CN116253625A - Fluorine-containing allyl compound, modified bismaleimide resin, preparation method and application thereof - Google Patents
Fluorine-containing allyl compound, modified bismaleimide resin, preparation method and application thereof Download PDFInfo
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- CN116253625A CN116253625A CN202211694316.6A CN202211694316A CN116253625A CN 116253625 A CN116253625 A CN 116253625A CN 202211694316 A CN202211694316 A CN 202211694316A CN 116253625 A CN116253625 A CN 116253625A
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- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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Abstract
The invention relates to a fluorine-containing allyl compound, modified bismaleimide resin, and a preparation method and application thereof. The fluorine-containing allyl compound has a structure shown in a formula (I), and can be used for the modified bismaleimide resin, so that the modified bismaleimide resin has the advantages of excellent heat resistance, low water absorption, high modulus, low dielectric constant and dielectric loss, can be further used for preparing resin compositions, prepregs, laminated boards and printed circuit boards, and is applied to the fields of high-density interconnection integrated circuit packaging, high-frequency high-speed and other high-performance printed circuit boards.
Description
Technical Field
The invention relates to the technical field of polymer modification, in particular to a fluorine-containing allyl compound, modified bismaleimide resin, and a preparation method and application thereof.
Background
With the rapid development of the electronic industry, parts of electronic products are continuously developed in the directions of light weight, thin weight, short weight, small weight and the like, and electronic components need higher signal propagation speed and transmission efficiency, so that the market demands on high-frequency and high-speed printed circuit boards are increasing, and therefore, higher demands are also put forward on copper-clad plates serving as carriers and resin base materials used by the copper-clad plates.
Solutions for preparing high-frequency resin compositions excellent in dielectric properties by compounding fluorine-containing benzoxazine prepolymers with epoxy resins have been reported. The fluorine-containing benzoxazine prepolymer has an oxazine ring structure, can reduce the concentration of hydroxyl groups generated during resin curing, relatively improve the content of benzene rings, greatly reduce the dielectric constant and dielectric loss of products, but easily lead to insufficient heat resistance and reduced high-temperature modulus due to the addition of a large amount of benzoxazine.
The bismaleimide resin (BMI) has excellent heat resistance and thermal stability, low curing shrinkage and good thermal expansion performance, so that the bismaleimide resin becomes a common resin matrix in a high-performance copper-clad plate. However, unmodified bismaleimides have poor solubility, high crosslinking density, brittle cured properties, and difficulty in use alone, and can be used after modification with a modifier. Diamine modified bismaleimide resin is often used for preparing an electric plate substrate in the traditional technology, but the defects of high curing temperature, high water absorption, high dielectric constant, high loss value and the like exist.
In summary, how to obtain a novel modifier, which is used for modifying bismaleimide resin, and to prepare a resin substrate with excellent heat resistance, low water absorption, high modulus and low dielectric constant and dielectric loss value is a difficult problem in the field.
Disclosure of Invention
Based on this, the present invention provides a novel modifier which is used for the modification of bismaleimide resin to prepare a modified bismaleimide resin having excellent heat resistance, low water absorption, high modulus, low dielectric constant and dielectric loss at the same time, and which can be used for preparing a resin composition, a prepreg, a laminate and a printed circuit board.
The technical proposal is as follows:
a fluorine-containing allyl compound having a structure represented by formula (I):
the invention also provides a preparation method of the fluorine-containing allyl compound, which comprises the following steps:
mixing hexafluorobisphenol AF, alkali and a catalyst in a solvent to prepare a suspension;
the suspension was mixed with bromopropene and reacted.
In one embodiment, the molar ratio of the hexafluorobisphenol AF, the alkali and the bromopropene is 1 (0.2-4): 0.2-6.
In one embodiment, the base is selected from one or more of potassium cesium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
In one embodiment, the catalyst is selected from one or more of potassium iodide, cesium iodide and sodium iodide.
The invention also provides a modified bismaleimide resin, the raw materials of which comprise a modifier and the bismaleimide resin;
the modifier comprises a fluorine-containing allyl compound shown in the formula (I);
in one embodiment, the mass ratio of the fluorine-containing allyl compound to the bismaleimide resin is (0.5 to 1): 1.
in one embodiment, the modifier further comprises one or more of 2,2' diallyl bisphenol A, 2' diallyl bisphenol S, 2' diallyl bisphenol F, and bisphenol A bis allyl ether.
