Resin composition, prepreg, laminate and method for producing the same

Abstract

The application provides a resin composition, a prepreg, a laminated board and a preparation method thereof. The resin composition comprises the following components in parts by mass: 40-100 parts of phthalonitrile-terminated polyphenyl ether, 10-40 parts of phenolphthalein-based polyaryletheramine and 10-60 parts of inorganic filler; the structure of the phthalonitrile-terminated polyphenyl ether is shown in formula (I), and the structure of the phenolphthalein-based polyaryletheramine is shown in formula (II); wherein a, m and n are all positive integers, and Y is C1-C3 alkylene or a single bond. The laminated board prepared from the resin composition has high peeling strength, high decomposition temperature, high elastic modulus, good flame retardation, low dielectric coefficient, low water absorption and other excellent comprehensive properties.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of resin compositions, in particular to a resin composition, prepreg, laminated board and a preparation method thereof. BACKGROUND

[0002] With the development of electronic circuits towards miniaturization, diversification and high-density interconnection, higher requirements are put forward for the performance of copper-clad plates. Compared with traditional epoxy resin-based copper-clad plates, new copper-clad plates must have higher glass transition temperature, high thermal decomposition temperature, flame retardancy, high modulus, low thermal expansion coefficient, and low dielectric constant and dielectric loss, etc.

[0003] Poly 2,6-dimethyl-1,4-phenyl ether, also known as polyphenyl ether, is abbreviated as PPO. As a resin with low dielectric constant and dielectric loss, low thermal expansion coefficient and low water absorption, it can be applied to the preparation of high-frequency high-speed copper-clad plates. However, as a thermoplastic resin, it has the disadvantages of low glass transition temperature, insufficient initial thermal decomposition temperature, poor mechanical strength and poor solvent resistance, which limits its further application.

[0004] In order to improve this situation, researchers have made chemical modifications to polyphenyl ether to have higher glass transition temperature, initial thermal decomposition temperature, low dielectric loss and low water absorption. However, its glass transition temperature and initial thermal decomposition temperature are still low, which cannot meet the application requirements of copper-clad plate laminates.

[0005] Therefore, the traditional technology still needs to be further improved. SUMMARY

[0006] Therefore, the traditional technology still needs to be further improved.

[0007] According to a first aspect of the present application, a resin composition is provided, which comprises the following components in parts by mass: 40-100 parts of phthalonitrile-terminated polyphenyl ether, 10-40 parts of phenolphthalein-based polyaryletheramine and 10-60 parts of inorganic filler.

[0008] The structure of the phthalonitrile-terminated polyphenyl ether is shown in formula (I), and the structure of the phenolphthalein-based polyaryletheramine is shown in formula (II):

[0009]

[0010]

[0011] wherein a, m and n are positive integers, and Y is C1-C3 alkylene or a single bond.

[0012] In some embodiments, the resin composition satisfies at least one of the following characteristics:

[0013] (1) the mass fraction of the phthalonitrile-terminated polyphenyl ether is 40-60 parts;

[0014] (2) the mass fraction of the phenolphthalein-based polyaryletheramine is 10-30 parts;

[0015] (3) the mass fraction of the inorganic filler is 30-60 parts.

[0016] In some embodiments, the inorganic filler comprises one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, lithium spodumene, silicon dioxide, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc 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.

[0017] In some embodiments, the components of the resin composition further comprise one or more of a curing accelerator, a coupling agent, a toughening agent, and an organic solvent.

[0018] Optionally, the curing accelerator comprises one or more of 4,4'-methylenebis(2-ethyl)aniline, 2,2'-diallyl bisphenol A, and anhydrous copper chloride.

[0019] Optionally, the coupling agent comprises one or more of KH-550 and KH-560.

[0020] According to a second aspect of the present application, there is provided a method for preparing the resin composition as described above, comprising the following steps: mixing the components of the resin composition to obtain the resin composition.

[0021] In some embodiments, the method for preparing the phthalonitrile-terminated polyphenyl ether comprises the following steps:

[0022] mixing polyphenyl ether and 4-nitrophthalonitrile in a solvent, and reacting at 50-60°C for 10-12 hours to obtain the phthalonitrile-terminated polyphenyl ether.

[0023] In some embodiments, the method for preparing the phenolphthalein-based polyaryletheramine comprises the following steps:

[0024] mixing phenolphthalein and 1,3-dichloro-2-nitrobenzene in a solvent, and reacting at 180°C to obtain a nitro-containing polyaryletherketone;

[0025] The nitro-containing polyaryletherketone is mixed with cyclohexanone, glacial acetic acid and iron powder, and refluxed at 80℃ for 12h to prepare the phenolphthalein-containing polyaryletheramine.

[0026] According to a third aspect of the present application, a method for preparing a prepreg is provided, comprising the following steps:

[0027] The resin composition described above or the resin composition prepared by the method described above is attached to the surface of a reinforcing material, and semi-cured to prepare the prepreg.

[0028] In some embodiments, the semi-curing temperature is 150℃-250℃, and the time is 2min-10min.

[0029] In some embodiments, the reinforcing material comprises one or more of inorganic fiber materials and organic fiber materials.

[0030] Optionally, the inorganic fiber material comprises one or more of glass fiber, carbon fiber, silicon carbide fiber and asbestos fiber.

[0031] Optionally, the organic fiber material comprises one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber and cotton fiber.

