CN117362638A - Autocatalysis imide-ring-containing phthalonitrile resin and preparation method and application thereof - Google Patents
Autocatalysis imide-ring-containing phthalonitrile resin and preparation method and application thereof Download PDFInfo
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- CN117362638A CN117362638A CN202311366772.2A CN202311366772A CN117362638A CN 117362638 A CN117362638 A CN 117362638A CN 202311366772 A CN202311366772 A CN 202311366772A CN 117362638 A CN117362638 A CN 117362638A
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- imide
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- phthalonitrile
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- 229920005989 resin Polymers 0.000 title claims abstract description 120
- 239000011347 resin Substances 0.000 title claims abstract description 120
- XQZYPMVTSDWCCE-UHFFFAOYSA-N phthalonitrile Chemical compound N#CC1=CC=CC=C1C#N XQZYPMVTSDWCCE-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229920006391 phthalonitrile polymer Polymers 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005844 autocatalytic reaction Methods 0.000 title abstract description 9
- 150000003949 imides Chemical class 0.000 claims abstract description 67
- 239000003822 epoxy resin Substances 0.000 claims abstract description 64
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 64
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 30
- -1 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile Chemical compound 0.000 claims abstract description 29
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 21
- NTZMSBAAHBICLE-UHFFFAOYSA-N 4-nitrobenzene-1,2-dicarbonitrile Chemical compound [O-][N+](=O)C1=CC=C(C#N)C(C#N)=C1 NTZMSBAAHBICLE-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 15
- GCWYXRHXGLFVFE-UHFFFAOYSA-N 4-hydroxy-2,6-dimethylaniline Chemical compound CC1=CC(O)=CC(C)=C1N GCWYXRHXGLFVFE-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229960000583 acetic acid Drugs 0.000 claims abstract description 12
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000010 aprotic solvent Substances 0.000 claims abstract description 10
- 150000004982 aromatic amines Chemical class 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 15
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 10
- 239000012670 alkaline solution Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000007935 neutral effect Effects 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- 239000012153 distilled water Substances 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
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 3
- 238000002844 melting Methods 0.000 abstract description 26
- 230000008018 melting Effects 0.000 abstract description 24
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 4
- 125000006615 aromatic heterocyclic group Chemical group 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010992 reflux Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical group C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- 125000004093 cyano group Chemical group *C#N 0.000 description 6
- 230000009477 glass transition Effects 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 4
- 238000000113 differential scanning calorimetry Methods 0.000 description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 4
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 230000000930 thermomechanical effect Effects 0.000 description 3
- VBCXQKMINMOFDB-UHFFFAOYSA-N 4-(4-aminophenoxy)benzene-1,2-dicarbonitrile Chemical compound C1=CC(N)=CC=C1OC1=CC=C(C#N)C(C#N)=C1 VBCXQKMINMOFDB-UHFFFAOYSA-N 0.000 description 2
- LWOAIKNLRVQTFT-UHFFFAOYSA-N 4-amino-n-(4-aminophenyl)benzenesulfonamide Chemical compound C1=CC(N)=CC=C1NS(=O)(=O)C1=CC=C(N)C=C1 LWOAIKNLRVQTFT-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 125000006267 biphenyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229960002317 succinimide Drugs 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 description 1
- WCXGOVYROJJXHA-UHFFFAOYSA-N 3-[4-[4-(3-aminophenoxy)phenyl]sulfonylphenoxy]aniline Chemical compound NC1=CC=CC(OC=2C=CC(=CC=2)S(=O)(=O)C=2C=CC(OC=3C=C(N)C=CC=3)=CC=2)=C1 WCXGOVYROJJXHA-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
An autocatalysis imide-containing phthalonitrile resin and a preparation method and application thereof relate to the technical field of aromatic heterocyclic resin, in particular to an autocatalysis imide-containing phthalonitrile resin and a preparation method and application thereof. The preparation method aims to solve the problems of high melting point, improper curing speed and complex preparation process of the existing autocatalytic phthalonitrile resin. Unsaturated double bond and imide ring are introduced into the structure of the self-catalytic phthalonitrile resin containing imide ring, and dimethyl is simultaneously introduced on the benzene ring. The method comprises the following steps: stirring 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate in an aprotic solvent, reacting, washing the product with water, and drying to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile; and adding glacial acetic acid, heating and refluxing, cooling to separate out a product, washing with water, and drying to obtain a target product. The resin has a moderate curing speed and a low melting point. The resin disclosed by the invention is used for modifying epoxy resin.
Description
Technical Field
The invention relates to the technical field of aromatic heterocyclic resins, in particular to an autocatalytic imide-containing phthalonitrile resin and a preparation method and application thereof.