In one embodiment, the bismaleimide resin contains two or more maleimide groups.
In one embodiment, the monomer of the bismaleimide resin is selected from one or more of N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, polyphenyl methane bismaleimide, bismaleimide containing biphenyl structures, and polymaleimide.
The invention also provides a preparation method of the modified bismaleimide resin, which comprises the following steps:
mixing the modifier with bismaleimide resin and reacting at 100-150 ℃.
In one embodiment, the reaction time is 60min to 120min.
In one embodiment, the method for preparing the modified bismaleimide resin further comprises the following steps of preparing the fluorine-containing allyl compound shown in the formula (I):
mixing hexafluorobisphenol AF, alkali and a catalyst in a solvent to prepare a suspension;
the suspension was mixed with bromopropene and reacted.
The invention also provides application of the modified bismaleimide resin, and the technical scheme is as follows:
a resin composition comprises the following components in parts by weight:
30-80 parts of modified bismaleimide resin;
20-60 parts of cyanate resin; and
5-20 parts of functional resin.
In one embodiment, the cyanate resin is selected from one or more of bisphenol a type cyanate resin, phenolic type cyanate resin, bisphenol F type cyanate resin, multifunctional type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin, and dicyclopentadiene bisphenol type cyanate resin.
In one embodiment, the functional resin is selected from one or more of epoxy resin, benzoxazine and polybutadiene.
In one embodiment, the resin composition further comprises one or more of a flame retardant, a filler, a curing accelerator, a coupling agent, and a toughening agent.
In one embodiment, the resin composition includes 5 to 20 parts by mass of a flame retardant and 0 to 40 parts by mass of a filler.
In one embodiment, the flame retardant is selected from one or more of decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate compound and phosphorus-containing cyanate.
In one embodiment, the filler is selected from one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramic, eucryptite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay, and kaolin.
A prepreg comprising a modified bismaleimide resin as described above, or a resin composition as described above.
A laminate comprising a modified bismaleimide resin as described above, or a resin composition as described above, or a prepreg as described above.
In one embodiment, the laminate further comprises at least one layer of metal foil on one or both sides of the prepreg.
A printed circuit board comprising a modified bismaleimide resin as described above, or a resin composition as described above, or a prepreg as described above, or a laminate as described above.
The invention has the following beneficial effects:
the invention provides a fluorine-containing allyl compound shown in a formula (I), which is prepared by modifying bismaleimide by adopting a modifier containing the fluorine-containing allyl compound shown in the formula (I), wherein a carbon-carbon unsaturated double bond in the molecular structure of the bismaleimide is an electron-deficient double bond due to the electron-withdrawing effect of carbonyl, the double bond and the fluorine-containing allyl compound firstly undergo ene addition reaction to generate an intermediate, the double bond of BMI and the intermediate undergo Diels-Alder cyclization reaction, and finally the modified bismaleimide resin with a trapezoid structure and high crosslinking degree is prepared, and has excellent heat resistance, low water absorption rate, high modulus, low dielectric constant and dielectric loss.
The modified bismaleimide resin is used for preparing a resin composition, has excellent heat resistance, low water absorption, high modulus and excellent dielectric property, and can be used for preparing prepregs and laminated boards, and further applied to the fields of high-density interconnection integrated circuit packaging, high-frequency high-speed and other high-performance printed circuit boards.
Detailed Description
The following detailed description of the present invention will provide further details in order to make the above-mentioned objects, features and advantages of the present invention more comprehensible. In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. The present invention may be embodied in many other forms than described herein and similarly modified by those skilled in the art without departing from the spirit of the invention, whereby the invention is not limited to the specific embodiments disclosed below.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
In the present invention, the numerical ranges are referred to as continuous, and include the minimum and maximum values of the ranges, and each value between such minimum and maximum values, unless otherwise specified. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a treatment within a predetermined temperature range. The constant temperature process allows the temperature to fluctuate within the accuracy of the instrument control.
In the present invention, referring to a unit of a data range, if a unit is only carried behind a right end point, the units indicating the left and right end points are the same. For example, 150-160 ℃ means that the units of the left end point "150" and the right end point "160" are both ℃ (degrees celsius).
