CN114031719B - 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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- CN114031719B CN114031719B CN202111424770.5A CN202111424770A CN114031719B CN 114031719 B CN114031719 B CN 114031719B CN 202111424770 A CN202111424770 A CN 202111424770A CN 114031719 B CN114031719 B CN 114031719B
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- bismaleimide
- triazine resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 63
- 239000011347 resin Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 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 abstract description 38
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 37
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical group CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 14
- 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
- 239000002994 raw material Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000011342 resin composition Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011256 inorganic filler Substances 0.000 claims description 5
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 5
- 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
- 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
- 238000001035 drying Methods 0.000 claims 1
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 abstract description 9
- 125000005504 styryl group Chemical group 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 19
- 239000012456 homogeneous solution Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 5
- 230000008569 process Effects 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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- -1 allyl compound Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000013557 residual solvent Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 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 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000006266 etherification reaction 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
- 239000011810 insulating material Substances 0.000 description 1
- 125000005439 maleimidyl group Chemical group C1(C=CC(N1*)=O)=O 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 238000004321 preservation Methods 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
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- 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
- 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
- C08J2425/18—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
- 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
- C08J2471/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2471/12—Polyphenylene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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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 resins. The bismaleimide-triazine resin disclosed by the invention adopts the isocyanurate containing styryl and triazine ring structures to modify bismaleimide, and can be subjected to addition reaction at a low temperature without a catalyst, so that the simplicity of an addition path and the controllability of a product structure in the preparation of the bismaleimide-triazine resin are realized. The bismaleimide-triazine resin disclosed by the invention can be used for preparing a high-frequency copper-clad plate.
Description
Technical Field
The invention relates to the technical field of resins, in particular to a bismaleimide-triazine resin and a preparation method and application thereof.
Background
Bismaleimide-triazine resins are obtained by blending a cyanate resin and a bismaleimide resin, also referred to as BT resin. The BT resin has better dielectric property, heat resistance, electrical insulation property and flame retardance, and has lower cost of raw materials, so the BT resin is widely applied to substrates, high-temperature-resistant adhesives and insulating materials serving as materials in the fields of electronic industry and the like. Although the BT resin has the above advantages, the BT resin is required to be modified in order to meet the requirements of high-performance substrate materials.
The Bismaleimide (BMI) has the advantages of low cost, simple curing process, low thermal expansion coefficient, high heat resistance, radiation resistance, dimensional stability and the like, and is a compound widely applied to the electronic communication industry and aerospace. The bismaleimide monomer has two maleimide functional group molecules at two ends, so that the conventional BMI has lower reactivity, and the olefinic bond reaction can be triggered at about 300 ℃ under the condition of no catalyst addition.
The modified BT resin is high-performance BT resin obtained by introducing substances with good reactivity, reacting with imide ring heterocycle, triazine ring and other structures and changing internal crosslinking structures. At present, the main modification method is to introduce an allyl compound to modify BMI resin, but the process has the advantages of complex reaction mechanism and reaction components, higher reaction temperature requirement, long-time sectional curing reaction from low temperature to high temperature, and anionic imide oligomerization side reaction during the reaction. Therefore, the development of a new BT resin is of great importance.
Disclosure of Invention
In view of the above, it is necessary to provide a method for producing a bismaleimide-triazine resin, which is capable of reacting at a low temperature without a catalyst by modifying bismaleimide with an isocyanurate having a styryl group and a triazine ring structure.
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 prepared through addition reaction.
The existing synthesis of bismaleimide-triazine resin involves a relatively complex mechanism, in general, the olefinic bond of bismaleimide and an allyl structure undergo various forms of addition and repeated rearrangement under the condition of a catalyst, so that the requirements on the reaction conditions are severe, and the structure of a reaction product is uncontrollable.
In the preparation method of the invention, modified isocyanurate (Zhuhai Hongchang electronic materials Co., ltd.) developed by the applicant is adopted to modify bismaleimide, and the preparation method can be seen in Chinese patent application with application number 202110972509.2. The isocyanurate is produced by etherification of p-chlorostyrene and sodium cyanate and has three styryl structures and a centrally symmetrical triazine ring structure. It is more advantageous to effect the addition reaction at low temperature than the conventional allyl compound. The c=c double bond of bismaleimide is reactive, and can be subjected to Diels-Alder reaction (Diels-Alder reaction) with the isocyanurate, and the styryl conjugated double bond with triazine ring is utilized to carry out addition with the imide double bond to form a structure with triazine ring and condensed ring, and rearrangement of 1,4 double bonds is inhibited in the synthesis process, so that the bismaleimide can complete the addition reaction at a lower temperature without catalyst. The preparation method of the invention realizes the simplicity of the addition route and the controllability of the product structure when preparing the bismaleimide-triazine resin.