Background
Phthalonitrile resin is one of aromatic heterocyclic resins, and the resin has excellent mechanical property, thermal stability, flame retardant property and chemical stability, and has wide application prospect in the fields of aerospace, electronic and electric, chemical industry, automobile manufacturing and the like. However, such resins have a very slow curing rate, and it is necessary to add curing accelerators such as amine compounds, phenol compounds, metal salts, acid anhydrides, and carboxylic acids. The scholars at home and abroad can realize autocatalytic curing under the condition of not strengthening the accelerator by designing the molecular structure of the phthalonitrile resin grafted with amino, hydroxyl, benzimidazole or benzoxazine, and the resin is called as autocatalytic phthalonitrile resin. The amino autocatalytic phthalonitrile resin has high amino catalytic activity, narrow processing temperature window and high curing speed, so that the product has a plurality of air hole defects, and the phthalonitrile resin with hydroxyl and benzimidazole can be autocatalytically cured, but has very slow speed, and obvious exothermic peaks are difficult to observe on a Differential Scanning Calorimetry (DSC) curve. In addition, conventional phthalonitrile resins have relatively high melting points, typically exceeding 190 ℃, and researchers have often incorporated soft segments into the molecular backbone of the resin to lower the melting point, but this can compromise the heat resistance of the resin. Therefore, the autocatalytic phthalonitrile resin with the characteristics of low melting point, wide processing temperature window and moderate curing speed has yet to be developed.
In application, phthalonitrile resin is also commonly used for improving the thermal stability, the thermo-mechanical property and the adhesive property of epoxy resin, but most of the mixing modes are solvent methods, and the solvent needs to be removed before curing; zhao et al prepared modified epoxy resins (Journal of applied polymer science,2013,127 (6): 4873-4878) from E44 epoxy, non-autocatalytic bisphenol A phthalonitrile, 4' -diaminodiphenyl sulfone as raw materials by melt mixing in a solvent-free manner at a mixing temperature up to 200 ℃. Other scholars also prepare modified epoxy resins by melt mixing, but the temperature is generally over 150 ℃ and the modified epoxy resins are required to reach above the melting point of phthalonitrile resin per se to be uniformly mixed. Overall, the process is relatively complex. Patent CN113201302B discloses a diamino bisphthalonitrile modified epoxy resin adhesive and a preparation method thereof, and adopts an active diluent with cyano groups to mainly solve the problems that the phthalonitrile modified epoxy resin adhesive is toxic, not environment-friendly and lower in ageing resistance, but the preparation process is relatively complex.
Therefore, the existing autocatalytic phthalonitrile resin has the problems of high melting point, improper curing speed and complex preparation process.
Disclosure of Invention
The invention provides an autocatalytic phthalonitrile resin containing imide ring and a preparation method and application thereof, aiming at solving the problems of high melting point, improper curing speed and complex preparation process of the existing autocatalytic phthalonitrile resin.
The invention provides an autocatalytic phthalonitrile resin containing imide ring, which has the molecular structure as follows:
the invention also provides a preparation method of the self-catalyzed imide-ring-containing phthalonitrile resin, which specifically comprises the following steps:
step one: uniformly stirring 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate in an aprotic solvent, heating to 35-80 ℃ for reaction for 6-24 hours, then pouring into an alkaline solution to precipitate a product, washing the product to neutrality, filtering, and vacuum-drying to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a reaction vessel filled with glacial acetic acid for stirring, heated and refluxed for 3-12h, cooled to room temperature, poured into distilled water to separate out a product, repeatedly washed to be neutral, filtered and dried in vacuum, thus obtaining the target product autocatalytic imide-containing phthalonitrile resin.
Further, in the first step, the molar ratio of 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate is 1 (1-1.1): 1.2-2.
Further, in the first step, the aprotic solvent is dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the aprotic solvent is used in an amount of 2 to 5 times the total weight of 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate.
Further, in the first step, the alkaline solution is an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution or an aqueous barium hydroxide solution. Preferably, the molar concentration of the alkaline solution is 0.1-1.0mol/L.
Further, in the second step, the molar ratio of maleic anhydride to 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile is (2-1.2): 1.
Further, the addition amount of glacial acetic acid in the second step is 3-5 times of the total weight of maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile.
In the first step and the second step, stirring, precipitation, washing, filtering and vacuum drying are all conventional operation means in the field, and the technical personnel in the field can reasonably select tools and parameters according to actual conditions.
The invention provides application of an autocatalytic imide-containing phthalonitrile resin as a modifier of epoxy resin.
