CN109535628B - Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same - Google Patents
Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same Download PDFInfo
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- 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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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
- C08F283/045—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides on to unsaturated polycarbonamides, polyesteramides or polyimides
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- C—CHEMISTRY; METALLURGY
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2351/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2351/08—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/34—Silicon-containing compounds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- C08K7/14—Glass
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
Abstract
The invention discloses a flame-retardant resin prepolymer which is prepared by at least pre-polymerizing bismaleimide resin and allyl compounds. Compared with the prior art, the allyl compound containing the DOPO or DPPO structure is used as the bismaleimide resin modifier, and on the basis of not affecting the performance of the bismaleimide resin, the phosphorus-containing group is well introduced into the cross-linked network structure of the bismaleimide resin, so that the nitrogen element and the phosphorus element in one cross-linked network structure are cooperatively flame-retardant, the flame retardance of the cured product can be reduced to reach the phosphorus content required by UL94V-0, other flame retardants are not required to be added, and the cured product with excellent halogen-free flame retardance, high heat resistance, high adhesion, toughness and thermal expansion coefficient is obtained.
Description
Technical Field
The invention relates to the technical field of electronic materials, in particular to a flame-retardant resin prepolymer and a resin composition, a prepreg and a laminated board prepared from the same.
Background
In recent years, with the continuous development of mobile internet technology, the multi-functionalization, portability, and lightness and thinness are continuously the targets sought for electronic products, which means that more components are loaded on electronic products, more printed circuits adopt High Density Interconnect (HDI) technology, and the thickness of the whole printed circuit board is thinner, so that a higher requirement is put on a substrate-copper clad plate for manufacturing the printed circuit board, and the copper clad plate is required to have performance similar to a package substrate, i.e., a package material of the type rising in the industry is required to have high heat resistance, high glass transition temperature, excellent adhesion, good processability, and more importantly, the plate has better modulus retention rate at high temperature.
The bismaleimide resin as a high-performance resin material has excellent heat resistance and higher high-temperature modulus retention rate, but is poor in solubility, can only be dissolved in some high-boiling-point solvents such as N, N-dimethylformamide, N-methylpyrrolidone and the like, and is harsh in process conditions, and meanwhile, a cured bismaleimide resin is high in crosslinking density and high in brittleness, and other service performances are seriously affected. Therefore, in the prior art, aromatic diamine or diallyl compound is generally adopted for modification, and the modified bismaleimide resin has good processability and excellent performance, but the intrinsic flame retardance can not reach UL94V-0 grade no matter the maleimide resin is modified by the diamine or the diallyl compound, and a halogen-free flame retardant is required to be added to meet the requirement of EU instruction.
Halogen-free flame retardation of laminates for printed circuits is generally achieved by adding a resin containing flame retardant elements such as nitrogen, phosphorus, and silicon and an inorganic filler (e.g., an inorganic compound containing crystal water such as aluminum hydroxide and magnesium hydroxide) to a resin matrix. Compared with the flame retardant containing phosphorus resin, the flame retardant containing silicon and nitrogen resin or inorganic filler has the problem of low flame retardant efficiency, and cannot meet the requirement of UL 94V-0. Therefore, the phosphorus-containing resin is dominant as a main flame retardant in the current halogen-free substrate material. These phosphorus-containing flame retardants are mainly reactive resins and additive flame retardants such as phosphorus-containing epoxy resins, phosphazene compounds, phosphoric esters or phosphorus-containing phenolic resins, and the like. After the components are introduced, the flame retardance of the board can be improved, but the flame retardant resin taking the epoxy resin or the phenolic resin as the matrix greatly reduces the heat resistance, the glass transition temperature, the high-temperature lower mold quantity retention rate and the like of a modified bismaleimide resin system, and is difficult to meet the application requirements of the modified bismaleimide resin system in high-performance fields such as high-density interconnection or integrated circuit packaging/class packaging.
Therefore, in order to obtain a halogen-free flame-retardant high-performance bismaleimide resin, a scheme of adding a phosphorus-containing flame retardant to a bismaleimide resin system is disclosed in the prior art.