[0032] According to a fourth aspect of the present application, a prepreg is provided, which is prepared by the method described above.

[0033] According to a fifth aspect of the present application, a method for preparing a laminate is provided, comprising the following steps:

[0034] The prepreg described above is subjected to vacuum hot pressing to prepare the laminate.

[0035] In some embodiments, the method for preparing the laminate satisfies at least one of the following features:

[0036] (1) the temperature of the vacuum hot pressing is 150℃-300℃;

[0037] (2) the pressure of the vacuum hot pressing is 10kgf / cm 2 -30kgf / cm 2 ;

[0038] (3) the vacuum degree of the vacuum hot pressing is <2kPa;

[0039] (4) the time of the vacuum hot pressing is 200min-400min.

[0040] According to a sixth aspect of the present application, a laminate is provided, which is prepared by the method described above.

[0041] In some embodiments, one or both sides of the laminate is covered with a metal foil.

[0042] Compared with the conventional technology, the present application has the following beneficial effects:

[0043] The present application improves the glass transition temperature, initial thermal decomposition temperature, mechanical strength, flame retardant performance, etc. of the polyphenyl ether by chemical modification of the polyphenyl ether, capping the polyphenyl ether with a reactive phthalonitrile group, forming a phthalocyanine ring and a triazine ring structure through self-polymerization of the phthalonitrile, introducing a phenolphthalein-containing polyaryletheramine structure and a phthalonitrile group to copolymerize, further reducing the dielectric constant and dielectric loss of the resin composition, and improving the elastic modulus. The laminate prepared from the resin composition of the present application has excellent properties such as high heat resistance, high modulus, intrinsic flame retardancy, low dielectric loss, and low water absorption. DETAILED DESCRIPTION

[0044] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail. In the following description, a large number of specific details are set forth in order to facilitate a full understanding of the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, therefore the present application is not limited by the specific embodiments disclosed below.

[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the present application belongs. The terms used in the specification of the present application are only for the purpose of describing the specific embodiments of the present application and are not intended to limit the present application. Unless otherwise specified, various raw materials, reagents, instruments and equipment, etc. used in the present application can be purchased from the market or can be prepared by existing methods.

[0046] In the present application, "alkylene" refers to a hydrocarbon group derived by removal of a hydrogen atom from an alkyl group, which has two monovalent radical centers and can be a branched saturated alkyl group or a straight-chain saturated alkyl group. For example, "C1-C9 alkylene" refers to an alkyl moiety containing 1-9 carbon atoms, and each occurrence thereof, independently, can be C1 alkylene, C2 alkylene, C3 alkylene, C4 alkylene, C5 alkylene, C6 alkylene, C7 alkylene, C8 alkylene, or C9 alkylene. Suitable examples include, but are not limited to, methylene (-CH2-), 1,1-ethyl (-CH(CH3)-), 1,2-ethyl (-CH2CH2-), 1,1-propyl (-CH(CH2CH3)-), 1,2-propyl (-CH2CH(CH3)-), 1,3-propyl (-CH2CH2CH2-), and 1,4-butyl (-CH2CH2CH2CH2-).

[0047] In the present application, "a plurality of", "a plurality of kinds", "a plurality of times", "a plurality of elements", and the like, if not otherwise specified, refer to more than 2 or equal to 2 in number. For example, "one or more" means one or more than two.

[0048] In the present application, "further", "even further", "in particular", and the like are used for the purpose of description and indicate a difference in content, but should not be understood as limiting the scope of protection of the present application.

[0049] In the present application, in the technical features described in an open-ended manner, both a closed technical solution consisting of the listed features and an open technical solution containing the listed features are included.

[0050] In the present application, with respect to a numerical interval (i.e., a numerical range), if not otherwise specified, the optional numerical distribution within the numerical interval is considered to be continuous, and includes both numerical end points (i.e., the minimum value and the maximum value) of the numerical range and every numerical value between the two numerical end points. If not otherwise specified, when a numerical interval refers only to integers within the numerical interval, including both end point integers of the numerical range and every integer between the two end points, in this document, it is equivalent to directly listing each integer, for example, t is an integer selected from 1-10, which means that t is any one integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9, and 10. In addition, when multiple ranges are provided to describe a feature or a characteristic, these ranges can be combined. In other words, unless otherwise specified, the ranges disclosed herein should be understood to include any and all sub-ranges subsumed therein.

[0051] In a first aspect of the present application, a resin composition is provided, comprising the following components in parts by mass: 40-100 phr of phthalonitrile-terminated polyphenyl ether, 10-40 phr of a phenolphthalein-based polyaryletheramine, and 10-60 phr of an inorganic filler.

[0052] The structure of the phthalonitrile-terminated polyphenylene ether is shown as formula (I), and the structure of the polyphenyl ether amine containing phenolphthalein group is shown as formula (II):

[0053]

[0054]

[0055] wherein a, m and n are positive integers, and Y is C1-C3 alkylene or a bond.

[0056] The present application modifies the polyphenylene ether by chemical modification, uses the phthalonitrile group with reactivity to terminate the polyphenylene ether, and forms the phthalocyanine ring and triazine ring structure through the self-polymerization of the phthalonitrile group, so as to obtain a high-performance thermosetting resin, and improve the glass transition temperature, initial thermal decomposition temperature, mechanical strength, flame retardant performance and the like. In order to reduce the thermosetting temperature of the phthalonitrile group, the polyphenyl ether amine structure containing phenolphthalein group is introduced to copolymerize with the phthalonitrile group, which can further reduce the dielectric constant and dielectric loss of the resin composition, and improve the elastic modulus.

