4-aminophenyl) -1,2, 4-triazole and N, N' -bis (dimethylaminomethylene) hydrazine, adding dimethylbenzene under nitrogen atmosphere, heating to 150-160 ℃, carrying out reflux reaction for 45-48 hours, pouring dimethylbenzene, standing for 20-24 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): adding Zn (NO) into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 10-20min, dropwise adding a mixed solution of a ligand compound and methanol, stirring for reacting for 24-48h after 1-2h, centrifuging for multiple times, washing, and vacuum drying at 70-80 ℃ for 24-48h to obtain modified BN micro powder.
In the technical scheme, BN and sucrose are used as raw materials to prepare hydroxylated modified BN, an active site is introduced, and then dopamine hydrochloride is used for grafting treatment on the BN surface to prepare polydopamine grafted BN; by reacting the amino group of 4- (4-aminophenyl) -1,2, 4-triazole with N, N' -bis (dimethylaminomethylene) hydrazine, a ligand compound is produced, in which the N atom is reacted with Zn (NO) 3 ) 2 ·6H 2 Zn in O 2+ Has stronger interaction, thereby preparing a metal-organic framework; because the catechol group of the polydopamine has stronger metal chelating ability, the polydopamine can be matched with Zn 2+ Forming a stable chelate complexA material; meanwhile, the aromatic group of the polydopamine has hydrophobicity, and the metal organic framework is similar to a hydrophobic material, and the hydrophobic interaction enhances the mutual attraction between the polydopamine surface and the metal organic framework, so that the adsorption, nucleation and growth of the metal organic framework on the polydopamine surface can be promoted. Therefore, through the interactions, a core-shell composite material can be formed on the surface of the polydopamine, and the loading and the fixing of the metal-organic framework are realized, so that the BN is protected, and the dispersibility and the heat conductivity of the BN are improved.
Further, in the step (1), the mass ratio of BN to sucrose is 1: (4-6).
Further, the ball milling process conditions in the step (1) are as follows: the rotating speed of the ball mill is 450-550r/min, and the ball milling time is 11-13h; the ultrasonic process conditions are as follows: the ultrasonic power is 500-650W, and the ultrasonic time is 30-50min; the centrifugal process conditions are as follows: the centrifugal speed is 4000-7000rpm, and the centrifugal time is 5-20min.
Further, the concentration of the Tris buffer solution in the step (2) is 10-15mmol/L, and the pH value is 8-9.
Further, the mass ratio of the hydroxylation modified BN, ethanol and Tris buffer solution in the step (2) is 1: (30-40): (70-90).
Further, the mass of the dopamine hydrochloride in the step (2) is 10-16% of that of the hydroxylation modified BN.
Further, the mass ratio of 4- (4-aminophenyl) -1,2, 4-triazole to N, N' -bis (dimethylaminomethylene) hydrazine in the step (3) is 1: (2.8-3.2).
Further, the mass of the xylene in the step (3) is 10 to 15 times that of the 4- (4-aminophenyl) -1,2, 4-triazole.
Further, in the step (4), zn (NO 3 ) 2 ·6H 2 The mass of O is 1 of the mass of the hydroxylation modified BN: (3-5).
Further, in the step (4), zn (NO 3 ) 2 ·6H 2 The mass ratio of O to the ligand compound is 1: (0.5-0.8)
Further, in the step (4), the mass ratio of the ligand compound to methanol is 1: (15-20).
Further, the centrifugation process conditions in the step (4) are as follows: the centrifugal speed is 5000-7000rpm, and the centrifugal time is 5-10min.
Further, the halogen-free heat-resistant phenolic resin glue solution in the step S2 comprises the following components in parts by weight:
110-130 parts of modified phenolic resin, 50-70 parts of epoxy resin, 15-30 parts of flame retardant, 10-20 parts of curing agent, 0.2-1.0 part of curing accelerator, 20-40 parts of modified BN micro powder, 10-20 parts of nano organic montmorillonite, 120-200 parts of isopropanol and 80-120 parts of propylene glycol.
Further, the flame retardant is ammonium polyphosphate.
Further, the curing agent is melamine.
Further, the curing accelerator is triethanolamine phosphate.