For example, patent CN102276837A discloses a technical scheme of adding a phosphorus-containing compound (phosphazene) to a bismaleimide resin system, although a cured product which does not contain halogen and has good flame retardant performance can be obtained, these flame retardants do not form a good cross-linked network structure with the bismaleimide resin system, and under the high-temperature curing condition (often higher than 200 ℃) of the bismaleimide resin, the phosphazene compound which does not participate in the reaction emerges on the surface of the substrate in a manner similar to "sweating", which not only affects the heat resistance of the board, but also affects the bonding force between the board and the copper foil.
For example, patent CN103665864 discloses allyl modified bismaleimide resin, and organic phosphorus flame retardant or organic nitrogen compound is added to the glue solution, in this technical scheme, although the problem of solubility of bismaleimide resin can be solved, and halogen-free high flame retardant sheet can be obtained, but the addition of flame retardant component affects heat resistance, humidity resistance and water absorption of the final cured product, so it is difficult to obtain high performance sheet with excellent overall performance.
For example, JP2012153896 discloses a technical scheme of adding phosphorus-containing epoxy resin into a bismaleimide resin system, which can also meet the halogen-free flame retardant requirement, but the glass transition temperature, heat resistance and modulus retention rate at high temperature of the resin are greatly reduced due to the presence of the epoxy resin.
In view of the above, there is a need to develop a high-performance substrate material for printed circuit boards suitable for the field of class carrier boards, package carrier boards and high-density interconnection technologies, and the laminated board or copper-clad board prepared by using the material has excellent halogen-free flame retardancy, high heat resistance, low thermal expansion coefficient and high modulus retention rate at high temperature.
Disclosure of Invention
The invention aims to provide a flame-retardant resin prepolymer for solving the technical problems, and a thermosetting resin composition, a prepreg and a laminated board prepared by using the same, wherein the flame-retardant resin prepolymer has excellent halogen-free flame retardance, high heat resistance, high-temperature modulus retention rate, high cohesiveness, excellent toughness, thermal expansion coefficient and high modulus retention rate, particularly meets the requirements of halogen-free flame retardance of UL94V-0, and has excellent high-temperature modulus retention rate and low thermal expansion coefficient, so that the flame-retardant resin prepolymer is well suitable for high-performance circuit substrates such as IC packaging substrates.
The flame-retardant resin prepolymer is prepared by at least pre-polymerizing bismaleimide resin and allyl compounds, wherein the allyl compounds contain phosphorus-containing allyl compounds represented by the following structural formula (1) or structural formula (2):
wherein R is1Is a linear alkylene or substituted alkylene of C1-C10 or an aromatic group of C6-C20.
As a further improvement of the invention, the weight ratio of the bismaleimide resin to the allyl compound is 100: 10-100.
As a further improvement of the invention, R1 is a C2-C6 straight chain alkylene.
As a further improvement of the present invention, the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
in a further improvement of the present invention, the allyl compound further contains a phosphorus-free allyl compound, and the phosphorus-free allyl compound is one or a mixture of two or more of diallyl bisphenol a, diallyl bisphenol S, allyl phenol-oxygen resin, allyl phenol-formaldehyde resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts by mass based on 100 parts by mass of the total allyl compound. Accordingly, the present invention also provides a flame retardant resin composition comprising, by solid weight:
the flame-retardant resin prepolymer according to any one of the above: 100 parts of (A);
filling: 0-150 parts;
curing accelerator: 0.001-5 parts;
elastomer: 0-50 parts.
As a further improvement of the present invention, the filler is an inorganic filler or an organic filler, and the inorganic filler is one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus; the organic filler is selected from one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
Correspondingly, the invention also provides a prepreg, which is prepared by adding the solvent into the flame-retardant resin composition to dissolve the flame-retardant resin composition to prepare a glue solution, dipping the reinforcing material into the glue solution, and heating and drying the dipped reinforcing material.
Correspondingly, the invention also provides a laminated board, wherein the double surfaces of at least one prepreg are covered with release films, and the laminated board can be obtained by hot press forming.
