CN117903087A - N-phenyl-p-phenylenediamine epoxy resin and preparation method and application thereof - Google Patents
N-phenyl-p-phenylenediamine epoxy resin and preparation method and application thereof Download PDFInfo
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- CN117903087A CN117903087A CN202410075309.0A CN202410075309A CN117903087A CN 117903087 A CN117903087 A CN 117903087A CN 202410075309 A CN202410075309 A CN 202410075309A CN 117903087 A CN117903087 A CN 117903087A
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- phenyl
- phenylenediamine
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- epoxy
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 95
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 95
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000004593 Epoxy Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000007142 ring opening reaction Methods 0.000 claims abstract description 15
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 18
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 14
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 14
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 11
- 239000003444 phase transfer catalyst Substances 0.000 claims description 11
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 7
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 5
- KXHPPCXNWTUNSB-UHFFFAOYSA-M benzyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC1=CC=CC=C1 KXHPPCXNWTUNSB-UHFFFAOYSA-M 0.000 claims description 4
- 150000007529 inorganic bases Chemical class 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- QLCJOAMJPCOIDI-UHFFFAOYSA-N 1-(butoxymethoxy)butane Chemical compound CCCCOCOCCCC QLCJOAMJPCOIDI-UHFFFAOYSA-N 0.000 claims description 3
- HOMDJHGZAAKUQV-UHFFFAOYSA-N 1-(propoxymethoxy)propane Chemical compound CCCOCOCCC HOMDJHGZAAKUQV-UHFFFAOYSA-N 0.000 claims description 3
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 3
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 3
- 239000012779 reinforcing material Substances 0.000 claims description 3
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 3
- 229920005989 resin Polymers 0.000 abstract description 11
- 239000011347 resin Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 9
- 125000003700 epoxy group Chemical group 0.000 abstract description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 6
- -1 N-phenyl-p-phenylenediamine oxygen Chemical compound 0.000 abstract description 4
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 28
- 238000006243 chemical reaction Methods 0.000 description 26
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 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 12
- 239000003795 chemical substances by application Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 238000006386 neutralization reaction Methods 0.000 description 6
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 5
- 235000019799 monosodium phosphate Nutrition 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000010348 incorporation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 230000003472 neutralizing effect Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000000805 composite resin Substances 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- FAUAZXVRLVIARB-UHFFFAOYSA-N 4-[[4-[bis(oxiran-2-ylmethyl)amino]phenyl]methyl]-n,n-bis(oxiran-2-ylmethyl)aniline Chemical compound C1OC1CN(C=1C=CC(CC=2C=CC(=CC=2)N(CC2OC2)CC2OC2)=CC=1)CC1CO1 FAUAZXVRLVIARB-UHFFFAOYSA-N 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000003733 fiber-reinforced composite Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 239000004850 liquid epoxy resins (LERs) Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 150000002924 oxiranes Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HPOKESDSMZRZLC-UHFFFAOYSA-N propan-2-one;hydrochloride Chemical compound Cl.CC(C)=O HPOKESDSMZRZLC-UHFFFAOYSA-N 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004634 thermosetting polymer Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
-
- 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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention provides N-phenyl-p-phenylenediamine epoxy resin, and a preparation method and application thereof, and relates to the technical field of resin materials. The structure of the N-phenyl-p-phenylenediamine oxygen resin (ADPTGA) provided by the invention contains a rigid benzene ring structure, so that the rigidity strength of an epoxy system can be improved; in addition, ADPTGA has multiple epoxy groups, similar to E-51 in structure, can be uniformly dispersed in the system, and can reduce the brittleness of pure E-51, thereby improving the mechanical property of the epoxy resin cured product. In addition, the N-phenyl-p-phenylenediamine epoxy resin provided by the invention has high epoxy value and low viscosity, can enhance the rigidity, toughness, high temperature resistance and processability of the E-51 epoxy resin cured product, and has excellent product performance. The invention adopts a two-step method (ring opening reaction and ring closing reaction) to prepare, ensures the epoxidation degree of the raw materials, has wide raw material sources and simple operation, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of resin materials, in particular to N-phenyl-p-phenylenediamine epoxy resin, and a preparation method and application thereof.