An application of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
uniformly coating BN micropowder reinforced phenolic resin on glass fiber cloth, and baking at 150-200 ℃ for 10-30min to obtain a prepreg; 3-8 prepregs are stacked together to prepare a laminated sheet, a copper foil is respectively placed on the upper surface and the lower surface of the laminated sheet, and the laminated sheet and the copper foil are heated and pressed together by using a lamination process and cooled to room temperature to prepare the copper-clad plate.
Further, the coating weight of the BN micro powder reinforced phenolic resin is 110-150g/m 2 。
Further, the thickness of the prepreg is 2-8mm.
Further, the lamination process conditions are: laminating temperature is 200-250 ℃, laminating pressure is 5-10MPa, and laminating time is 1-5h.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the BN micro powder reinforced phenolic resin for the copper-clad plate and the preparation method thereof, the BN and the sucrose are used as raw materials to prepare the hydroxylation modified BN, an active site is introduced, and then the surface of the BN is subjected to grafting treatment by utilizing dopamine hydrochloride to prepare polydopamine grafted BN; by reacting 4- (4-aminophenyl) -1,the amino group of 2, 4-triazole reacts with N, N' -bis (dimethylaminomethylene) hydrazine to produce a ligand compound, the N atom of which is reacted with Zn (NO) 3 ) 2 ·6H 2 Zn in O 2+ Has stronger interaction, thereby preparing a metal-organic framework; because the catechol group of the polydopamine has stronger metal chelating ability, the polydopamine can be matched with Zn 2+ Forming a stable chelate complex; meanwhile, the aromatic group of the polydopamine has hydrophobicity, and the metal organic framework is similar to a hydrophobic material, and the hydrophobic interaction enhances the mutual attraction between the polydopamine surface and the metal organic framework, so that the adsorption, nucleation and growth of the metal organic framework on the polydopamine surface can be promoted. Therefore, through the interactions, a core-shell composite material can be formed on the surface of the polydopamine, and the loading and the fixing of the metal-organic framework are realized, so that the effect of protecting BN is achieved, and the dispersibility of the BN is improved.
2. According to the BN micro powder reinforced phenolic resin for the copper-clad plate and the preparation method thereof, provided by the invention, the interaction between polydopamine and BN is enhanced by forming the polydopamine coating layer on the surface of the hydroxylated BN. Not only can improve the oxidation resistance and heat conduction capability of BN, protect BN micro powder and prolong the service life of BN micro powder, but also can improve the dispersibility of BN micro powder and avoid the phenomena of agglomeration, precipitation and the like of particles so that the BN micro powder is more uniformly distributed in a system; in addition, the metal ions in the metal organic framework have higher heat conduction performance, so that the heat conduction performance of the copper-clad plate material can be improved, the metal organic framework is loaded on the polydopamine coating layer, the effective combination of polydopamine, the metal organic framework and BN micro powder is realized, and the interface cohesiveness, the dispersity, the heat conduction performance and the chemical stability of the BN micro powder are obviously improved.
3. According to the BN micro powder reinforced phenolic resin for the copper-clad plate and the preparation method thereof, the BN micro powder reinforced phenolic resin is prepared by adding modified BN micro powder and nano organic montmorillonite into modified phenolic resin and epoxy resin and combining the synergistic effect of a flame retardant, a curing agent, a curing accelerator, isopropanol and propylene glycol. In the preparation process of the copper-clad plate, the BN micro-powder reinforced resin prepared by the invention endows the copper-clad plate with excellent heat conducting property. The high thermal conductivity of the modified BN micro powder enables the copper-clad plate to conduct heat out more quickly, effectively reduces the temperature of electronic elements and ensures the stable operation of a circuit. In addition, by adding modified BN micro powder and nano organic montmorillonite, the peel strength of the copper-clad plate is obviously enhanced, so that the copper-clad plate has better durability in a complex environment. Meanwhile, the BN micro powder reinforced phenolic resin copper-clad plate prepared by the method has excellent oxidation resistance. The addition of the modified BN micro powder effectively prevents the oxidation process of the copper-clad plate in long-time use and prolongs the service life of the copper-clad plate. Not only is favorable for improving the heat radiation effect and the working stability of the electronic equipment, but also the durability of the copper-clad plate can be enhanced and the service life of the copper-clad plate can be prolonged.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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.