[0057] Understandably, when Y is a direct bond, it means that Y does not represent any group, and the adjacent two benzene rings are directly bonded.

[0058] As an example, the mass fraction of the phthalonitrile-terminated polyphenylene ether can be 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, 61 parts, 62 parts, 63 parts, 64 parts, 65 parts, 66 parts, 67 parts, 68 parts, 69 parts, 70 parts, 71 parts, 72 parts, 73 parts, 74 parts, 75 parts, 76 parts, 77 parts, 78 parts, 79 parts, 80 parts, 81 parts, 82 parts, 83 parts, 84 parts, 85 parts, 86 parts, 87 parts, 88 parts, 89 parts, 90 parts, 91 parts, 92 parts, 93 parts, 94 parts, 95 parts, 96 parts, 97 parts, 98 parts, 99 parts, 100 parts, or any value within the range of any two point values.

[0059] Further, the mass fraction of the phthalonitrile-terminated polyphenylene ether is 40 parts to 60 parts; further, the mass fraction of the phthalonitrile-terminated polyphenylene ether is 40 parts to 50 parts.

[0060] As an example, the phenolphthalein group-containing polyaryletheramine can be present in a mass fraction of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 34 parts, 39 parts, 40 parts, or any value within a range defined by any two of the above-mentioned values.

[0061] Further, the phenolphthalein group-containing polyaryletheramine is present in a mass fraction of 10 parts to 30 parts; further, the phenolphthalein group-containing polyaryletheramine is present in a mass fraction of 10 parts to 20 parts.

[0062] As an example, the inorganic filler can be present in a mass fraction of 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, 16 parts, 17 parts, 18 parts, 19 parts, 20 parts, 21 parts, 22 parts, 23 parts, 24 parts, 25 parts, 26 parts, 27 parts, 28 parts, 29 parts, 30 parts, 31 parts, 32 parts, 33 parts, 34 parts, 35 parts, 36 parts, 37 parts, 34 parts, 39 parts, 40 parts, 41 parts, 42 parts, 43 parts, 44 parts, 45 parts, 46 parts, 47 parts, 48 parts, 49 parts, 50 parts, 51 parts, 52 parts, 53 parts, 54 parts, 55 parts, 56 parts, 57 parts, 58 parts, 59 parts, 60 parts, or any value within a range defined by any two of the above-mentioned values.

[0063] Further, the inorganic filler is present in a mass fraction of 30 parts to 60 parts; further, the inorganic filler is present in a mass fraction of 30 parts to 40 parts.

[0064] In some embodiments, the inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, petalite, silica, quartz, mica powder, titanium dioxide, magnesium oxide, magnesium hydroxide, talc 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.

[0065] Further, the inorganic filler is selected from silica; further, the inorganic filler is selected from spherical silica.

[0066] In some embodiments, the components of the resin composition further include one or more of a curing accelerator, a coupling agent, a toughening agent, and an organic solvent.

[0067] Further, the curing accelerator includes one or more of 4,4'-methylenebis(2-ethyl)aniline, 2,2'-diallylbisphenol A, and anhydrous copper chloride.

[0068] wherein the CAS number of 4,4'-methylenebis(2-ethyl)aniline is 19900-65-3; the CAS number of 2,2'-diallyl bisphenol A is 1745-89-7; and the CAS number of anhydrous copper chloride is 7447-39-4.

[0069] Further, the coupling agent includes one or more of KH-550 and KH-560.

[0070] In some embodiments, the components of the resin composition further include a solvent.

[0071] Further, the solvent includes one or more of toluene and N,N-dimethylformamide. Still further, the solvent includes toluene and N,N-dimethylformamide; and still further, the mass ratio of toluene and N,N-dimethylformamide is 1:1.

[0072] The resin composition prepared by using the improved phthalonitrile-terminated polyphenyl ether and the phenolphthalein-based polyaryletheramine described above has high peel strength, high decomposition temperature, high elastic modulus, good flame retardant performance, low dielectric coefficient, and low water absorption, and has excellent comprehensive performance.

[0073] In a second aspect, the present application provides a preparation method of the resin composition described above, including the following steps:

[0074] Mixing the components of the resin composition described above to obtain the resin composition.

[0075] In some embodiments, the preparation method of the phthalonitrile-terminated polyphenyl ether includes the following steps:

[0076] Mixing the polyphenyl ether and 4-nitrophthalonitrile in a solvent, and reacting at 50-60°C for 10-12h to obtain the phthalonitrile-terminated polyphenyl ether.

[0077] In some embodiments, the preparation method of the phthalonitrile-terminated polyphenyl ether includes the following steps:

[0078] Mixing the dissolved polyphenyl ether and 4-nitrophthalonitrile, and heating to 50-60°C in an oil bath, and stirring at high speed for 10-12h to obtain the phthalonitrile-terminated polyphenyl ether.

[0079] In some embodiments, the preparation method of the phthalonitrile-terminated polyphenyl ether further includes the following steps: after the reaction is completed, the reaction product is subjected to suction filtration, and the precipitate is collected; and the precipitate is subjected to washing treatment and vacuum drying treatment in sequence.