In the description of the invention, the meaning of "several" in the present invention is at least two, for example, two, three, etc., unless explicitly defined otherwise. In the description of the present application, the meaning of "several" means at least one, such as one, two, etc., unless explicitly defined otherwise.
All embodiments of the invention and alternative embodiments may be combined with each other to form new solutions, unless otherwise specified.
All the steps of the present invention may be performed sequentially or randomly, preferably sequentially, unless otherwise specified. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further comprise step (c), meaning that step (c) may be added to the method in any order, e.g., the method may comprise steps (a), (b) and (c), steps (a), (c) and (b), steps (c), (a) and (b), etc.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, unless a specifically defined term is used, such as "consisting of … … only," etc., another component may be added.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
The invention provides a novel modifier which is used for modifying bismaleimide resin to prepare modified bismaleimide resin with excellent heat resistance, low water absorption, high modulus, low dielectric constant and dielectric loss, and can be used for preparing resin compositions, prepregs, laminated boards and printed circuit boards.
The technical proposal is as follows:
a fluorine-containing allyl compound having a structure represented by formula (I):
the invention also provides a preparation method of the fluorine-containing allyl compound, which comprises the following steps:
mixing hexafluorobisphenol AF, alkali and a catalyst in a solvent to prepare a suspension;
the suspension was mixed with bromopropene and reacted.
In one embodiment, the molar ratio of hexafluorobisphenol AF to base is 1 (0.2-4).
In one embodiment, the base is selected from one or more of potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
In one embodiment, the mass ratio of hexafluorobisphenol AF to catalyst is 100: (0.1-10).
In one embodiment, the catalyst is selected from one or more of potassium iodide, cesium iodide and sodium iodide.
In one embodiment, the molar ratio of hexafluorobisphenol AF to bromopropene is 1 (0.2-6).
In one embodiment, the solvent is selected from one or more of acetone, N-dimethylformamide, N-dimethylacetamide, tetrahydrofuran, methyltetrahydrofuran and dimethylsulfoxide.
In one embodiment, the suspension is mixed with bromopropene and the reaction step is performed in a protective gas atmosphere (e.g., nitrogen, argon).
In one embodiment, the fluoroallyl compound of formula (I) is prepared as follows:
1. hexafluorobisphenol AF (0.4 mol,134.5 g) was weighed into a three-necked flask, 300mL of acetone was weighed and stirred to dissolve completely, anhydrous potassium carbonate (0.1 mol,138.2 g) and potassium iodide (3 wt.% hexafluorobisphenol AF,4.035 g) were weighed into the flask, and the rotational speed was adjusted to suspend the solid in the solution;
2. bromopropene (0.1 mol,120.98 g) was added under nitrogen, and the mixture was refluxed under stirring at 60℃for 26 hours, and the reaction was finally detected by a spot plate;
3. after the reaction is finished, filtering out potassium carbonate and potassium iodide solids; distilling the liquid under reduced pressure to remove acetone;
4. Purifying the liquid obtained after reduced pressure distillation by chromatography (eluent: pure petroleum ether), removing petroleum ether by rotary evaporation to obtain colorless oily liquid, and drying to obtain fluorine-containing allyl compound shown in formula (I), named as 2, 2-bis (4-allyloxyphenyl) hexafluoropropane.
The invention also provides a modified bismaleimide resin, the raw materials of which comprise a modifier and the bismaleimide resin;
the modifier comprises a fluorine-containing allyl compound shown in a formula (I);
the invention adopts a modifier containing fluorine-containing allyl compounds shown in a formula (I) to modify bismaleimide, wherein, due to electron-withdrawing effect of carbonyl groups, carbon-carbon unsaturated double bonds in the molecular structure of the bismaleimide are electron-deficient double bonds, the double bonds and the fluorine-containing allyl compounds firstly undergo ene addition reaction to generate an intermediate, the double bonds of BMI and the intermediate undergo Diels-Alder cyclization reaction, and finally the trapezoid structure modified bismaleimide resin with high crosslinking degree is generated, which has excellent heat resistance, low water absorption rate, high modulus, low dielectric constant and dielectric loss.