Epoxy resin in this example: the Hansen EPIKOTE 828 oily liquid epoxy resin is from Guangzhou City pick rhyme chemical industry Co., ltd; ammonium polyphosphate: 100 mesh, from Zibo transoceanic chemical engineering Co., ltd; BN micropowder: hexagonal boron nitride with granularity of 20-45 μm; sucrose: from Shanghai Ala Biochemical technology Co., ltd; nano organic montmorillonite: TY-710C with a particle size of 20-50nm, from Guangzhou Yifeng chemical technology Co., ltd; glass fiber cloth: specification 2116, thickness 0.08mm, gram weight 105g/m 2 From Guangzhou and Taihe composite Co., ltd; copper foil: t2 red copper is from Shanghai Xin light metal products Co.
In the following examples and comparative examples 1 part equals 10g.
Example 1: a preparation method of BN micro powder reinforced phenolic resin for copper-clad plate comprises the following steps:
s1: uniformly mixing 110 parts of phenol and 132 parts of 37wt% formaldehyde solution, heating to 70 ℃, dropwise adding 10wt% sodium hydroxide solution until the pH value is 9, stopping dropwise adding, heating to 85 ℃, carrying out reflux reaction for 1h, adding 11 parts of phenylboronic acid, continuously carrying out reaction for 1h, and cooling to room temperature to obtain modified phenolic resin;
s2: uniformly mixing 110 parts of modified phenolic resin prepared in S1 with 50 parts of epoxy resin, heating to 50 ℃, adding 15 parts of ammonium polyphosphate, 10 parts of melamine, 0.2 part of triethanolamine phosphate, 20 parts of modified BN micro powder, 10 parts of nano montmorillonite, 120 parts of isopropanol and 80 parts of propylene glycol, uniformly mixing, and reacting for 4 hours to prepare halogen-free heat-resistant phenolic resin glue solution;
the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing 20 parts of BN micro powder and 80 parts of sucrose, and carrying out ball milling (the rotation speed of a ball mill is 450r/min, the ball milling time is 13 h), washing, ultrasonic (the ultrasonic power is 500W, the ultrasonic time is 50 min), centrifuging (the centrifugal rotation speed is 4000rpm, the centrifugal time is 20 min), and carrying out vacuum drying at 70 ℃ for 48h to obtain hydroxylated modified BN;
step (2): dispersing 20 parts of hydroxylated modified BN in a mixed solution of 600 parts of ethanol and 1400 parts of Tris buffer solution (10 mmol/L, pH value is 8), carrying out ultrasonic treatment for 30min, adding 2 parts of dopamine hydrochloride, heating to 20 ℃, and stirring at the speed of 450r/min for 6h to obtain polydopamine grafted BN;
step (3): mixing 30 parts of 4- (4-aminophenyl) -1,2, 4-triazole and 84 parts of N, N' -bis (dimethylaminomethylene) hydrazine, adding 300 parts of dimethylbenzene under nitrogen atmosphere, heating to 150 ℃, carrying out reflux reaction for 45 hours, pouring out dimethylbenzene, standing for 20 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): 60 parts of Zn (NO) is added into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 10min, dropwise adding a mixed solution of 30 parts of ligand compound and 450 parts of methanol, stirring for reacting for 24h after 1h, centrifuging for 10min at a centrifugal speed of 5000rpm for a plurality of times, washing, and carrying out vacuum drying at 70 ℃ for 48h to obtain modified BN micro powder;
an application of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
uniformly coating BN micropowder reinforced phenolic resin on glass fiber cloth (coating amount is 110 g/m) 2 ) Baking at 150deg.C for 30min to obtain prepreg; 3 prepregs are stacked together to prepare a laminate, a copper foil is placed on each of the upper surface and the lower surface of the laminate, and the laminate is heated and pressed together by using a lamination process (lamination temperature 200 ℃, lamination pressure 10MPa, lamination time 1 h), and cooled to room temperature to prepare the copper-clad plate.