[0080] As an example, the temperature of the reaction can be 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, or any value within a range defined by any two of the above values.

[0081] In some embodiments, the method for preparing the phenolphthalein group-containing polyaryletheramine comprises the following steps:

[0082] The phenolphthalein is mixed with 1,3-dichloro-2-nitrobenzene in a solvent, and reacted at 180℃ to obtain a nitro group-containing polyaryletherketone;

[0083] The nitro group-containing polyaryletherketone is mixed with cyclohexanone, glacial acetic acid and iron powder, and refluxed at 80℃ for 12h to prepare a phenolphthalein group-containing polyaryletheramine.

[0084] In some embodiments, the method for preparing the phenolphthalein group-containing polyaryletheramine comprises the following steps:

[0085] The dissolved 1,3-dichloro-2-nitrobenzene is added dropwise to the dissolved phenolphthalein, heated to 150℃ in an oil bath for azeotropic distillation for 3h, and then heated to 180℃ until the product shows obvious climbing rod phenomenon. The reaction is quenched by adding a large amount of distilled water, and the precipitate is collected. The precipitate is washed and vacuum dried to obtain the nitro group-containing polyaryletherketone;

[0086] The intermediate product is dissolved in a mixed solvent of cyclohexanone and appropriate glacial acetic acid, and iron powder is added. After refluxing at 80℃ for 12h, the obtained product is placed on diatomite and filtered to obtain an organic layer. The solvent is removed by rotary evaporation, and the precipitate obtained by filtration is washed with distilled water and vacuum dried to constant weight to obtain the phenolphthalein group-containing polyaryletheramine.

[0087] In a third aspect, the present application provides a method for preparing a prepreg, comprising the following steps:

[0088] The resin composition described above or the resin composition prepared by the method described above is attached to the surface of a reinforcing material, semi-cured, and a prepreg is prepared.

[0089] In some embodiments, the semi-curing temperature is 150℃-250℃, and the time is 2min-10min.

[0090] Understandably, the method for covering the resin composition on the surface of the reinforcing material comprises one or more of dipping, padding and coating.

[0091] As an example, the temperature of the semi-curing process can be 150℃, 155℃, 160℃, 165℃, 170℃, 175℃, 180℃, 185℃, 190℃, 195℃, 200℃, 205℃, 210℃, 215℃, 220℃, 225℃, 230℃, 235℃, 240℃, 245℃, 250℃, or any value within a range defined by any two of the above values. The time of the semi-curing process can be 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, 10min, or any value within a range defined by any two of the above values.

[0092] In some embodiments, the reinforcing material comprises one or more of inorganic fiber materials and organic fiber materials.

[0093] Further, the inorganic fiber material comprises one or more of glass fiber, carbon fiber, silicon carbide fiber, and asbestos fiber. Still further, the inorganic fiber material comprises 2116 glass fiber cloth.

[0094] Further, the organic fiber material comprises one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

[0095] In a fourth aspect, the present application provides a prepreg prepared by the method described above.

[0096] In a fifth aspect, the present application provides a method for preparing a laminate, comprising the following steps:

[0097] The prepreg described above is subjected to vacuum hot pressing to prepare a laminate.

[0098] In some embodiments, the number of prepregs is one or more.

[0099] Further, before the vacuum hot pressing of the plurality of prepregs, the method further comprises the step of stacking the plurality of prepregs.

[0100] In some embodiments, the temperature of the vacuum hot pressing is 150℃-300℃. As an example, the temperature of the vacuum hot pressing can be 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, or any value within a range defined by any two of the above values.

[0101] In some embodiments, the pressure of the vacuum hot pressing is 10kgf / cm 2 ~30kgf / cm 2; as an example, the pressure of the vacuum hot-pressing treatment can be 10 kgf / cm 2 , 15 kgf / cm 2 , 20 kgf / cm 2 , 25 kgf / cm 2 , 30 kgf / cm 2 , or any value within the range constituted by any two of the above-mentioned values.

[0102] In some embodiments, the vacuum degree of the vacuum hot-pressing treatment is < 2 kPa; as an example, the vacuum degree of the vacuum hot-pressing treatment can be 1.8 kPa, 1.7 kPa, 1.5 kPa, 1.2 kPa, 1 kPa, 0.5 kPa, 0.2 kPa, 0.1 kPa, 0.05 kPa, 0.02 kPa, 0.01 kPa, or any value within the range constituted by any two of the above-mentioned values.

[0103] In some embodiments, the time of the vacuum hot-pressing treatment is 200 min to 400 min; as an example, the time of the vacuum hot-pressing treatment can be 200 min, 220 min, 240 min, 260 min, 280 min, 300 min, 320 min, 340 min, 360 min, 380 min, 400 min, or any value within the range constituted by any two of the above-mentioned values.

[0104] In a sixth aspect, the present application provides a laminated board prepared by the method described above.

[0105] In some embodiments, one side or both sides of the laminated board is covered with a metal foil.

[0106] In some examples, the metal foil comprises a copper foil.

[0107] In some examples, the thickness of the metal foil is 3 μm to 70 μm; as an example, the thickness of the metal foil can be 3 μm, 5 μm, 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm.

[0108] The laminated board comprising the resin composition described above has excellent comprehensive properties such as high peel strength, high decomposition temperature, high elastic modulus, good flame retardant performance, low dielectric coefficient, and low water absorption.