In one of the embodiments, the molar ratio will be (1-3): 2 mixing bismaleimide with the isocyanurate, adding an organic solvent, and performing an 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 generally needs to use various catalysts and has 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, a catalyst is not required to be added, the addition reaction can be carried out at a lower temperature (105-130 ℃) without the step curing reaction, 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 and butanone.
In one embodiment, the bismaleimide is N, N '- (4, 4' -methylenediphenyl) bismaleimide.
In one embodiment, no catalyst is added during the addition reaction, and the time of the addition reaction is 5-12min. Compared with the existing BT resin preparation method, the preparation method provided by the invention can shorten the reaction time to below 12min under the condition of no catalyst addition, realize gelation and primary solidification in the time period, and remarkably improve the production efficiency. And the BT resin in the gel state can be directly added with other components to prepare a resin composition and is used for preparing the copper-clad plate.
In one embodiment, the gel is further cured at 130-150 ℃, then dried at 70-90 ℃ under vacuum, and the solid bismaleimide-triazine resin is obtained after the solvent volatilizes. The solid bismaleimide-triazine resin is more convenient to store and transport.
The invention also provides the bismaleimide-triazine resin obtained by the preparation method, and the bismaleimide-triazine resin comprises a cross-linked structure shown in the formulas III and IV.
The above bismaleimide-triazine resin has a relatively defined crosslinked structure. Therefore, innovation of the molecular structure of the bismaleimide-triazine resin is realized, the structural design and development capability 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 high-frequency copper-clad plates, and endows high-frequency circuit boards with excellent dielectric properties, heat resistance, electrical insulation, flame retardance and other characteristics.
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 application of the bismaleimide-triazine resin or the resin composition in preparing 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 centrally symmetrical triazine ring structure and a conjugated styryl structure, so that the cyclic addition is realized at low temperature. The C=C double bond of the bismaleimide is reactive, can generate Diels-Alder reaction with the isocyanurate, utilizes the styryl conjugated double bond with a triazine ring to carry out addition with an imide double bond to form a structure with the triazine ring and a condensed ring, and inhibits the rearrangement of 1,4 double bonds in the synthesis process, so that the bismaleimide can carry out addition reaction at a lower temperature without a catalyst. The preparation method of the invention realizes the simplicity of the addition route and the controllability of the product structure when preparing the bismaleimide-triazine resin.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of modified isocyanurate (Ps-TAIC).
FIG. 2 is a diagram showing a differential thermal analysis 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 gel chromatogram of the mixed raw material of Experimental example 3.
FIG. 6 shows a chromatogram of the Ps-TAIC gel of Experimental example 3.
Detailed Description
In order that the invention may be understood more fully, a more particular description of the invention will be rendered by reference to the preferred embodiments that are now set forth. 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 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 raw materials and reagents used in the following examples and comparative examples were all commercially available ones unless otherwise specified. The experimental/test methods in examples and comparative examples are conventional experimental/test methods or existing experimental/test methods in the art unless otherwise specified.
Example 1
A method for preparing bismaleimide-triazine resin, comprising the following steps: 107g of 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 in a molar ratio of 3:2 are weighed, added into a reaction vessel, stirred uniformly, 200g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 110 ℃ and kept for 7min, and the reaction system is partially gelled. And pouring the gelled solution into a mould after the solution viscosity rises rapidly, slowly volatilizing the solvent at 130 ℃ and further curing to obtain the BT resin cured film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
The preparation method of the Ps-TAIC comprises the following steps: a500 ml four-necked flask was taken and equipped with a stirrer, a constant pressure dropping funnel, a thermometer and a serpentine reflux condenser. Into a four-necked flask, 350ml of DMAC and 70g of sodium tripolycyanate were poured, after dissolution, 5.6g of triethylamine was added, the mixture was heated to 90℃and stirred until the temperature became constant, 164.35g of 4-vinylbenzyl chloride was added dropwise over half an hour, and the reaction was continued at a constant temperature of 90℃for 1.5 hours. Cooling to room temperature after the reaction is finished, filtering, taking filtrate, reducing the solution to 210ml by reduced pressure distillation, adding 2L of methanol into the crude product, stirring for 2 hours at normal temperature, filtering, and vacuum drying filter residues for 12 hours at 30 ℃ for later use. The product was subjected to nuclear magnetic resonance analysis (Bruker, switzerland, inc., AVANCE III HD MHz) and its molecular structure was as shown in FIG. 1.