Correspondingly, the invention also provides a laminated plate, wherein the laminated plate can be obtained by coating metal foil on one side or two sides of at least one prepreg and performing hot press forming.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
(1) according to the invention, the allyl compound containing the DOPO or DPPO structure is used as the bismaleimide resin modifier, on the basis of not affecting the performance of the bismaleimide resin, the phosphorus-containing group is well introduced into the crosslinking network structure of the bismaleimide resin, so that the nitrogen element and the phosphorus element in one crosslinking network structure are cooperatively flame-retardant, the phosphorus content required by the flame retardance of the cured product to reach UL94V-0 can be reduced, other flame retardants are not required to be added, and the cured product with excellent halogen-free flame retardance, high heat resistance, high adhesion, excellent toughness and thermal expansion coefficient is obtained;
(2) when the straight-chain alkyl is arranged at the middle position of DOPO or DPPO in the allyl compound structure, the crosslinking density of the whole bismaleimide polymer crosslinking network structure can be adjusted, the brittleness of the bismaleimide resin is effectively reduced, the generation of stress in the curing reaction process is relieved, the thermal expansion coefficient of the plate is reduced, and meanwhile, the excellent high-temperature modulus is kept.
(3) When the modified bismaleimide prepolymer is prepared, the phosphorus-free allyl compound is properly added, so that the preparation process of the prepolymer can be effectively controlled, the allyl compound plays a role in polymerization inhibition in the addition reaction of maleimide and allyl, the solubility of the bismaleimide resin is improved, the overall polymerization reaction rate can be well controlled, and a final cured product with more excellent comprehensive performance is obtained.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments. These embodiments are not intended to limit the present invention, and structural, methodological, or functional changes made by those skilled in the art according to these embodiments are included in the scope of the present invention. Variations in reaction conditions, amounts of reactants or starting materials, which may be made by one of ordinary skill in the art in light of these examples, are within the scope of the invention.
In a specific embodiment of the present invention, a flame retardant resin prepolymer, specifically a modified bismaleimide prepolymer, is prepared by at least pre-polymerizing bismaleimide resin and an allyl compound, wherein the allyl compound contains a phosphorus-containing allyl compound represented by structural formula (1) or structural formula (2):
wherein R is1Is a linear or substituted alkyl of C1-C10 or an aromatic group of C6-C20;
the weight ratio of the bismaleimide resin to the allylic compound is 100:10-100, preferably 100:20-60, and specifically may be 100:10, 100:15, 100:20, 100:25, 100:30, 100:35, 100:40, 100:45, 100:50, 100:55, 100:60, 100:65, 100:70, 100:75, 100:80, 100:85, 100:90, 100:95, or 100: 100.
Further, in the allyl compound structural formulas (1) and (2), R1 is a C2-C6 straight-chain alkyl group, and when R1 is a straight-chain alkylene group and is arranged at the middle position containing DOPO or DPPO on both sides, the crosslinking density of the whole bismaleimide polymer crosslinking network structure can be adjusted, the brittleness of the bismaleimide resin is effectively reduced, and the generation of stress in the curing reaction process is relieved. But when R is1When the chain length of the linear alkylene group is too long, the linear long chain is easily broken under high temperature conditions, which affects the heat resistance of the cured product, and when R is too long1When the chain length of the linear alkylene group is too short, the above-described effect is difficult to obtain.
In the above allyl compound structural formulas (1) and (2), the aromatic group in R1 is
Or
Among them, preferred is
Or
Straight chain alkylene is
Or substituted alkylene groups thereof, among which preferred is
Or
Further, the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
the allyl compound further contains a phosphorus-free allyl compound, preferably, the phosphorus-free allyl compound is one or a mixture of two or more selected from diallyl bisphenol a, diallyl bisphenol S, allyl phenoxy resin, allyl phenolic resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts, preferably 30 to 50 parts, more preferably 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 38 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, and 50 parts, based on 100 parts by mass of the total allyl compound.
When the allyl compound also contains phosphorus-free allyl compound, the weight ratio of the bismaleimide resin to the allyl compound is 100: 20-150. When the prepolymer is prepared, the phosphorus-free allyl compound is properly added, so that the preparation process of the prepolymer can be effectively controlled, the phosphorus-free allyl compound plays a role in polymerization slowing in the addition reaction of maleimide groups and allyl groups, the solubility of the bismaleimide resin is improved, but when the content is higher, the reaction of the phosphorus-containing allyl groups and the maleimide groups is influenced, and DOPO or DPPO cannot be well introduced into a bismaleimide system.