Background
Bisphenol A epoxy resin (EP) has the advantages of higher storage stability, good processing performance, flexible and various formulation designs, lower volume shrinkage rate in the curing process and the like, and the EP cured product has excellent mechanical property, chemical resistance, electrical property and bonding property, so the EP cured product is widely applied to the fields of machinery, electronics, electricity, aerospace, transportation, construction and the like as a thermosetting resin. However, the rapid development of high-tech fields such as aerospace and electronic appliances provides new challenges for thermosetting polymers, which must have sufficient heat resistance and high modulus composite properties to meet the requirements of high performance engineering. Based on the general correlation between resin structure and properties, it was found that higher crosslink density can effectively improve the properties of the resin. Therefore, the development of multifunctional (trifunctional or tetrafunctional) epoxides is one of the most effective methods to achieve this requirement. Among them, the multifunctional glycidylamine type epoxy resin has attracted a lot of attention because of its excellent high temperature resistance and mechanical properties. The epoxy resin contains aromatic ring, ether bond and methylene bond, and can form a highly cross-linked three-dimensional network structure after being cured by curing agent with proper dosage, and the heat resistance of the epoxy resin is greatly improved compared with that of general epoxy resin, so the epoxy resin has wide application in the fields of high-temperature resistant adhesive, high-temperature resistant paint, high-temperature resistant advanced composite material and the like.
N, N, N ', N ' -tetraglycidylamine-4, 4' -diaminodiphenylmethane (TGDDM), a typical representation of multifunctional amine epoxides, has shown superior performance as a matrix for aerospace fiber-reinforced composites since the 70 s of the 20 th century. However, they still have some disadvantages such as high viscosity, hard and brittle cured products, and reduced processability in common organic solvents, which greatly limit the application sites. Therefore, the development of the multifunctional glycidylamine epoxy resin with excellent heat stability, processability and the like has great significance.
Disclosure of Invention
In view of the above, the invention aims to provide an N-phenyl-p-phenylenediamine epoxy resin, and a preparation method and application thereof. The N-phenyl-p-phenylenediamine epoxy resin provided by the invention can obviously improve the rigidity, toughness, high temperature resistance and processability of the bisphenol A type E-51 epoxy resin condensate.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides N-phenyl-p-phenylenediamine epoxy resin, which has a structure shown in a formula I:
the epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is more than or equal to 0.58eq/100g, and the viscosity is less than or equal to 7000 mPa.s.
Preferably, the epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is 0.58-0.68 eq/100g, and the viscosity is 5000-7000 mPa.s.
The invention provides a preparation method of N-phenyl-p-phenylenediamine epoxy resin, which comprises the following steps:
mixing N-phenyl p-phenylenediamine, epoxy chloropropane, a phase transfer catalyst and an organic solvent, performing ring opening reaction, and then adding an inorganic alkali solution to perform ring opening reaction to obtain the N-phenyl p-phenylenediamine epoxy resin.
Preferably, the molar ratio of the N-phenyl-p-phenylenediamine to the epichlorohydrin is 1:3-10.
Preferably, the mol ratio of the N-phenyl-p-phenylenediamine to the inorganic alkali in the inorganic alkali solution is 1:3-3.6.
Preferably, the organic solvent comprises one or more of diethoxymethane, dipropoxymethane, dibutoxymethane, toluene and xylene.
Preferably, the phase transfer catalyst comprises one or more of benzyl triethyl ammonium chloride, benzyl trimethyl ammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride;
The mass of the phase transfer catalyst is 0.05 to 0.5 percent of the total mass of N-phenyl-p-phenylenediamine, epoxy chloropropane and inorganic alkali.
Preferably, the temperature of the ring-opening reaction is 30-130 ℃ and the time is 2-8 h.
Preferably, the temperature of the ring-closure reaction is 30-100 ℃ and the time is 0.5-5 h.
The invention provides the application of the N-phenyl-p-phenylenediamine epoxy resin prepared by the technical scheme or the preparation method of the technical scheme in the epoxy resin modification as a reinforcing material.
