CN114031719A - Bismaleimide-triazine resin and preparation method and application thereof - Google Patents
Bismaleimide-triazine resin and preparation method and application thereof Download PDFInfo
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- CN114031719A CN114031719A CN202111424770.5A CN202111424770A CN114031719A CN 114031719 A CN114031719 A CN 114031719A CN 202111424770 A CN202111424770 A CN 202111424770A CN 114031719 A CN114031719 A CN 114031719A
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- bismaleimide
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- triazine resin
- triazine
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- 229920005989 resin Polymers 0.000 claims description 57
- 239000011347 resin Substances 0.000 claims description 57
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 claims description 39
- 229920003192 poly(bis maleimide) Polymers 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 238000002360 preparation method Methods 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 13
- 238000007259 addition reaction Methods 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920001955 polyphenylene ether Polymers 0.000 claims description 4
- 229910052582 BN Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical group N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 239000000243 solution Substances 0.000 description 17
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000012456 homogeneous solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001879 gelation Methods 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 125000005504 styryl group Chemical group 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 anionic imide Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
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- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- QHFDHWJHIAVELW-UHFFFAOYSA-M sodium;4,6-dioxo-1h-1,3,5-triazin-2-olate Chemical compound [Na+].[O-]C1=NC(=O)NC(=O)N1 QHFDHWJHIAVELW-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- VJJZJBUCDWKPLC-UHFFFAOYSA-N 3-methoxyapigenin Chemical compound O1C2=CC(O)=CC(O)=C2C(=O)C(OC)=C1C1=CC=C(O)C=C1 VJJZJBUCDWKPLC-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
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- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000004643 cyanate ester Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229920013638 modified polyphenyl ether Polymers 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/36—Amides or imides
- C08F222/40—Imides, e.g. cyclic imides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/34—Monomers containing two or more unsaturated aliphatic radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0373—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement containing additives, e.g. fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
- C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2335/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C08J2425/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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- C08J2435/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
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- C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2471/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract
The invention provides bismaleimide-triazine resin and a preparation method and application thereof, and relates to the technical field of resin. The bismaleimide-triazine resin disclosed by the invention adopts isocyanurate containing styryl and triazine ring structures to modify bismaleimide, so that addition reaction can be carried out at a lower temperature without a catalyst, and the simplicity of an addition path and the controllability of a product structure during the preparation of the bismaleimide-triazine resin are realized. The bismaleimide-triazine resin can be used for preparing a high-frequency copper-clad plate.
Description
Technical Field
The invention relates to the technical field of resin, in particular to bismaleimide-triazine resin and a preparation method and application thereof.
Background
The bismaleimide-triazine resin is obtained by blending a cyanate ester resin and a bismaleimide resin, and is also called as a BT resin. BT resin has good dielectric properties, heat resistance, electrical insulation, and flame retardancy, and low raw material cost, and is therefore widely used as a substrate, a high temperature resistant adhesive, and an insulating material of a material in the fields of the electronic industry and the like. Although the BT resin has the above advantages, the BT resin is modified to meet the requirements of high-performance substrate materials.
The Bismaleimide (BMI) has low cost and simple curing process, is a compound widely applied to the electronic communication industry and aerospace, and has the advantages of low thermal expansion coefficient, high heat resistance, radiation resistance, dimensional stability and the like. The two ends of the bismaleimide monomer are provided with two maleimide functional group molecules, the conventional BMI reaction activity is low, and the olefinic bond reaction can be triggered only at about 300 ℃ under the condition of not adding a catalyst.
The modified BT resin is high-performance BT resin obtained by introducing a substance with good reaction activity to react with structures such as imide ring heterocycle, triazine ring and the like and changing an internal cross-linking structure. At present, the main modification method is to introduce allyl compounds to modify BMI resin, but the process not only has complex reaction mechanism and reaction components and higher reaction temperature requirement, but also needs a long-time segmented curing reaction from low temperature to high temperature, and the reaction period is accompanied by the generation of anionic imide oligomerization side reaction. Therefore, development of a new BT resin is of great significance.
Disclosure of Invention
In view of the above, it is necessary to provide a method for producing a bismaleimide-triazine resin, in which bismaleimide is modified with isocyanurate having a styryl group and a triazine ring structure, and the reaction can be carried out at a relatively low temperature without a catalyst.