In one embodiment, the mass ratio of the fluorine-containing allyl compound to the bismaleimide resin is (0.5 to 1): 1, if the fluorine-containing allyl compound is too small, there is a limit in improving the electric properties of the bismaleimide resin, and if the fluorine-containing allyl compound is too large, the processability of the bismaleimide resin is affected. It will be appreciated that the mass ratio of the fluorine-containing allyl compound to the bismaleimide resin includes, but is not limited to, 0.5: 1. 0.55: 1. 0.6: 1. 0.65: 1. 0.7: 1. 0.75: 1. 0.8: 1. 0.85: 1. 0.9: 1. 0.95:1 and 1:1, preferably, the mass ratio of the fluorine-containing allyl compound to the bismaleimide resin is (0.5 to 0.8): 1.
In one embodiment, the modifier further comprises one or more of 2,2' diallyl bisphenol A, 2' diallyl bisphenol S, 2' diallyl bisphenol F and bisphenol A diallyl ether, and the fluorine-containing allyl compound and the modifier are compounded to give the bismaleimide resin substrate better adhesion.
Preferably, in one embodiment, the modifier is compounded by a fluorine-containing allyl compound shown in the formula (I) and 2,2' -diallyl bisphenol A according to the mass ratio of (0.1-10): 1.
Preferably, in one embodiment, the modifier is compounded by a fluorine-containing allyl compound shown in the formula (I) and 2,2' -diallyl bisphenol S according to the mass ratio of (0.1-10): 1.
Preferably, in one embodiment, the modifier is compounded by a fluorine-containing allyl compound shown in the formula (I) and diallyl bisphenol F according to the mass ratio of (0.1-10): 1.
Preferably, in one embodiment, the modifier is compounded by fluorine-containing allyl compound shown in formula (I) and bisphenol A diallyl ether according to a mass ratio of (0.1-10): 1.
In one embodiment, the bismaleimide resin contains two or more maleimide groups.
In one embodiment, the monomer of the bismaleimide resin is selected from one or more of N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, polyphenyl methane bismaleimide, bismaleimide containing biphenyl structures, and polymaleimide.
The invention also provides a preparation method of the modified bismaleimide resin, which comprises the following steps:
mixing the modifier with bismaleimide resin and reacting at 100-150 ℃.
In one embodiment, the reaction time is 60min to 120min.
In one embodiment, the preparation method of the modified bismaleimide resin comprises the following steps:
heating a fluorine-containing allyl compound shown in a formula (I) to a molten state, adding bismaleimide resin, performing reaction and prepolymerization at 100-150 ℃ for 60-120min, and cooling to room temperature to obtain the modified bismaleimide resin.
The invention also provides application of the modified bismaleimide resin, and the technical scheme is as follows:
a resin composition comprises the following components in parts by weight:
30-80 parts of modified bismaleimide resin;
20-60 parts of cyanate resin; and
5-20 parts of functional resin.
The modified bismaleimide resin, the cyanate resin and the functional resin are compounded for use to prepare a resin composition, so that the resin composition also has excellent heat resistance, low water absorption, high modulus and excellent dielectric properties.
It is understood that in the present invention, the resin composition contains 30 to 80 parts by mass of the modified bismaleimide resin, including but not limited to 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts and 80 parts, preferably 40 to 60 parts.
It is understood that in the present invention, the resin composition contains 20 parts to 60 parts by mass of the cyanate resin, including but not limited to 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts and 60 parts, preferably 30 parts to 50 parts.
In one embodiment, the cyanate resin is selected from one or more of bisphenol a type cyanate resin, phenolic type cyanate resin, bisphenol F type cyanate resin, multifunctional type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin, and dicyclopentadiene bisphenol type cyanate resin.
It is understood that in the present invention, the resin composition contains 5 to 20 parts by mass of the functional resin, including but not limited to 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, 18 parts and 20 parts, preferably 5 to 15 parts.
In one embodiment, the functional resin is selected from one or more of epoxy resin, benzoxazine and polybutadiene.
In one embodiment, the epoxy resin is selected from one or more of bisphenol a type epoxy resin, bisphenol F type epoxy resin, novolac type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, biphenyl type epoxy resin, anthracene type epoxy resin, multifunctional epoxy resin, and hydrogenated epoxy resin.
In one embodiment, the benzoxazine is selected from one or more of bisphenol a type benzoxazine, bisphenol F type benzoxazine, DCPD type benzoxazine, phenolphthalein type benzoxazine, phosphorus-containing benzoxazine, ODA type benzoxazine, allylbenzoxazine and diamine type benzoxazine.
