CN114773596B - BT resin prepreg glue solution and preparation method and application thereof - Google Patents
BT resin prepreg glue solution and preparation method and application thereof Download PDFInfo
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- CN114773596B CN114773596B CN202210325166.5A CN202210325166A CN114773596B CN 114773596 B CN114773596 B CN 114773596B CN 202210325166 A CN202210325166 A CN 202210325166A CN 114773596 B CN114773596 B CN 114773596B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/0644—Poly(1,3,5)triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
- C08G73/065—Preparatory processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
Abstract
The invention relates to BT resin prepreg glue solution, a preparation method and application thereof, and belongs to the technical field of preparation of composite materials. The invention solves the technical problem of providing a preparation method suitable for solution impregnation processing of BT resin prepreg glue solution. The method adopts fluorine-containing allyl polysulfone as a modifier, and bismaleimide resin and bisphenol A type cyanate resin are used as raw materials to prepare BT resin suitable for prepreg processing by a solution method. The BT resin prepreg glue solution has good dielectric property, low dielectric loss and good solubility and dispersibility in a low-boiling point solvent, can reduce the crosslinking density of a cured product and improve the toughness of the cured product; the adhesion force of the BT resin on the fiber can be increased, so that the resin can be better adhered on the fiber, and the mechanical property of the cured product is improved. The solvent with low boiling point and low toxicity is adopted, and can be removed at a lower temperature after impregnation, so that the energy consumption is reduced, and the method is more suitable for industrial production.
Description
Technical Field
The invention relates to BT resin prepreg glue solution, a preparation method and application thereof, and belongs to the technical field of preparation of composite materials.
Background
The prepreg is a composition of a resin matrix and reinforcing fibers, and the production process of the prepreg mainly comprises a solution impregnation method and a hot melting method. Although the hot melting method can avoid the influence of the solvent, after cooling, BT resin (bismaleimide-triazine resin) is very easy to fall off and the process is not mature, so that the formed laminated board is lacked; in the solvent method, polar solvents such as DMF and DMAC, which are high boiling solvents, are often used, and removal of the solvent is very difficult for BT resins, so that in the process of use, a prepreg solution having a low boiling point and good solubility is required to be developed.
The BT resin is obtained by the reaction of BMI resin (bismaleimide resin) and CE resin (triazine resin), has the advantages of the two resins, and overcomes the defects of the two resins. The BT resin composite material has the advantages of high temperature resistance, heat and humidity resistance, excellent dielectric properties, radiation resistance, and good mechanical properties of cured products, and the resin with excellent comprehensive properties can meet the use requirements under high frequency, high speed, high function and severe environments, so that some developed countries in recent years have succeeded in using it as high-performance wave-transparent materials, high-frequency substrates, insulating materials for electric products for strong electric fields, and the like (laminated materials, impregnated fiber winding materials, casting materials, insulating materials, and the like). Particularly in the PCB industry, BT resin has been widely used in the aspect of high-performance application substrates such as 5.0G mobile communication and the like due to the excellent performance of the BT resin.
Because the BMI and CE resins are different in type and content, the melting points are different, the melting point of the BT resin is higher, the BT resin is generally between 150.0 and 190.0 ℃, the rigidity after solidification is stronger, and allyl compounds are often added for modification in the use process, for example, allyl bisphenol A modification can reduce the melting point of the BT resin and improve the brittleness of the BT resin; thermoplastic resins are added to enhance the toughness of BT resins, such as: polyphenylene Oxide (PPO), epoxy resin, polysulfone.
However, the following problems are also encountered in the current processing applications of BT resins:
1. the processing technology is not mature enough: for some BT resins, if the BT resins are processed by adopting a hot melting method, the processing temperature range of the BT resins is obviously reduced along with the increase of the content of BMI resins, so that processing equipment is complicated, the cost input and the instrument loss are increased, and the BT resins are very unfavorable for industrial production.
2. BT resins have poor compatibility with low boiling solvents: if the BT resin is processed by the solvent method, in order to ensure that the viscosity of the BT resin glue solution reaches the standard under the condition that the BT resin is not modified, a polar solvent with a high boiling point such as: DMF, DMAC, NMP, which is very difficult to remove during processing, often results in very many bubbles remaining after the resin is cured; if a low boiling point solvent is used, the phase separation of the resin gum solution system is easy to cause.
3. The rigidity of the resin is improved by adding thermoplastic resin to the resin after the resin is cured with BT, but the compatibility of the thermoplastic resin and BT resin is generally poor, and when the content of the thermoplastic resin is too large, the phase separation is easy to cause.
Disclosure of Invention
The invention provides a preparation method of a BT resin prepreg glue solution suitable for solution impregnation processing, which aims to solve the problems of poor compatibility of toughening components in the existing bismaleimide-triazine resin and a glue solution system thereof and higher boiling point of a solvent required by the solvent processing.