The structure of the N-phenyl-p-phenylenediamine oxygen resin (ADPTGA) provided by the invention contains a rigid benzene ring structure, so that the rigidity strength of an epoxy system can be improved; in addition, ADPTGA has multiple epoxy groups, similar to the E-51 structure, can be uniformly dispersed in the system, and can improve the mechanical properties of the E-51 epoxy resin cured product when added into the E-51 epoxy resin system. In addition, the N-phenyl-p-phenylenediamine epoxy resin provided by the invention has high epoxy value and low viscosity, can enhance the rigidity, toughness, high temperature resistance and processability of the E-51 epoxy resin cured product, and has excellent product performance.
The invention also provides a preparation method of the epoxy resin. The invention uses N-phenyl p-phenylenediamine as a raw material for modification, adopts a two-step method (ring opening reaction and ring closing reaction) for preparation, ensures the epoxidation degree of the raw material, obtains the novel liquid epoxy resin with low viscosity and high epoxy value, is used for modifying bisphenol A type epoxy resin, can effectively enhance and enhance the mechanical properties such as rigidity, toughness and the like of an E-51 epoxy resin cured product, can effectively enhance the high temperature resistance and processability of an apparatus, and has excellent comprehensive performance. In addition, the preparation method provided by the invention has the advantages of wide raw material sources, simplicity in operation and suitability for industrial production.
Further, the invention ensures the epoxidation degree of the raw materials by proportioning the raw materials, controlling the temperature, time and pressure of ring opening reaction and ring closing reaction, and obtains the N-phenyl p-phenylenediamine oxygen resin with the epoxy value of 0.58-0.68 eq/100g and the viscosity of 5000-7000 mPa.s.
Drawings
FIG. 1 is an infrared spectrum of N-phenyl-p-phenylenediamine (ADPA) and N-phenyl-p-phenylenediamine epoxy resin (ADPTGA) prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of N-phenyl-p-phenylenediamine;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of N-phenyl-p-phenylenediamine epoxy resin prepared in example 1;
FIG. 4 is an impact fracture surface scanning electron microscope image of a cured product (a) of pure E-51 epoxy resin and a cured product (b) of N-phenyl-p-phenylenediamine having an incorporation of 10 wt%;
FIG. 5 is a graph of thermal weight loss of a cured product of pure E-51 epoxy resin and a cured product of N-phenyl-p-phenylenediamine epoxy resin incorporated at 10 weight percent.
Detailed Description
The invention provides N-phenyl-p-phenylenediamine epoxy resin, which has a structure shown in a formula I:
the epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is more than or equal to 0.58eq/100g, and the viscosity is less than or equal to 7000 mPa.s.
In the present invention, the epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is preferably 0.58 to 0.68eq/100g, preferably 0.6 to 0.65eq/100g, particularly preferably 0.60eq/100g, 0.61eq/100g, 0.62eq/100g or 0.64eq/100g; the viscosity of the N-phenyl-p-phenylenediamine epoxy resin is preferably 5000 to 7000mpa·s, more preferably 5400 to 6500mpa·s, particularly preferably 5400mpa·s, 5800mpa·s, 6000mpa·s or 6300mpa·s. The N-phenyl-p-phenylenediamine epoxy resin provided by the invention has higher epoxy value and lower viscosity, and can be used for enhancing the toughness, rigidity and high temperature resistance of the epoxy resin.
The invention provides a preparation method of N-phenyl-p-phenylenediamine epoxy resin, which comprises the following steps: mixing N-phenyl p-phenylenediamine, epoxy chloropropane, a phase transfer catalyst and an organic solvent, performing ring opening reaction, and then adding an inorganic alkali solution to perform ring opening reaction to obtain the N-phenyl p-phenylenediamine epoxy resin.
In the present invention, materials and equipment used are commercially available in the art unless otherwise specified.
In the present invention, the molar ratio of the N-phenyl-p-phenylenediamine to epichlorohydrin is preferably 1:3 to 10, more preferably 1:3 to 5, particularly preferably 1:3, 1:4 or 1:5.