The invention also provides a flame-retardant resin composition, which comprises the following components in percentage by weight based on solid weight:
the above flame retardant type resin prepolymer, i.e., modified bismaleimide prepolymer: 100 parts of (A);
filling: 0-150 parts;
curing accelerator: 0.001-5 parts;
elastomer: 0-50 parts.
Further, the filler is selected from an organic filler or an inorganic filler, wherein the inorganic filler is selected from one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate or inorganic phosphorus, preferably any one or a mixture of at least any two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica or glass fiber powder; the organic filler is one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder and polyether sulfone powder.
In the present invention, the filler is preferably an inorganic filler, more preferably a surface-treated inorganic filler, and most preferably a surface-treated silica. The surface treating agent for carrying out surface treatment on the inorganic filler is selected from any one or a mixture of at least two of a silane coupling agent, an organic silicon oligomer or a titanate coupling agent, the particle size median value of the filler is 0.2-20 mu m, preferably 0.5-15 mu m, more preferably 0.5-5 mu m, and the filler in the particle size section has good dispersibility and good processability.
More preferably, the surface treatment agent is used in an amount of 0.1 to 5.0%, preferably 0.5 to 3.0%, and further preferably 0.75 to 2.0%, based on 100% by mass of the inorganic filler.
Further, the curing accelerator is selected from dimethylaminopyridine, tertiary amines and salts thereof, imidazole, organometallic salts, triphenylphosphine and phosphonium salts thereof, and the like. The curing accelerator may be added according to the actual condition, and is selected from dimethylaminopyridine, tertiary amine and salts thereof, imidazole, organic metal salts, triphenylphosphine and phosphonium salts thereof, etc., and the content thereof is preferably 0.01 to 2.0 parts based on 100 parts of the flame-retardant resin prepolymer.
The elastomer is a low-modulus component, and is selected from at least one of polybutadienes, styrenes, olefins, polyurethanes, polyesters, polyamines, acrylates, and silicones, preferably a low-modulus component containing a reactive group, which may be an epoxy group, a hydroxyl group, an amino group, an acid anhydride group, a carboxyl group, or a vinyl group, and is more preferably selected from epoxy-modified polybutadiene, acid anhydride-modified polybutadiene, a styrene butadiene copolymer, a styrene propylene copolymer, or a styrene acrylic copolymer, and the content of the elastomer is preferably 5 to 20 parts based on 100 parts of the flame-retardant resin prepolymer.
When the low-modulus elastomer is properly added to the flame-retardant resin composition, the generation of stress can be reduced in the curing reaction process, the thermal expansion coefficient of the plate can be effectively improved, and meanwhile, the brittleness of the bismaleimide resin can be further improved.
Further, an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, or the like may be added to the resin composition according to the actual circumstances. These various additives may be used alone or in combination of two or more.
The invention also provides a prepreg prepared by adopting the resin composition, which comprises the following preparation steps:
dissolving the flame-retardant resin composition by using a solvent, uniformly stirring and curing the mixture until the solid content is 60-75 percent to prepare a resin composition glue solution;
and (3) soaking the reinforcing material in the resin composition glue solution, and then baking the soaked reinforcing material at the temperature of 50-170 ℃ for 1-10min to dry to obtain the prepreg.
Among them, the reinforcing material is natural fiber, organic synthetic fiber, organic fabric or inorganic fabric, and the inorganic fabric is particularly preferably glass fiber cloth, and the glass fiber cloth is preferably open fiber cloth or flat cloth. In addition, in order to improve the interfacial bonding between the resin and the glass cloth, the glass cloth generally needs to be chemically treated, mainly by a coupling agent such as epoxy silane, amino silane, etc.
The solvent is selected from one or the combination of any of acetone, butanone, toluene, methyl isobutyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, ethylene glycol methyl ether, propylene glycol methyl ether, benzene, toluene and cyclohexane.