A preparation method of bismaleimide-triazine resin is characterized in that bismaleimide and isocyanurate with a structure shown in a formula I are adopted as raw materials to be subjected to addition reaction to prepare the bismaleimide-triazine resin.
The existing bismaleimide-triazine resin synthesis involves a complex mechanism, generally speaking, the olefinic bond of bismaleimide and an allyl structure generate various forms of addition and multiple rearrangements under the condition of a catalyst, so that the requirement on reaction conditions is severe, and the structure of a reaction product has uncontrollable property.
In the preparation method of the invention, the bismaleimide is modified by modified isocyanurate (the preparation method can be referred to as Chinese patent application with the application number of 202110972509.2, produced by Zhuhai Hongchang electronic material Co., Ltd.). The isocyanurate is produced by etherifying p-chlorostyrene and sodium cyanate, and has three styryl structures and a triazine ring structure with central symmetry. The addition reaction is more facilitated at a low temperature than the conventional allyl compound. The C ═ C double bond of the bismaleimide has reactivity, can react with the isocyanurate in a Diels-Alder reaction (Diels-Alder reaction), and is added with the imide double bond by utilizing the styryl conjugated double bond with the triazine ring to form a structure with the triazine ring and a condensed ring, the rearrangement of the 1, 4 double bond is inhibited in the synthesis process, so that the bismaleimide can complete the addition reaction at a lower temperature without a catalyst. The preparation method provided by the invention realizes the simplicity of an addition path and the controllability of a product structure in the preparation of the bismaleimide-triazine resin.
In one embodiment, the molar ratio is (1-3): 2, mixing the bismaleimide and the isocyanurate, adding an organic solvent, and carrying out addition reaction at 105-130 ℃ to obtain bismaleimide-triazine resin gel; the reaction process is shown as a formula II.
The existing BT resin preparation process usually needs to use a plurality of catalysts and higher gel curing temperature, for example, triphenylphosphine is used for catalyzing bismaleimide addition, and multi-step high-temperature gel curing is carried out at 180-220 ℃.
In the reaction process, no catalyst is required to be added, the addition reaction can be carried out at a lower temperature (105- & lt- & gt & gt 130 ℃) and no segmented curing reaction is required, so that the preparation process of the bismaleimide-triazine resin is greatly simplified, and the preparation cost of the bismaleimide-triazine resin is reduced.
In one embodiment, the organic solvent is selected from: dimethylacetamide, dimethylformamide, butanone.
In one embodiment, the bismaleimide is N, N '- (4,4' -methylenediphenyl) bismaleimide.
In one embodiment, no catalyst is added in the addition reaction, and the time of the addition reaction is 5-12 min. Compared with the existing BT resin preparation method, the preparation method can shorten the reaction time to be less than 12min under the condition of not adding a catalyst, realize gelation and primary curing in the time period, and remarkably improve the production efficiency. And the gel-state BT resin can be directly added with other components to prepare a resin composition and is used for preparing a copper-clad plate.
In one embodiment, the gel is further cured at the temperature of 130-150 ℃, and then is dried at the temperature of 70-90 ℃ under vacuum, and after the solvent is volatilized, the solid bismaleimide-triazine resin is obtained. The solid bismaleimide-triazine resin is more convenient to store and transport.
The invention also provides bismaleimide-triazine resin obtained by the preparation method, which comprises a crosslinking structure shown in a formula III and a formula IV.
The bismaleimide-triazine resin has a relatively definite cross-linked structure. Therefore, the innovation of the molecular structure of the bismaleimide-triazine resin is realized, the structural design and development capacity of the novel high-frequency resin are improved, and the development of the 5G industry is promoted.
The present invention also provides a resin composition comprising the bismaleimide-triazine resin of the present invention. The resin composition can be used for preparing a high-frequency copper-clad plate, and endows a high-frequency circuit board with excellent dielectric property, heat resistance, electric insulation property, flame retardance and the like.
In one embodiment, the resin composition comprises the following raw materials in parts by weight: 30-50 parts of bismaleimide-triazine resin, 30-40 parts of polyphenyl ether and 10-40 parts of inorganic filler.
In one embodiment, the polyphenylene ether is a vinyl-modified polyphenylene ether and the inorganic filler is boron nitride.
