CN116102712B - Epoxy resin toughening agent and preparation method and application thereof - Google Patents
Epoxy resin toughening agent and preparation method and application thereof Download PDFInfo
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- CN116102712B CN116102712B CN202211690844.4A CN202211690844A CN116102712B CN 116102712 B CN116102712 B CN 116102712B CN 202211690844 A CN202211690844 A CN 202211690844A CN 116102712 B CN116102712 B CN 116102712B
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 86
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 86
- 239000012745 toughening agent Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 40
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 36
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 14
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960005489 paracetamol Drugs 0.000 claims abstract description 6
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 32
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 26
- -1 diphenol compound Chemical class 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 150000001263 acyl chlorides Chemical class 0.000 claims description 18
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 15
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006482 condensation reaction Methods 0.000 claims description 12
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 12
- 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 10
- 239000005416 organic matter Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 9
- 125000002252 acyl group Chemical group 0.000 claims description 8
- 238000005660 chlorination reaction Methods 0.000 claims description 8
- 238000006735 epoxidation reaction Methods 0.000 claims description 8
- 238000005886 esterification reaction Methods 0.000 claims description 8
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 5
- GOUHYARYYWKXHS-UHFFFAOYSA-N para-formylbenzoic acid Natural products OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 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 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000011534 incubation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 claims 1
- 238000005452 bending Methods 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000004973 liquid crystal related substance Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 3
- 238000012986 modification Methods 0.000 abstract description 3
- 239000004593 Epoxy Substances 0.000 abstract description 2
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 description 9
- 229930185605 Bisphenol Natural products 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000004974 Thermotropic liquid crystal Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229920001410 Microfiber Polymers 0.000 description 1
- HSJKGGMUJITCBW-UHFFFAOYSA-N beta-hydroxybutyraldehyde Natural products CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010998 test method Methods 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
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
- C08G59/063—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols with epihalohydrins
-
- 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
- C07D301/28—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms by reaction with hydroxyl radicals
-
- 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
- C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
- C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
- C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
- C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
- C07D303/27—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds having all hydroxyl radicals etherified with oxirane containing compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of epoxy resin modification, and particularly relates to an epoxy resin toughening agent, a preparation method and application thereof. The epoxy resin toughening agent provided by the invention is used for epoxy resin, so that an epoxy resin product has higher impact strength, bending strength and modulus, good compatibility, better heat resistance and wide application prospect. The results of the examples show that the epoxy resin toughening agent provided by the invention has excellent toughening effect, and can improve the impact strength of epoxy resin by 5-8 kJ/m 2, improve the bending strength by 10-15 MPa and improve the bending modulus by 0.2-0.4 GPa. The epoxy resin toughening agent of the block liquid crystal with the end group epoxy is prepared by taking polyethylene glycol, organic acid containing benzene ring, paracetamol and epichlorohydrin as raw materials through four-step reaction. The epoxy resin toughening agent provided by the invention is especially suitable for bisphenol A epoxy resin, and has excellent toughening effect.
Description
Technical Field
The invention belongs to the technical field of epoxy resin modification, and particularly relates to an epoxy resin toughening agent, a preparation method and application thereof.
Background
The epoxy resin is a low molecular polymer containing two or more epoxy groups in a molecular structure, can generate a body type structure after undergoing a crosslinking reaction with a curing agent, and has the advantages of good bonding performance, mechanical property, electrical insulation performance, wear resistance, heat resistance and the like, so that the epoxy resin can be used as a resin matrix for adhesives, coatings, sealants, potting materials, composite materials and the like, and can be widely applied to the fields of machinery, buildings, electronic devices, adhesives, coatings and the like.
However, the cured epoxy resin also has the defects of poor toughness, easiness in cracking, poor fatigue resistance and the like due to high crosslinking density, so that the application of the epoxy resin in more fields is limited. In recent years, high performance materials such as structural adhesive materials, fiber reinforced materials, laminates, and integrated circuits require epoxy resins having more excellent properties, including higher toughness, lower internal stress, higher heat resistance and chemical resistance, and the like. Therefore, a great deal of research work is carried out on the modification of the epoxy resin by a plurality of scholars at home and abroad so as to expand the application range of the epoxy resin.