In one embodiment, the polybutadiene preferably has a number average molecular weight of 1000g/mol to 5000g/mol.
In one embodiment, the resin composition further comprises one or more of a flame retardant, a filler, a curing accelerator, a coupling agent, and a toughening agent.
In the invention, the fluorine-containing allyl compound shown in the formula (I) can reach the UL94V0 flame retardant grade by adding a small amount of flame retardant under the synergistic flame retardant effect of fluorine and nitrogen, so that the negative problem caused by adding a large amount of flame retardant in the traditional mode is avoided.
In one embodiment, the resin composition includes 5 parts to 20 parts of flame retardant, including but not limited to 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 16 parts, 18 parts, and 20 parts, preferably 5 parts to 10 parts, by mass.
In one embodiment, the flame retardant is selected from one or more of decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate compound and phosphorus-containing cyanate.
In one embodiment, the resin composition includes 0 to 40 parts of filler, including but not limited to 0, 0.01, 0.1, 1, 2, 5, 8, 10, 12, 15, 16, 18, 20, 25, 30, 35 and 40 parts, preferably 0.1 to 40 parts, and more preferably 10 to 30 parts, by mass.
In one embodiment, the filler is selected from one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramic, eucryptite, silica (spherical, composite and fused), quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.
In one embodiment, the curing accelerator is selected from one or more of tertiary amine accelerators, imidazole accelerators, peroxide accelerators, organophosphorus accelerators and transition metal carboxylate accelerators.
In one embodiment, the coupling agent is selected from one or more of silane coupling agent, titanate coupling agent, aluminate coupling agent, metal composite coupling agent, phosphate coupling agent and borate coupling agent.
In one embodiment, the toughening agent is selected from one or more of styrene-butadiene rubber, phenol-oxygen resin, nitrile rubber and polyurethane.
In one embodiment, the resin composition comprises the following components in parts by weight:
In one embodiment, the resin composition comprises the following components in parts by weight:
in one embodiment, the resin composition comprises the following components in parts by weight:
the invention also provides a prepreg comprising a modified bismaleimide resin as described above, or a resin composition as described above.
The invention also provides a preparation method of the prepreg, which comprises the following steps:
and (3) covering the surface of the reinforcing material with the resin composition by adopting an impregnation method, and heating to semi-solidification to obtain the prepreg.
The semi-curing process parameters are as follows: heating to 150-250 deg.c for 2-10 min.
The reinforcing material is an inorganic fibrous material or an organic fibrous material, and the inorganic fibrous reinforcing material includes, but is not limited to, glass fibers (including E, NE, D, S, T and other types), carbon fibers, silicon carbide fibers, asbestos fibers and the like. Organic fiber-reinforced materials include, but are not limited to, nylon, ultra-high molecular weight polyethylene fibers, aramid fibers, polyimide fibers, polyester fibers, cotton fibers, and the like.
The invention also provides a laminate comprising a modified bismaleimide resin as described above, or a resin composition as described above, or a prepreg as described above.
In one embodiment, the laminate further comprises at least one layer of metal foil on one or both sides of the prepreg.
The invention also provides a preparation method of the laminated board, which comprises the following steps:
several of the above prepregs were laminated.
In one embodiment, the lamination process parameters are: at a temperature of 150 to 300 ℃ and a pressure of 10kgf/cm 2 ～30kgf/cm 2 And hot-press forming for 200-400 min under the condition that the vacuum degree is less than 2 kPa.
It will be understood that the "number of said prepregs" refers to at least one of said prepregs.
It will be appreciated that it is also possible to laminate a plurality of said prepregs, i.e. laminates, on one or both sides of the laminate, with metal foil, and then laminate to obtain a metal foil clad laminate.
In one embodiment, the metal copper foil has a thickness of 3 μm to 105 μm, including but not limited to 3 μm, 5 μm, 8 μm, 10 μm, 15 μm, 18 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, and 105 μm.
The invention also provides a printed circuit board comprising a modified bismaleimide resin as described above, or a resin composition as described above, or a prepreg as described above, or a laminate as described above.
The following is a description of the specific examples (the examples below are not specifically described and do not contain other components not explicitly indicated except for unavoidable impurities).
(1) The raw material description:
the following raw materials are all available from commercial products:
bismaleimide resin-1 is available from KI chemistry under the model BMI-80;
bismaleimide resin-2 is commercially available from large and chemical industries under the model BMI-5100.