The invention also provides an application of the bismaleimide-triazine resin or the resin composition in preparation of a high-frequency copper-clad plate.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method, the bismaleimide is modified by adopting the modified isocyanurate, and the isocyanurate has a centrosymmetric triazine ring structure and a conjugated styryl structure, so that cyclic addition can be realized at low temperature. The C ═ C double bond of the bismaleimide has reactivity, can react with the isocyanurate in a Diels-Alder reaction, and is added with the imide double bond by utilizing the styryl conjugated double bond with the triazine ring to form a structure with the triazine ring and a condensed ring, so that the rearrangement of the 1, 4 double bond is inhibited in the synthetic process, and the bismaleimide can perform addition reaction at a lower temperature without a catalyst. The preparation method provided by the invention realizes the simplicity of an addition path and the controllability of a product structure in the preparation of the bismaleimide-triazine resin.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of modified isocyanurate (Ps-TAIC).
FIG. 2 is a differential thermogram of Experimental example 1.
FIG. 3 is an optical photograph of the mixed raw material solution and the Ps-TAIC solution of Experimental example 2.
Fig. 4 is an optical photograph of the BT-resin cured film obtained in example 1.
FIG. 5 is a chromatogram of a mixed raw material gel of Experimental example 3.
FIG. 6 is a Ps-TAIC gel chromatogram of Experimental example 3.
Detailed Description
To facilitate an understanding of the invention, a more complete description of the invention will be given below in terms of preferred embodiments. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The starting materials and reagents mentioned in the following examples and comparative examples are all commercially available reagents unless otherwise specified. The experimental/testing methods in the examples and comparative examples are conventional experimental/testing methods or existing experimental/testing methods in the art, unless otherwise specified.
Example 1
A preparation method of bismaleimide-triazine resin comprises the following steps: 107g N, N '- (4,4' -methylenediphenyl) bismaleimide and 95.4g of isocyanurate (molecular weight 477g/mol, hereinafter referred to as Ps-TAIC) shown in formula I are weighed according to the molar ratio of 3:2, added into a reaction vessel and uniformly stirred, 200g of dimethylacetamide is added to be used as a solvent to be dissolved into a homogeneous solution, the temperature is increased to 110 ℃, the temperature is kept for 7min, and the reaction system is partially gelled. And pouring the gelation solution into a mould when the viscosity of the solution rises rapidly, slowly volatilizing the solvent at 130 ℃, and further curing to obtain the BT resin curing film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
Wherein, the preparation method of the Ps-TAIC comprises the following steps: a500 ml four-necked flask was equipped with a stirrer, a constant pressure dropping funnel, a thermometer and a serpentine reflux condenser. 350ml of DMAC and 70g of sodium cyanurate are poured into a four-mouth flask, after the DMAC and the sodium cyanurate are dissolved, 5.6g of triethylamine is added, the temperature is heated to 90 ℃, the mixture is stirred until the temperature is constant, 164.35g of 4-vinylbenzyl chloride is dropwise added, the dropwise addition is completed within half an hour, and the constant temperature reaction at 90 ℃ is continued for 1.5 hours. Cooling to room temperature after reaction, filtering, collecting filtrate, distilling under reduced pressure to reduce the volume of the solution to 210ml, adding 2L methanol into the crude product, stirring at room temperature for 2h, filtering, and vacuum drying the filter residue at 30 deg.C for 12 h. The product prepared was subjected to nuclear magnetic resonance analysis (Bruker, Switzerland, AVANCE III HD 400MHz), and its molecular structure is shown in FIG. 1.