Example 2: a preparation method of BN micro powder reinforced phenolic resin for copper-clad plate comprises the following steps:
a preparation method of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
s1: uniformly mixing 120 parts of phenol and 160 parts of 38wt% formaldehyde solution, heating to 75 ℃, dropwise adding 15wt% sodium hydroxide solution until the pH value is 9.5, stopping dropwise adding, heating to 90 ℃, carrying out reflux reaction for 1.5 hours, adding 18 parts of phenylboronic acid, continuously reacting for 1.5 hours, and cooling to room temperature to obtain modified phenolic resin;
s2: uniformly mixing 120 parts of modified phenolic resin prepared in S1 and 60 parts of epoxy resin, heating to 50 ℃, adding 20 parts of ammonium polyphosphate, 15 parts of melamine, 0.5 part of triethanolamine phosphate, 30 parts of modified BN micro powder, 15 parts of nano montmorillonite, 160 parts of isopropanol and 100 parts of propylene glycol, uniformly mixing, and reacting for 4 hours to prepare halogen-free heat-resistant phenolic resin glue solution;
the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing 30 parts of BN micro powder and 150 parts of sucrose, and carrying out ball milling (the rotation speed of a ball mill is 500r/min, the ball milling time is 12 h), washing, ultrasonic treatment (the ultrasonic power is 600W, the ultrasonic time is 40 min), centrifugation (the centrifugal rotation speed is 5000rpm, the centrifugal time is 15 min), and carrying out vacuum drying at 75 ℃ for 36h to obtain hydroxylated modified BN;
step (2): dispersing 30 parts of hydroxylated modified BN in a mixed solution of 1000 parts of ethanol and 2400 parts of Tris buffer solution (12 mmol/L, pH value is 8.5), carrying out ultrasonic treatment for 35min, adding 4.5 parts of dopamine hydrochloride, heating to 25 ℃, and stirring at a speed of 500r/min for 5h to obtain polydopamine grafted BN;
step (3): mixing 4- (4-aminophenyl) -1,2, 4-triazole and N, N' -bis (dimethylaminomethylene) hydrazine, adding dimethylbenzene under nitrogen atmosphere, heating to 150-160 ℃, refluxing for 45-48 hours, pouring dimethylbenzene, standing for 22 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): 120 parts of Zn (NO) is added into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 15min, dropwise adding a mixed solution of 72 parts of ligand compound and 1200 parts of methanol, stirring for reacting for 36h after 1.5h, centrifuging for 5-10min at a centrifugal speed of 5000-7000rpm for multiple times, washing, and carrying out vacuum drying at 75 ℃ for 36h to obtain modified BN micro powder;
an application of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
uniformly coating BN micropowder reinforced phenolic resin on glass fiber cloth (coating amount is 130 g/m) 2 ) Baking at 180 ℃ for 15min to obtain a prepreg; 5 prepregs are stacked together to obtain a laminate, a copper foil is placed on each of the upper surface and the lower surface of the laminate, and the laminate is heated and pressed together by using a lamination process (lamination temperature 240 ℃, lamination pressure 8MPa, lamination time 3 h), and cooled to room temperature to obtain the copper-clad plate.