In the present invention, the organic solvent preferably includes one or more of diethoxymethane, dipropoxymethane, dibutoxymethane, toluene and xylene. In the present invention, the mass ratio of the N-phenyl-p-phenylenediamine to the organic solvent is preferably 1:2 to 3.6, more preferably 1:2 to 3.
In the present invention, the phase transfer catalyst preferably includes one or more of benzyltriethylammonium chloride (BTEAC), benzyltrimethylammonium chloride (BTMAC), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride (TBAC), tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride, more preferably benzyltriethylammonium chloride (BTEAC), tetrabutylammonium bromide (TBAB) or tetrabutylammonium chloride; the mass of the phase transfer catalyst is preferably 0.05 to 0.5% of the total mass of N-phenyl-p-phenylenediamine, epichlorohydrin and inorganic base, more preferably 0.1 to 0.2%.
In the present invention, the mixing of N-phenyl-p-phenylenediamine, epichlorohydrin, phase transfer catalyst and organic solvent is preferably: mixing N-phenyl-p-phenylenediamine, epoxy chloropropane and an organic solvent until the N-phenyl-p-phenylenediamine is completely dissolved, and then dropwise adding the epoxy chloropropane. In the present invention, the time for dropping epichlorohydrin is preferably 0.5 to 6 hours, more preferably 1 to 2 hours. The invention has the advantage of stable reaction by adopting a dripping mode, and can prevent the sudden temperature rise caused by severe ring-opening reaction from influencing the product quality and causing danger.
In the present invention, the temperature of the ring-opening reaction is 30 to 130 ℃, more preferably 30 to 100 ℃, still more preferably 40 to 90 ℃; the time of the ring-opening reaction is preferably 2 to 8 hours, more preferably 2 to 5 hours, and still more preferably 3 to 4 hours; the pressure of the ring-opening reaction is preferably normal pressure.
In the present invention, the mass concentration of the inorganic alkali solution is preferably 20 to 40%, more preferably 25 to 40%, and the inorganic alkali in the inorganic alkali solution preferably includes NaOH and/or KOH. In the present invention, the molar ratio of the N-phenyl-p-phenylenediamine to the inorganic base is preferably 1:3 to 3.6, more preferably 1:3.1 to 3.5, and still more preferably 1:3.1 to 3.2. In the present invention, the inorganic alkaline solution is preferably added dropwise, and the dropwise time is preferably 0.5 to 6 hours, more preferably 1 to 2 hours.
In the present invention, the temperature of the ring-closure reaction is 30 to 100 ℃, more preferably 30 to 70 ℃, still more preferably 30 to 60 ℃; the time of the ring closure reaction is preferably 0.5 to 5 hours, more preferably 0.5 to 2 hours, and still more preferably 1 to 2 hours; the pressure of the ring closure reaction is preferably atmospheric pressure.
The invention adopts the open-loop and closed-loop reaction of the two-step method, controls the temperature, time and pressure of the open-loop reaction and the closed-loop reaction, ensures the glycidol amination degree of the raw materials, and ensures that the epoxy value of the finally obtained N-phenyl-p-phenylenediamine epoxy resin is 0.58-0.68 eq/100g and the viscosity is 5000-7000 mPa.s.
After the ring closure reaction, the present invention preferably further includes refining including: and (3) carrying out solid-liquid separation on the ring-closure reaction liquid obtained by the ring-closure reaction, layering the obtained liquid components, and sequentially washing, neutralizing and distilling the obtained organic phase to obtain the N-phenyl-p-phenylenediamine epoxy resin. The solid-liquid separation is not particularly limited, and may be performed by a solid-liquid separation method known to those skilled in the art, such as filtration, suction filtration, or centrifugal separation. In the present invention, the purpose of the stratification is to expel brine. In the present invention, the neutralizing agent used for the neutralization preferably includes one or more of sodium dihydrogen phosphate, potassium dihydrogen phosphate and acetic acid; the amount of the neutralizing agent used in the present invention is not particularly limited, and the pH after neutralization may be controlled to 7 to 8 (more preferably 7 to 7.5). The conditions for the distillation are not particularly limited, and the organic solvent and unreacted epichlorohydrin may be completely recovered.
