CN116515244A - Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same - Google Patents

Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same Download PDF

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CN116515244A
CN116515244A CN202310520490.7A CN202310520490A CN116515244A CN 116515244 A CN116515244 A CN 116515244A CN 202310520490 A CN202310520490 A CN 202310520490A CN 116515244 A CN116515244 A CN 116515244A
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epoxy resin
parts
boron nitride
weight
nitrogen
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CN116515244B (en
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朱利明
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Jiangsu Yaohong Electronics Co ltd
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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 a nitrogen-phosphorus composite modified epoxy resin and a copper-clad plate prepared from the same. The invention modifies the hexagonal boron nitride nanosheets to prepare the flame retardant additive. By utilizing the self-polymerization property of polydopamine, the polydopamine and polyethyleneimine are jointly deposited on the surface of boron nitride, and active groups such as amino, hydroxyl and the like are introduced, so that the boron nitride is prevented from agglomerating. The lignin is used as a charring agent, has strong carbon forming capability, can inhibit the combustion of a polymer, is grafted onto polyethyleneimine, and simultaneously is introduced with triethylene tetramine and 9.10-dihydro-10-phosphaphenanthrene-10 oxide to prepare the intumescent flame retardant additive with high-efficiency flame retardant property. The hexagonal boron nitride nanosheets have good heat conducting property, so that the heat release of the epoxy resin material is controlled on one hand; on the other hand, the flame retardant efficiency is improved after the modification of nitrogen and phosphorus, and the high-efficiency flame retardance can be realized with less additive amount.

Description

Phosphorus-nitrogen composite modified epoxy resin and copper-clad plate prepared from same
Technical Field
The invention relates to the technical field of copper-clad plates, in particular to a nitrogen-phosphorus composite modified epoxy resin and a copper-clad plate prepared from the same.
Background
The copper-clad plate is a substrate material in a printed circuit board and plays an important role in the printed circuit board. Its main functions include connection and conduction of printed circuit board, support, insulation, etc. The material of the copper-clad plate can affect the transmission rate, capacity loss and characteristic resistance of the circuit signal.
The epoxy resin is a common high molecular polymer, can show various excellent performances such as chemical corrosion resistance, good insulativity and the like after being heated and solidified, and has obvious advantages in the field of copper-clad plate preparation. However, since the epoxy resin material itself is flammable and has poor heat conductive properties, if no modification process is performed, thermal runaway may occur in the microelectronics field where a large amount of heat is accumulated, and fire is caused in serious cases, resulting in property loss and casualties. Traditional halogen flame retardants, such as bromine flame retardants, have higher flame retardant efficiency and price advantages, but can discharge toxic gases harmful to human bodies in the use process, and seriously pollute the atmosphere. Therefore, the application of halogen-free flame retardant, especially phosphorus and nitrogen containing flame retardant in epoxy resin is a new direction of research.
Disclosure of Invention
The invention aims to provide nitrogen-phosphorus composite modified epoxy resin and a copper-clad plate prepared from the same, so as to solve the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a nitrogen-phosphorus composite modified epoxy resin and a copper-clad plate prepared from the same, comprising the following steps:
step 1: mixing trihydroxy aminomethane with deionized water, adding dilute hydrochloric acid, regulating the pH value, adding dopamine hydrochloride and polyethylenimine, stirring for 15-30 min, adding hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 3-6 h, heating to 50-65 ℃ in a water bath, standing for 20-30 h, carrying out vacuum filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution, and stirring in a water bath for 1-2 h; adding hydrochloric acid to regulate pH of the solution, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding purified alkali lignin and modified boron nitride nanosheets into a sodium hydroxide solution, adding glutaraldehyde after ultrasonic dispersion treatment, continuously stirring for 1-2 h, and obtaining lignin modified boron nitride after suction filtration, washing and drying;
step 4: mixing lignin modified boron nitride, triethylene tetramine and polyethylene glycol 1500, stirring and reacting for 30-40 min, washing, filtering, drying, grinding, dispersing in absolute ethyl alcohol, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tin tetrachloride, reacting for 10-15 min at 60-80 ℃, washing, filtering, and drying to obtain a flame retardant additive;
step 5: heating bisphenol A epoxy resin to 40-50 ℃, adding a curing agent, a curing accelerator, acetone, a flame retardant additive and an antioxidant, and uniformly mixing and stirring to obtain epoxy resin glue solution; immersing the glass fiber cloth into the glass fiber cloth, taking out, drying at 100-120 ℃ for 5-8 min to obtain a prepreg, attaching copper foil, and hot-press molding at 180-200 ℃ and 2-2.5 MPa to obtain the copper-clad plate.