[0109] The present application will be further described below in conjunction with specific examples and comparative examples, but should not be construed as limiting the scope of protection of the present application. The raw materials involved in the following specific examples can be sourced from the market if not otherwise specified, the instruments used can be sourced from the market if not otherwise specified, and the processes involved can be routinely selected by those skilled in the art if not otherwise specified.

[0110] The sources and models of some raw materials used in Examples 1-5 and Comparative Examples 1-3 of the present application are shown below.

[0111] The polyphenylene ether was purchased from SABIC, model SA-90; the methacrylate-terminated polyphenylene ether was purchased from SABIC, model SA9000; the 4-nitrophthalonitrile was purchased from Inokai, analytical pure; the phenothalin was purchased from Inokai, analytical pure; the 1,3-dichloro-2-nitrobenzene was purchased from Inokai, analytical pure; the 1,3-dichlorobenzene was purchased from Inokai, analytical pure; the anhydrous potassium carbonate was purchased from Aldrich, analytical pure; the glacial acetic acid was purchased from Inokai, analytical pure; the iron powder was purchased from Aldrich, analytical pure; the spherical silica was purchased from Jowat, model SC6500-SXD.

[0112] Example 1

[0113] (1) Preparation of phthalonitrile-terminated polyphenylene ether resin: polyphenylene ether SA90 (0.1 mol, 160 g) was weighed into a three-necked flask, 600 mL of N,N-dimethylformamide was added to stir to completely dissolve, then anhydrous potassium carbonate (0.1 mol, 13.82 g) and 4-nitrophthalonitrile (0.11 mol, 19.04 g) were added, an oil bath was kept at 50°C, and high-speed stirring was carried out for 12 h; after the reaction was completed, deionized water was added to collect the precipitate by filtration, then the precipitate was washed several times with deionized water and ethyl acetate, respectively, and the obtained product was dried to constant weight in a vacuum oven at 80°C to obtain a phthalonitrile-terminated polyphenylene ether resin.

[0114] (2) Preparation of poly(arylene ether amine) containing phenothalin group: phenothalin (0.3 mol, 95.5 g) was dissolved in 200 mL of a mixed solution of N-methylpyrrolidone and toluene (mass ratio 3:1), then anhydrous potassium carbonate (0.4 mol, 55.28 g) was added to stir at room temperature; 1,3-dichloro-2-nitrobenzene (0.305 mol, 58.56 g) was dissolved in 50 mL of a mixed solution of N-methylpyrrolidone and toluene, then the solution containing 1,3-dichloro-2-nitrobenzene was added dropwise to the above mixed solution, after the dropwise addition was completed, the solution was evaporated to remove water and toluene under the condition of an oil bath heated at 150°C for 3 h, then the temperature was increased to 180°C, and the reaction was carried out until the product showed obvious climbing rod phenomenon, then a large amount of distilled water was added to quench the reaction, the precipitate was collected, then the precipitate was washed several times with anhydrous ethanol and deionized water, respectively, and dried to constant weight in a vacuum oven at 100°C to obtain an intermediate product of poly(arylene ether ketone) containing nitro group; the intermediate product was dissolved in a mixed solvent of cyclohexanone and appropriate glacial acetic acid, iron powder (5 eq) was added, and the solution was refluxed at 80°C for 12 h, then the obtained product was collected by filtration on diatomite to obtain an organic layer, the solvent was removed by rotary evaporation, the precipitate was collected by filtration after washing with distilled water, and dried to constant weight in a vacuum oven at 80°C to obtain a poly(arylene ether amine) containing phenothalin group.

[0115] (3) Take 55 parts of the phthalonitrile-terminated polyphenyl ether resin prepared in step (1) and 5 parts of the poly(arylene ether amine) containing phenolphthalein group prepared in step (2) and dissolve them in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide in a mass ratio of 1:1. Under stirring, add 40 parts of spherical silica, and continue stirring to obtain a uniform glue solution, i.e. the resin composition.

[0116] (4) Dip the 2116 glass fiber cloth (basis weight 105 g / m2) into the above resin composition, and bake in a hot air circulating oven at 210°C for 3 min to obtain a prepreg with a resin content of 50%.

[0117] (5) Stack 6 pieces of the above prepreg, cover each of the upper and lower surfaces of the stack with an electrolytic copper foil with a thickness of 18 μm, and place them in a programmable temperature and pressure controlled vacuum press. After curing at 280°C for 3 h under a vacuum and a pressure of 30 kgf / cm2, a copper-clad laminate with a thickness of 0.6 mm is prepared. 2

[0118] Example 2

[0119] The same as Example 1, except that steps (3)-(5) are different, and other steps and parameters are consistent with Example 1.

[0120] (3) Take 55 parts of the phthalonitrile-terminated polyphenyl ether resin prepared in step (1) and 5 parts of the poly(arylene ether amine) containing phenolphthalein group prepared in step (2) and dissolve them in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide in a mass ratio of 1:1. Under stirring, add 40 parts of spherical silica, and continue stirring to obtain a uniform glue solution, i.e. the resin composition.

[0121] (4) Dip the 2116 glass fiber cloth (basis weight 105 g / m2) into the above resin composition, and bake in a hot air circulating oven at 210°C for 3 min to obtain a prepreg with a resin content of 50%.