The apparatus used in the preparation of the N-phenyl-p-phenylenediamine epoxy resin is not particularly limited, and a reaction apparatus well known to those skilled in the art may be used. Specifically, for example, the opening and closing ring reaction of the two-step method is carried out in a four-mouth flask, N-phenyl p-phenylenediamine, an organic solvent and a phase transfer catalyst are added into the four-mouth flask provided with a mechanical stirrer, a reflux condenser and a thermometer which are mechanically sealed, the temperature is raised to the opening ring reaction temperature of the two-step method, epichlorohydrin is dripped to carry out the opening ring reaction of the two-step method, after the reaction is finished, the temperature is reduced to the closing ring reaction temperature of the two-step method, and an inorganic alkali solution is added to carry out the closing ring reaction of the two-step method.
The invention provides the application of the N-phenyl-p-phenylenediamine epoxy resin prepared by the technical scheme or the preparation method of the technical scheme in the epoxy resin modification as a reinforcing material.
In the present invention, the method of application preferably comprises the steps of: and mixing the N-phenyl-p-phenylenediamine epoxy resin, bisphenol A type epoxy resin and a curing agent, and curing to obtain an epoxy resin cured product. In the present invention, the mass of the N-phenyl-p-phenylenediamine epoxy resin is preferably 5 to 20% of the mass of the bisphenol a type epoxy resin, more preferably 10 to 15%. In the present invention, the bisphenol A type epoxy resin preferably includes E-51 bisphenol A type epoxy resin. In the present invention, the curing agent preferably includes a 4,4' -diaminodiphenylmethane curing agent. In the present invention, the curing is preferably a staged curing, which preferably includes sequentially performing curing under conditions of 100 to 120 ℃ (more preferably 100 to 110 ℃) for 1 to 3 hours (more preferably 2 hours), curing under conditions of 130 to 140 ℃ (more preferably 130 to 135 ℃) for 1 to 3 hours (more preferably 2 hours), and curing under conditions of 150 to 160 ℃ (more preferably 155 to 160 ℃) for 1 to 3 hours (more preferably 2 hours), and then aging at normal temperature for 5 to 10 days (more preferably 6 to 7 days). The N-phenyl-p-phenylenediamine epoxy resin provided by the invention can obviously improve the rigidity, toughness and high temperature resistance of the bisphenol A type E-51 epoxy resin condensate.
For further explanation of the present invention, the following description of the N-phenyl-p-phenylenediamine epoxy resin, and the methods of making and using it, are described in detail in connection with the accompanying drawings and examples, which are not to be construed as limiting the scope of the present invention.
The raw materials used in the examples: n-phenyl-p-phenylenediamine (ADPA), tetrabutylammonium bromide, tetrabutylammonium chloride, benzyl triethylammonium chloride, sodium hydroxide, potassium hydroxide, epichlorohydrin (ECH), E-51 bisphenol A epoxy resin and 4,4' -diaminodiphenylmethane are industrial grade and provided by Anhui New and remote technology Co., ltd; hydrochloric acid, acetone, xylene, toluene were all analytically pure, manufactured by Nanjing chemical reagents, inc.
The epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is detected by a hydrochloric acid-acetone method;
FTIR testing was performed using a Nicolet FTIR-360 fourier transform infrared spectrometer in the united states: the potassium bromide film coating method is adopted, and the measuring range is 400-4000 cm -1.
The structure of the polymer was characterized using BurkerFourierTrnasofmrAVANCE600,600 spectrometer with deuterated chloroform as solvent.
Scanning electron microscope test: after striking the fracture surface of the sample and plating the surface with gold, the cell morphology was observed with an environmental scanning electron microscope model Quanta200 in the united states.
The thermal stability of the cured product was tested and analyzed using a TGA/DSCl/1100SF thermogravimetric analyzer, the test parameters of which were set as follows: the temperature rising range is 30-700 ℃, the temperature rising rate is 10 ℃/min, the carrier gas is nitrogen, and the flow rate is 40mL/min.