Further, in the step 1, the components are mixed by weight of 0.7 to 0.9 part of trihydroxy aminomethane, 450 to 500 parts of deionized water, 1 to 2 parts of dopamine hydrochloride, 1 to 2 parts of polyethyleneimine and 3 to 5 parts of hexagonal boron nitride nano-sheet.
Further, in the step 1, dilute hydrochloric acid is added to adjust the pH value to 7.5-8.5.
Further, in the step 2, the pH value of the alkaline solution is 8-10.
In step 2, the pH of the solution is adjusted to 3-4 by hydrochloric acid.
Further, in the step 3, the amount of each component is 1 to 2 parts by weight of purified alkali lignin, 5 to 8 parts by weight of modified boron nitride nano-sheet, 200 to 350 parts by weight of sodium hydroxide solution and 3.5 to 4.8 parts by weight of glutaraldehyde.
Further, in the step 4, the dosage of each component is, by weight, 8-10 parts of lignin modified boron nitride, 20-27.5 parts of triethylene tetramine, 2-3 parts of polyethylene glycol 1500, 200-300 parts of absolute ethyl alcohol, 2-4.8 parts of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1-1.5 parts of stannic chloride.
Further, in the step 5, the usage amount of each component is 90-100 parts by weight of bisphenol A epoxy resin, 4.5-6.9 parts by weight of curing agent, 0.3-0.4 part by weight of curing accelerator, 30-40 parts by weight of acetone, 20-35 parts by weight of flame retardant additive and 1-2 parts by weight of antioxidant.
Further, in the step 5, the curing agent is any one of diethylenetriamine, tetraethylenepentamine, phthalic anhydride and m-phenylenediamine; the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole and 2-phenylimidazole; the antioxidant is any one or more of antioxidant 1010, antioxidant 168 and antioxidant 264.
Compared with the prior art, the invention has the following beneficial effects: according to the invention, the hexagonal boron nitride nanosheets are modified to prepare the flame retardant additive, and the flame retardant additive is applied to the preparation of the epoxy resin-based copper-clad plate. Because boron nitride is easy to agglomerate, the compatibility with epoxy resin is poor, and the boron nitride needs to be modified for use. By utilizing the self-polymerization property of polydopamine, the polydopamine and polyethyleneimine are jointly deposited on the surface of boron nitride, and active groups such as amino, hydroxyl and the like are introduced while the dispersibility of the boron nitride is improved. The lignin contains an aromatic structure, has strong carbon forming capability and can reduce the combustion rate of the polymer, so that the lignin is used as a carbonizing agent to be grafted onto the polyethyleneimine; simultaneously introducing triethylene tetramine and 9, 10-dihydro-10-phosphaphenanthrene-10 oxide to carry out phosphorus-nitrogen modification on lignin, and preparing the intumescent flame retardant additive with high-efficiency flame retardant property. The hexagonal boron nitride nanosheets have good heat conducting property, are beneficial to controlling the heat release of the epoxy resin material, and have better flame retardant effect after being modified by nitrogen and phosphorus.
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.