The preparation method of the BT resin prepreg glue solution comprises the following steps:
a. preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution: mixing fluorine-containing allyl polysulfone with a solvent, adding bismaleimide resin, heating to 130-150.0 ℃ for reaction for 30.0-60 min, cooling to below 70.0 ℃, adding the solvent again, and uniformly stirring to obtain fluorine-containing allyl polysulfone modified bismaleimide resin glue solution; wherein the mass ratio of the fluorine-containing allyl polysulfone to the bismaleimide resin is 1-3:1;
b. preparing triazine resin prepolymer: adding bisphenol A type cyanate resin into a flask, adding a curing agent, heating to 140.0-160.0 ℃, and reacting for 60-120 min to obtain a triazine resin prepolymer;
c. preparing BT resin prepreg glue solution: uniformly stirring the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution obtained in the step a and the triazine resin prepolymer obtained in the step b, heating to 170-190.0 ℃, reacting for 20-30 min, cooling to below 70.0 ℃, adding a solvent, and uniformly stirring to obtain BT resin prepreg glue solution; wherein the mass ratio of the triazine resin prepolymer in the step b to the bismaleimide resin in the step a is 4.5-7:3.
In some embodiments of the invention, in step a, the bismaleimide resin is at least one of 3,3 '-dimethyl-5, 5' -diethyl-4, 4 '-diphenylmethane bismaleimide, 4', 4-diaminodiphenylmethane bismaleimide, 4-diaminodiphenyl ether bismaleimide, and the like.
In a specific embodiment, the solvent in the step a is at least one of acetone, butanone, chloroform, 1,4' -dioxane and ethylene glycol dimethyl ether; and c, the solvent in the step is at least one of acetone, butanone, chloroform, 1,4' -dioxane and ethylene glycol dimethyl ether.
In one embodiment of the invention, the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution has a solid content of 60-80%. In a preferred embodiment, the fluorine-containing allyl polysulfone modified bismaleimide resin dope has a solids content of 70 to 75%.
In one embodiment of the present invention, the fluorine-containing allyl polysulfone has a weight average molecular weight of 20000 to 40000.0g/mol.
In one embodiment, the fluorine-containing allyl polysulfone is prepared by the following method:
1) Under the protective atmosphere, mixing diallyl bisphenol A, bisphenol AF,4' 4-dichloro diphenyl sulfone and a solvent, and heating to 65.0-75.0 ℃ to obtain a homogeneous transparent solution; adding an alkaline salifying agent, heating to 150.0-170.0 ℃, starting dehydration, reacting until no water is removed, heating to 190.0-210.0 ℃, and reacting for 120-240 min to obtain a product; the alkaline salifying agent is potassium carbonate, sodium hydroxide or potassium hydroxide;
2) Crushing the product obtained in the step 1), washing until the conductivity is below 20.0us/cm, and drying to obtain the fluorine-containing allyl polysulfone.
In one embodiment of the invention, the molar ratio of diallyl bisphenol A, bisphenol AF and 4' 4-dichloro diphenyl sulfone is 1:3-5:4-6, and the salt forming agent is excessive by 10-20%.
In a preferred embodiment, the molar ratio of total diallyl bisphenol A, bisphenol AF to 4', 4-dichlorodiphenyl sulfone is 1:1.
The second technical problem solved by the invention is to provide a BT resin prepreg glue solution.
The BT resin prepreg glue solution is prepared by the preparation method of the BT resin prepreg glue solution. The fluorine-containing allyl polysulfone is used for modifying the bismaleimide resin, so that the dielectric loss of the BT resin can be reduced and the dielectric property of the BT resin is improved due to the fact that the fluorine-containing allyl polysulfone contains a large amount of F atoms; the allyl reacts with double bonds of the bismaleimide resin, so that the compatibility of the modifier and the BT resin is increased, the solubility of the BT resin in a solvent is increased, the crosslinking density of a cured product is reduced, and the toughness of the cured product is improved; the modifier is used as a flexible chain with certain molecular weight, so that the adhesion of the BT resin on the fiber can be increased, and the bismaleimide resin can be better adhered on the fiber.
The BT resin prepreg glue solution is toughened and does not split phases, and can reduce the energy consumption and environmental problems caused by the processing of a high-boiling-point solvent and a strong-polarity solvent required by the processing of the existing partial BT resin. The prepreg can enable the cured product to have better dielectric property by controlling the fluorine atom content in fluorine-containing allyl polysulfone.
The invention also provides application of the BT resin prepreg glue solution in preparation of prepregs.
The BT resin prepreg glue solution can be used for preparing prepregs.
In one embodiment, the application comprises the steps of: and (3) coating the BT resin prepreg glue solution on the reinforced fiber material, and drying to obtain the BT resin prepreg.
Common reinforcing fiber materials are suitable for use in the present invention, including but not limited to at least one of carbon fiber, glass fiber, aramid fiber, PBO fiber, polyimide fiber, basalt fiber.
The prepreg can be cured by a conventional method to obtain a cured product, i.e., a fiber composite material. In one embodiment of the invention, the prepreg is pressed into a laminate by a hot press and the temperature of the hot press is raised in a gradient as it rises above the initial cure temperature. In a preferred embodiment, the gradient ramp up parameter is 200.0deg.C/1 h, 220.0deg.C/1 h, 240.0deg.C/1 h, 260.0deg.C/2 h, 280.0deg.C/6 h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The BT resin prepreg glue solution has good dielectric property, low dielectric loss and good solubility and dispersibility in a low-boiling point solvent, can reduce the crosslinking density of a cured product and improve the toughness of the cured product; the adhesion force of the BT resin on the fiber can be increased, so that the resin can be better adhered on the fiber, and the mechanical property of the cured product is improved.