The liquid crystal material is a substance with a one-dimensional or two-dimensional remote ordered structure, loses the rigidity of a solid substance after being heated and melted or dissolved by a proper solvent, obtains the fluidity of the liquid substance, and simultaneously, the molecular part keeps a special orientation to show anisotropy. The thermotropic liquid crystal material can form a liquid crystal domain with orientation in the epoxy resin, so as to prevent the development of stress and cracks, thereby achieving the purpose of toughening, and introducing epoxy groups and flexible chains into the liquid crystal molecule can also enhance the compatibility of the liquid crystal molecule and the epoxy resin, reduce internal stress and the like. However, the toughness of the existing liquid crystal material to the epoxy resin is improved, and the requirement on the toughness of the epoxy resin can not be completely met.
Disclosure of Invention
The invention aims to provide an epoxy resin toughening agent, a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an epoxy resin toughening agent, the structural formula of which is shown as formula I:
wherein a=0 or 1, b=0 or 1, c=5 or 14.
Preferably, the values of a, b and c include: a=0, b=0 and c=5, or a=0, b=0 and c=14, or a=0, b=1 and c=5, or a=0, b=1 and c=14, or a=1, b=0 and c=5, or a=1, b=0 and c=14, or a=1, b=1 and c=5, or a=1, b=1 and c=14.
The invention also provides a preparation method of the epoxy resin toughening agent, which comprises the following steps:
(1) Mixing benzene ring-containing organic acid, thionyl chloride and DMF for acyl chlorination reaction to obtain benzene ring-containing acyl chloride, wherein the structural formula is shown in formula II:
Wherein a=0 or 1, b=0 or 1;
The structural general formula of the benzene ring-containing organic acid is shown in a formula III:
Wherein a=0 or 1, b=0 or 1;
(2) Mixing the benzene ring-containing acyl chloride, polyethylene glycol and a nitrogen-containing organic matter for esterification reaction to obtain a PEG dialdehyde intermediate, wherein the structural formula of the PEG dialdehyde intermediate is shown in formula IV:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(3) Mixing the PEG dialdehyde intermediate, p-aminophenol, p-toluenesulfonic acid and ethanol for aldehyde-amine condensation reaction to obtain a diphenol compound intermediate, wherein the structural formula of the diphenol compound intermediate is shown as formula V:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(4) Mixing the diphenol compound intermediate, epoxy chloropropane and benzyl trimethyl ammonium chloride for epoxidation reaction to obtain the epoxy resin toughening agent with the structure shown in the formula I.
Preferably, the mass ratio of the benzene ring-containing organic acid to the thionyl chloride is 1-1.2:1.58-2.34;
the mass ratio of the benzene ring-containing acyl chloride to the polyethylene glycol is 1.68-1.96:1-3.46;
The mass ratio of the benzene ring-containing acyl chloride to the nitrogen-containing organic matter is 1-1.2:0.51-0.72;
The mass ratio of the PEG dialdehyde intermediate to the paracetamol is 2.12-4.87:1-1.2;
The mass ratio of the PEG dialdehyde intermediate to the p-toluenesulfonic acid is 100-120:0.37-0.44;
The mass ratio of the PEG dialdehyde intermediate to the ethanol is 1-1.2:10-12;
The mass ratio of the diphenol compound intermediate to the epichlorohydrin is 1-1.2:3.53-6.84;
The mass ratio of the diphenol compound intermediate to the benzyl trimethyl ammonium chloride is 100-120:0.1-0.12.
Preferably, the aldol-amine condensation reaction is carried out in a protective gas, the temperature of the aldol-amine condensation reaction is 50-80 ℃, and the heat preservation time is 5-10 h.
Preferably, the temperature of the epoxidation reaction is 90-120 ℃, and the heat preservation time is 8-12 h.
Preferably, the temperature of the esterification reaction is 10-30 ℃, and the heat preservation time is 3-10 h.
Preferably, the temperature of the acyl chlorination reaction is 50-80 ℃, and the heat preservation time is 2-10 h.