Further, the specific method for modifying the epoxy resin comprises the following steps:
adding an aromatic amine curing agent into epoxy resin according to an equal stoichiometric ratio, heating at 90-150 ℃ to enable the aromatic amine curing agent to be completely melted, then adding self-catalyzed phthalonitrile resin powder containing imide rings, continuously stirring until the mixture is clear and transparent, and heating and curing the mixture to obtain the modified epoxy resin.
Further, the epoxy resin is E44, E51, AG70 or TDE85 low-viscosity liquid epoxy resin.
Further, the aromatic amine curing agent is 4,4' -diaminodiphenyl sulfone, 4' -bis (3-aminophenoxy) diphenyl or 4,4' -diaminobenzenesulfonanilide.
Further, the mass ratio of the epoxy resin to the autocatalytic imide-containing phthalonitrile resin is (0.6-1.5): 1.
Further, the temperature-rising curing program is to keep the temperature at 180 ℃ for 3 hours, and then to keep the temperature at 250 ℃ for 2 hours.
The invention has the beneficial effects that:
1. the self-catalyzed phthalonitrile resin containing imide ring contains unsaturated double bond, imide ring and cyano group, and the succinimide produced by the copolymerization reaction of the structures can produce trace amine, such as aniline and benzyl amine, at high temperature, so that the curing reaction of cyano group can be promoted, the curing speed is moderate, large-size products with compact structures can be easily produced, and the industrial application is facilitated.
2. The self-catalyzed imide-ring-containing phthalonitrile resin provided by the invention has relatively low melting point on the premise of relatively moderate curing speed, and is convenient to process and use, and the rigidity of the main chain structure of the resin molecule is not affected by introducing dimethyl into the benzene ring, so that the self-catalyzed imide-ring-containing phthalonitrile resin can still maintain excellent thermal stability and thermomechanical property.
3. The preparation method of the autocatalysis imide-containing phthalonitrile resin provided by the invention is mainly based on stirring, heating, water washing and other operations to realize the preparation of target resin, and does not need further refining and purification, so that the preparation method is simple in flow, convenient to operate, high in production efficiency and low in production cost.
4. The self-catalyzed imide-ring-containing phthalonitrile resin provided by the invention can be used as a modifier of epoxy resin, is based on Michael addition reaction of amino and double bonds, and can be enabled to be 'forced to melt' at a temperature lower than the self-melting point, and the modification process is very simple without the aid of a solvent. The melting temperature can be obviously lower than the self-melting point of the self-catalyzed imide-containing phthalonitrile resin, and finally the glass transition temperature and the high-temperature adhesive property of the epoxy resin are improved through a multiple curing mechanism.
Drawings
FIG. 1 is a DSC curve of the autocatalytic imide ring containing phthalonitrile resin prepared in example 1;
FIG. 2 shows nuclear magnetic resonance spectrum of the autocatalytic imide ring-containing phthalonitrile resin prepared in example 1 1 H NMR) spectrum;
FIG. 3 is an infrared (FT-IR) spectrum of an autocatalytic imide ring containing phthalonitrile resin prepared in example 1.
Detailed Description
The technical scheme of the invention is not limited to the specific embodiments listed below, and also includes any combination of the specific embodiments.
The first embodiment is as follows: the self-catalyzed phthalonitrile resin containing imide ring has the molecular structure as follows:
from the standpoint of molecular structure design, through imidization reaction of maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile, unsaturated double bond and imide ring are simultaneously introduced, and the succinimide formed by copolymerization reaction of these structures can generate trace amine, such as aniline and benzyl amine, at high temperature, so that the curing reaction of cyano can be promoted, the reaction activity is much more moderate than that of autocatalytic phthalonitrile resin with amino, but the reaction speed is much faster than that of phthalonitrile resin with hydroxyl and benzimidazole, and obvious exothermic peak can be observed on DSC curve, therefore, the autocatalytic imide-containing phthalonitrile resin has relatively moderate curing speed, and a large-size product with compact structure can be easily prepared. Meanwhile, from the aspect of molecular structure design, dimethyl is simultaneously introduced on the benzene ring to break the structural symmetry and regularity of the phthalonitrile resin and weaken the interaction force between molecules and in the molecules, so that the self-catalyzed imide-ring-containing phthalonitrile resin has relatively low melting point. The rigidity of the main chain structure of the phthalonitrile resin molecule is not influenced on the whole, so that the excellent thermal stability and thermal mechanical property can be maintained.