[0122] (5) Stack 6 pieces of the above prepreg, cover each of the upper and lower surfaces of the stack with an electrolytic copper foil with a thickness of 18 μm, and place them in a programmable temperature and pressure controlled vacuum press. After curing at 280°C for 3 h under a vacuum and a pressure of 30 kgf / cm2, a copper-clad laminate with a thickness of 0.6 mm is prepared. 2

[0123] Example 3

[0124] The same as Example 1, except that steps (3)-(5) are different, and other steps and parameters are consistent with Example 1.​​

[0125] (3) Take 45 parts of the phthalonitrile-terminated polyphenylene ether resin obtained in step (1) and 15 parts of the phenolphthalein-containing polyarylene ether amine obtained in step (2), and dissolve them in a mixed solvent of 140 parts of toluene and N,N-dimethylformamide, wherein the mass ratio of toluene and N,N-dimethylformamide is 1:1. Under stirring conditions, add 40 parts of spherical silica and continue stirring to obtain a uniform adhesive solution, i.e., the resin composition.

[0126] (4) Impregnate 2116 glass fiber cloth (basic weight 105g / m²) in the above resin composition and bake in a hot air circulating oven at 200°C for 2 minutes to obtain a prepreg with a resin content of 50%.

[0127] (5) Six sheets of the above-mentioned prepreg are stacked, and an electrolytic copper foil with a thickness of 18 μm is placed on each of the upper and lower surfaces of the stack. The stack is then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum at 30 kgf / cm². 2 Under pressure, a copper-clad laminate with a thickness of 0.6 mm is produced after curing at 260℃ for 3 hours.

[0128] Example 4

[0129] It is basically the same as Example 1, except that steps (3) to (5) are different, while other steps and parameters are the same as in Example 1.

[0130] (3) Take 40 parts of the phthalonitrile-terminated polyphenylene ether resin obtained in step (1) and 20 parts of the phenolphthalein-containing polyarylene ether amine obtained in step (2), and dissolve them in a mixed solvent of 140 parts of toluene and N,N-dimethylformamide, wherein the mass ratio of toluene and N,N-dimethylformamide is 1:1. Under stirring conditions, add 40 parts of spherical silica and continue stirring to obtain a uniform adhesive solution, i.e., the resin composition.

[0131] (4) Impregnate 2116 glass fiber cloth (basic weight 105g / m²) in the above resin composition and bake in a hot air circulating oven at 180°C for 2 minutes to obtain a prepreg with a resin content of 50%.

[0132] (5) Six sheets of the above-mentioned prepreg are stacked, and an electrolytic copper foil with a thickness of 18 μm is placed on each of the upper and lower surfaces of the stack. The stack is then placed in a programmable temperature and pressure controlled vacuum press and subjected to a vacuum at 30 kgf / cm². 2 Under pressure, a copper-clad laminate with a thickness of 0.6 mm is produced after curing at 240℃ for 3 hours.

[0133] Example 5

[0134] The same as Example 1 except that steps (3)-(5) are different, and other steps and parameters are consistent with Example 1.

[0135] (3) 30 parts of the phthalonitrile-terminated poly(phenylene ether) resin prepared in step (1) and 30 parts of the poly(phenylene ether) amine containing phenolphthalein group prepared in step (2) were dissolved in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide, wherein the toluene and N,N-dimethylformamide were mixed in a mass ratio of 1:1. Under stirring, 40 parts of spherical silica was added, and the stirring was continued to obtain a uniform glue solution, i.e. the resin composition.

[0136] (4) The 2116 glass fiber cloth (basis weight 105 g / m²) was immersed in the above resin composition, and baked in a hot air circulating oven at 180°C for 2 min to obtain a prepreg with a resin content of 50%.

[0137] (5) Six pieces of the above prepreg were laminated, and one piece of electrolytic copper foil with a thickness of 18 μm was covered on the upper and lower surfaces of the laminate, respectively. The laminate was placed in a programmable temperature and pressure controlled vacuum press, and cured at 240°C for 3 h under a pressure of 30 kgf / cm 2 to prepare a copper-clad laminate with a thickness of 0.6 mm.

[0138] Comparative Example 1

[0139] The same as Example 1 except that steps (3)-(5) are different, and other steps and parameters are consistent with Example 1.

[0140] (3) 60 parts of the phthalonitrile-terminated poly(phenylene ether) resin prepared in step (1) were dissolved in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide, wherein the toluene and N,N-dimethylformamide were mixed in a mass ratio of 1:1. Under stirring, 40 parts of spherical silica was added, and the stirring was continued to obtain a uniform glue solution, i.e. the phthalonitrile-terminated poly(phenylene ether) resin composition.

[0141] (4) The 2116 glass fiber cloth (basis weight 105 g / m²) was immersed in the above resin composition, and baked in a hot air circulating oven at 210°C for 3 min to obtain a prepreg with a resin content of 50%.

[0142] (5) Six pieces of the above prepreg were laminated, and one piece of electrolytic copper foil with a thickness of 18 μm was covered on the upper and lower surfaces of the laminate, respectively. The laminate was placed in a programmable temperature and pressure controlled vacuum press, and cured at 280°C for 3 h under a pressure of 30 kgf / cm 2 to prepare a copper-clad laminate with a thickness of 0.6 mm.

[0143] Comparative Example 2

[0144] (1) Provide methacrylate-terminated polyphenylene ether resin: purchased from SABIC, model SA9000.