Example 2
A method for preparing bismaleimide-triazine resin, comprising the following steps: 35.8g of N, N '- (4, 4' -methylenediphenyl) bismaleimide and 95.4g of Ps-TAIC are weighed, the mol ratio of the two is 1:2, the mixture is added into a reaction vessel and stirred uniformly, 120g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 105 ℃ and the temperature is kept for 12min, and the reaction system is partially gelled. And pouring the gelled solution into a mould after the solution viscosity rises rapidly, slowly volatilizing the solvent at 130 ℃ and further curing to obtain the BT resin cured film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
Example 3
A method for preparing bismaleimide-triazine resin, comprising the following steps: 107g of N, N '- (4, 4' -methylenediphenyl) bismaleimide and 95.4g of Ps-TAIC are weighed, the mol ratio of the two is 3:2, the mixture is added into a reaction vessel and stirred uniformly, 200g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 130 ℃ and the temperature is kept for 5min, and the reaction system is partially gelled. And pouring the gelled solution into a mold after the solution viscosity rises rapidly, slowly volatilizing the solvent at 150 ℃ and further curing to obtain the BT resin cured film. The obtained BT resin cured film was placed in a vacuum oven at 80 ℃ to remove the residual solvent.
Example 4
A method for preparing bismaleimide-triazine resin, comprising the following steps: 107g of N, N '- (4, 4' -methylenediphenyl) bismaleimide and 95.4g of Ps-TAIC are weighed, the mol ratio of the two is 3:2, the mixture is added into a reaction vessel and stirred uniformly, 200g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 110 ℃ and kept for 10min, and the reaction system is partially gelled. After the solution viscosity rises rapidly, 15g of vinyl modified polyphenyl ether and 5g of boron nitride inorganic filler are added, uniformly mixed, coated on glass fiber cloth, and hot pressed to prepare the high-frequency copper-clad plate.
Comparative example 1
107g of N, N '- (4, 4' -methylenediphenyl) bismaleimide is weighed and added into a reaction vessel, 100g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 150 ℃, the heat preservation is carried out for 60min, no obvious reaction is carried out, part of the solution is taken and poured into a mold, and the solvent is slowly volatilized at 130 ℃, so as to obtain unreacted BMI solid.
Comparative example 2
Weighing 95.4g of Ps-TAIC, adding 100g of dimethylacetamide as a solvent to dissolve into a homogeneous solution, heating to 100 ℃, preserving heat for 16min without obvious reaction, pouring part of the solution into a mould, slowly volatilizing the solvent at 100 ℃, obtaining a powdery solid which cannot form a film, wherein the powdery solid is presumed to be a mixture of oligomer and unreacted powder.
Comparative example 3
Weighing 95.4g of Ps-TAIC, 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 relatively brittle, almost powder, and difficult to prepare into a film-forming material.
Comparative example 4
107g of N, N '- (4, 4' -methylenediphenyl) bismaleimide and 49.8g of triallyl isocyanurate are weighed, the molar ratio of the two is 3:2, the mixture is added into a reaction vessel and stirred uniformly, 200g of dimethylacetamide is added as a solvent to be dissolved into a homogeneous solution, the temperature is raised to 110 ℃ and the temperature is kept for 30min without obvious reaction, a part of the solution is poured into a mold, and the solvent is slowly volatilized at 130 ℃ to obtain a mixture of unreacted BMI solid and oligomer.
Experimental example 1
The results of differential thermal analysis were carried out on the mixed raw materials of N, N '- (4, 4' -methylenediphenyl) bismaleimide, BMI and Ps-TAIC in a molar ratio of 3:2, respectively, as shown in FIG. 2. The results show that the pure BMI is in melting transition near 166 ℃ and has no chemical reaction activity at 300 ℃, and the mixed raw material has an obvious exothermic peak of chemical reaction near 173 ℃, which indicates that the addition of Ps-TAIC effectively reduces the temperature of BMI monomer polymerization reaction.