The 4,4' -diaminodiphenyl methane is a curing agent of an epoxy resin cured product, and the calculated amount of the curing agent is shown as a formula 1:
G= (mxe)/Hn formula 1;
in formula 1: G-100G of curing agent required by epoxy resin; m-molecular weight of the curing agent, g/mol; the epoxy value of the E-epoxy resin, eq/100g; hn-the total number of active hydrogens in the hardener molecule.
Example 1
46G N-phenyl-p-phenylenediamine, 120g of toluene and 1.2g of benzyl triethyl ammonium chloride are added into a four-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, the temperature is raised to 70 ℃, 69.4g of ECH is added dropwise after the solid N-phenyl-p-phenylenediamine is completely dissolved, the reaction is carried out for 4 hours at 70 ℃ after the 1 hour is completed, the temperature is reduced to 40 ℃, 93.7g of 32% NaOH aqueous solution by mass concentration is added dropwise after the 1 hour is completed, and the reaction is carried out for 1 hour at a temperature of heat preservation. And after the reaction is finished, carrying out suction filtration, layering the obtained filtrate, removing a salt water phase, adding sodium dihydrogen phosphate into an organic phase for neutralization, washing with water, controlling the vacuum degree to be-0.09 MPa, controlling the kettle temperature to be less than or equal to 130 ℃, and distilling and recovering toluene as a solvent to obtain the N-phenyl-p-phenylenediamine epoxy resin, wherein the epoxy value is 0.61eq/100g and the viscosity is 5400 mPa.s.
FIG. 1 is an infrared spectrum of N-phenyl-p-phenylenediamine (ADPA) and N-phenyl-p-phenylenediamine epoxy resin (ADPTGA); it can be seen that the peak at 2919cm -1 is a c—h scalable vibration absorption peak on the alkyl chain, the peaks at 1598cm -1 and 1515cm -1 are c=c skeletal vibration absorption peaks on the benzene ring, the peak at 827cm -1 is determined as a position indication peak of the benzene ring, and no other indication peak is found on the benzene ring, so that it can be confirmed that no other group is attached to the benzene ring after the reaction. The peak at 1373cm -1 is a C-N peak, the peak at 1234cm -1 is an asymmetric telescopic vibration absorption peak of C-O-C structure, and the characteristic absorption peak of epoxy group appears at 906cm -1.
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum of N-phenyl-p-phenylenediamine.
FIG. 3 is a nuclear magnetic resonance spectrum of N-phenyl-p-phenylenediamine epoxy resin, as follows: the peaks at δ=3.78x10 -6 and δ=3.57x10 -6 are those belonging to a hydrogen atom in a methylene group attached to an epoxy group, the peak at δ=2.87 x 10 -6 is a hydrogen atom belonging to a last methyl group of an epoxy group, and the peaks around δ=3.26 x 10 -6 and δ=2.6 x 10 -6 are those belonging to a methylene group of an epoxy group.
The main component structural formula of the N-phenyl-p-phenylenediamine epoxy resin is shown as a formula I by integrating infrared spectrum and nuclear magnetic hydrogen spectrum data analysis.
Example 2
46G N-phenyl-p-phenylenediamine, 100g of dimethylbenzene and 0.8g of tetrabutylammonium bromide are added into a four-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, the temperature is raised to 70 ℃, 74g of ECH is added dropwise after all the solid N-phenyl-p-phenylenediamine is dissolved, the reaction is carried out for 5 hours at 80 ℃ after the 1 hour is completed, the temperature is reduced to 30 ℃, 124g of NaOH aqueous solution with the mass concentration of 25% is added dropwise after the 1 hour is completed, and the reaction is carried out for 1 hour at a constant temperature. And after the reaction is finished, carrying out suction filtration, layering the obtained filtrate, removing a salt water phase, adding sodium dihydrogen phosphate into an organic phase for neutralization, washing with water, controlling the vacuum degree to be-0.095 MPa, controlling the kettle temperature to be less than or equal to 130 ℃, and distilling and recovering solvent dimethylbenzene to obtain the N-phenyl-p-phenylenediamine epoxy resin, wherein the epoxy value is 0.60eq/100g, and the viscosity is 5800 mPa.s.