The main materials and sources thereof in the following examples are as follows:
trihydroxyaminomethane (CAS number: 77-86-1), acetone (CAS number: 67-64-1), dilute hydrochloric acid (CAS number: 7647-01-0), tin tetrachloride (CAS number: 7646-78-8), dopamine hydrochloride (CAS number: 62-31-7), absolute ethyl alcohol (CAS number: 64-17-5), sodium hydroxide (CAS number: 1310-73-2), glutaraldehyde (CAS number: 111-30-8), triethylenetetramine (CAS number: 112-24-3) were purchased from Ala-dine; hexagonal boron nitride nanoplatelets are purchased from napus material, su zhou and polyethylene glycol 1500 from Jiangsu de Chemie Co., ltd; polyethyleneimine (CAS number 9002-98-6) purchased from Baiolaibo, has an average molecular weight of 5000; alkali lignin (CAS number: 8068-05-1) purchased from Yu Lingyu chemical Co., ltd; 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (CAS number 35948-25-5) was purchased from alpha chemical Co., ltd; bisphenol A epoxy resin is purchased from a new material, product number WSR 6101; phthalic anhydride (CAS number: 85-44-9) was purchased from Chu Hong chemical industry; 2-methylimidazole (CAS number 693-98-1) was purchased from Kangzhuang environmental protection technology Co., ltd; antioxidant 1010 is purchased from very easy new materials limited.
Example 1:
step 1: mixing 0.7g of trihydroxy aminomethane with 450g of deionized water, adding dilute hydrochloric acid to adjust the pH value to 8.0, adding 1g of dopamine hydrochloride and 1g of polyethylenimine, stirring for 15min, adding 3g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 3h, heating to 50 ℃ in a water bath, standing for 20h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in alkaline solution with pH value of 8.0, and stirring in water bath for 1h; adding hydrochloric acid to adjust the pH of the solution to 3, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1g of purified alkali lignin and 5g of modified boron nitride nanosheets into 200g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 10min, adding 3.5g of glutaraldehyde, continuously stirring for 1h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 8g of lignin modified boron nitride, 20g of triethylene tetramine and 2g of polyethylene glycol 1500, stirring and reacting for 30min, washing, filtering, drying, grinding, dispersing in 200g of absolute ethyl alcohol, adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1g of stannic chloride, reacting for 10min at 60 ℃, washing, filtering and drying to obtain a flame retardant additive;
step 5: 90kg of bisphenol A epoxy resin is heated to 40 ℃, 4.5kg of phthalic anhydride, 0.3kg of 2-methylimidazole, 30kg of acetone, 20kg of flame retardant additive and 1kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 100 ℃ for 5min to obtain a prepreg, attaching copper foil, and hot-press molding at 180 ℃ and 2MPa to obtain the copper-clad plate.
Example 2:
step 1: mixing 0.7g of trihydroxy aminomethane with 460g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 7.9, adding 1.1g of dopamine hydrochloride and 1g of polyethyleneimine, stirring for 20min, adding 3.3g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 3h, heating to 55 ℃ in a water bath, standing for 22h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution with the pH value of 9, and stirring in a water bath for 1h; adding hydrochloric acid to adjust the pH value of the solution to 3.5, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.3g of purified alkali lignin and 5.4g of modified boron nitride nanosheets into 230g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 15min, adding 3.6g of glutaraldehyde, continuously stirring for 1h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 8.2g of lignin modified boron nitride, 22.4g of triethylene tetramine and 2.2g of polyethylene glycol 1500, stirring and reacting for 35min, washing, filtering, drying, grinding, dispersing in 220g of absolute ethyl alcohol, adding 2.6g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.4g of stannic chloride, reacting for 15min at 70 ℃, washing, filtering, and drying to obtain a flame retardant additive;
step 5: 92kg of bisphenol A epoxy resin is heated to 45 ℃, 4.8kg of phthalic anhydride, 0.37kg of 2-methylimidazole, 32kg of acetone, 23.5kg of flame retardant additive and 1.3kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 105 ℃ for 7min to obtain a prepreg, attaching copper foil, and hot-press molding at 185 ℃ and 2.1MPa to obtain the copper-clad plate.