[0145] (2) The preparation of phenolphthalein-based polyaryletheramine is the same as in Example 1.

[0146] (3) Take 30 parts of the methacrylate-terminated polyphenylene ether resin prepared in step (1) and 30 parts of the phenolphthalein-based polyaryletheramine prepared in step (2), dissolved in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide, with toluene and N,N-dimethylformamide in a mass ratio of 1:1. Under stirring conditions, 40 parts of spherical silica is added, and stirring is continued to obtain a uniform glue solution, i.e. the resin composition.

[0147] (4) The 2116 glass fiber cloth (basis weight 105 g / m²) is immersed in the above resin composition, and baked in a hot air circulating oven at 180°C for 3 min to obtain a prepreg with a resin content of 50%.

[0148] (5) Stack 6 pieces of the above prepreg, cover each of the upper and lower surfaces of the stack with an electrolytic copper foil with a thickness of 18 μm, and place it in a programmable temperature and pressure controlled vacuum press. Under vacuum, a copper-clad laminate with a thickness of 0.6 mm is prepared after curing at 240°C for 3h under a pressure of 30 kgf / cm 2 .

[0149] Comparative Example 3

[0150] (1) The preparation of phthalonitrile-terminated polyphenylene ether is the same as in Example 1.

[0151] (2) Preparation of phenolphthalein-based polyaryletherketone: phenolphthalein (0.3 mol, 95.5 g) is dissolved in 200 mL of a mixed solution of N-methylpyrrolidone and toluene (mass ratio 3:1), then anhydrous potassium carbonate (0.4 mol, 55.28 g) is added and stirred at room temperature at high speed; 1,3-dichlorobenzene (0.305 mol, 44.835 g) is dissolved in 50 mL of a mixed solution of N-methylpyrrolidone and toluene, then the solution containing 1,3-dichlorobenzene is added dropwise to the above mixed solution, after the addition is completed, the oil bath is heated to 150°C for 3h co-boiling reaction, then evaporate water and toluene, then heated to 180°C until the product appears obvious climbing rod phenomenon, add a large amount of distilled water to quench the reaction, collect the precipitate, then wash with anhydrous ethanol and deionized water several times, dry in a vacuum oven at 100°C to constant weight to obtain phenolphthalein-based polyaryletherketone.

[0152] (3) 30 parts of the phthalonitrile-terminated polyphenyl ether resin prepared in step (1) and 30 parts of the poly(arylene ether ketone) containing phenolphthalein group prepared in step (2) were dissolved in 140 parts of a mixed solvent of toluene and N,N-dimethylformamide in a mass ratio of 1:1. Under stirring, 40 parts of spherical silica was added, and the stirring was continued to obtain a uniform glue solution, i.e. the resin composition.

[0153] (4) The 2116 glass fiber cloth (basis weight 105 g / m2) was impregnated in the above resin composition, and baked in a hot air circulating oven at 210°C for 3 min to obtain a prepreg with a resin content of 50%.

[0154] (5) Six pieces of the above prepreg were laminated, and one piece of electrolytic copper foil with a thickness of 18 μm was covered on the upper and lower surfaces of the laminate, respectively. The laminate was placed in a programmable temperature and pressure controlled vacuum press, and cured at 280°C for 3 h under a pressure of 30 kgf / cm2in a vacuum state to obtain a copper-clad laminate with a thickness of 0.6 mm. 2

[0155] The composition and ratio of the resin compositions in the above examples 1-5 and comparative examples 1-3 are shown in the following table.

[0156] Table 1

[0157]

[0158] The copper-clad laminates prepared in the above examples and comparative examples were respectively subjected to performance tests, and the test results are shown in Table 2.

[0159] The test method of the peel strength was performed according to the IPC-TM-650 standard part 2.4.8; the glass transition temperature (Tg) was tested according to the IPC-TM650 standard 2.4.25D; the thermal decomposition temperature (Td) was tested according to the IPC-TM650 standard 2.4.24.6; the elastic modulus was tested according to the GB / T 22315-2008 standard; the water absorption was tested according to the IPC-TM650 2.6.2.1 standard; the dielectric constant / dielectric loss factor (Dk / Df) was tested according to the IPC-TM650 2.5.5.2 standard; and the flame retardant grade was tested according to the IPC-TM650 2.3.10 standard.

[0160] Table 2

[0161]

[0162] ​As shown in the above table, the copper-clad laminate prepared in Examples 1-5 has a peel strength ≥ 5.2 lb / in; a glass transition temperature ≥ 320℃; a thermal decomposition temperature ≥ 462℃; a dielectric constant ≤ 3.42, a dielectric loss factor ≤ 0.006; a flame retardant level of V0 level; and a water absorption ≤ 0.08%. It can be seen that the copper-clad laminate prepared in the present application has good peel strength, heat resistance, dielectric properties, flame retardant level and water absorption.

[0163] In Comparative Example 1, no phenolphthalein-based polyaryletheramine was added, and thus the heat resistance of the copper-clad laminate prepared was significantly reduced, and the dielectric coefficient was relatively high. In Comparative Example 2, the phthalonitrile-terminated polyphenyl ether was replaced by methacrylate-terminated polyphenyl ether, and the peel strength of the copper-clad laminate prepared finally was slightly reduced, and the heat resistance and elastic modulus were significantly reduced. In Comparative Example 3, the phenolphthalein-based polyaryletheramine was replaced by phenolphthalein-based polyaryletherketone, and the peel strength, heat resistance and elastic modulus of the copper-clad laminate prepared finally were significantly reduced, and the dielectric coefficient was relatively high, indicating that the phenolphthalein-based polyaryletheramine can effectively reduce the dielectric coefficient of the copper-clad laminate.