Example 3
46G N-phenyl-p-phenylenediamine, 100g of dimethylbenzene and 1.4g of tetrabutylammonium chloride are added into a four-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, the temperature is raised to 90 ℃, 115.6g of ECH is added dropwise after the solid N-phenyl-p-phenylenediamine is completely dissolved, the reaction is carried out for 6 hours at 70 ℃, the temperature is reduced to 50 ℃, 80g of 40% KOH aqueous solution is added dropwise after the dropwise addition is completed within 1 hour, and the reaction is carried out for 1 hour at a temperature of the reaction. And after the reaction is finished, carrying out suction filtration, layering the obtained filtrate, removing a salt water phase, adding sodium dihydrogen phosphate into an organic phase for neutralization, washing with water, controlling the vacuum degree to be-0.095 MPa, controlling the kettle temperature to be less than or equal to 130 ℃, and distilling and recovering solvent dimethylbenzene to obtain the N-phenyl-p-phenylenediamine epoxy resin, wherein the epoxy value is 0.64eq/100g and the viscosity is 6000 mPa.s.
Example 4
46G N-phenyl-p-phenylenediamine, 120g of diethoxymethane and 0.6g of benzyl triethyl ammonium chloride are added into a four-neck flask provided with a reflux condenser, a thermometer and a constant pressure dropping funnel, the temperature is raised to 70 ℃, 138.8g of ECH is added dropwise after the solid N-phenyl-p-phenylenediamine is completely dissolved, the reaction is carried out for 3 hours at 90 ℃, the temperature is reduced to 50 ℃, 144.6g of 32% KOH aqueous solution is added dropwise after the dropwise addition within 1 hour, and the reaction is carried out for 1 hour at a temperature of the reaction. And after the reaction is finished, carrying out suction filtration, layering the obtained filtrate, removing a salt water phase, adding sodium dihydrogen phosphate into an organic phase for neutralization, washing with water, carrying out normal pressure and then reducing pressure (controlling the vacuum degree to-0.05 MPa), controlling the kettle temperature to be less than or equal to 130 ℃, and distilling to recover the solvent diethoxymethane to obtain the N-phenyl-p-phenylenediamine epoxy resin, wherein the epoxy value is 0.62eq/100g, and the viscosity is 6300 mPa.s.
Application example 1
The N-phenyl-p-phenylenediamine epoxy resin prepared in example 1 was incorporated into 65g E-51 bisphenol A epoxy resin and then cured by adding 3.25g of 4,4' -diaminodiphenylmethane under the following conditions: the curing property data are shown in Table 1, which are obtained by heating the temperature from room temperature to 100℃and then keeping the temperature for 2 hours, then heating the temperature to 130℃and then keeping the temperature for 2 hours, then heating the temperature to 160℃and keeping the temperature for 2 hours (100 ℃/2h+130 ℃/2h+160 ℃/2 h), and aging the mixture at room temperature for 7 days. The method for calculating the doping amount of the N-phenyl-p-phenylenediamine epoxy resin comprises the following steps: the N-phenyl p-phenylenediamine epoxy resin accounts for the mass fraction of the bisphenol A epoxy resin.
TABLE 1 Performance results after incorporation of N-phenyl-p-phenylenediamine epoxy resins
As is clear from Table 1, the incorporation of N-phenyl-p-phenylenediamine epoxy resin significantly improves the tensile strength (52.2 to 62.84 MPa), flexural strength (104.35 to 115.39 MPa), elongation at break (3.44 to 5.15%) and impact strength (24.2 to 25.28kJ/m 2) of the E-51 epoxy resin cured product. Wherein, the N-phenyl-p-phenylenediamine epoxy resin with 15 percent of doping amount has the advantages of optimal tensile strength and elongation at break of the cured product, high bending strength and impact strength and optimal comprehensive mechanical property.