The second embodiment is as follows: the preparation method of the self-catalyzed imide-ring-containing phthalonitrile resin in the embodiment specifically comprises the following steps:
step one: uniformly stirring 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate in an aprotic solvent, heating to 35-80 ℃ for reaction for 6-24 hours, then pouring into an alkaline solution to precipitate a product, washing the product to neutrality, filtering, and vacuum-drying to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a reaction vessel filled with glacial acetic acid for stirring, heated and refluxed for 3-12h, cooled to room temperature, poured into distilled water to separate out a product, repeatedly washed to be neutral, filtered and dried in vacuum, thus obtaining the target product autocatalytic imide-containing phthalonitrile resin.
And a third specific embodiment: the second difference between this embodiment and the second embodiment is that: in the first step, the molar ratio of the 4-amino-3, 5-xylenol, the 4-nitrophthalonitrile and the anhydrous potassium carbonate is 1 (1-1.1) to 1.2-2. The other is the same as in the second embodiment.
The specific embodiment IV is as follows: the second difference between this embodiment and the second embodiment is that: the aprotic solvent in the first step is dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the aprotic solvent is used in an amount of 2 to 5 times the total weight of 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate. The other is the same as in the second embodiment.
Fifth embodiment: the second difference between this embodiment and the second embodiment is that: the alkaline solution in the first step is sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, calcium hydroxide aqueous solution or barium hydroxide aqueous solution. Preferably, the molar concentration of the alkaline solution is 0.1-1.0mol/L. The other is the same as in the second embodiment.
Specific embodiment six: the second difference between this embodiment and the second embodiment is that: in the second step, the molar ratio of maleic anhydride to 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile is (2-1.2): 1. The other is the same as in the second embodiment.
Seventh embodiment: the second difference between this embodiment and the second embodiment is that: the addition amount of glacial acetic acid in the second step is 3-5 times of the total weight of maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile. The other is the same as in the second embodiment.
Eighth embodiment: the embodiment is the application of the self-catalyzed imide-ring-containing phthalonitrile resin as a modifier of epoxy resin.
Can be uniformly mixed with epoxy resin by a simple heating and melting mode, and based on Michael addition reaction of amino and double bonds, the melting temperature can be obviously lower than the self melting point of the self-catalyzed imide-containing phthalonitrile resin, and finally the glass transition temperature and high-temperature bonding performance of the epoxy resin are improved by a multiple curing mechanism.
Detailed description nine: this embodiment differs from the eighth embodiment in that: the specific method for modifying the epoxy resin comprises the following steps:
adding an aromatic amine curing agent into epoxy resin according to an equal stoichiometric ratio, heating at 90-150 ℃ to enable the aromatic amine curing agent to be completely melted, then adding self-catalyzed phthalonitrile resin powder containing imide rings, continuously stirring until the mixture is clear and transparent, and heating and curing the mixture to obtain the modified epoxy resin. The other is the same as in embodiment eight.
Preferably at 100-130 ℃ to completely melt the aromatic amine in the epoxy resin, otherwise the aromatic amine can be precipitated during the curing process, so that the performance of the cured product is unstable. If the heating temperature is too high, the modified resin may be gelled. The conventional operation is to melt the self-catalyzed phthalonitrile resin containing imide ring and epoxy resin at high temperature, and then add aromatic amine, so that the mixture cannot be uniformly mixed.
Detailed description ten: this embodiment differs from the ninth embodiment in that: the epoxy resin is E44, E51, AG70 or TDE85 low-viscosity liquid epoxy resin. The other is the same as in the ninth embodiment.
Eleventh embodiment: this embodiment differs from the ninth embodiment in that: the aromatic amine curing agent is 4,4' -diaminodiphenyl sulfone, 4' -bis (3-aminophenoxy) diphenyl or 4,4' -diaminobenzenesulfonanilide. The other is the same as in the ninth embodiment.
Twelve specific embodiments: this embodiment differs from the ninth embodiment in that: the mass ratio of the epoxy resin to the self-catalyzed phthalonitrile resin containing imide ring is (0.6-1.5): 1. The other is the same as in the ninth embodiment.
When the mass ratio of the epoxy resin to the autocatalytic imide-containing phthalonitrile resin is lower than 0.6:1, the autocatalytic imide-containing phthalonitrile resin occupies too much, so that the modified epoxy resin is a harder solid at room temperature, the processability is poor, and the modified epoxy resin cannot be used for a pasty adhesive; when the mass ratio of the two is higher than 1.5:1, the self-catalyzed phthalonitrile resin containing imide ring has low ratio, the formed heat-resistant crosslinking points are few, and the performance change of the modified epoxy resin is not obvious.
Thirteen specific embodiments: this embodiment differs from the ninth embodiment in that: the temperature rise and solidification program is that the temperature is kept for 3 hours at 180 ℃, and then the temperature is kept for 2 hours at 250 ℃. The other is the same as in the ninth embodiment.