The invention also provides a laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a release film on the double surfaces of at least one prepreg, and performing hot press forming to obtain the laminated board, wherein the number of the prepregs can be determined according to the thickness of the required laminated board, and one or more prepregs can be used. The release film can be a PET film or a release aluminum foil.
The invention also provides another laminated board prepared by adopting the prepreg, which comprises the following preparation steps:
and covering a metal foil on one or two sides of one prepreg, or covering a metal foil on one or two sides of at least 2 prepregs after laminating, and performing hot press forming to obtain the metal foil laminated board.
The number of prepregs may be determined according to the thickness of the laminate desired, and one or more prepregs may be used. The metal foil may be a copper foil or an aluminum foil, and the thickness thereof is not particularly limited.
The pressing condition of the laminated board is that the laminated board is pressed for 2-4 hours under the pressure of 0.2-2 MPa and the temperature of 180-250 ℃.
The prepreg, the laminated board and the metal foil laminated board are all used for preparing circuit boards.
In order to better illustrate the present invention, the following specific examples are provided to further describe the present invention, and the following specific synthetic examples of the preparation of the flame retardant bismaleimide resin prepolymer:
synthesis example 1
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:80:20, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 1 with the solid content of 75%.
Synthesis example II
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-2 (aromatic type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:60:20, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 2 with the solid content of 75%.
Synthesis example three
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, allyl compound A-3 (linear chain type) containing DPPO group and diallyl diphenyl ether into the three-neck flask in sequence according to the mass ratio of 100:40:30, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 3 with the solid content of 75%.
Synthesis example four
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, allyl compound A-4 (aromatic type) containing DPPO group and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:30:50, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 4 with the solid content of 75%.
Synthesis example five (different content ratio compared with Synthesis example one)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl diphenyl ether into the three-neck flask in sequence according to the mass part of 100:20:40, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 5 with the solid content of 75%.
Synthesis example six
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl bisphenol A into the three-neck flask in sequence according to the mass part of 100:30:70, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, and continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 6 with the solid content of 75%.
Synthesis example seven
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, DOPO-containing allyl compound A-1 (linear chain type) and diallyl diphenyl ether into the three-neck flask in sequence according to the mass part of 100:10:40, continuously stirring under the condition of an oil bath at 110 ℃, starting timing after the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain a modified bismaleimide prepolymer 7 with the solid content of 75%.
Synthesis example eight (prepolymerization of bismaleimide with phosphorus-containing allyl Compound)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide and allyl compound A-1 (linear chain type) containing DOPO group into the three-neck flask in sequence according to the mass part of 100:50, continuously stirring under the condition of an oil bath at 110 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 8 with the solid content of 75%.
Comparative Synthesis example 1 (bismaleimide + allyl Compound copolymerization)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, sequentially adding 4, 4' -diphenylmethane bismaleimide and diallyl bisphenol A into the three-neck flask according to the mass part of 100:60, continuously stirring under the condition of an oil bath at 110 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 9 with the solid content of 75%.
Comparative Synthesis example 2 (bismaleimide + allyl + phosphorus-containing Compound copolymerization)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, diallyl bisphenol A and a phosphorus compound (DOPO) into the three-neck flask in sequence according to the mass part of 100:60:10, continuously stirring under the condition of an oil bath at 110 ℃, timing when the solid in the flask is completely dissolved, continuously stirring for 1hr, and distilling the obtained product to obtain the modified bismaleimide prepolymer 10 with the solid content of 75%.
Comparative Synthesis example 3 (bismaleimide + allyl Compound + phosphorus-containing epoxy resin copolymerization)
Adding 100 parts of solvent N, N-dimethylformamide into a 500mL three-neck flask, putting 4, 4' -diphenylmethane bismaleimide, an allyl compound and phosphorus-containing epoxy resin into the three-neck flask in sequence according to the mass part of 100:50:30, stirring and reacting for 2 hours under the condition of 110 ℃ oil bath, distilling the obtained product to obtain a solid substance, and preparing the modified bismaleimide prepolymer 11 with the solid content of 75% by using an organic solvent.