When the N-phenyl-p-phenylenediamine epoxy resin content was measured to be 10wt%, the resulting cured product showed an impact fracture surface, and FIG. 4 shows an impact fracture surface scanning electron microscope image of a cured product (a) of pure E-51 epoxy resin and a cured product (b) of N-phenyl-p-phenylenediamine epoxy resin content of 10wt%, as can be seen from FIG. 4: the surface of the pure E-51 cured product was rough, whereas when 10wt% of ADPTGA was added, the fracture surface of the cured product became smooth, the crack direction was single and regular, and the characteristic of typical rigid fracture was exhibited. This is because the addition of a small amount ADPTGA instead of E-51 increases the crosslinking density of the composite resin. Thus, the rigidity of the composite resin is enhanced compared to the pure E-51 resin, and both the tensile strength and the flexural strength are greater than those of the E-51 resin.
The thermal weight loss graph of the obtained cured product with 10wt% of the N-phenyl-p-phenylenediamine epoxy resin and the cured product of E-51 epoxy resin was tested by using a Shimadzu DTG-60 thermogravimetric analyzer, and the results are shown in FIG. 5, and it can be seen from FIG. 5: the initial decomposition temperature of the cured product of N-phenyl-p-phenylenediamine epoxy resin incorporated in an amount of 10wt% was slightly lowered as compared with that of the cured product of pure E-51 epoxy resin, and therefore, it was found that the thermal properties of the cured product were not substantially lowered after the incorporation of ADPTGA.
As can be seen from the above embodiments: the N-phenyl-p-phenylenediamine epoxy resin provided by the invention has a higher epoxy value, and after being doped into E-51 resin, the toughness, rigidity and high temperature resistance of a cured product can be improved.
While the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments of the invention can be made and still fall within the scope of the invention without undue effort.
Claims (10)
1. An N-phenyl-p-phenylenediamine epoxy resin having a structure of formula I:
the epoxy value of the N-phenyl-p-phenylenediamine epoxy resin is more than or equal to 0.58eq/100g, and the viscosity is less than or equal to 7000 mPa.s.
2. The N-phenyl-p-phenylenediamine epoxy resin according to claim 1, wherein the N-phenyl-p-phenylenediamine epoxy resin has an epoxy value of 0.58 to 0.68eq/100g and a viscosity of 5000 to 7000 mPa-s.
3. A process for the preparation of an N-phenyl-p-phenylenediamine epoxy resin according to claim 1 or 2, comprising the steps of:
mixing N-phenyl p-phenylenediamine, epoxy chloropropane, a phase transfer catalyst and an organic solvent, performing ring opening reaction, and then adding an inorganic alkali solution to perform ring opening reaction to obtain the N-phenyl p-phenylenediamine epoxy resin.
4. The process according to claim 3, wherein the molar ratio of N-phenyl-p-phenylenediamine to epichlorohydrin is 1:3-10.
5. The method according to claim 3, wherein the molar ratio of the N-phenyl-p-phenylenediamine to the inorganic base in the inorganic base solution is 1:3-3.6.
6. The method according to claim 3, wherein the organic solvent comprises one or more of diethoxymethane, dipropoxymethane, dibutoxymethane, toluene and xylene.
7. The preparation method according to claim 3, wherein the phase transfer catalyst comprises one or more of benzyltriethylammonium chloride, benzyltrimethylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethylammonium chloride, dodecyltrimethylammonium chloride and tetradecyltrimethylammonium chloride;
The mass of the phase transfer catalyst is 0.05 to 0.5 percent of the total mass of N-phenyl-p-phenylenediamine, epoxy chloropropane and inorganic alkali.
8. The method according to claim 3, wherein the ring-opening reaction is carried out at a temperature of 30 to 130℃for a period of 2 to 8 hours.
9. The method according to claim 3, wherein the temperature of the ring-closure reaction is 30 to 100℃and the time is 0.5 to 5 hours.
10. Use of the N-phenyl-p-phenylenediamine epoxy resin of any of claims 1-2 or the N-phenyl-p-phenylenediamine epoxy resin prepared by the preparation method of any of claims 3-9 as a reinforcing material in epoxy resin modification.
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