The following examples of the present invention are described in detail, and are provided by taking the technical scheme of the present invention as a premise, and the detailed embodiments and specific operation procedures are given, but the scope of the present invention is not limited to the following examples.
The test instruments and methods used in the following examples were:
1 h NMR: adopts BrukerAVANCE III HD MHz nuclear magnetic resonance spectrometer to test, uses tetramethyl silane as internal standard, deuterated dimethyl sulfoxide (DMSO-d) 6 ) Is a solvent.
DSC: the temperature is raised at a rate of 10 ℃/min in a nitrogen atmosphere by using a TA company Q20 differential scanning calorimeter.
Processing temperature window: the temperature difference between the temperature at the top of the curing exothermic peak of the DSC curve of the resin and the melting point of the resin is defined as the processing temperature window in degrees celsius.
FT-IR: testing with a TENSOR-27 Fourier infrared spectrometer of Bruker company, tabletting with potassium bromide, and scanning with 4000-400cm -1 Resolution of 2cm -1 。
Glass transition temperature: the test is carried out by adopting a TA company Q800 dynamic thermo-mechanical analyzer, wherein the temperature rising rate is 5 ℃/min in a single cantilever mode.
Lap shear strength: the lap shear strength is one of the most basic and important indexes for representing the adhesive property of the material, and the lap shear strength at 300 ℃ is measured according to the GJB 444-1988 standard.
Example 1:
the preparation method of the autocatalysis imide-ring-containing phthalonitrile resin comprises the following steps:
step one: uniformly stirring 0.5mol of 4-amino-3, 5-xylenol, 0.52mol of 4-nitrophthalonitrile and 0.7mol of anhydrous potassium carbonate in 540 g of N, N-dimethylformamide, heating to 35 ℃ for reaction for 24 hours, pouring into 0.5mol/L sodium hydroxide aqueous solution to precipitate a product, washing to neutrality, filtering, and vacuum drying at 60 ℃ to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: 0.8mol of maleic anhydride and 0.4mol of 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a three-neck flask filled with 560 g of glacial acetic acid, stirred, heated and refluxed for 4 hours, cooled to room temperature, poured into distilled water to precipitate a product, repeatedly washed to be neutral, filtered and dried in vacuum at 70 ℃ to obtain the target product autocatalytic imide-containing phthalonitrile resin, wherein the yield is 91 percent and the melting point is 150 ℃.
The molecular structure of the autocatalytic phthalonitrile-containing resin containing imide ring prepared in this example is:
the result of DSC analysis of the autocatalytic imide-ring-containing phthalonitrile resin prepared in this example is shown in FIG. 1. From the DSC test result, the melting point of the self-catalyzed imide-containing phthalonitrile resin is 150 ℃, a distinct exothermic peak can be observed on the DSC curve, the exothermic peak top temperature appears at 348 ℃, the heating temperature window is 198 ℃, and the curing speed is moderate.
The autocatalytic phthalonitrile resin containing imide ring prepared in this example was subjected to 1 H NMR analysis, as shown in fig. 2, gave the following analytical data: 1 H NMR(600MHz，DMSO-d6，δ，ppm)8.13，8.14(d，1H，Ar-H)；7.90，7.91(d，1H，Ar-H)；7.45-7.47(dd，1H，Ar-H)；7.27(s，2H，Ar-H)；7.05(s，2H，-CH＝CH)；2.04(s，6H，-CH 3 )。
the self-catalyzed imide-ring-containing phthalonitrile resin prepared in the embodiment is subjected to FT-IR analysis, and the result is shown in figure 3, and the analysis data are as follows: FTIR [ ]KBr，cm -1 ):698，829(C＝C)，1718，1780(C＝O)，2230(-CN)，1093，744(C-N-C)，1250(C-O-C)，2968(-CH 3 )。
From the slave 1 As can be seen from the results of H NMR and FT-IR analysis, the prepared autocatalytic phthalonitrile resin containing imide ring has a molecular structure consistent with the designed molecular structure, which indicates that the target product is successfully synthesized.
Example 2:
the preparation method of the autocatalysis imide-ring-containing phthalonitrile resin comprises the following steps:
step one: uniformly stirring 0.5mol of 4-amino-3, 5-xylenol, 0.5mol of 4-nitrophthalonitrile and 1mol of anhydrous potassium carbonate in 1400 g of dimethyl sulfoxide, heating to 65 ℃ for reaction for 10 hours, then pouring into 0.2mol/L potassium hydroxide aqueous solution to precipitate a product, washing to neutrality, filtering, and vacuum drying at 60 ℃ to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: 0.64mol of maleic anhydride and 0.4mol of 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a three-neck flask filled with 672 g of glacial acetic acid, stirred, heated and refluxed for reaction for 10 hours, cooled to room temperature, poured into distilled water to precipitate a product, repeatedly washed to be neutral, filtered and dried in vacuum at 70 ℃ to obtain the target product of the autocatalytic imide-containing phthalonitrile resin, wherein the yield is 87 percent and the melting point is 150 ℃.