Experimental example 2
N, N '- (4, 4' -methylenediphenyl) bismaleimide and Ps-TAIC in a molar ratio of 1:2 are mixed, and after a proper amount of dimethylacetamide is added, the mixture is reacted for 5 to 7 minutes at 100 ℃ to obtain a yellow transparent partially gelled product, and an optical photograph is shown in figure 3.
Taking Ps-TAIC, adding appropriate amount of dimethylacetamide, and heating at 110deg.C for 5-7min to obtain yellow transparent solution, and optical photograph is shown in figure 3.
An optical photograph of the BT resin cured film obtained in example 1, which was a yellow transparent film sheet having a flat surface, is shown in fig. 4.
Experimental example 3
N, N '- (4, 4' -methylenediphenyl) bismaleimide and Ps-TAIC in a molar ratio of 1:2 are mixed, dimethylacetamide is added to obtain a solution with a solid content of 50%, the solution is stirred and reacted for 16min at 100 ℃, the reactant is partially gelled, and a gelled product is taken for gel chromatography detection, and the result is shown in figure 5.
Taking Ps-TAIC, adding dimethylacetamide to obtain 50% solid solution, stirring at 100deg.C for 16min to obtain partially gelled product, and detecting gel chromatography to obtain the result shown in figure 6.
The result shows that the molecular weight Mn of the mixed raw material reaction solution is increased to 1947, and no obvious small molecular peak exists; the molecular weight Mn of the Ps-TAIC solution increased to 2114. The molecular weight test result shows that the polymerization capability of the two reaction solutions is achieved under the lower temperature without catalyst; and the mixed solution has no obvious micromolecular BMI residue after gelation for a short time, which proves that BMI and Ps-TAIC have copolymerization reaction.
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 (6)
1. A method for preparing bismaleimide-triazine resin, which is characterized by comprising the following steps: the molar ratio is (1-3): 2 and isocyanurate with a structure shown in a formula I are mixed, an organic solvent is added, and an addition reaction is carried out at 105-130 ℃ to obtain bismaleimide-triazine resin gel; further curing the bismaleimide-triazine resin gel at 130-150 ℃, then drying at 70-90 ℃ under vacuum, and volatilizing the solvent to obtain solid bismaleimide-triazine resin;
the reaction process is shown as a formula II; the organic solvent is dimethylacetamide; the bismaleimide is N, N '- (4, 4' -methylenediphenyl) bismaleimide;
i
II type
No catalyst is added in the addition reaction, and the time of the addition reaction is 5-12min.
2. A bismaleimide-triazine resin obtained by the preparation method according to claim 1, wherein the bismaleimide-triazine resin comprises a crosslinked structure represented by the following formulas III and IV
III
Formula IV.
3. A resin composition comprising the bismaleimide-triazine resin according to claim 2.
4. A resin composition according to claim 3, 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.
5. The resin composition according to claim 4, wherein the polyphenylene ether is a vinyl-modified polyphenylene ether and the inorganic filler is boron nitride.
6. Use of the bismaleimide-triazine resin of claim 2 or the resin composition of any one of claims 3-5 in the preparation of a high frequency copper clad laminate.
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| JPS4842088A (en) * | 1971-09-27 | 1973-06-19 | ||
| JPS5638310A (en) * | 1979-09-07 | 1981-04-13 | Hitachi Ltd | Bismaleimide-triallyl isocyanurate polymer and its preparation |
| 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 |
| CN113683576A (en) * | 2021-08-24 | 2021-11-23 | 珠海宏昌电子材料有限公司 | Isocyanurate, preparation method thereof and application thereof in high-frequency and high-speed resin |
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| DK2889624T3 (en) * | 2009-08-10 | 2018-12-10 | Ucl Business Plc | Reversible covalent bonding of functional molecules |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4842088A (en) * | 1971-09-27 | 1973-06-19 | ||
| JPS5638310A (en) * | 1979-09-07 | 1981-04-13 | Hitachi Ltd | Bismaleimide-triallyl isocyanurate polymer and its preparation |
| 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 |
| CN113683576A (en) * | 2021-08-24 | 2021-11-23 | 珠海宏昌电子材料有限公司 | Isocyanurate, preparation method thereof and application thereof in high-frequency and high-speed resin |
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