Example 2
A preparation method of bismaleimide-triazine resin comprises the following steps: weighing 35.8g N, N '- (4,4' -methylene diphenyl) bismaleimide and 95.4g of Ps-TAIC according to the molar ratio of 1:2, adding the materials into a reaction vessel, uniformly stirring, adding 120g of dimethylacetamide serving as a solvent to dissolve into a homogeneous solution, heating to 105 ℃, keeping the temperature for 12min, and partially gelling the reaction system. And pouring the gelation solution into a mould when the viscosity of the solution rises rapidly, slowly volatilizing the solvent at 130 ℃, and further curing to obtain the BT resin curing film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
Example 3
A preparation method of bismaleimide-triazine resin comprises the following steps: weighing 107g N, N '- (4,4' -methylenediphenyl) bismaleimide and 95.4g of Ps-TAIC according to the molar ratio of 3:2, adding the materials into a reaction vessel, uniformly stirring, adding 200g of dimethylacetamide serving as a solvent to dissolve into a homogeneous solution, heating to 130 ℃, preserving heat for 5min, and partially gelling the reaction system. And pouring the gelation solution into a mould when the viscosity of the solution rises rapidly, slowly volatilizing the solvent at 150 ℃ and further curing to obtain the BT resin curing film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
Example 4
A preparation method of bismaleimide-triazine resin comprises the following steps: weighing 107g N, N '- (4,4' -methylenediphenyl) bismaleimide and 95.4g of Ps-TAIC according to the molar ratio of 3:2, adding the materials into a reaction vessel, uniformly stirring, adding 200g of dimethylacetamide serving as a solvent to dissolve into a homogeneous solution, heating to 110 ℃, preserving heat for 10min, and partially gelling the reaction system. And when the viscosity of the solution rises rapidly, adding 15g of vinyl modified polyphenyl ether and 5g of boron nitride inorganic filler, uniformly mixing, coating on glass fiber cloth, and performing hot-pressing to obtain the high-frequency copper-clad plate.
Comparative example 1
Weighing 107g N, adding N '- (4,4' -methylene diphenyl) bismaleimide into a reaction container, adding 100g of dimethylacetamide as a solvent to dissolve into a homogeneous solution, heating to 150 ℃, keeping the temperature for 60min without obvious reaction, pouring part of the solution into a mold, and slowly volatilizing the solvent at 130 ℃ to obtain an unreacted BMI solid.
Comparative example 2
Weighing 95.4g of Ps-TAIC, adding into a reaction container, adding 100g of dimethylacetamide as a solvent to dissolve into a homogeneous solution, heating to 100 ℃, keeping the temperature for 16min without obvious reaction, pouring part of the solution into a mold, slowly volatilizing the solvent at 100 ℃, and obtaining a product which is a powdery solid and cannot be formed into a film, wherein the powdery solid is supposed to be a mixture of oligomer and unreacted powder.
Comparative example 3
Weighing 95.4g of Ps-TAIC, adding into a reaction container, adding 100g of dimethylacetamide as a solvent to dissolve into a homogeneous solution, heating to 120 ℃, reacting and curing after 5min, wherein the obtained solid is brittle and almost powdery, and is difficult to prepare into a film material.
Comparative example 4
Weighing 107g N, N '- (4,4' -methylenediphenyl) bismaleimide and 49.8g of triallyl isocyanurate in a molar ratio of 3:2, adding the materials into a reaction vessel, uniformly stirring, adding 200g of dimethylacetamide serving as a solvent to dissolve the materials into a homogeneous solution, heating to 110 ℃, keeping the temperature for 30min to ensure that no obvious reaction occurs, pouring part of the solution into a mold, and slowly volatilizing the solvent at 130 ℃ to obtain a mixture of unreacted BMI solid and oligomer.
Experimental example 1
The results of differential thermal analysis of a mixture of N, N '- (4,4' -methylenediphenyl) bismaleimide and BMI and Ps-TAIC at a molar ratio of 3:2 are shown in FIG. 2. The results show that pure BMI is melted and transformed at the temperature of about 166 ℃, no chemical reaction activity exists at the temperature of 300 ℃, and the mixed raw material has an obvious exothermic peak of chemical reaction at the temperature of about 173 ℃, which shows that the temperature of BMI monomer polymerization reaction is effectively reduced by adding Ps-TAIC.
Experimental example 2
Mixing N, N '- (4,4' -methylenediphenyl) bismaleimide and Ps-TAIC at a molar ratio of 1:2, adding a proper amount of dimethylacetamide, and reacting at 100 ℃ for 5-7min to obtain a yellow and transparent partially gelled product, wherein an optical photograph is shown in FIG. 3.
Taking Ps-TAIC, adding appropriate amount of dimethylacetamide, heating at 110 deg.C for 5-7min to obtain yellow transparent solution, and taking an optical photograph as shown in FIG. 3.
An optical photograph of the BT-resin cured film obtained in example 1 is shown in fig. 4, and the BT-resin cured film is a yellow transparent film with a flat surface.