Preferably, in the step (1), the benzene ring-containing organic acid includes one or more of paraformylbenzoic acid, paraformylphenylacetic acid, paraacetylbenzoic acid and paraacetylphenylacetic acid.
The invention also provides application of the epoxy resin toughening agent obtained by the scheme or the preparation method of the scheme in epoxy resin.
The invention provides an epoxy resin toughening agent. The epoxy resin toughening agent provided by the invention is a segmented thermotropic liquid crystal material, can form a uniform liquid crystal domain with orientation in a cured cross-linked network of epoxy resin, has a toughening effect similar to micro fiber, can be used for toughening the epoxy resin, can enable an epoxy resin product to have higher impact strength, bending strength and modulus, and has good compatibility, better heat resistance and wide application prospect. The results of the examples show that the epoxy resin toughening agent provided by the invention has excellent toughening effect, and can improve the impact strength of epoxy resin by 5-8 kJ/m 2, improve the bending strength by 10-15 MPa and improve the bending modulus by 0.2-0.4 GPa.
The invention also provides a preparation method of the epoxy resin toughening agent. The epoxy resin toughening agent of the block liquid crystal with the end group epoxy is prepared by taking polyethylene glycol, organic acid containing benzene ring, paracetamol and epichlorohydrin as raw materials through four-step reaction. The preparation method provided by the invention has the advantages of simple steps, convenient operation, low cost, safety and high efficiency.
The invention also provides application of the epoxy resin toughening agent obtained by the scheme or the preparation method of the scheme in epoxy resin. The epoxy resin toughening agent provided by the invention is especially suitable for bisphenol A epoxy resin, and has excellent toughening effect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance spectrum of an epoxy resin toughening agent prepared in example 1 of the present invention;
FIG. 2 is a graph comparing the mechanical properties of example 1 of the present invention and a conventional commercially available epoxy resin E-51.
Detailed Description
The invention provides an epoxy resin toughening agent, the structural formula of which is shown as formula I:
wherein a=0 or 1, b=0 or 1, c=5 or 14.
In the present invention, the values of a, b and c preferably include: a=0, b=0 and c=5, or a=0, b=0 and c=14, or a=0, b=1 and c=5, or a=0, b=1 and c=14, or a=1, b=0 and c=5, or a=1, b=0 and c=14, or a=1, b=1 and c=5, or a=1, b=1 and c=14. The epoxy resin toughening agent provided by the invention is used for epoxy resin, so that an epoxy resin product has higher impact strength, bending strength and modulus, good compatibility and better heat resistance. The epoxy resin toughening agent provided by the invention has excellent toughening effect, and can improve the impact strength of epoxy resin by 5-8 kJ/m 2, improve the bending strength by 10-15 MPa and improve the bending modulus by 0.2-0.4 GPa.
The invention also provides a preparation method of the epoxy resin toughening agent, which comprises the following steps:
(1) Mixing benzene ring-containing organic acid, thionyl chloride and DMF for acyl chlorination reaction to obtain benzene ring-containing acyl chloride, wherein the structural formula is shown in formula II:
Wherein a=0 or 1, b=0 or 1;
The structural general formula of the benzene ring-containing organic acid is shown in a formula III:
Wherein a=0 or 1, b=0 or 1;
(2) Mixing the benzene ring-containing acyl chloride, polyethylene glycol and a nitrogen-containing organic matter for esterification reaction to obtain a PEG dialdehyde intermediate, wherein the structural formula of the PEG dialdehyde intermediate is shown in formula IV:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(3) Mixing the PEG dialdehyde intermediate, p-aminophenol, p-toluenesulfonic acid and ethanol for aldehyde-amine condensation reaction to obtain a diphenol compound intermediate, wherein the structural formula of the diphenol compound intermediate is shown as formula V:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(4) Mixing the diphenol compound intermediate, epoxy chloropropane and benzyl trimethyl ammonium chloride for epoxidation reaction to obtain the epoxy resin toughening agent with the structure shown in the formula I.