[0164] Any technical features of the above-described embodiments can be combined, and to make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, however, as long as the combinations of the technical features do not exist contradictions, they should be considered as the scope of the present disclosure.

[0165] The above-described embodiments only express several embodiments of the present application, and the description is more specific and detailed, but it should not be understood as a limitation on the scope of the patent. It should be noted that for ordinary skilled in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of the present application should be subject to the appended claims.

Claims

1. A resin composition, characterized in that, By weight, it includes the following components: 40 to 100 parts phthalonitrile-terminated polyphenylene ether, 10 to 40 parts phenolphthalein-containing polyarylene ether amine and 10 to 60 parts inorganic filler; The structure of the phthalonitrile-terminated polyphenylene ether is shown in Formula (I), and the structure of the phenolphthalein-containing polyarylene ether amine is shown in Formula (II). Where a, m, and n are all positive integers, and Y is a C1~C3 alkylene group or a single bond.

2. The resin composition according to claim 1, characterized in that, The resin composition satisfies at least one of the following characteristics: (1) The mass fraction of the phthalonitrile-terminated polyphenylene ether is 40 to 60 parts; (2) The mass fraction of the phenolphthalein-containing polyaryletheramine is 10 to 30 parts; (3) The inorganic filler has a mass fraction of 30 to 60 parts.

3. The resin composition according to any one of claims 1 to 2, characterized in that, The inorganic filler includes one or more of zirconium vanadate, zirconium tungstate, hafnium tungstate, microcrystalline glass, nepheline, silicon dioxide, 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.

4. The resin composition according to any one of claims 1 to 2, characterized in that, The resin composition also includes one or more of the following: a curing accelerator, a coupling agent, a toughening agent, and an organic solvent.

5. The resin composition according to claim 4, characterized in that, The curing accelerator includes one or more of 4,4'-methylenebis(2-ethyl)aniline, 2,2'-diallylbisphenol A, and anhydrous copper chloride.

6. The resin composition according to claim 4, characterized in that, The coupling agent includes one or more of KH-550 and KH-560.

7. A method for preparing a resin composition according to any one of claims 1 to 6, characterized in that, The process includes the following steps: mixing the components of the resin composition to obtain the resin composition.

8. The method for preparing the resin composition according to claim 7, characterized in that, The preparation method of the phthalonitrile-terminated polyphenylene ether includes the following steps: The phthalonitrile-terminated polyphenylene ether was prepared by mixing polyphenylene ether with 4-nitrophthalonitrile in a solvent and reacting at 50℃~60℃ for 10h~12h.

9. The method for preparing the resin composition according to claim 7, characterized in that, The preparation method of the phenolphthalein-containing polyaryletheramine includes the following steps: Phenolphthalein was mixed with 1,3-dichloro-2-nitrobenzene in a solvent and reacted at 180°C to obtain a nitro-containing polyarylether ketone. The nitro-containing polyarylether ketone was mixed with cyclohexanone, glacial acetic acid and iron powder, and refluxed at 80°C for 12 h to prepare the phenolphthalein-containing polyarylether amine.

10. A method for preparing a prepreg, characterized in that, Includes the following steps: The resin composition prepared by the method of any one of claims 1 to 6 or any one of claims 7 to 9 is attached to the surface of the reinforcing material and subjected to semi-curing treatment to obtain the prepreg.

11. The method for preparing the prepreg according to claim 10, characterized in that, The temperature for the semi-curing treatment is 150℃~250℃, and the time is 2min~10min.

12. The method for preparing the prepreg according to claim 10, characterized in that, The reinforcing material includes one or more of inorganic fiber materials and organic fiber materials.

13. The method for preparing the prepreg according to claim 12, characterized in that, The inorganic fiber material includes one or more of glass fiber, carbon fiber, silicon carbide fiber and asbestos fiber.

14. The method for preparing the prepreg according to claim 12, characterized in that, The organic fiber material includes one or more of nylon, ultra-high molecular weight polyethylene fiber, aramid fiber, polyimide fiber, polyester fiber, and cotton fiber.

15. A prepreg, characterized in that, The prepreg is prepared using the method described in any one of claims 10 to 14.

16. A method for preparing a laminate, characterized in that, Includes the following steps: The prepreg of claim 15 is subjected to vacuum hot pressing to prepare the laminate.

17. The method for preparing a laminate according to claim 16, characterized in that, The method for preparing the laminate satisfies at least one of the following characteristics: (1) The temperature of the vacuum hot pressing treatment is 150℃~300℃; (2) The pressure of the vacuum hot pressing treatment is 10 kgf / cm. 2 ~30kgf / cm 2 ; (3) The vacuum degree of the vacuum hot pressing treatment is <2kPa; (4) The vacuum hot pressing treatment time is 200 min to 400 min.

18. A laminate, characterized in that, The laminate is prepared by the method described in any one of claims 16-17.

19. The laminate according to claim 18, characterized in that, The laminate is covered with metal foil on one or both sides.

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