Example 3:
step 1: mixing 0.75g of trihydroxy aminomethane with 460g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 7.8, adding 1.5g of dopamine hydrochloride and 1.4g of polyethyleneimine, stirring for 20min, adding 3.6g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 4h, heating to 60 ℃ in a water bath, standing for 24h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in alkaline solution with pH value of 8.5, and stirring in water bath for 2h; adding hydrochloric acid to adjust the pH value of the solution to 3.45, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.7g of purified alkali lignin and 7.4g of modified boron nitride nanosheets into 250g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 18min, adding 3.9g of glutaraldehyde, continuously stirring for 1.5h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 8.8g of lignin modified boron nitride, 26.4g of triethylene tetramine and 2.4g of polyethylene glycol 1500, stirring and reacting for 36min, washing, filtering, drying, grinding, dispersing in absolute ethyl alcohol of which the concentration is 230g, adding 3.2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.3g of stannic chloride, reacting for 12min at 75 ℃, washing, filtering and drying to obtain a flame retardant additive;
step 5: 93kg of bisphenol A epoxy resin is heated to 50 ℃, 5.8kg of phthalic anhydride, 0.34kg of 2-methylimidazole, 34kg of acetone, 24kg of flame retardant additive and 1.3kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 110 ℃ for 6.5min to obtain a prepreg, attaching copper foil, and hot-press molding at 190 ℃ and 2.4MPa to obtain the copper-clad plate.
Example 4:
step 1: mixing 0.81g of trihydroxy aminomethane with 480g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 7.85, adding 1.65g of dopamine hydrochloride and 1.89g of polyethyleneimine, stirring for 25min, adding 4.2g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 3.5h, heating to 65 ℃ in a water bath, standing for 27h, carrying out vacuum filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution with the pH value of 9.5, and stirring in a water bath for 1.6h; adding hydrochloric acid to adjust the pH value of the solution to 3.45, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.75g of purified alkali lignin and 7.2g of modified boron nitride nanosheets into 300g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 15min, adding 4g of glutaraldehyde, continuously stirring for 1.5h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 8.4g of lignin modified boron nitride, 24.3g of triethylene tetramine and 2.6g of polyethylene glycol 1500, stirring and reacting for 35min, washing, filtering, drying, grinding, dispersing in 250g of absolute ethyl alcohol, adding 3.3g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.25g of stannic chloride, reacting for 13min at 75 ℃, washing, filtering, and drying to obtain a flame retardant additive;
step 5: heating 95kg of bisphenol A epoxy resin to 45 ℃, adding 5.6kg of phthalic anhydride, 0.33kg of 2-methylimidazole, 34kg of acetone, 29kg of flame retardant additive and 1.45kg of antioxidant 1010, and uniformly mixing and stirring to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 115 ℃ for 5min to obtain a prepreg, attaching copper foil, and hot-press molding at 195 ℃ and 2.1MPa to obtain the copper-clad plate.
Example 5:
step 1: mixing 0.85g of trihydroxy aminomethane with 495g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 8.2, adding 1.7g of dopamine hydrochloride and 1.8g of polyethyleneimine, stirring for 25min, adding 4.3g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 5h, heating to 60 ℃ in a water bath, standing for 26h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution with the pH value of 9.5, and stirring in a water bath for 1.5h; adding hydrochloric acid to adjust the pH value of the solution to 3.65, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.68g of purified alkali lignin and 7.42g of modified boron nitride nanosheets into 325g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 18min, adding 4.5g of glutaraldehyde, continuously stirring for 2h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 9.3g of lignin modified boron nitride, 27g of triethylene tetramine and 2.8g of polyethylene glycol 1500, stirring and reacting for 35min, washing, filtering, drying, grinding, dispersing in 275g of absolute ethyl alcohol, adding 4g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.6g of stannic chloride, reacting at 75 ℃ for 12min, washing, filtering and drying to obtain a flame retardant additive;
step 5: heating 98kg of bisphenol A epoxy resin to 50 ℃, adding 6.2kg of phthalic anhydride, 0.37kg of 2-methylimidazole, 36kg of acetone, 31kg of flame retardant additive and 1.58kg of antioxidant 1010, and uniformly mixing and stirring to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 115 ℃ for 7.5min to obtain a prepreg, attaching copper foil, and hot-press molding at 190 ℃ and 2.4MPa to obtain the copper-clad plate.