Bisphenol A type cyanate ester is available from Dragon sand group under the model BA-230S.
2,2' -diallyl bisphenol A was purchased from Honghu bismaleimide resin plants;
2,2' -diallyl bisphenol S is available from Japanese chemical under the model ARM019;
bisphenol a bis allyl ether is available from lagoons bis horse resin factories.
DCPD-type benzoxazines are available from Henschel under the model number LPY 11051;
DCPD type epoxy resins are commercially available from Japan chemical under the model XD-1000.
Flame retardants are commercially available from Daba chemistry, model number PX200.
Spherical silica is available from jacobian under the model number SC6500-SXD.
2-methylimidazole is available from four kingdoms.
(2) Synthesis example:
the preparation method of the fluorine-containing allyl compound shown in the formula (I) comprises the following steps:
1. hexafluorobisphenol AF (0.4 mol,134.5 g) was weighed into a three-necked flask, 300mL of acetone was weighed and stirred to dissolve completely, anhydrous potassium carbonate (0.1 mol,138.2 g) and potassium iodide (3 wt.% hexafluorobisphenol AF,4.035 g) were weighed into the flask, and the rotational speed was adjusted to suspend the solid in the solution;
2. Bromopropene (0.1 mol,120.98 g) was added under nitrogen, and the mixture was refluxed under stirring at 60℃for 26 hours, and the reaction was finally detected by a spot plate;
3. after the reaction is finished, filtering out potassium carbonate and potassium iodide solids; distilling the liquid under reduced pressure to remove acetone;
4. the liquid obtained after distillation under reduced pressure was purified by column chromatography (eluent: pure petroleum ether), and petroleum ether was removed by rotary distillation to obtain colorless oily liquid, which was dried to obtain a fluorine-containing allyl compound represented by the formula (I), named 2, 2-bis (4-allyloxyphenyl) hexafluoropropane, as a modifier for bismaleimide resin in the following examples.
Example 1:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin A is obtained.
(2) 40 parts of the modified bismaleimide resin A, 40 parts of bisphenol A type cyanate resin and 10 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 10 parts of spherical silicon dioxide, 10 parts of flame retardant and 3 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Example 2:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin A is obtained.
(2) 50 parts of the modified bismaleimide resin A, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Example 3:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin A is obtained.
(2) 60 parts of the modified bismaleimide resin A, 30 parts of bisphenol A type cyanate resin and 5 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, adding 20 parts of spherical silicon dioxide, 8 parts of flame retardant and 1 part of 2-methylimidazole, and continuing stirring to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Impregnating the modified bismaleimide resin compositionBaking at 180deg.C for 3min in a heated air circulation oven to obtain prepreg with resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Example 4:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) 50 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane, 20 parts of 2,2' -diallyl bisphenol A and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin B is obtained.
(2) 50 parts of the modified bismaleimide resin B, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Example 5:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin A is obtained.
(2) 50 parts of the modified bismaleimide resin A, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type benzoxazine are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Example 6:
the embodiment provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, uniformly mixing 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-2, carrying out reaction and prepolymerization for 90min at 120 ℃, and cooling to room temperature to obtain modified bismaleimide resin C.
(2) 50 parts of the modified bismaleimide resin C, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Comparative example 1:
the comparative example provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) 70 parts of 2,2' -diallyl bisphenol A are firstly added
And 100 parts of bismaleimide resin are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin D is obtained.
(2) 50 parts of the modified bismaleimide resin D, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Impregnating the modified bismaleimide resin composition withBaking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Comparative example 2:
the comparative example provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) 70 parts of 2,2' -diallyl bisphenol S
And 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide prepolymer E is obtained.
(2) 50 parts of the modified bismaleimide resin E, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Comparative example 3:
the comparative example provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) 70 parts of bisphenol A bis allyl ether are first prepared
And 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90min at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin F is obtained.
(2) 50 parts of the modified bismaleimide resin F, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Comparative example 4:
the comparative example provides a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) 50 parts of bismaleimide resin-1, 50 parts of bisphenol A type cyanate resin and 15 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, 30 parts of spherical silicon dioxide, 5 parts of flame retardant and 5 parts of 2-methylimidazole are added, and stirring is continued to obtain uniform glue solution, namely the bismaleimide resin composition.