The DSC curve of the autocatalytic imide-containing cyclic phthalonitrile resin in this example is the same as that in example 1.
Example 3:
the preparation method of the autocatalysis imide-ring-containing phthalonitrile resin comprises the following steps:
step one: uniformly stirring 0.5mol of 4-amino-3, 5-xylenol, 0.54mol of 4-nitrophthalonitrile and 0.61mol of anhydrous potassium carbonate in 860 g of N, N-dimethylacetamide, heating to 75 ℃ for reaction for 7 hours, pouring into 0.8mol/L of calcium hydroxide aqueous solution to precipitate a product, washing to neutrality, filtering, and vacuum drying at 60 ℃ to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: 0.5mol of maleic anhydride and 0.4mol of 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a three-neck flask filled with 710 g of glacial acetic acid, stirred, heated and refluxed for 7h, cooled to room temperature, poured into distilled water to precipitate a product, repeatedly washed to be neutral, filtered and dried in vacuum at 70 ℃ to obtain the target product autocatalytic imide-containing phthalonitrile resin, wherein the yield is 90 percent and the melting point is 150 ℃.
The DSC curve of the autocatalytic imide-containing cyclic phthalonitrile resin in this example is the same as that in example 1.
Example 4:
the preparation method of the autocatalysis imide-ring-containing phthalonitrile resin comprises the following steps:
step one: uniformly stirring 0.5mol of 4-amino-3, 5-xylenol, 0.53mol of 4-nitrophthalonitrile and 0.79mol of anhydrous potassium carbonate in 675 g of dimethyl sulfoxide, heating to 60 ℃ for reaction for 16 hours, then pouring into 0.4mol/L sodium hydroxide aqueous solution to precipitate a product, washing to neutrality, filtering, and vacuum drying at 60 ℃ to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: 0.68mol of maleic anhydride and 0.4mol of 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a three-neck flask filled with 774 g of glacial acetic acid, stirred, heated and refluxed for 9 hours, cooled to room temperature, poured into distilled water to precipitate a product, repeatedly washed to be neutral, filtered and dried in vacuum at 70 ℃ to obtain the target product of the autocatalytic imide-containing phthalonitrile resin, wherein the yield is 88 percent and the melting point is 150 ℃.
The DSC curve of the autocatalytic imide-containing cyclic phthalonitrile resin in this example is the same as that in example 1.
Comparative example 1:
this example provides another autocatalytic imide-ring-containing phthalonitrile resin, which lacks a dimethyl structure on the benzene ring compared to the autocatalytic imide-ring-containing phthalonitrile resin of example 1, and has the specific molecular structure:
the preparation procedure of this comparative example is as follows:
step one: uniformly stirring 0.5mol of 4-aminophenol, 0.5mol of 4-nitrophthalonitrile and 0.7mol of anhydrous potassium carbonate in 852 g of dimethyl sulfoxide, heating to 65 ℃ for reaction for 9 hours, then pouring into 0.2mol/L sodium hydroxide aqueous solution to precipitate a product, washing to be neutral, filtering, and vacuum drying at 60 ℃ to obtain 4- (4-aminophenoxy) phthalonitrile;
step two: 0.64mol of maleic anhydride and 0.4mol of 4- (4-aminophenoxy) phthalonitrile are added into a three-neck flask filled with 695 g of glacial acetic acid, stirred, heated and refluxed for reaction for 6 hours, cooled to room temperature, poured into distilled water to precipitate a product, repeatedly washed to be neutral, filtered and dried in vacuum at 70 ℃ to obtain the target product of the autocatalytic imide-containing phthalonitrile resin, the yield is 90 percent, and the melting point is 210 ℃.
The melting point of the self-catalytic imide-containing phthalonitrile resin is 213 ℃, obvious exothermic peaks can be observed on a DSC curve, the exothermic peak top temperature appears at 328 ℃, and the heating temperature window is 115 ℃, so that the temperature is relatively narrow. Compared with examples 1-4, the autocatalytic imide-containing phthalonitrile resin of the comparative example has higher melting point and too high curing speed, and cannot prepare large-size products with compact structures.