According to the invention, benzene ring-containing organic acid, thionyl chloride and DMF are mixed for acyl chlorination reaction, so that benzene ring-containing acyl chloride is obtained, and the structural formula is shown as formula II. In the present invention, the benzene ring-containing organic acid preferably includes one or more of paraformylbenzoic acid, paraformylphenylacetic acid, paraacetylbenzoic acid and paraacetylphenylacetic acid; the mass ratio of the benzene ring-containing organic acid to the thionyl chloride is preferably 1-1.2:1.58-2.34, and more preferably 1:1.58-1.95; the mass ratio of the benzene ring-containing organic acid to DMF is preferably 10-12:1-1.2, more preferably 10:1-1.2; the mixture of the benzene ring-containing organic acid, the thionyl chloride and the DMF is preferably carried out in a three-neck flask; the mixture of the benzene ring-containing organic acid, thionyl chloride and DMF is preferably: sequentially and dropwise adding thionyl chloride and DMF into benzene ring-containing organic acid; the rates of addition of thionyl chloride and DMF are independently preferably 50 to 70 drops/min, more preferably 60 drops/min; the temperature of the acyl chlorination reaction is preferably 50-80 ℃, more preferably 60-70 ℃, and the heat preservation time is preferably 2-10 h, more preferably 4-8 h; the product obtained after the acyl chlorination reaction is preferably distilled under reduced pressure; the temperature of the reduced pressure distillation is preferably 60 to 100 ℃, more preferably 70 to 90 ℃, and the pressure is preferably 1 to 10kPa, more preferably 3 to 7kPa; the invention removes the excess thionyl chloride by distillation under reduced pressure.
After benzene ring-containing acyl chloride is obtained, the benzene ring-containing acyl chloride, polyethylene glycol and nitrogen-containing organic matter are mixed for esterification reaction, and a PEG dialdehyde intermediate is obtained, wherein the structural formula of the PEG dialdehyde intermediate is shown as a formula IV. In the invention, the mass ratio of the benzene ring-containing acyl chloride to the polyethylene glycol is preferably 1.68-1.96:1-3.46, more preferably 1.68-1.96:1; the mass ratio of the benzene ring-containing acyl chloride to the nitrogen-containing organic matter is preferably 1-1.2:0.51-0.72, more preferably 1:0.51-0.6; the mixture of benzene ring-containing acyl chloride, polyethylene glycol and nitrogen-containing organic matter is preferably: placing benzene ring-containing acyl chloride into a three-neck flask with an ice bath device for stirring, and then dripping polyethylene glycol and nitrogen-containing organic matters; the dropping rate of the polyethylene glycol and the nitrogen-containing organic matter is independently preferably 50 to 70 drops/min, more preferably 60 drops/min; the nitrogen-containing organic matter is preferably triethylamine or anhydrous pyridine; the polyethylene glycol preferably has a number average molecular weight of 200 to 600, more preferably 200; the polyethylene glycol and the nitrogenous organic matters are preferably subjected to water removal treatment before being added dropwise; the temperature of the esterification reaction is preferably 10-30 ℃, more preferably 15-25 ℃, and the heat preservation time is preferably 3-10 h, more preferably 5-7 h; washing, separating and distilling under reduced pressure the obtained product after the esterification reaction; the washing reagent is preferably saturated NaHCO 3 aqueous solution or saturated Na 2CO3 aqueous solution; the separation is preferably: centrifuging the washed product, and collecting an organic layer; the reduced pressure distillation is preferably carried out on the separated organic layer, and moisture is removed to obtain yellow-white viscous liquid; the temperature of the reduced pressure distillation is preferably 60 to 100 ℃, more preferably 70 to 90 ℃, and the pressure is preferably 1 to 10kPa, more preferably 3 to 7kPa.