Example 3: a preparation method of BN micro powder reinforced phenolic resin for copper-clad plate comprises the following steps:
a preparation method of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
s1: uniformly mixing 130 parts of phenol and 195 parts of 40wt% formaldehyde solution, heating to 80 ℃, dropwise adding 20wt% sodium hydroxide solution until the pH value is 10, stopping dropwise adding, heating to 95 ℃, carrying out reflux reaction for 2 hours, adding 26 parts of phenylboronic acid, continuously carrying out reaction for 2 hours, and cooling to room temperature to obtain modified phenolic resin;
s2: uniformly mixing 130 parts of modified phenolic resin prepared in S1 with 70 parts of epoxy resin, heating to 60 ℃, adding 30 parts of ammonium polyphosphate, 20 parts of melamine, 1.0 part of triethanolamine phosphate, 40 parts of modified BN micro powder, 20 parts of nano montmorillonite, 200 parts of isopropanol and 120 parts of propylene glycol, uniformly mixing, and reacting for 5 hours to prepare halogen-free heat-resistant phenolic resin glue solution;
the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing 40 parts of BN micro powder and 240 parts of sucrose, and carrying out ball milling (the rotation speed of a ball mill is 550r/min, the ball milling time is 11 h), washing, ultrasonic (the ultrasonic power is 650W, the ultrasonic time is 30 min), centrifuging (the centrifugal rotation speed is 7000rpm, the centrifugal time is 5 min), and carrying out vacuum drying at 80 ℃ for 24h to obtain hydroxylated modified BN;
step (2): dispersing 40 parts of hydroxylated modified BN in a mixed solution of 1600 parts of ethanol and 3600 parts of Tris buffer solution (15 mmol/L, pH value is 9), carrying out ultrasonic treatment for 40min, adding 6.4 parts of dopamine hydrochloride, heating to 30 ℃, and stirring for 4h at the speed of 550r/min to obtain polydopamine grafted BN;
step (3): mixing 4- (4-aminophenyl) -1,2, 4-triazole and N, N' -bis (dimethylaminomethylene) hydrazine, adding dimethylbenzene under nitrogen atmosphere, heating to 150-160 ℃, refluxing for 45-48 hours, pouring dimethylbenzene, standing for 20-24 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): 200 parts of Zn (NO) is added into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 20min, dropwise adding a mixed solution of 160 parts of ligand compound and 3200 parts of methanol, stirring for 48h after completion of the dropwise adding, centrifuging for multiple times (the centrifugal speed is 7000rpm, the centrifugal time is 5 min), washing, and carrying out vacuum drying at 80 ℃ for 24h to obtain modified BN micro powder;
an application of BN micro powder reinforced phenolic resin for copper-clad plates comprises the following steps:
uniformly coating BN micropowder reinforced phenolic resin on glass fiber cloth (coating amount is 150 g/m) 2 ) Baking at 200deg.C for 10min to obtain prepreg; and stacking 8 prepregs together to obtain a laminated sheet, placing a piece of copper foil on each of the upper surface and the lower surface of the laminated sheet, heating and pressing the laminated sheet and the copper foil together by using a lamination process (the lamination temperature is 250 ℃, the lamination pressure is 5MPa, and the lamination time is 5 h), and cooling the laminated sheet to room temperature to obtain the copper-clad plate.
Comparative example 1: the BN micro powder reinforced phenolic resin comprises the following components in parts by weight: 110 parts of modified phenolic resin, 50 parts of epoxy resin, 15 parts of flame retardant, 10 parts of curing agent, 0.2 part of curing accelerator, 20 parts of BN micro powder, 10 parts of nano organic montmorillonite, 120 parts of isopropanol and 80 parts of propylene glycol, wherein in comparative example 1, the modified BN micro powder is replaced by common BN micro powder with the same quality, the preparation steps of the modified BN micro powder are omitted, and other steps and processes are the same as in example 1.
Comparative example 2: the BN micro powder reinforced phenolic resin comprises the following components in parts by weight: 110 parts of phenolic resin, 50 parts of epoxy resin, 15 parts of flame retardant, 10 parts of curing agent, 0.2 part of curing accelerator, 20 parts of modified BN micro powder, 10 parts of nano organic montmorillonite, 120 parts of isopropanol and 80 parts of propylene glycol, wherein the modified phenolic resin is replaced by the phenolic resin with the same quality (brand 2123, from Jinan Dahui chemical technology Co., ltd.) in comparative example 2, and other steps and processes are the same as in example 1.
Comparative example 3: the BN micro powder reinforced phenolic resin comprises the following components in parts by weight: 110 parts of modified phenolic resin, 50 parts of epoxy resin, 15 parts of flame retardant, 10 parts of curing agent, 0.2 part of curing accelerator, 20 parts of modified BN micro powder, 20 parts of isopropanol and 80 parts of propylene glycol, and no nano organic montmorillonite is added in comparative example 3, and the other steps and processes are the same as in example 1.