(2) The method adopts a solvent with low boiling point and low toxicity. After the dipping, the solvent can be removed at a lower temperature, so that the energy consumption is reduced, and the method is more suitable for industrial production.
Detailed Description
The preparation method of the BT resin prepreg glue solution comprises the following steps:
a. preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution: mixing fluorine-containing allyl polysulfone with a solvent, heating to 130.0-150.0 ℃, adding bismaleimide resin, carrying out dissolution reaction for 30-60 min, cooling to below 70.0 ℃, adding the solvent, and uniformly stirring to obtain fluorine-containing allyl polysulfone modified bismaleimide resin glue solution; wherein the mass ratio of the fluorine-containing allyl polysulfone to the bismaleimide resin is 1-3:1;
b. preparing triazine resin prepolymer: adding bisphenol A type cyanate resin into a flask, adding a curing agent, heating to 140.0-160.0 ℃, and reacting for 60-120 min to obtain a liquid triazine resin prepolymer;
c. preparing BT resin prepreg glue solution: uniformly mixing the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution obtained in the step a and the triazine resin prepolymer obtained in the step b, heating to 170.0-190.0 ℃, reacting for 20-30 min, cooling to below 70.0 ℃, adding a proper amount of solvent, and uniformly stirring to obtain BT resin prepreg glue solution; wherein the mass ratio of the triazine resin prepolymer in the step b to the bismaleimide resin in the step a is 4.5-7:3.
The invention adopts fluorine-containing allyl polysulfone as a modifier, and adopts bismaleimide resin and bisphenol A type cyanate resin as raw materials to prepare BT resin suitable for prepreg processing by a solution method. Compared with the existing modifiers such as polyphenyl ether, polyether sulfone, allyl bisphenol A and the like, the modifier contains active functional allyl and can be subjected to copolymerization with BT resin, so that the thermal stability and compatibility of the polymer are not obviously affected by the introduction of the modifier; compared with the prior polysulfone resin, the modifier has better heat resistance and dielectric property than the conventional polysulfone resin (dielectric constant is less than 3.0), and meanwhile, the modifier can greatly reduce the crosslinking density of the BT resin due to the copolymerization reaction with the BT resin matrix, and the fluorine-containing allyl polysulfone is a flexible chain and can further improve the brittleness of a solidified product. In addition, the compatibility with a solvent can be increased along with the introduction of the allyl group, the processing performance of the material can be greatly improved, and the performance and dielectric loss of the material can be improved along with the introduction of the fluorine-containing group, so that the material can be better applied to a high-frequency PCB circuit.
and a step a is to prepare fluorine-containing allyl polysulfone modified bismaleimide resin glue solution, wherein fluorine-containing allyl polysulfone reacts with bismaleimide resin to obtain homogeneous transparent yellow glue solution, namely fluorine-containing allyl polysulfone modified bismaleimide resin glue solution.
Specifically, the following operations may be adopted: placing fluorine-containing allyl polysulfone into a flask, adding a proper amount of solvent, heating to 130.0-150.0 ℃, stirring until the fluorine-containing allyl polysulfone is completely dissolved, adding bismaleimide resin, stirring until the fluorine-containing allyl polysulfone is completely dissolved, reacting for 30-60 min, cooling to below 70.0 ℃, adding a proper amount of solvent, and stirring uniformly to obtain homogeneous transparent yellow glue solution.
In some embodiments of the invention, in step a, the bismaleimide resin is at least one of 3,3 '-dimethyl-5, 5' -diethyl-4, 4 '-diphenylmethane bismaleimide, 4', 4-diaminodiphenylmethane bismaleimide, 4-diaminodiphenyl ether bismaleimide, and the like.
In a preferred embodiment, the bismaleimide resin is 3,3' -dimethyl-5, 5' -diethyl-4, 4' -diphenylmethane bismaleimide.
The mass ratio of fluorine-containing allyl polysulfone to bismaleimide resin is 1-3:1, and is higher than the ratio, the phase separation is easy to cause, the viscosity of the system is increased, the later processing technology is not facilitated, and the ratio lower than the ratio causes the phase separation of the resin and the solvent, and the later dipping processing is not facilitated.
Solvents commonly used in the art are suitable for use in the present invention. In a specific embodiment, the solvent in the step a is at least one of acetone, butanone, chloroform, 1,4' -dioxane and ethylene glycol dimethyl ether. These solvents have low boiling points, are easily removed during processing, and do not cause phase separation of the resin gum system.
In a preferred embodiment, the solvent is butanone. Butanone is adopted as a solvent used in the solution impregnation method, the butanone has low boiling point, no solvent residue exists after the butanone is impregnated, the toxicity is low, the volatilization speed is low at normal temperature, and the solubility is high.
In one embodiment of the invention, the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution has a solid content of 60-80%. In a preferred embodiment, the fluorine-containing allyl polysulfone modified bismaleimide resin dope has a solids content of 70 to 75%.