Example 5:
in this example, the modified epoxy resin was prepared by using the autocatalytic imide-containing phthalonitrile resin prepared in example 1 as a modifier for epoxy resin. The specific operation is as follows:
3.2 g of aromatic amine curing agent 4,4' -diaminodiphenyl sulfone is added into 10 g of E51 epoxy resin, the aromatic amine is heated at 130 ℃ to be completely melted, then 8.2 g of self-catalyzed imide-containing phthalonitrile resin powder is added, stirring is continued until the mixture is clear and transparent, heat preservation is carried out for 3h at 180 ℃, heat preservation is carried out for 2h at 250 ℃, and the modified epoxy resin A is obtained after curing.
Example 6:
in this example, the modified epoxy resin was prepared by using the autocatalytic imide-containing phthalonitrile resin obtained in example 1 as a modifier for epoxy resin. The specific operation is as follows:
3.2 g of aromatic amine curing agent 4,4' -diaminodiphenyl sulfone is added into 10 g of E51 epoxy resin, the aromatic amine is heated at 130 ℃ to be completely melted, then 15 g of self-catalyzed imide-ring-containing phthalonitrile resin powder is added, stirring is continued until the mixture is clear and transparent, heat preservation is carried out for 3h at 180 ℃, heat preservation is carried out for 2h at 250 ℃, and modified epoxy resin B is obtained after curing.
Comparative example 2:
the comparative example was a blank control, and the autocatalytic imide ring-containing phthalonitrile resin obtained in example 1 was not added. The specific operation is as follows:
3.2 g of aromatic amine curing agent 4,4' -diaminodiphenyl sulfone is added into 10 g of E51 epoxy resin, the aromatic amine is heated at 130 ℃ to be completely melted, the temperature is kept at 180 ℃ for 3 hours, the temperature is further kept at 250 ℃ for 2 hours, and the modified epoxy resin C is obtained after curing.
Comparative example 3:
in this comparative example, a modified epoxy resin was produced using the autocatalytic imide-containing phthalonitrile resin obtained in comparative example 1 as a modifier for epoxy resin. The specific operation is as follows:
to 10 g of E51 epoxy resin was added 3.2 g of aromatic amine curing agent 4,4' -diaminodiphenyl sulfone, and the aromatic amine was completely melted by heating at 130℃and then 8.2 g of autocatalytic imide-containing phthalonitrile resin powder was added and stirring was continued.
In the experimental process, the self-catalyzed imide-containing phthalonitrile resin obtained in the comparative example 1 has a melting point as high as 213 ℃, and can only be slightly melted in epoxy resin, so that the mixing is uneven, the stirring time is continuously prolonged or the heating temperature is increased, and the gel phenomenon occurs, namely, the modified epoxy resin cannot be prepared by the solvent-free method provided by the invention.
Example 7:
in this example, the modified epoxy resin was prepared by using the autocatalytic imide-containing phthalonitrile resin obtained in example 1 as a modifier for epoxy resin. The specific operation is as follows:
adding 4.8 g of aromatic amine curing agent 4,4' -bis (3-aminophenoxy) diphenyl sulfone into 10 g of E44 epoxy resin, heating at 110 ℃ to enable aromatic amine to be completely melted, adding 9.6 g of self-catalyzed phthalonitrile resin powder containing imide ring, continuously stirring until the powder is clear and transparent, preserving heat for 3h at 180 ℃, further preserving heat for 2h at 250 ℃ and curing to obtain modified epoxy resin D.
Example 8:
in this example, the modified epoxy resin was prepared by using the autocatalytic imide-containing phthalonitrile resin obtained in example 1 as a modifier for epoxy resin. The specific operation is as follows:
adding 4.6 g of aromatic amine curing agent 4,4' -diaminobenzene sulfonyl anilide into 10 g of AG70 epoxy resin, heating at 100 ℃ to enable the aromatic amine to be completely melted, then adding 13.8 g of self-catalyzed imide-ring-containing phthalonitrile resin powder, continuously stirring until the powder is clear and transparent, preserving heat for 3h at 180 ℃, further preserving heat for 2h at 250 ℃ and curing to obtain modified epoxy resin E.
Example 9:
in this example, the modified epoxy resin was prepared by using the autocatalytic imide-containing phthalonitrile resin obtained in example 1 as a modifier for epoxy resin. The specific operation is as follows:
5.6 g of aromatic amine curing agent 4,4' -diaminobenzene sulfonyl anilide is added into 10 g of TDE85 epoxy resin, the aromatic amine is heated at 100 ℃ to be completely melted, then 8.8 g of self-catalyzed phthalonitrile resin powder containing imide ring is added, stirring is continued until the resin powder is clear and transparent, heat preservation is carried out for 3h at 180 ℃, heat preservation is carried out for 2h at 250 ℃, and the modified epoxy resin F is obtained after curing.