Experimental example 3
Mixing N, N '- (4,4' -methylenediphenyl) bismaleimide and Ps-TAIC at a molar ratio of 1:2, adding dimethylacetamide to obtain a solution with a solid content of 50%, stirring at 100 ℃ for 16min for reaction, allowing the reactant to partially gel, and performing gel chromatography detection on the gelled product, wherein the result is shown in FIG. 5.
Taking Ps-TAIC, adding dimethylacetamide to obtain a solution with a solid content of 50%, stirring at 100 ℃ for 16min to obtain a partially gelatinized product, and performing gel chromatography detection on the gelatinized product, wherein the result is shown in FIG. 6.
The result shows that the molecular weight Mn of the mixed raw material reaction liquid is increased to 1947, and no obvious micromolecule peak exists; the molecular weight Mn of the Ps-TAIC solution is increased to 2114. The molecular weight test result shows the polymerization capability of the two reaction liquids at a lower temperature without a catalyst; and the mixed solution has no obvious small molecular BMI residue after short-time gelation, and the BMI and the Ps-TAIC are proved to have copolymerization reaction.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The preparation method of bismaleimide-triazine resin is characterized in that bismaleimide and isocyanurate with a structure shown in a formula I are used as raw materials and are subjected to addition reaction to prepare the bismaleimide-triazine resin.
2. The method according to claim 1, wherein the molar ratio of (1-3): 2, mixing the bismaleimide and the isocyanurate, adding an organic solvent, and carrying out addition reaction at 105-130 ℃ to obtain bismaleimide-triazine resin gel; the reaction process is shown as a formula II.
3. The method according to claim 2, wherein the organic solvent is selected from the group consisting of: dimethylacetamide, dimethylformamide, butanone; the bismaleimide is N, N '- (4,4' -methylene diphenyl) bismaleimide.
4. The process according to claim 2, wherein no catalyst is added in the addition reaction, and the time of the addition reaction is 5 to 12 min.
5. The method according to any one of claims 2 to 4, wherein the gel is further cured at a temperature of 130 ℃ and 150 ℃, and then dried under vacuum at a temperature of 70 ℃ to 90 ℃ to obtain the solid bismaleimide-triazine resin after the solvent is volatilized.
6. A bismaleimide-triazine resin obtained by the production method according to any one of claims 1 to 5, wherein the bismaleimide-triazine resin comprises a crosslinked structure represented by formula iii or formula iv.
7. A resin composition comprising the bismaleimide-triazine resin according to claim 6.
8. The resin composition according to claim 7, comprising the following raw materials in parts by weight: 30-50 parts of bismaleimide-triazine resin, 30-40 parts of polyphenyl ether and 10-40 parts of inorganic filler.
9. The resin composition according to claim 8, wherein the polyphenylene ether is a vinyl-modified polyphenylene ether, and the inorganic filler is boron nitride.
10. Use of the bismaleimide-triazine resin of claim 6 or the resin composition of any one of claims 7 to 9 in the preparation of a high frequency copper clad laminate.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116790213A (en) * | 2023-07-04 | 2023-09-22 | 江苏特丽亮新材料科技有限公司 | High-temperature-resistant conductive adhesive and preparation method thereof |
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| JP2000026553A (en) * | 1998-05-08 | 2000-01-25 | Toagosei Co Ltd | Curing composition |
| JP2007033675A (en) * | 2005-07-25 | 2007-02-08 | Fujifilm Corp | Photosensitive composition, photosensitive film, permanent pattern and method for forming the same |
| US20120190579A1 (en) * | 2009-08-10 | 2012-07-26 | Ucl Business Plc | Functionalisation of Solid Substrates |
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| JPH06122737A (en) * | 1992-10-09 | 1994-05-06 | Toagosei Chem Ind Co Ltd | Curable resin composition |
| JP2000026553A (en) * | 1998-05-08 | 2000-01-25 | Toagosei Co Ltd | Curing composition |
| JP2007033675A (en) * | 2005-07-25 | 2007-02-08 | Fujifilm Corp | Photosensitive composition, photosensitive film, permanent pattern and method for forming the same |
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| CN116790213A (en) * | 2023-07-04 | 2023-09-22 | 江苏特丽亮新材料科技有限公司 | High-temperature-resistant conductive adhesive and preparation method thereof |
| CN116790213B (en) * | 2023-07-04 | 2024-02-20 | 江苏特丽亮新材料科技有限公司 | High-temperature-resistant conductive adhesive and preparation method thereof |
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