Comparative example 4: a preparation method of BN micro powder reinforced phenolic resin for copper-clad plate comprises the following steps:
the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing 30 parts of BN micro powder and 150 parts of sucrose, and carrying out ball milling (the rotation speed of a ball mill is 500r/min, the ball milling time is 12 h), washing, ultrasonic treatment (the ultrasonic power is 600W, the ultrasonic time is 40 min), centrifugation (the centrifugal rotation speed is 5000rpm, the centrifugal time is 15 min), and carrying out vacuum drying at 75 ℃ for 36h to obtain hydroxylated modified BN;
step (2): dispersing 30 parts of hydroxylated modified BN in a mixed solution of 1000 parts of ethanol and 2400 parts of Tris buffer solution (12 mmol/L, pH value is 8.5), carrying out ultrasonic treatment for 35min, adding 30 parts of dopamine hydrochloride, heating to 25 ℃, and stirring at a speed of 500r/min for 5h to obtain polydopamine grafted BN;
step (3): mixing 4- (4-aminophenyl) -1,2, 4-triazole and N, N' -bis (dimethylaminomethylene) hydrazine, adding dimethylbenzene under nitrogen atmosphere, heating to 150-160 ℃, refluxing for 45-48 hours, pouring dimethylbenzene, standing for 22 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): 120 parts of Zn (NO) is added into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 15min, dropwise adding a mixed solution of 72 parts of ligand compound and 1200 parts of methanol, stirring for reacting for 36h after 1.5h, centrifuging for 5-10min at a centrifugal speed of 5000-7000rpm for multiple times, washing, and carrying out vacuum drying at 75 ℃ for 36h to obtain modified BN micro powder;
compared with example 2, the mass ratio of the hydroxylation modified BN to the dopamine hydrochloride in the comparative example 4 is 1:1, the rest of the procedure is the same as in example 2.
Experiment
Taking the copper clad laminates obtained in examples 1-3 and comparative examples 1-4, preparing samples, respectively detecting the performances of the samples and recording the detection results:
thermal conductivity was measured according to the steady state method of ASTM D5470 standard, experimental procedure: the square of specimen size 13 x 13mm was cut, the specimen was placed in a steady state thermal conductivity test instrument at room temperature, the test instrument was to apply a thermal power of 5W, test for 30min, and data recorded.
The peel strength was determined according to IPC-TM-650, 2.4.8 edition copper-clad plate peel and impact test method, experimental procedure: and bonding the copper-clad plate and the substrate together through hot pressing, and cutting a sample to be tested of 30mm multiplied by 50mm from the bonded sample. The test specimens were placed in the test grips of the peel strength tester at room temperature and secured as necessary. The test was started, the peeling speed was set at 50mm/min, the peeling angle was set at 90 °, and data were recorded.
Thermal aging test: and (3) placing the sample to be tested in a high-temperature environment of 150 ℃ for baking treatment, wherein the total duration is 240 hours. The aged samples were subjected to peel strength testing to investigate the effect of high temperature treatment time on peel strength. The method is used for evaluating the antioxidation effect of the copper-clad plate.
From the data in the above table, the following conclusions can be clearly drawn:
1. compared with comparative example 1, the samples of examples 1-3 have improved thermal conductivity, peeling strength and oxidation resistance, which shows that the modified BN micro powder prepared by the invention has obviously better enhancement effect than the common BN micro powder, and can obviously enhance the thermal conductivity, peeling strength and oxidation resistance of the copper-clad plate.
2. Compared with the examples 1-3, the thermal conductivity, the peeling strength and the antioxidation effect of the sample of the comparative example 2 are all obviously reduced, which proves that compared with the phenolic resin, the modified phenolic resin prepared by the invention can improve the thermal conductivity, the peeling strength and the antioxidation of the copper-clad plate; the peeling strength of comparative example 3 is reduced, and the invention can improve the peeling strength of the copper-clad plate by the synergistic effect of the nano organic montmorillonite and BN micro powder.