Example 6:
step 1: mixing 0.9g of trihydroxy aminomethane with 500g of deionized water, adding 1mol/L dilute hydrochloric acid, regulating the pH value to 8.5, adding 2g of dopamine hydrochloride and 2g of polyethylenimine, stirring for 30min, adding 5g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 6h, heating to 65 ℃ in a water bath, standing for 30h, carrying out vacuum filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution with the pH value of 10, and stirring in a water bath for 2h; adding hydrochloric acid to adjust the pH value of the solution to 4, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 2g of purified alkali lignin and 8g of modified boron nitride nanosheets into 350g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 20min, adding 4.8g of glutaraldehyde, continuously stirring for 2h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 10g of lignin modified boron nitride, 27.5g of triethylene tetramine and 3g of polyethylene glycol 1500, stirring and reacting for 40min, washing, filtering, drying, grinding, dispersing in 300g of absolute ethyl alcohol, adding 4.8g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.5g of stannic chloride, reacting for 15min at 80 ℃, washing, filtering and drying to obtain a flame retardant additive;
step 5: heating 100kg of bisphenol A epoxy resin to 50 ℃, adding 6.9kg of phthalic anhydride, 0.4kg of 2-methylimidazole, 40kg of acetone, 35kg of flame retardant additive and 2kg of antioxidant 1010, and uniformly mixing and stirring to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 120 ℃ for 8min to obtain a prepreg, attaching copper foil, and hot-press molding at 200 ℃ and 2.5MPa to obtain the copper-clad plate.
Comparative example 1:
the hexagonal boron nitride nanosheets are replaced by nanosilicon dioxide.
Step 1: mixing 0.7g of trihydroxy aminomethane with 450g of deionized water, adding dilute hydrochloric acid to adjust the pH value to 8.0, adding 1g of dopamine hydrochloride and 1g of polyethylenimine, stirring for 15min, adding 3g of nano silicon dioxide, carrying out ultrasonic dispersion treatment for 3h, heating to 50 ℃ in a water bath, standing for 20h, carrying out vacuum filtration, washing and drying to obtain modified nano silicon dioxide;
step 2: soaking alkali lignin in alkaline solution with pH value of 8.0, and stirring in water bath for 1h; adding hydrochloric acid to adjust the pH of the solution to 3, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1g of purified alkali lignin and 5g of modified nano silicon dioxide into 200g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 10min, adding 3.5g of glutaraldehyde, continuously stirring for 1h, and performing suction filtration, washing and drying to obtain lignin modified silicon dioxide;
step 4: mixing 8g of lignin modified silicon dioxide, 20g of triethylene tetramine and 2g of polyethylene glycol 1500, stirring and reacting for 30min, washing, filtering, drying, grinding, dispersing in absolute ethyl alcohol, adding 2g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1g of stannic chloride, reacting for 10min at 60 ℃, washing, filtering, and drying to obtain a flame retardant additive;
step 5: 90kg of bisphenol A epoxy resin is heated to 40 ℃, 4.5kg of phthalic anhydride, 0.3kg of 2-methylimidazole, 30kg of acetone, 20kg of flame retardant additive and 1kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 100 ℃ for 5min to obtain a prepreg, attaching copper foil, and hot-press molding at 180 ℃ and 2MPa to obtain the copper-clad plate.
Comparative example 2:
graphene oxide is used for replacing hexagonal boron nitride nano-sheets.