(2) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the bismaleimide resin composition, and baking at 180 ℃ for 3min in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(3) 6 prepregs are laminated, an electrolytic copper foil with a thickness of 18 μm is covered on the upper and lower surfaces of the laminated body, and the laminated body is placed in a vacuum press with programmable temperature and pressure control, and the laminated body is placed in a vacuum state at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
Comparative example 5:
the comparative example provides a modified bismaleimide resin and a preparation method thereof, a resin composition and a preparation method thereof, a prepreg and a preparation method thereof, a laminated board and a preparation method thereof, and the specific steps are as follows:
(1) Firstly, 70 parts of 2, 2-bis (4-allyloxyphenyl) hexafluoropropane and 100 parts of bismaleimide resin-1 are uniformly mixed, and the mixture is reacted and prepolymerized for 90 minutes at 120 ℃ and then cooled to room temperature, so that the modified bismaleimide resin A is obtained.
(2) 90 parts of the modified bismaleimide resin A, 30 parts of bisphenol A type cyanate resin and 5 parts of DCPD type epoxy resin are sequentially dissolved in a mixed solvent of butanone, toluene and propylene glycol methyl ether, wherein the butanone, the toluene and the propylene glycol methyl ether are mixed according to a mass ratio of 1:1:1. Under the stirring condition, adding 20 parts of spherical silicon dioxide, 8 parts of flame retardant and 1 part of 2-methylimidazole, and continuing stirring to obtain uniform glue solution, namely the modified bismaleimide resin composition.
(3) 2116 glass fiber cloth (basis weight 105 g/m) 2 ) Soaking in the modified bismaleimide resin composition, and baking for 3min at 180 ℃ in a hot air circulation oven to obtain the prepreg with the resin content of 50%.
(4) 6 prepregs are laminated, an electrolytic copper foil with the thickness of 18 mu m is respectively covered on the upper surface and the lower surface of the laminated body, and the laminated body is placed in a programmable temperature control and pressure control modeIn a vacuum press, in a vacuum state, at 30kgf/cm 2 And curing at 220 ℃ for 3 hours to prepare the copper clad laminate with the thickness of 0.6 mm.
1) The composition of the resin compositions in the above examples and comparative examples is shown in Table 1 below:
TABLE 1
2) The copper clad laminates produced in examples 1 to 6 and comparative examples 1 to 5 were subjected to performance test by the following method:
(1) Peel strength: the test method is carried out according to IPC-TM-650.2.4.8;
(2) Glass transition temperature (Tg): according to IPC-TM650 2.4.25D test;
(3) Thermal decomposition temperature (Td): according to IPC-TM650 2.4.24.6 test;
(4) Modulus of elasticity: according to GB/T22315-2008 test;
(5) Flame retardant: according to IPC-TM650 2.3.10 test;
(6) Water absorption rate: according to IPC-TM650 2.6.2.1 test;
(7) Dk/Df: tested according to IPC-TM650 2.5.5.2.
The test results are shown in Table 2 below:
TABLE 2
As is clear from Table 2, examples 1 to 6, which are within the scope of the present invention, are excellent in peel strength, heat resistance, water absorption, elastic modulus, dielectric properties, flame retardant properties, etc., and have greatly improved properties as compared with comparative examples 1 to 3 using conventional modifiers. While comparative example 4 is an unmodified bismaleimide, the performance is the worst, indicating that unmodified bismaleimide is difficult to use. It is understood from comparative example 5 that the addition amount of each raw material is important for the performance of the copper clad laminate.
In addition, the modifier provided by the invention contains fluorine element, so that the modifier can be synergistic with nitrogen element, the flame retardant property is greatly improved, and the UL94V0 grade can be achieved by only adding a small amount of flame retardant.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (17)
1. A fluorine-containing allyl compound having a structure represented by formula (I):
2. a process for the preparation of a fluorine-containing allyl compound as claimed in claim 1, comprising the steps of:
Mixing hexafluorobisphenol AF, alkali and a catalyst in a solvent to prepare a suspension;
the suspension was mixed with bromopropene and reacted.
3. The method for producing a fluorine-containing allyl compound according to claim 2, wherein the molar ratio of hexafluorobisphenol AF, base and bromopropene is 1 (0.2 to 4): (0.2 to 6); and/or
The alkali is selected from one or more of potassium carbonate, cesium carbonate, sodium carbonate, potassium hydroxide, sodium hydroxide, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide and tetrabutyl ammonium hydroxide; and/or
The catalyst is one or more selected from potassium iodide, cesium iodide and sodium iodide.