Preparing a prepreg: the components and the mixture ratio in the following table 1 and table 2 are adopted to prepare glue solution with 62 percent of solid content, the glue solution is soaked by glass fiber cloth, and the prepreg is prepared by drying in a 160 ℃ oven for 5 min.
Preparing a copper-clad laminate: and (3) superposing the 8 semi-solidified materials with the burrs cut off, attaching 35-micron copper foils to the upper part and the lower part of the semi-solidified materials, and placing the semi-solidified materials in a vacuum hot press for pressing to obtain the copper-clad plate. The specific pressing process is pressing for 4 hours under the pressure of 1.5Mpa and the temperature of 220 ℃.
The properties of the copper-clad laminate obtained are shown in tables 1 and 2:
table 1 shows specific examples of the present invention
Table 2 comparative examples of the invention
The preparation method of the allyl compounds A-1 to A-4 comprises the following steps:
the first step is as follows: 1mol of allylamine compound is taken and evenly mixed with a proper amount of organic solvent, 0.5mol of terephthalaldehyde is dripped into a reaction bottle at the temperature of 50-100 ℃, and the reaction is carried out for 1-5 hours under the protection of nitrogen;
the second step is that: after the reaction is finished, cooling the reaction mixture, performing suction filtration to obtain a crude product, dissolving the crude product in deionized water, heating, cooling and recrystallizing by the same method, repeating for 2-5 times, and finally drying in a vacuum drying oven at 60-90 ℃ for 24 hours to obtain an intermediate product;
step three: taking 0.5mol of intermediate product and 1mol of DOPO, adding a proper amount of organic solvent, gradually heating to completely dissolve the intermediate product and the DOPO, reacting for 5-7 hours at 90-120 ℃ under the protection of nitrogen, cooling to room temperature after the reaction is finished, dissolving and heating by deionized water, cooling and recrystallizing by the same method, repeating for 2-5 times, and finally drying for 24 hours at 60-90 ℃ in a vacuum drying oven to obtain the allyl compound.
In the above process different aldehyde compounds and phosphorus compounds are selected to obtain allyl compounds of the following structure:
allyl Compound A-1: structural formula (1), R1Is composed of
Allyl Compound A-2: structural formula (1), R1Is composed of
Allyl Compound A-3: structural formula (2), R1Is composed of
Allyl Compound A-4: structural formula (2), R1Is composed of
Allyl Compound A-5: structural formula (1), R1Is composed of
4, 4' -diphenylmethane bismaleimide: xian Shuangma new materials, Inc.;
unmodified bismaleimide: 4, 4' -diphenylmethane bismaleimide and new material of Xian bismaleimide;
filling: silicon dioxide, surface treatment is carried out on the silicon dioxide by using a silane coupling agent, the average grain diameter is 1.0 mu m, and Jiangsu birry;
curing accelerator: 2-methylimidazole, formed in four countries;
phosphorus-containing epoxy resin: KEG-H5138, Kolon;
phosphazene compound: SPB100, Otsuka chemistry;
elastomer: KMP-605, Beacon Chemicals.
The performance evaluation method comprises the following steps:
(1) glass transition temperature (DMA): measured with DMA, the Tg was measured at a temperature rise rate of 10 ℃/min and a frequency of 10Hz, the temperature range: 30-320 ℃.
(2) Peel Strength (PS): the peel strength of the metal cap was tested according to the "post thermal stress" experimental conditions in the IPC-TM-650 method.
(3) Tin immersion heat resistance: A50X 50mm sample with copper on both sides was immersed in solder at 288 ℃ and the time to delamination blistering of the sample was recorded.
(4) Tin immersion heat resistance after moisture treatment: after 3 pieces of 100X 100mm substrate samples were held in a pressure cooker at 121 ℃ and 105Kpa for 3 hours, the samples were immersed in a solder bath at 288 ℃ for 2 minutes to observe whether or not delamination bubbling occurred in the samples, 3/3 for 3 pieces, 2/3 for 2 pieces, 1/3 for 1 piece, and 0/3 for 0 piece.
(5) Water absorption: measured according to the standard method specified in IPC-TM-650 at D23 deg.C/24 hr.
(6) Modulus: the modulus values at 50 ℃ and 260 ℃ were determined in GPa at a heating rate of 10 ℃/min and a frequency of 10Hz, determined by DMA.