Step 1: mixing 0.7g of trihydroxy aminomethane with 460g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 7.9, adding 1.1g of dopamine hydrochloride and 1g of polyethyleneimine, stirring for 20min, adding 3.3g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 3h, heating to 55 ℃ in a water bath, standing for 22h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution with the pH value of 9, and stirring in a water bath for 1h; adding hydrochloric acid to adjust the pH value of the solution to 3.5, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.3g of purified alkali lignin and 5.4g of modified boron nitride nanosheets into 230g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 15min, adding 3.6g of glutaraldehyde, continuously stirring for 1h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: mixing 8.2g of lignin modified boron nitride, 22.4g of triethylene tetramine and 2.2g of polyethylene glycol 1500, stirring and reacting for 35min, washing, filtering, drying, grinding, dispersing in absolute ethyl alcohol, adding 2.6g of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1.4g of stannic chloride, reacting for 15min at 70 ℃, washing, filtering and drying to obtain the flame retardant additive;
step 5: 92kg of bisphenol A epoxy resin is heated to 45 ℃, 4.8kg of phthalic anhydride, 0.37kg of 2-methylimidazole, 32kg of acetone, 23.5kg of flame retardant additive and 1.3kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 105 ℃ for 7min to obtain a prepreg, attaching copper foil, and hot-press molding at 185 ℃ and 2.1MPa to obtain the copper-clad plate.
Comparative example 3:
no modification with nitrogen and phosphorus was performed.
Step 1: mixing 0.75g of trihydroxy aminomethane with 460g of deionized water, adding dilute hydrochloric acid, regulating the pH value to 7.8, adding 1.5g of dopamine hydrochloride and 1.4g of polyethyleneimine, stirring for 20min, adding 3.6g of hexagonal boron nitride nanosheets, carrying out ultrasonic dispersion treatment for 4h, heating to 60 ℃ in a water bath, standing for 24h, carrying out vacuum suction filtration, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in alkaline solution with pH value of 8.5, and stirring in water bath for 2h; adding hydrochloric acid to adjust the pH value of the solution to 3.45, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding 1.7g of purified alkali lignin and 7.4g of modified boron nitride nanosheets into 250g of sodium hydroxide solution, performing ultrasonic dispersion treatment for 18min, adding 3.9g of glutaraldehyde, continuously stirring for 1.5h, and performing suction filtration, washing and drying to obtain lignin modified boron nitride;
step 4: 93kg of bisphenol A epoxy resin is heated to 50 ℃, 5.8kg of phthalic anhydride, 0.34kg of 2-methylimidazole, 34kg of acetone, 24kg of lignin modified boron nitride and 1.3kg of antioxidant 1010 are added, and the mixture is uniformly mixed and stirred to obtain epoxy resin glue solution; immersing the glass fiber cloth therein, taking out, drying at 110 ℃ for 6.5min to obtain a prepreg, attaching copper foil, and hot-press molding at 190 ℃ and 2.4MPa to obtain the copper-clad plate.
Experiment:
flame retardancy: testing according to the method specified in UL 94;
thermal stability: heating to 800 ℃ at a heating rate of 5 ℃/min under nitrogen atmosphere, and recording the temperature at which 10% of the weight loss occurs, which is recorded as T 10％ ；
And (3) testing heat conduction performance: the thermal diffusivity (α) was measured using a laser flash instrument (FLA-467), the sample diameter was 100mm, the sample thickness was 2mm, and the sample thermal conductivity was calculated by the formula λ=α×c p ×ρ；
The experimental results are shown in the following table.
Conclusion:
from the data of examples 1-6 in the table, the invention grafts lignin on the boron nitride surface polydopamine and uses nitrogen and phosphorus for modification, and the prepared phosphorus-nitrogen composite modified epoxy resin copper-clad plate has good flame retardance, heat conduction and heat resistance. With the example 1 as a reference, the data of the comparative example 1 show that the flame retardant effect of modified boron nitride by lignin and nitrogen and phosphorus is better when the equivalent flame retardant is added, and meanwhile, the heat conduction performance of the material can be improved by the boron nitride; taking example 2 as a reference, the data of comparative example 2 shows that although graphene oxide and hexagonal boron nitride nanoplatelets have similar structures, the latter has more excellent heat conduction performance; the data of comparative example 3, which is referred to in example 3, shows that the flame retardant properties are improved after nitrogen and phosphorus modification.