The modified epoxy resins prepared in examples 5 to 9 and comparative example 2 were subjected to performance test, respectively, and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the modified epoxy resin C prepared in comparative example 2 was not added with the autocatalytic imide ring-containing phthalonitrile resin, and had a glass transition temperature of 234℃and a lap shear strength of only 1.9MPa at 300℃after curing by temperature programming. On the basis, after different parts of self-catalyzed phthalonitrile resin containing imide ring are introduced, the glass transition temperature and high-temperature bonding performance of the prepared modified epoxy resin A and the modified epoxy resin B are greatly improved. In particular, compared with the modified epoxy resin C, the overlap shear strength of the modified epoxy resin B at 300 ℃ is improved by 389 percent. The modified epoxy resins prepared in examples 7-9, which are also added with the autocatalytic imide ring-containing phthalonitrile resin, have higher glass transition temperature and high-temperature adhesive property. The modified resin is mainly characterized in that a plurality of reactive groups such as epoxy groups, double bonds, cyano groups, amino groups and the like in the modified resin system generate heat-resistant crosslinking points with different structures through a multiple curing mechanism, so that the movement and sliding of molecular chains are hindered, the bonding effect and bonding stability of interfaces are enhanced due to the existence of a plurality of polar reactive groups, and the high-temperature bonding performance is improved. In addition, the preparation process of the modified epoxy resin is very simple, no complicated equipment is needed, no sedimentation and precipitation phenomenon exists in the curing process, and the performance of the cured product is very stable.
Claims (10)
1. The self-catalyzed phthalonitrile resin containing imide ring is characterized in that the molecular structure of the self-catalyzed phthalonitrile resin containing imide ring is as follows:
2. the method for producing an autocatalytic imide-ring containing phthalonitrile resin as claimed in claim 1, characterized in that the method comprises the steps of:
step one: uniformly stirring 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate in an aprotic solvent, heating to 35-80 ℃ for reaction for 6-24 hours, then pouring into an alkaline solution to precipitate a product, washing the product to neutrality, filtering, and vacuum-drying to obtain 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile;
step two: maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile are added into a reaction vessel filled with glacial acetic acid for stirring, heated and refluxed for 3-12h, cooled to room temperature, poured into distilled water to separate out a product, repeatedly washed to be neutral, filtered and dried in vacuum, thus obtaining the target product autocatalytic imide-containing phthalonitrile resin.
3. The method for preparing the self-catalyzed imide-ring-containing phthalonitrile resin according to claim 2, wherein the molar ratio of 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate in the step one is 1 (1-1.1): 1.2-2.
4. A process for the preparation of an autocatalytic imide-containing cyclic phthalonitrile resin as claimed in claim 2 or 3, wherein in step one the aprotic solvent is dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide or N, N-dimethylacetamide; the aprotic solvent is used in an amount of 2 to 5 times the total weight of 4-amino-3, 5-xylenol, 4-nitrophthalonitrile and anhydrous potassium carbonate.
5. The method for preparing an autocatalytic imide-containing phthalonitrile resin as claimed in claim 4, wherein in the first step, the alkaline solution is an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, an aqueous calcium hydroxide solution or an aqueous barium hydroxide solution, and the molar concentration of the alkaline solution is 0.1-1.0mol/L.
6. The process for producing an autocatalytic imide-ring containing phthalonitrile resin as claimed in claim 5, wherein the molar ratio of maleic anhydride to 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile in the step two is (2-1.2): 1.
7. The process for producing an autocatalytic imide-containing cyclic phthalonitrile resin as claimed in claim 6, wherein the addition amount of glacial acetic acid in the second step is 3 to 5 times as much as the total weight of maleic anhydride and 4- (4-amino-3, 5-dimethylphenoxy) phthalonitrile.
8. Use of the autocatalytic imide ring containing phthalonitrile resin as claimed in claim 1 as an epoxy resin modifier.
9. The application of claim 8, wherein the specific method for modifying the epoxy resin is as follows:
adding an aromatic amine curing agent into epoxy resin according to an equal stoichiometric ratio, heating at 90-150 ℃ to enable the aromatic amine curing agent to be completely melted, then adding self-catalyzed phthalonitrile resin powder containing imide rings, continuously stirring until the mixture is clear and transparent, and heating and curing the mixture to obtain the modified epoxy resin.
10. The use according to claim 9, characterized in that the mass ratio of the epoxy resin to the autocatalytic imide ring containing phthalonitrile resin is (0.6-1.5): 1.
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