After benzene ring-containing acyl chloride is obtained, the PEG dialdehyde intermediate, p-aminophenol, p-toluenesulfonic acid and ethanol are mixed for aldehyde-amine condensation reaction to obtain the diphenol compound intermediate, wherein the structural formula of the diphenol compound intermediate is shown as a formula V. In the invention, the mass ratio of the PEG dialdehyde intermediate to the paracetamol is preferably 2.12-4.87:1-1.2, more preferably 2.12-4.05:1; the mass ratio of the PEG dialdehyde intermediate to the p-toluenesulfonic acid is preferably 100-120:0.37-0.44, more preferably 100:0.39-0.42; the mass ratio of the PEG dialdehyde intermediate to the ethanol is preferably 1-1.2:10-12, more preferably 1:10-12; the PEG dialdehyde intermediate, the paracetamol, the paratoluenesulfonic acid and the ethanol are mixed in a three-neck flask preferably; the aldehyde-amine condensation reaction is preferably carried out in a shielding gas; the shielding gas is preferably nitrogen or argon; the temperature of the aldehyde-amine condensation reaction is preferably 50-80 ℃, more preferably 60-70 ℃, and the heat preservation time is preferably 5-10 h, more preferably 7-9 h; the product obtained after the aldol amine condensation reaction is preferably distilled under reduced pressure; the temperature of the reduced pressure distillation is preferably 60 to 100 ℃, more preferably 70 to 90 ℃, and the pressure is preferably 1 to 10kPa, more preferably 3 to 7kPa. The invention obtains yellow green bisphenol compound intermediate through aldehyde-amine condensation reaction.
After obtaining the diphenol compound intermediate, the invention mixes the diphenol compound intermediate, epoxy chloropropane and benzyl trimethyl ammonium chloride for epoxidation reaction to obtain the epoxy resin toughening agent with the structure shown in the formula I. In the present invention, the mass ratio of the bisphenol compound intermediate to epichlorohydrin is preferably 1 to 1.2:3.53 to 6.84, more preferably 1:3.53 to 5.7; the mass ratio of the epoxy chloropropane to the benzyl trimethyl ammonium chloride is preferably 100-120:0.1-0.12, more preferably 100:0.1-0.12; the mixing of the bisphenol compound intermediate, epichlorohydrin and benzyl trimethyl ammonium chloride is preferably carried out in a three-neck flask; the temperature of the epoxidation reaction is preferably 90-120 ℃, more preferably 100-110 ℃, and the heat preservation time is preferably 8-12 h, more preferably 10h; the product obtained after the epoxidation reaction is preferably distilled under reduced pressure; the temperature of the reduced pressure distillation is preferably 90 to 120 ℃, more preferably 100 to 110 ℃, and the pressure is preferably 1 to 10kPa, more preferably 3 to 7kPa; the invention removes excess epichlorohydrin by distillation under reduced pressure.
The invention also provides application of the epoxy resin toughening agent obtained by the scheme or the preparation method of the scheme in epoxy resin.
In the present invention, the use of the epoxy resin toughening agent in an epoxy resin preferably comprises the steps of: and heating and stirring the epoxy resin toughening agent and the epoxy resin to obtain the toughened epoxy resin. In the invention, the mass ratio of the epoxy resin toughening agent to the epoxy resin is preferably 5-20:100, more preferably 10-15:100; the temperature of the heating and stirring is preferably 80 to 100 ℃, more preferably 85 to 95 ℃.
The following detailed description of the embodiments of the invention is provided in connection with the accompanying drawings and examples to further illustrate the invention, but should not be construed as limiting the scope of the invention.