(7) Coefficient of thermal expansion: adopting a TA instrument TMA to measure, wherein the temperature rise rate is 10 ℃/min from 30-350 ℃, and the linear expansion coefficient in the surface direction of 50-130 ℃ is measured, and the measurement directions are the transverse direction (X) and the longitudinal direction (Y) of the glass cloth surface, and the unit is X/Y ppm/DEG C.
(8) Flame retardancy: UL94 vertical burning (UL94V), test according to ASTM (D63-77) method, each material test sample number is 5.
According to the invention, the allyl compound containing the DOPO or DPPO structure is used as the bismaleimide resin modifier, on the basis of not affecting the performance of the bismaleimide resin, the phosphorus-containing group is well introduced into the crosslinking network structure of the bismaleimide resin, so that the nitrogen element and the phosphorus element in one crosslinking network structure are cooperatively flame-retardant, the phosphorus content required by the flame retardance of the cured product to reach UL94V-0 can be reduced, other flame retardants are not required to be added, and the cured product with excellent halogen-free flame retardance, high heat resistance, high adhesion, excellent toughness and thermal expansion coefficient is obtained.
It should be understood that although the present description refers to embodiments, not every embodiment contains only a single technical solution, and such description is for clarity only, and those skilled in the art should make the description as a whole, and the technical solutions in the embodiments can also be combined appropriately to form other embodiments understood by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (13)
1. The flame-retardant resin prepolymer is characterized by being prepared by at least pre-polymerizing bismaleimide resin and allyl compounds, wherein the weight ratio of the bismaleimide resin to the allyl compounds is 100:10-100:100, and the allyl compounds contain phosphorus-containing allyl compounds represented by the following structural formula (1) or structural formula (2):
wherein R is1Is a linear or substituted alkylene of C1-C10 or an aromatic group of C6-C20;
the bismaleimide resin has the following structural formula:
wherein, R group is selected from at least one of the following structural formulas:
2. the flame-retardant resin prepolymer according to claim 1, wherein R is1Is a straight-chain alkyl group of C2-C6.
3. The flame-retardant resin prepolymer according to claim 1, wherein the allyl compound further contains a phosphorus-free allyl compound, and the phosphorus-free allyl compound is one or a mixture of two or more of diallyl bisphenol a, diallyl bisphenol S, allyl phenoxy resin, allyl phenol resin, and diallyl diphenyl ether, and the content of the phosphorus-free allyl compound is 10 to 90 parts by mass based on 100 parts by mass of the total allyl compounds.
4. A flame-retardant resin composition comprising, by solid weight:
the flame-retardant resin prepolymer according to any one of claims 1 to 3: 100 parts of (A);
filling: 0-150 parts;
curing accelerator: 0.001-5 parts;
elastomer: 0-50 parts.
5. The flame-retardant resin composition according to claim 4, wherein the filler is an inorganic filler or an organic filler, and the inorganic filler is one or a mixture of at least any two of non-metal oxide, metal nitride, non-metal nitride, inorganic hydrate, inorganic salt, metal hydrate, and inorganic phosphorus; the organic filler is selected from one or a mixture of at least any two of polytetrafluoroethylene powder, polyphenylene sulfide powder or polyether sulfone powder.
6. The flame-retardant resin composition according to claim 4, wherein the filler is any one or a mixture of at least two of fused silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, strontium titanate, calcium carbonate, calcium silicate, mica, and glass fiber powder.
7. The flame-retardant resin composition according to claim 4, wherein the filler is surface-treated silica.
8. The flame-retardant resin composition according to claim 4, wherein the curing accelerator is selected from the group consisting of dimethylaminopyridine, tertiary amines and salts thereof, imidazoles, organic metal salts, triphenylphosphine and phosphonium salts thereof, and is contained in an amount of 0.01 to 2.0 parts based on 100 parts of the flame-retardant resin prepolymer.
9. The flame-retardant resin composition according to claim 4, wherein the elastomer is at least one selected from the group consisting of polybutadienes, styrenes, olefins, polyurethanes, polyesters, polyamines, acrylates and silicones.