In one embodiment of the present invention, the fluorine-containing allyl polysulfone has a weight average molecular weight of 20000 to 40000.0g/mol. The molecular weights in the present invention are all weight average molecular weights.
Fluorine-containing allyl polysulfones commonly used in the art are suitable for use in the present invention. In one embodiment, the fluorine-containing allyl polysulfone is prepared by the following method:
1) Under the protective atmosphere, mixing diallyl bisphenol A, bisphenol AF,4' 4-dichloro diphenyl sulfone and a solvent, and heating to 65.0-75.0 ℃ to obtain a homogeneous transparent solution; adding an alkaline salifying agent, heating to 150.0-170.0 ℃, starting dehydration, reacting until no water is removed, heating to 190.0-210.0 ℃, and reacting for 120-240 min to obtain a product; the alkaline salifying agent is one of potassium carbonate, sodium hydroxide and potassium hydroxide;
2) Crushing the product obtained in the step 1), washing until the conductivity is below 20.0us/cm, and drying to obtain the fluorine-containing allyl polysulfone.
In the preparation process of the fluorine-containing allyl polysulfone modifier, DMAC is selected as a reaction solvent, and the toxicity and the environmental pollution of the DMAC are obviously smaller. The alkaline salifying agent is added to react with the product in the reaction process to generate salt and water, so that the reaction is carried out towards the product.
In one embodiment of the invention, the molar ratio of diallyl bisphenol A, bisphenol AF and 4' 4-dichloro diphenyl sulfone is 1:3-5:4-6, and the salt forming agent is excessive by 10-20%. Fluorine atoms and allyl functional groups are introduced simultaneously, and when the bisphenol AF molar ratio exceeds the range, the compatibility between the modified BT resin and the solvent is poor; when the molar ratio of bisphenol AF is below the critical value, the molecular weight of the modifier is not up to standard.
In a preferred embodiment, the molar ratio of total diallyl bisphenol A, bisphenol AF to 4', 4-dichlorodiphenyl sulfone is 1:1.
b, preparing a triazine resin prepolymer, adding bisphenol A type cyanate resin into a flask, adding a proper amount of curing agent, heating to 140.0-160.0 ℃, and reacting for 60-120 min to obtain a homogeneous transparent liquid prepolymer, namely the triazine resin prepolymer. Most of cyanate resin in the step forms a stable triazine ring structure, and can endow the material with excellent mechanical properties.
Commonly used curing agents are suitable for use in the present invention. In a specific embodiment, the curing agent in step b is a transition metal shuttle salt or chelate including, but not limited to, zinc octoate, manganese octoate, and the like. In a preferred embodiment, the curing agent further comprises a synergistic catalyst containing active hydrogen with dissolved metal salts, usually alkylphenols.
In a preferred embodiment, the curing agent of step b is zinc acetylacetonate and the auxiliary catalyst is nonylphenol.
The curing agent is added in an amount conventional in the art.
Specifically, the step b adopts the following operations: adding a proper amount of curing agent into bisphenol A type cyanate resin, heating to 140.0-160.0 ℃, and reacting for 60-120 min to obtain a homogeneous transparent liquid prepolymer.
The step a and the step b do not have time sequence, and the step a and the step b can be performed firstly, the step a can be performed again, and the step a and the step b can be performed simultaneously.
And c, preparing BT resin prepreg glue solution, namely uniformly mixing the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution obtained in the step a with the triazine resin prepolymer obtained in the step b, heating to 170.0-190.0 ℃, reacting for 20-30 min, cooling to 70.0 ℃, and adding a proper amount of solvent to obtain homogeneous transparent glue solution, namely the BT resin prepreg glue solution. In the heating process, the allyl functional group has the function of catalyzing the cyanate resin to form a ring.
Solvents commonly used in the art are suitable for use in the present invention. In a specific embodiment, the solvent in the step c is at least one of acetone, butanone, chloroform and ethylene glycol dimethyl ether. These solvents have low boiling points, are easily removed during processing, and do not cause phase separation of the resin gum system.
In a preferred embodiment, the solvent of step c is butanone. Butanone is adopted as a solvent used in the solution impregnation method, the butanone has low boiling point, no solvent residue exists after the butanone is impregnated, the toxicity is low, the volatilization speed is low at normal temperature, and the solubility is high.
In a specific embodiment, the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution obtained in the step a is added into the triazine resin prepolymer obtained in the step b.
In a specific embodiment, the mass ratio of the triazine resin to the bismaleimide resin is 4.5 to 7:3. above this ratio, the BT resin becomes more rigid and more costly, and is not easy to be produced industrially; below this ratio, the flexural modulus becomes smaller and the mechanical properties become worse.
In one specific embodiment, the bisphenol A type cyanate ester resin comprises 45 to 75 percent by weight of the total resin; the total resin herein refers to fluorine-containing allyl polysulfone, bismaleimide resin, and bisphenol a type cyanate resin.