Example 1
A preparation method of an epoxy resin toughening agent comprises the following steps:
(1) Placing 50g of paraformylbenzoic acid in a three-neck flask, gradually dropwise adding 67.46g of thionyl chloride and 5 drops of DMF reagent, heating the system to 80 ℃ through an oil bath, reacting for 10 hours after complete dissolution, and then distilling under reduced pressure at 100 ℃ and 1kPa to remove excessive thionyl chloride to obtain paraformylbenzoyl chloride for later use;
(2) Placing 30g of paraformylbenzoyl chloride into a three-neck flask with an ice bath device, and uniformly stirring; dripping 17.79g polyethylene glycol 200 and 18g triethylamine which are subjected to water removal treatment at the rate of 60 drops per minute, controlling the reaction to be carried out at 30 ℃ for 3 hours, washing the reaction mixture with saturated NaHCO 3 aqueous solution, separating an organic layer, and distilling under reduced pressure at 100 ℃ and 1kPa to remove water to obtain yellow-white viscous liquid, namely PEG dialdehyde intermediate for later use;
(3) Placing 30g of PEG dialdehyde intermediate, 14.1g of para-aminophenol, 0.11g of para-toluenesulfonic acid and 150g of ethanol solvent into a three-neck flask, stirring and mixing uniformly, introducing argon for protection, heating the reaction system to 80 ℃ through an oil bath for reaction for 5 hours, and then distilling under reduced pressure at 60 ℃ and 10kPa to remove the solvent to obtain a yellow-green bisphenol compound intermediate for later use;
(4) 30g of bisphenol compound intermediate, 171.26g of epichlorohydrin and 0.03g of benzyl trimethyl ammonium chloride are placed in a three-neck flask, uniformly stirred, the reaction temperature of the system is controlled to be 120 ℃ for 8 hours, reduced pressure distillation is carried out at 120 ℃ and 1kPa, and excessive epichlorohydrin is removed, so that the epoxy resin toughening agent is obtained, and the structural formula is shown as formula I, wherein a=0, b=0 and c=5.
FIG. 1 shows a nuclear magnetic resonance spectrum of an epoxy resin toughening agent prepared in the embodiment, and as can be seen from FIG. 1, the compound prepared in the embodiment has a structure shown in a formula I.
Example 2
A preparation method of an epoxy resin toughening agent comprises the following steps:
(1) Placing 50g of paraformylbenzoic acid in a three-neck flask, gradually dropwise adding 67.46g of thionyl chloride and 5 drops of DMF reagent, heating the system to 50 ℃ through an oil bath, reacting for 10 hours after complete dissolution, and then distilling under reduced pressure at 60 ℃ and 1kPa to remove excessive thionyl chloride to obtain paraformylbenzoyl chloride for later use;
(2) Placing 30g of paraformylbenzoyl chloride into a three-neck flask with an ice bath device, uniformly stirring, dropwise adding 53.37g of polyethylene glycol 600 and 14.07g of anhydrous pyridine which are subjected to water removal treatment at the rate of 60 drops per minute, controlling the reaction temperature to react for 10 hours at 10 ℃, washing the reaction mixture with saturated Na 2CO3 aqueous solution, separating an organic layer, and distilling under reduced pressure at 60 ℃ and 10kPa to remove water to obtain a yellow-white viscous liquid which is a PEG dialdehyde intermediate for later use;
(3) Placing 30g of PEG dialdehyde intermediate, 7.57g of para-aminophenol, 0.11g of para-toluenesulfonic acid and 150g of ethanol solvent into a three-neck flask, stirring and mixing uniformly, introducing argon for protection, heating the reaction system to 50 ℃ through an oil bath for reaction for 10 hours, and distilling under reduced pressure at 60 ℃ and 10kPa to remove the solvent to obtain a yellow-green bisphenol compound intermediate for later use;
(4) 30g of bisphenol compound intermediate, 106.11g of epichlorohydrin and 0.03g of benzyl trimethyl ammonium chloride are placed in a three-neck flask, uniformly stirred, the reaction temperature of the system is controlled to be 90 ℃ for 8 hours, reduced pressure distillation is carried out at 90 ℃ and 1kPa, and excessive epichlorohydrin is removed, so that the epoxy resin toughening agent is obtained, and the structural formula is shown as formula I, wherein a=0, b=0 and c=14.
The performance test of the epoxy resin E-51 of the invention example 1 and the common commercial epoxy resin E-51 is carried out by the following test method: the epoxy resin toughening agent prepared in the embodiment 1 of the invention and the common commercially available epoxy resin E-51 are modified according to the mass ratio of 5:100, 10:100, 15:100 or 20:100, and the performance test is carried out on the obtained modified epoxy resin, and the result is shown in figure 2. As can be seen from FIG. 2, the epoxy resin toughening agent prepared in the embodiment 1 of the present invention can obviously improve the toughness of the epoxy resin, and the epoxy resin is modified by adding the toughening agent into the epoxy resin, so that the impact strength of the obtained epoxy resin is improved by 5-8 kJ/m 2, the bending strength is improved by 10-15 MPa, and the bending modulus is improved by 0.2-0.4 GPa.