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 nitrogen-phosphorus composite modified epoxy resin is characterized in that: the preparation method of the epoxy resin comprises the following steps:
step 1: mixing trihydroxy aminomethane with deionized water, adding dilute hydrochloric acid, regulating the pH value, adding dopamine hydrochloride and polyethylenimine, stirring, adding hexagonal boron nitride nanosheets, carrying out ultrasonic treatment for 3-6 hours, heating, standing, vacuum suction filtering, washing and drying to obtain modified boron nitride nanosheets;
step 2: soaking alkali lignin in an alkaline solution, and stirring in a water bath; adding hydrochloric acid to regulate pH of the solution, centrifuging, filtering, washing and drying to constant weight to obtain purified alkali lignin;
step 3: adding purified alkali lignin and modified boron nitride nanosheets into a sodium hydroxide solution, adding glutaraldehyde after ultrasonic dispersion treatment, continuously stirring for 1-2 h, and obtaining lignin modified boron nitride after suction filtration, washing and drying;
step 4: mixing lignin modified boron nitride, triethylene tetramine and polyethylene glycol 1500, stirring, washing, filtering, drying, grinding, dispersing in absolute ethyl alcohol, adding 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and tin tetrachloride, reacting for 10-15 min at 60-80 ℃, washing, filtering, drying to obtain a flame retardant additive;
step 5: heating bisphenol A epoxy resin to 40-50 ℃, adding a curing agent, a curing accelerator, acetone, a flame retardant additive and an antioxidant, mixing and stirring uniformly to obtain the epoxy resin.
2. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 1, the components are mixed by weight of 0.7 to 0.9 part of trihydroxy aminomethane, 450 to 500 parts of deionized water, 1 to 2 parts of dopamine hydrochloride, 1 to 2 parts of polyethyleneimine and 3 to 5 parts of hexagonal boron nitride nano-sheet.
3. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 1, dilute hydrochloric acid is added to adjust the pH value to 7.5-8.5.
4. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 2, the pH value of the alkaline solution is 8-10.
5. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 2, the pH of the solution is regulated to 3-4 by hydrochloric acid.
6. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 3, the consumption of each component is 1-2 parts by weight of purified alkali lignin, 5-8 parts by weight of modified boron nitride nano-sheet, 200-350 parts by weight of sodium hydroxide solution and 3.5-4.8 parts by weight of glutaraldehyde.
7. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 4, the dosage of each component is 8 to 10 parts by weight of lignin modified boron nitride, 20 to 27.5 parts by weight of triethylene tetramine, 2 to 3 parts by weight of polyethylene glycol 1500, 200 to 300 parts by weight of absolute ethyl alcohol, 2 to 4.8 parts by weight of 9, 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 1 to 1.5 parts by weight of stannic chloride.
8. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 5, the usage amount of each component is 90-100 parts by weight of bisphenol A epoxy resin, 4.5-6.9 parts by weight of curing agent, 0.3-0.4 part by weight of curing accelerator, 30-40 parts by weight of acetone, 20-35 parts by weight of flame retardant additive and 1-2 parts by weight of antioxidant.
9. The nitrogen-phosphorus composite modified epoxy resin according to claim 1, wherein: in the step 5, the curing agent is any one of diethylenetriamine, tetraethylenepentamine, phthalic anhydride and m-phenylenediamine; the curing accelerator is any one of 4-dimethylaminopyridine, 2-methylimidazole and 2-phenylimidazole; the antioxidant is any one or more of antioxidant 1010, antioxidant 168 and antioxidant 264.
10. A copper-clad plate prepared from nitrogen-phosphorus composite modified epoxy resin is characterized in that: the preparation method of the copper-clad plate specifically comprises the following steps: immersing glass fiber cloth into the epoxy resin glue solution according to any one of claims 1-9, taking out, drying at 100-120 ℃ for 5-8 min to obtain a prepreg, covering with copper foil, and hot-press molding at 180-200 ℃ and 2-2.5 MPa to obtain the copper-clad plate.
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