The BT resin prepreg glue solution is prepared by the preparation method of the BT resin prepreg glue solution. The fluorine-containing allyl polysulfone is used for modifying the bismaleimide resin, so that the dielectric loss of the BT resin can be reduced and the dielectric property of the BT resin is improved due to the fact that the fluorine-containing allyl polysulfone contains a large amount of F atoms; the allyl reacts with double bonds of the bismaleimide resin, so that the compatibility of the modifier and the BT resin is increased, the solubility of the BT resin in a solvent is increased, the crosslinking density of a cured product is reduced, and the toughness of the cured product is improved; the modifier is used as a flexible chain with certain molecular weight, so that the adhesion of the BT resin on the fiber can be increased, and the bismaleimide resin can be better adhered on the fiber.
The BT resin prepreg glue solution is toughened and does not split phases, and can reduce the energy consumption and environmental problems caused by the processing of a high-boiling-point solvent and a strong-polarity solvent required by the processing of the existing partial BT resin. The prepreg can enable the cured product to have better dielectric property by controlling the fluorine atom content in fluorine-containing allyl polysulfone.
The invention also provides application of the BT resin prepreg glue solution in preparation of prepregs.
The BT resin prepreg glue solution can be used for preparing prepregs.
In one embodiment, the application comprises the steps of: and (3) coating the BT resin prepreg glue solution on the reinforced fiber material, and drying to obtain the BT resin prepreg.
Common reinforcing fiber materials are suitable for use in the present invention, including but not limited to at least one of carbon fiber, glass fiber, aramid fiber, PBO fiber, polyimide fiber, basalt fiber.
The prepreg can be cured by a conventional method to obtain a cured product, i.e., a fiber composite material. In one embodiment of the invention, the prepreg is pressed into a laminate by a hot press and the temperature of the hot press is raised in a gradient as it rises above the initial cure temperature. In a preferred embodiment, the gradient ramp up parameter is 200.0deg.C/1 h, 220.0deg.C/1 h, 240.0deg.C/1 h, 260.0deg.C/2 h, 280.0deg.C/6 h.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
The preparation of the BT resin prepreg glue solution suitable for solution impregnation processing comprises the following steps:
1. synthesizing fluorine-containing allyl polysulfone:
(1) Potassium carbonate was dried in a high temperature oven for 180min, under nitrogen protection, 9.25g of diallyl bisphenol A,40.35g of bisphenol AF,43.07g of 4' 4-dichlorodiphenyl sulfone (DCS), 200.0 ml of Dimethylacetamide (DMAC) were added, and the temperature was raised to 70.0℃to obtain a homogeneous transparent solution. 49.72g of potassium carbonate is added, the temperature is raised to 160.0 ℃, dehydration is started, the reaction is carried out until no water is removed, the temperature is raised to 200.0 ℃, the reaction is carried out for 180min, and the reaction is finished.
(2) The product is crushed, washed by deionized water until the conductivity is 20.0us/cm, and dried in a high-temperature oven for 24 hours to obtain fluorine-containing allyl polysulfone. The weight average molecular weight of the fluorine-containing allyl polysulfone was determined to be 32458g/mol.
2. Preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution:
20.0g of fluorine-containing allyl polysulfone is placed in a flask, 15.0ml of butanone is added, the mixture is heated to 70.0 ℃ and stirred until the butanone is completely dissolved, 10.0g of bismaleimide resin is added, the mixture is stirred and dissolved completely, the temperature is raised to 140.0 ℃, at the moment, the solvent content is low in the whole process, the solvent is used for dissolving, dispersing and diluting the viscosity, the butanone volatilizes in the heating process, the butanone is reduced, the whole mixture is gradually saturated, the boiling point is raised, the reaction is carried out for 50 minutes, and 15.0ml of butanone is added after the mixture is cooled to 70.0 ℃, so that the homogeneous transparent yellow glue solution is obtained. At this time, the solid content of the dope was 71.27%. Since butanone is volatilized continuously in the heating process, the viscosity of the system becomes high after the reaction, and the solvent is added to dilute the viscosity, the temperature is required to be reduced, the solvent is added to dilute the butanone, and the residual amount of the butanone is small at a high Wen Xiading ketone content, so that the butanone is added later when the solid content is calculated.
3. Preparing triazine resin prepolymer:
23.4g of bisphenol A type cyanate ester resin was added to the flask, and 0.10mmol/mol of zinc acetylacetonate (the ratio of the amount of cyanate ester resin substance) and 2% of nonylphenol (the mass of cyanate ester resin) were added, and the temperature was raised to 150.0℃to react for 90 minutes, thereby obtaining a homogeneous transparent glue solution.
4. Preparing bismaleimide-triazine (BT) resin glue solution:
and (3) adding the glue solution obtained in the step (2) into the liquid prepolymer in the step (3), heating to 180.0 ℃, reacting for 25min, cooling to 70.0 ℃, adding 23.0ml of butanone, and uniformly stirring to obtain a homogeneous transparent glue solution, namely the BT resin prepreg glue solution suitable for solution dipping processing. At this time, the solid content of the dope was 74.23%.
The prepreg glue solution is applied:
40.0g of the prepreg glue solution was uniformly applied to a glass cloth (15 layers, 15 cm. Times.15 cm,45.0 g), dried in an oven at 80.0℃for 24 hours, and then taken out to obtain a prepreg.
Cutting, layering and hot-press forming the prepreg (keeping gradient temperature rise according to the temperature rise conditions of 200.0.0 ℃/1h, 220.0.0 ℃/1h, 240.0.0 ℃/1h, 260.0.0 ℃/2h and 280.0.0 ℃/6h after the resin is completely melted) to obtain the BT resin/fiber composite material.