10. The flame-retardant resin composition according to claim 4, wherein the elastomer is selected from the group consisting of epoxy-modified polybutadiene, anhydride-modified polybutadiene, styrene-butadiene copolymer, styrene-propylene copolymer and styrene-acrylic copolymer, and the content of the elastomer is 5 to 20 parts based on 100 parts of the flame-retardant resin prepolymer.
11. A prepreg, characterized in that a solvent is added to the flame-retardant resin composition according to any one of claims 4 to 10 to dissolve the flame-retardant resin composition to prepare a glue solution, a reinforcing material is immersed in the glue solution, and the immersed reinforcing material is heated and dried to obtain the prepreg.
12. A laminate obtained by coating at least one prepreg according to claim 11 on both sides with a release film and hot press forming.
13. A laminate which is obtained by coating at least one prepreg according to claim 11 on one or both sides with a metal foil and hot-press forming.
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| PCT/CN2019/119074 WO2020108334A1 (en) | 2018-11-28 | 2019-11-18 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminate prepared using same |
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| CN113061217B (en) * | 2021-05-13 | 2023-04-28 | 泰安亚荣生物科技有限公司 | Preparation method of novel flame retardant for polylactic acid |
| CN114316115B (en) * | 2021-12-31 | 2023-12-26 | 广东盈骅新材料科技有限公司 | Allyl flame-retardant prepolymer, resin composition, composite resin, prepreg and laminated board |
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| CN104725828A (en) * | 2015-03-04 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
| CN104725857A (en) * | 2015-03-05 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
| CN104961895A (en) * | 2014-11-24 | 2015-10-07 | 西安元创化工科技股份有限公司 | Flame-retardant bismaleimide resin |
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| JP2001323268A (en) * | 2000-05-16 | 2001-11-22 | Sanko Kk | Organophosphorus-based flame retardant, method for producing the same and resin composition comprising the same |
| CN101768269B (en) * | 2008-12-29 | 2012-07-18 | 沁阳市天益化工有限公司 | Bismaleimides resin pre-polymer preparation method |
| CN102199351B (en) * | 2011-04-08 | 2012-12-05 | 苏州生益科技有限公司 | Thermosetting resin composition, prepreg and laminated board |
| DE102011116178A1 (en) * | 2011-10-14 | 2013-04-18 | Schill + Seilacher "Struktol" Gmbh | Halogen-free, phosphorus-containing flame retardant |
| CN103755742B (en) * | 2014-02-11 | 2015-07-01 | 厦门大学 | Flame-retardant monomer containing DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) groups and preparation method and application of flame-retardant monomer |
| CN104448823A (en) * | 2014-11-25 | 2015-03-25 | 华东理工大学 | Flame-retardant bismaleimide resin composition and preparation method thereof |
| CN104877134B (en) * | 2015-05-28 | 2017-04-05 | 苏州生益科技有限公司 | Halogen-free flameproof polyimide resin composition and the prepreg made using which and laminate |
| CN105037723B (en) * | 2015-06-26 | 2017-07-07 | 苏州生益科技有限公司 | A kind of Halogen-free flame-retardant prepolymer and the prepreg and laminate that are made using it |
| TWI601753B (en) * | 2016-05-27 | 2017-10-11 | 台光電子材料股份有限公司 | Phosphorus-containing olefin polymer, method for preparing the same, and composition and article comprising the same |
| CN107815033A (en) * | 2016-09-14 | 2018-03-20 | 广东广山新材料股份有限公司 | A kind of flame-proofed polystyrene plastics and preparation method thereof |
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| CN109535628B (en) * | 2018-11-28 | 2020-11-24 | 苏州生益科技有限公司 | Flame-retardant resin prepolymer, and thermosetting resin composition, prepreg and laminated board prepared from same |
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| CN104961895A (en) * | 2014-11-24 | 2015-10-07 | 西安元创化工科技股份有限公司 | Flame-retardant bismaleimide resin |
| CN104725828A (en) * | 2015-03-04 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
| CN104725857A (en) * | 2015-03-05 | 2015-06-24 | 广东生益科技股份有限公司 | Resin composition, prepreg using resin composition and laminate |
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