The performance test results of the epoxy resin toughening agent of the embodiment 2 of the present invention are similar to those of the embodiment 1, and are not repeated here.
According to the embodiment, the epoxy resin toughening agent provided by the invention can enable the epoxy resin product to have higher impact strength, bending strength and modulus, and the comprehensive mechanical property is obviously optimized.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (9)
1. An epoxy resin toughening agent is characterized in that the structural formula is shown as formula I:
Wherein a=0, b=0 and c=5, or a=0, b=0 and c=14, or a=0, b=1 and c=5, or a=0, b=1 and c=14, or a=1, b=0 and c=5, or a=1, b=0 and c=14, or a=1, b=1 and c=5, or a=1, b=1 and c=14.
2. The method for preparing the epoxy resin toughening agent according to claim 1, which comprises the following steps:
(1) Mixing benzene ring-containing organic acid, thionyl chloride and DMF for acyl chlorination reaction to obtain benzene ring-containing acyl chloride, wherein the structural formula is shown in formula II:
Wherein a=0 or 1, b=0 or 1;
The structural general formula of the benzene ring-containing organic acid is shown in a formula III:
Wherein a=0 or 1, b=0 or 1;
(2) Mixing the benzene ring-containing acyl chloride, polyethylene glycol and a nitrogen-containing organic matter for esterification reaction to obtain a PEG dialdehyde intermediate, wherein the structural formula of the PEG dialdehyde intermediate is shown in formula IV:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(3) Mixing the PEG dialdehyde intermediate, p-aminophenol, p-toluenesulfonic acid and ethanol for aldehyde-amine condensation reaction to obtain a diphenol compound intermediate, wherein the structural formula of the diphenol compound intermediate is shown as formula V:
wherein a=0 or 1, b=0 or 1, c=5 or 14;
(4) Mixing the diphenol compound intermediate, epoxy chloropropane and benzyl trimethyl ammonium chloride for epoxidation reaction to obtain the epoxy resin toughening agent with the structure shown in the formula I.
3. The preparation method according to claim 2, wherein the mass ratio of the benzene ring-containing organic acid to the thionyl chloride is 1-1.2:1.58-2.34;
the mass ratio of the benzene ring-containing acyl chloride to the polyethylene glycol is 1.68-1.96:1-3.46;
The mass ratio of the benzene ring-containing acyl chloride to the nitrogen-containing organic matter is 1-1.2:0.51-0.72;
The mass ratio of the PEG dialdehyde intermediate to the paracetamol is 2.12-4.87:1-1.2;
The mass ratio of the PEG dialdehyde intermediate to the p-toluenesulfonic acid is 100-120:0.37-0.44;
The mass ratio of the PEG dialdehyde intermediate to the ethanol is 1-1.2:10-12;
The mass ratio of the diphenol compound intermediate to the epichlorohydrin is 1-1.2:3.53-6.84;
The mass ratio of the diphenol compound intermediate to the benzyl trimethyl ammonium chloride is 100-120:0.1-0.12.
4. The preparation method according to claim 2, wherein the aldol-amine condensation reaction is carried out in a protective gas, the aldol-amine condensation reaction is carried out at a temperature of 50-80 ℃ for a holding time of 5-10 h.
5. The preparation method according to claim 2, wherein the temperature of the epoxidation reaction is 90-120 ℃ and the holding time is 8-12 h.
6. The preparation method according to claim 2, wherein the esterification reaction temperature is 10-30 ℃ and the incubation time is 3-10 h.
7. The preparation method according to claim 2, wherein the temperature of the acyl chlorination reaction is 50-80 ℃ and the heat preservation time is 2-10 h.
8. A production method according to claim 2 or 3, wherein in the step (1), the benzene-ring-containing organic acid comprises one or more of paraformylbenzoic acid, paraformylphenylacetic acid, paraacetylbenzoic acid and paraacetylphenylacetic acid.
9. The use of the epoxy resin toughening agent of claim 1 or the epoxy resin toughening agent obtained by the preparation method of any one of claims 2 to 8 in epoxy resins.
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