Example 2
The preparation of the BT resin prepreg glue solution suitable for solution impregnation processing comprises the following steps:
1. synthesizing fluorine-containing allyl polysulfone:
(1) The potassium carbonate was dried in a high temperature oven for 240min, under nitrogen protection, 9.25g of diallyl bisphenol A and 30.26g of bisphenol AF,34.46g DCS,160.0ml DMAC were added, and the temperature was raised to 70.0℃to obtain a homogeneous transparent solution. 38.12g of potassium carbonate is added, the temperature is raised to 160.0 ℃, dehydration is started, the reaction is carried out until no water is removed, the temperature is raised to 200.0 ℃, the reaction is carried out for 180min, and the reaction is finished.
(2) The product is crushed, washed by deionized water until the conductivity is 20us/cm, and dried for 24 hours in a high-temperature oven to obtain fluorine-containing allyl polysulfone. Only the molecular weight of the fluorine-containing allyl polysulfone was determined to be 33482g/mol.
2. Preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution:
20.0g of fluorine-containing allyl polysulfone is placed in a flask, 15.0ml of butanone is added, stirring is carried out until the butanone is completely dissolved, 10.0g of bismaleimide resin is added, stirring and dissolving are carried out completely, heating is carried out to 140.0 ℃, reaction is carried out for 50min, cooling is carried out to 70.0 ℃, 15.0ml of butanone is added, and homogeneous transparent yellow glue solution is obtained, and the solid content of the glue solution is 71.28%.
3. Preparing triazine resin prepolymer:
23.4g of bisphenol A type cyanate ester resin was charged into a flask, 0.10mmol/mol of zinc acetylacetonate (ratio of the amount of cyanate ester resin substance) and 2% of nonylphenol (mass of cyanate ester resin) were added, and the temperature was raised to 150.0℃to react for 90 minutes, to obtain a homogeneous transparent liquid prepolymer.
4. The preparation method of the bismaleimide-triazine (BT) resin glue solution comprises the following steps:
adding the glue solution obtained in the step 2 into the liquid prepolymer in the step 3, heating to 180.0 ℃, reacting for 25min to obtain a homogeneous transparent glue solution, cooling to 70.0 ℃, adding 23.0ml of butanone, and uniformly stirring to obtain the homogeneous transparent glue solution, namely the BT resin prepreg glue solution suitable for solution dipping processing, wherein the solid content of the glue solution is 74.23%.
The prepreg glue solution is applied:
40.0g of the prepreg glue solution was uniformly applied to a glass cloth (15 layers, 15 cm. Times.15 cm,45.0 g), dried in an oven at 80.0℃for 24 hours, and then taken out to obtain a prepreg.
Cutting, layering and hot-press forming the prepreg (keeping gradient heating according to the heating conditions of 200.0.0 ℃/1h, 220.0.0 ℃/1h, 240.0 ℃/1h, 260.0 ℃/2h and 280.0 ℃/6h after the resin is completely melted), so as to obtain the BT resin/fiber composite material.
Example 3
The preparation of BT resin prepreg glue solution suitable for solution impregnation processing comprises the following steps
1. Synthesizing fluorine-containing allyl polysulfone:
(1) The potassium carbonate was dried in a high temperature oven for 240min, under nitrogen protection, 9.25g of diallyl bisphenol A and 30.26g of bisphenol AF,34.46g DCS,160.0ml DMAC were added, and the temperature was raised to 70.0℃to obtain a homogeneous transparent solution. 38.12g of potassium carbonate is added, the temperature is raised to 160.0 ℃, dehydration is started, the reaction is carried out until no water is removed, the temperature is raised to 200.0 ℃, the reaction is carried out for 180min, and the reaction is finished.
(2) The product is crushed, washed by deionized water until the conductivity is 20us/cm, and dried for 24 hours in a high-temperature oven to obtain fluorine-containing allyl polysulfone. Only the weight average molecular weight of the fluorine-containing allyl polysulfone was determined to be 32073g/mol.
2. Preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution:
20.0g of fluorine-containing allyl polysulfone is placed in a flask, 15.0ml of butanone is added, stirring is carried out until the butanone is completely dissolved, 10.0g of bismaleimide resin is added, stirring and dissolving are carried out completely, heating is carried out to 140.0 ℃, reaction is carried out for 50min, cooling is carried out to 70.0 ℃, 15.0ml of butanone is added, and homogeneous transparent yellow glue solution is obtained, and the solid content of the glue solution is 71.28%.
3. Preparing triazine resin prepolymer:
15.0g of bisphenol A type cyanate ester resin was added to the flask, and 0.10mmol/mol of zinc acetylacetonate (ratio of the amount of cyanate ester resin substance) and 2% of nonylphenol (mass of cyanate ester resin) were added, and the mixture was heated to 150.0℃and reacted for 90 minutes to obtain a homogeneous transparent liquid prepolymer.