3. Compared with examples 1-3, the thermal conductivity, the peeling strength and the antioxidation effect of the sample in comparative example 4 are all reduced, which shows that the modified BN micro powder prepared by the invention is influenced by the mixture ratio of each reagent in the preparation process, and the selection of the reagent mixture ratio in the range can improve each performance of the modified BN micro powder, thereby enhancing the heat dissipation effect and the working stability of the copper-clad plate and prolonging the service life of the copper-clad plate.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of BN micro powder reinforced phenolic resin for copper-clad plates is characterized by comprising the following steps: the method comprises the following steps:
s1: uniformly mixing phenol and formaldehyde solution, heating to 70-80 ℃, dropwise adding sodium hydroxide solution until the pH value is 9-10, stopping dropwise adding, heating to 85-95 ℃, carrying out reflux reaction for 1-2h, adding phenylboronic acid, continuously carrying out reaction for 1-2h, and cooling to room temperature to obtain modified phenolic resin;
s2: uniformly mixing the modified phenolic resin prepared in the step S1 with epoxy resin, heating to 40-60 ℃, adding a flame retardant, a curing agent, a curing accelerator, modified BN micro powder, nano organic montmorillonite, isopropanol and propylene glycol, uniformly mixing, and reacting for 3-5 hours to prepare the BN micro powder reinforced phenolic resin.
2. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is disclosed in claim 1, is characterized in that: the preparation method of the modified BN micro powder comprises the following steps:
step (1): uniformly mixing BN micro powder and sucrose, ball milling, washing, ultrasonic treatment, centrifuging, and vacuum drying at 70-80 ℃ for 24-48 hours to obtain hydroxylated modified BN;
step (2): dispersing the hydroxylation modified BN in a mixed solution of ethanol and Tris buffer solution, carrying out ultrasonic treatment for 30-40min, adding dopamine hydrochloride, heating to 20-30 ℃, and stirring at the speed of 450-550r/min for 4-6h to obtain polydopamine grafted BN;
step (3): mixing 4- (4-aminophenyl) -1,2, 4-triazole and N, N' -bis (dimethylaminomethylene) hydrazine, adding dimethylbenzene under nitrogen atmosphere, heating to 150-160 ℃, carrying out reflux reaction for 46-48 hours, pouring dimethylbenzene, standing for 20-24 hours to separate out crystals, and filtering, cleaning and drying to obtain a ligand compound;
step (4): adding Zn (NO) into the reaction system of the step (2) 3 ) 2 ·6H 2 O, carrying out ultrasonic treatment for 10-20min, dropwise adding a mixed solution of a ligand compound and methanol, stirring for reacting for 24-48h after 1-2h, centrifuging for multiple times, washing, and vacuum drying at 70-80 ℃ for 24-48h to obtain modified BN micro powder.
3. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is characterized by comprising the following steps of: in the step (1), the mass ratio of BN to sucrose is 1: (4-6).
4. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is characterized by comprising the following steps of: the concentration of the Tris buffer solution in the step (2) is 10-15mmol/L, and the pH value is 8-9.
5. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is disclosed in claim 1, is characterized in that: the BN micro powder reinforced phenolic resin in the step S2 comprises the following components in parts by weight:
110-130 parts of modified phenolic resin, 50-70 parts of epoxy resin, 15-30 parts of flame retardant, 10-20 parts of curing agent, 0.2-1.0 part of curing accelerator, 20-40 parts of modified BN micro powder, 10-20 parts of nano organic montmorillonite, 120-200 parts of isopropanol and 80-120 parts of propylene glycol.
6. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is disclosed in claim 5, is characterized in that: the curing agent is melamine.
7. The preparation method of the BN micro powder reinforced phenolic resin for the copper-clad plate, which is disclosed in claim 5, is characterized in that: the curing accelerator is triethanolamine phosphate.
8. A BN micropowder reinforced phenolic resin for copper-clad plates produced by the production method according to any one of claims 1 to 7.
9. The use of BN micropowder reinforced phenolic resin for copper-clad plates according to claim 8, characterized in that: the method comprises the following steps:
uniformly coating BN micropowder reinforced phenolic resin on glass fiber cloth, and baking at 150-200 ℃ for 10-30min to obtain a prepreg; 3-8 prepregs are stacked together to prepare a laminated sheet, a copper foil is respectively placed on the upper surface and the lower surface of the laminated sheet, and the laminated sheet and the copper foil are heated and pressed together by using a lamination process and cooled to room temperature to prepare the copper-clad plate.
10. The application of the BN micro powder reinforced phenolic resin for the copper-clad plate as claimed in claim 9, which is characterized in that: the lamination process conditions were: laminating temperature is 200-250 ℃, laminating pressure is 5-10MPa, and laminating time is 1-5h.
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