4. The modified bismaleimide resin is characterized in that the raw materials comprise a modifier and the bismaleimide resin;
the modifier comprises a fluorine-containing allyl compound represented by the formula (I) as claimed in any one of claims 1 to 3;
5. the modified bismaleimide resin according to claim 4 wherein the mass ratio of the fluorine-containing allyl compound to the bismaleimide resin is (0.5 to 1): 1.
6. the modified bismaleimide resin according to claim 4 wherein the modifier further comprises one or more of 2,2' -diallylbisphenol a, 2' -diallylbisphenol S, 2' -diallylbisphenol F and bisphenol a bis allyl ether.
7. The modified bismaleimide resin according to any one of claims 4 to 6 wherein the bismaleimide resin contains two or more maleimide groups.
8. The modified bismaleimide resin according to claim 7 wherein the monomer of the bismaleimide resin is selected from one or more of N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methylphenyl) maleimide, N- (2, 6-dimethylphenyl) maleimide, bis (4-maleimidophenyl) methane, 2-bis (4- (4-maleimidophenoxy) -phenyl) propane, bis (3, 5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3, 5-diethyl-4-maleimidophenyl) methane, polyphenylmethane bismaleimide, bismaleimide containing biphenyl structures and polymaleimide.
9. The method for producing a modified bismaleimide resin according to any one of claims 4 to 8 comprising the steps of:
mixing the modifier with bismaleimide resin and reacting at 100-150 ℃.
10. The resin composition is characterized by comprising the following components in parts by weight:
30 to 80 parts of the modified bismaleimide resin according to any one of claims 4 to 8;
20-60 parts of cyanate resin; and
5-20 parts of functional resin.
11. The resin composition according to claim 10, wherein the cyanate resin is one or more selected from the group consisting of bisphenol a type cyanate resin, phenolic type cyanate resin, bisphenol F type cyanate resin, multifunctional type cyanate resin, bisphenol M type cyanate resin, bisphenol E type cyanate resin and dicyclopentadiene bisphenol type cyanate resin; and/or
The functional resin is selected from one or more of epoxy resin, benzoxazine and polybutadiene.
12. The resin composition according to claim 10 or 11, further comprising one or more of a flame retardant, a filler, a curing accelerator, a coupling agent and a toughening agent.
13. The resin composition according to claim 12, wherein the resin composition comprises 5 to 20 parts by mass of the flame retardant and 0 to 40 parts by mass of the filler; and/or
The flame retardant is one or more selected from decabromodiphenylethane, tetrabromobisphenol A, brominated epoxy resin, phosphorus-containing phenolic resin, phosphazene compound, phosphate compound and phosphorus-containing cyanate; and/or
The filler is one or more selected from zirconium vanadate, zirconium tungstate, hafnium tungstate, glass ceramics, eucryptite, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talcum powder, aluminum oxide, silicon carbide, boron nitride, aluminum nitride, molybdenum oxide, barium sulfate, zinc molybdate, zinc borate, zinc stannate, zinc oxide, strontium titanate, barium titanate, calcium titanate, clay and kaolin.
14. A prepreg comprising the modified bismaleimide resin according to any one of claims 4 to 8 or the resin composition according to any one of claims 10 to 13.
15. A laminate comprising the modified bismaleimide resin according to any one of claims 4 to 8 or the resin composition according to any one of claims 10 to 13 or the prepreg according to claim 14.
16. The laminate of claim 15, further comprising at least one layer of metal foil on one or both sides of the prepreg.
17. A printed circuit board comprising the modified bismaleimide resin according to any one of claims 4 to 8 or the resin composition according to any one of claims 10 to 13 or the prepreg according to claim 14 or the laminate according to claim 15 or 16.
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| CN202211694316.6A CN116253625A (en) | 2022-12-28 | 2022-12-28 | Fluorine-containing allyl compound, modified bismaleimide resin, preparation method and application thereof |
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|---|---|---|---|
| CN202211694316.6A CN116253625A (en) | 2022-12-28 | 2022-12-28 | Fluorine-containing allyl compound, modified bismaleimide resin, preparation method and application thereof |
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