4. The preparation method of the bismaleimide-triazine (BT) resin glue solution comprises the following steps:
and (3) adding the glue solution obtained in the step (2) into the liquid prepolymer in the step (3), heating to 180.0 ℃, reacting for 25min to obtain a homogeneous transparent glue solution, cooling to 70.0 ℃, adding 22.0ml of butanone, and uniformly stirring to obtain the homogeneous transparent glue solution, namely the BT resin prepreg glue solution suitable for solution dipping processing. The solid content of the glue solution was 71.73%.
The prepreg glue solution is applied:
40.0g of the prepreg glue solution was uniformly applied to a glass cloth (15 layers, 15 cm. Times.15 cm,45.0 g), dried in an oven at 80.0℃for 24 hours, and then taken out to obtain a prepreg.
Cutting, layering and hot-press forming the prepreg (keeping gradient heating according to the heating conditions of 200.0 ℃/1h, 220.0 ℃/1h, 240.0 ℃/1h, 260.0 ℃/2h and 280.0 ℃/6h after the resin is completely melted), so as to obtain the BT resin/fiber composite material.
Example 4
1. Synthesizing fluorine-containing allyl polysulfone:
(1) The potassium carbonate was dried in a high temperature oven for 240min, under nitrogen protection, 9.25g of diallyl bisphenol A and 30.26g of bisphenol AF,34.46g DCS,160.0ml DMAC were added, and the temperature was raised to 70.0℃to obtain a homogeneous transparent solution. 38.12g of potassium carbonate is added, the temperature is raised to 160.0 ℃, dehydration is started, the reaction is carried out until no water is removed, the temperature is raised to 200.0 ℃, the reaction is carried out for 180min, and the reaction is finished.
(2) The product is crushed, washed by deionized water until the conductivity is 20us/cm, and dried for 24 hours in a high-temperature oven to obtain fluorine-containing allyl polysulfone. Only the molecular weight of the fluorine-containing allyl polysulfone was determined to be 29467g/mol.
2. Preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution:
10.0g of fluorine-containing allyl polysulfone is placed in a flask, 10.0ml of butanone is added, stirring is carried out until the butanone is completely dissolved, then 10.0g of bismaleimide resin is added, stirring is carried out until the bismaleimide resin is completely dissolved, the temperature is raised to 140.0 ℃, the reaction is carried out for 50min, the temperature is reduced to 70.0 ℃, 10.0ml of butanone is added, stirring is carried out uniformly, and the homogeneous transparent yellow glue solution is obtained, and the solid content of the glue solution is 71.21%.
3. Preparing triazine resin prepolymer:
15.0g of bisphenol A type cyanate ester resin was added to the flask, and 0.10mmol/mol of zinc acetylacetonate (ratio of the amount of cyanate ester resin substance) and 2% of nonylphenol (mass of cyanate ester resin) were added, and the mixture was heated to 150.0℃and reacted for 90 minutes to obtain a homogeneous transparent liquid prepolymer.
4. The preparation method of the bismaleimide-triazine (BT) resin glue solution comprises the following steps:
adding the glue solution obtained in the step 2 into the liquid prepolymer in the step 3, heating to 180.0 ℃, reacting for 25min, uniformly stirring to obtain a homogeneous transparent glue solution, cooling to 70.0 ℃, adding 18.0ml butanone, and uniformly stirring to obtain the homogeneous transparent glue solution, namely the BT resin prepreg glue solution suitable for solution dipping processing. The solid content of the glue solution was 70.70%.
The prepreg glue solution is applied:
40.0g of the prepreg glue solution was uniformly applied to a glass cloth (15 layers, 15 cm. Times.15 cm,45.0 g), dried in an oven at 80.0℃for 24 hours, and then taken out to obtain a prepreg.
Cutting, layering and hot-press forming the prepreg (keeping gradient heating according to the heating conditions of 200.0 ℃/1h, 220.0 ℃/1h, 240.0 ℃/1h, 260.0 ℃/2h and 280.0 ℃/6h after the resin is completely melted), so as to obtain the BT resin/fiber composite material.
Comparative example 1
1. The preparation of the triazine resin prepolymer comprises the following preparation processes:
30.0g of bisphenol A type cyanate ester resin was added to the flask, and 0.10mmol/mol of zinc acetylacetonate (ratio of the amount of cyanate ester resin substance) and 2% of nonylphenol (mass of cyanate ester resin) were added, and the mixture was heated to 150.0℃and reacted for 90 minutes to obtain a homogeneous transparent liquid prepolymer.
2. The preparation of bismaleimide-triazine (BT) resin glue solution comprises the following preparation processes:
6.0g of bismaleimide-triazine (BT) resin is added into the glue solution in the step 1, the temperature is raised to 150.0 ℃, the reaction is carried out for 25min, and 16.0ml of butanone is added to obtain the homogeneous transparent glue solution, namely the bismaleimide-triazine (BT) resin glue solution, and the solid content of the glue solution is 72.35%.
The glue solution is applied:
40.0g of BT resin glue solution is evenly smeared on glass fiber cloth (15 layers, 15cm multiplied by 15cm,45.0 g), and is taken out after being dried for 24 hours in an oven at 80.0 ℃ to obtain prepreg.
Cutting, layering and hot-press forming the prepreg (keeping gradient heating according to the heating conditions of 200.0 ℃/1h, 220.0 ℃/1h, 240.0 ℃/1h, 260.0 ℃/2h and 280.0 ℃/6h after the resin is completely melted), so as to obtain the BT resin/fiber composite material.
The viscosity of the resin system is a recorded value which is kept for 30 minutes at a specific temperature, and the test standard is GB/T22314; the bending strength of the composite material is obtained by testing by a universal testing machine, and the testing standard is GB 2567-2008; glass transition temperature T .g Obtained by Dynamic Mechanical Analyzer (DMA) test, the test frequency range is 1HZ-1MZ, the diameter of the sample is 25.0mm, and the thickness is 2.0mm. The test data are shown in Table 1.
TABLE 1
As a result of the above test, examples 1 to 4, which access fluorine-containing groups and thermoplastic segments into the cured network of BT resin, have more excellent film manufacturability and window period than the conventional allylbisphenol a, thermoplastic material toughening modification; and compared with comparative example 1, the bending resistance of the modified resin is slightly reduced, but the dielectric property is obviously improved, and no precipitation and phase separation phenomena are found in the preparation process of the prepreg glue solution.
Claims (12)
- The preparation method of the BT resin prepreg glue solution is characterized by comprising the following steps:a. preparing fluorine-containing allyl polysulfone modified bismaleimide resin glue solution: mixing fluorine-containing allyl polysulfone with a solvent, adding bismaleimide resin, heating to 130-150.0 ℃ for reaction for 30.0-60 min, cooling to below 70.0 ℃, adding the solvent again, and uniformly stirring to obtain fluorine-containing allyl polysulfone modified bismaleimide resin glue solution; wherein the mass ratio of fluorine-containing allyl polysulfone to bismaleimide resin is 1-3:1;b. preparing triazine resin prepolymer: adding bisphenol A type cyanate resin into a flask, adding a curing agent, heating to 140.0-160.0 ℃, and reacting for 60-120 min to obtain a triazine resin prepolymer;c. preparing BT resin prepreg glue solution: uniformly stirring the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution obtained in the step a and the triazine resin prepolymer obtained in the step b, heating to 170-190.0 ℃, reacting for 20-30 min, cooling to below 70.0 ℃, adding a solvent, and uniformly stirring to obtain BT resin prepreg glue solution; wherein the mass ratio of the triazine resin prepolymer in the step b to the bismaleimide resin in the step a is 4.5-7:3;the solvent in the step c is at least one of acetone, butanone, chloroform, 1, 4-dioxane and ethylene glycol dimethyl ether;the fluorine-containing allyl polysulfone is prepared by the following method:1) Under the protective atmosphere, mixing diallyl bisphenol A, bisphenol AF,4' 4-dichloro diphenyl sulfone and a solvent, and heating to 65.0-75.0 ℃ to obtain a homogeneous transparent solution; adding an alkaline salifying agent, heating to 150.0-170.0 ℃, starting dehydration, reacting until no water is removed, heating to 190.0-210.0 ℃, and reacting for 120-240 min to obtain a product; the alkaline salifying agent is potassium carbonate, sodium hydroxide or potassium hydroxide; wherein, the mol ratio of diallyl bisphenol A, bisphenol AF and 4' 4-dichloro diphenyl sulfone is 1:3-5:4-6;2) Crushing the product obtained in the step 1), washing until the conductivity is below 20.0us/cm, and drying to obtain the fluorine-containing allyl polysulfone.
- 2. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: in the step a, the bismaleimide resin is at least one of 3,3 '-dimethyl-5, 5' -diethyl-4, 4 '-diphenyl methane bismaleimide, 4', 4-diamino diphenyl methane bismaleimide and 4, 4-diamino diphenyl ether bismaleimide resin.
- 3. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: the solvent in the step a is at least one of acetone, butanone, chloroform, 1, 4-dioxane and ethylene glycol dimethyl ether.
- 4. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: the solid content of the fluorine-containing allyl polysulfone modified bismaleimide resin glue solution is 60-80%.
- 5. The method for preparing the BT resin prepreg glue solution according to claim 4, characterized in that: the solid content of fluorine-containing allyl polysulfone modified bismaleimide resin glue solution is 70-75%.
- 6. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: the weight average molecular weight of the fluorine-containing allyl polysulfone is 20000-40000.0 g/mol.
- 7. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: the salt forming agent is excessive by 10-20%.
- 8. The method for preparing the BT resin prepreg glue solution according to claim 1, characterized in that: the molar ratio of the total amount of diallyl bisphenol A and bisphenol AF to 4' 4-dichlorodiphenyl sulfone is 1:1.
- 9. The BT resin prepreg according to any one of claims 1 to 8.
- 10. Use of the BT resin prepreg glue of claim 9 in the preparation of prepregs.
- 11. Use of BT resin prepreg glue according to claim 10 for the preparation of prepregs, comprising the steps of: and (3) coating the BT resin prepreg glue solution on a reinforced fiber material or fabric, and drying to obtain the BT resin prepreg.
- 12. The use of BT resin prepreg glue according to claim 11 for the preparation of prepregs, characterized in that: the reinforced fiber material comprises at least one of carbon fiber, glass fiber, aramid fiber, PBO fiber, polyimide fiber and basalt fiber.
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