CN114350116B - Epoxy thermosetting resin and preparation method thereof - Google Patents
Epoxy thermosetting resin and preparation method thereof Download PDFInfo
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- CN114350116B CN114350116B CN202210198913.3A CN202210198913A CN114350116B CN 114350116 B CN114350116 B CN 114350116B CN 202210198913 A CN202210198913 A CN 202210198913A CN 114350116 B CN114350116 B CN 114350116B
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- 239000004593 Epoxy Substances 0.000 title claims abstract description 71
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 46
- 239000011347 resin Substances 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000003822 epoxy resin Substances 0.000 claims abstract description 33
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 33
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 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 abstract description 9
- -1 amine compound Chemical class 0.000 claims description 30
- 239000002904 solvent Substances 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 238000007731 hot pressing Methods 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 11
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 10
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- XIMIGUBYDJDCKI-UHFFFAOYSA-N diselenium Chemical compound [Se]=[Se] XIMIGUBYDJDCKI-UHFFFAOYSA-N 0.000 claims description 9
- XUCHXOAWJMEFLF-UHFFFAOYSA-N bisphenol F diglycidyl ether Chemical compound C1OC1COC(C=C1)=CC=C1CC(C=C1)=CC=C1OCC1CO1 XUCHXOAWJMEFLF-UHFFFAOYSA-N 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 abstract description 6
- 230000004927 fusion Effects 0.000 abstract description 5
- 239000007790 solid phase Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000003431 cross linking reagent Substances 0.000 abstract description 2
- 230000006870 function Effects 0.000 abstract description 2
- 239000002952 polymeric resin Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000012528 membrane Substances 0.000 description 5
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 description 4
- 238000010008 shearing Methods 0.000 description 4
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 description 3
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- FDKWRPBBCBCIGA-REOHCLBHSA-N (2r)-2-azaniumyl-3-$l^{1}-selanylpropanoate Chemical compound [Se]C[C@H](N)C(O)=O FDKWRPBBCBCIGA-REOHCLBHSA-N 0.000 description 1
- DHBYUMXLFYJURP-UHFFFAOYSA-N 2-(2-sulfanylanilino)benzenethiol Chemical compound SC1=CC=CC=C1NC1=CC=CC=C1S DHBYUMXLFYJURP-UHFFFAOYSA-N 0.000 description 1
- CTCGHLVDQKKOCB-UHFFFAOYSA-N 2-[(2-aminophenyl)diselanyl]aniline Chemical compound NC1=CC=CC=C1[Se][Se]C1=CC=CC=C1N CTCGHLVDQKKOCB-UHFFFAOYSA-N 0.000 description 1
- YKWRUFUXIJXQGC-UHFFFAOYSA-N 4-[(4-aminophenyl)diselanyl]aniline Chemical compound C1=CC(N)=CC=C1[Se][Se]C1=CC=C(N)C=C1 YKWRUFUXIJXQGC-UHFFFAOYSA-N 0.000 description 1
- FDKWRPBBCBCIGA-UWTATZPHSA-N D-Selenocysteine Natural products [Se]C[C@@H](N)C(O)=O FDKWRPBBCBCIGA-UWTATZPHSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- OOTFVKOQINZBBF-UHFFFAOYSA-N cystamine Chemical compound CCSSCCN OOTFVKOQINZBBF-UHFFFAOYSA-N 0.000 description 1
- 229940099500 cystamine Drugs 0.000 description 1
- NXPNPYNCKSWEHA-WDSKDSINSA-N methyl (2r)-2-amino-3-[[(2r)-2-amino-3-methoxy-3-oxopropyl]disulfanyl]propanoate Chemical compound COC(=O)[C@@H](N)CSSC[C@H](N)C(=O)OC NXPNPYNCKSWEHA-WDSKDSINSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- ZKZBPNGNEQAJSX-UHFFFAOYSA-N selenocysteine Natural products [SeH]CC(N)C(O)=O ZKZBPNGNEQAJSX-UHFFFAOYSA-N 0.000 description 1
- 229940055619 selenocysteine Drugs 0.000 description 1
- 235000016491 selenocysteine Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Epoxy Resins (AREA)
Abstract
The invention belongs to the technical field of high polymer resin, and discloses an epoxy thermosetting resin and a preparation method thereof. According to the invention, two different dynamic covalent bonds-S-S-and-Se-Se-are introduced into epoxy resins with different structures, so that the epoxy resins with different structures and different cross-linking agents are prepared, and the-S-Se-cross-linked epoxy thermosetting resin composition is formed through high-temperature solid phase fusion. The preparation method is simple, and the prepared epoxy thermosetting resin composition containing different structures has the same mechanical property as the crosslinked epoxy resin with a single structure, so that the mixing of the thermosetting epoxy resins with different structures is realized, and the composition also has the functions of self-repairing, shape memory and the like.
Description
Technical Field
The invention relates to the technical field of high polymer resin, in particular to epoxy thermosetting resin and a preparation method thereof.
Background
Epoxy resins are a common class of crosslinked resins, also often referred to directly as thermosets. Due to the high crosslinking density, good chemical resistance, high mechanical strength, good adhesion performance and the like, the adhesive is widely applied to the fields of aerospace, ship transportation, mechanical manufacturing, adhesive and the like. However, it is because of its stable crosslinked network that makes it difficult to melt mix thermosetting resins like thermoplastic resins, and it is also difficult to reprocess and reuse them after breakage.
In order to solve the above problems, scientists introduce dynamic covalent bonds into resins, and a common method is to introduce dynamic covalent bonds, such as Diels-Alder reaction-dynamic epoxy networks, imine-dynamic epoxy networks, transesterification reaction-dynamic epoxy networks, disulfide exchange-dynamic epoxy networks and the like, and the resins can relax the internal stress of the resins through the exchange action of the dynamic covalent bonds, so that the materials have the performances of crack repair, reworking, self-assembly and the like. However, the thermosetting resin compositions reported so far only contain resins of a single structure, and thermosetting resin compositions containing different structures cannot be prepared by simple solid phase fusion, which greatly limits the application range of materials.
Therefore, how to combine epoxy thermosetting resins with different structures through solid phase fusion to obtain a composition material with excellent performance has important significance for application of the thermosetting resins.
Disclosure of Invention
The invention aims to provide an epoxy thermosetting resin and a preparation method thereof, which solve the problem that the epoxy resin composition with different structures cannot be obtained through solid phase fusion in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of epoxy thermosetting resin, which comprises the following steps:
(1) Mixing epoxy resin, amine compound containing disulfide and solvent, standing, volatilizing the solvent, and standing for 10-14 h at 110-130 ℃ to obtain disulfide bond exchange-dynamic epoxy network;
(2) Mixing epoxy resin, amine compound containing diselenide and solvent, standing, volatilizing the solvent, and standing for 10-14 h at 110-130 ℃ to obtain diselenide bond exchange-dynamic epoxy network;
(3) Mixing and hot-pressing a disulfide bond exchange-dynamic epoxy network and a diselenide bond exchange-dynamic epoxy network to obtain epoxy thermosetting resin;
wherein, step (1) and step (2) are not limited in order.
Preferably, in the method for preparing an epoxy thermosetting resin, the epoxy resin in the step (1) and the step (2) is independently one or more of ethylene glycol diglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, epoxy vegetable oil, triglycidyl isocyanurate, alicyclic glycidyl ester, bisphenol F diglycidyl ether, bisphenol a diglycidyl ether and bisphenol S diglycidyl ether, and the epoxy resin in the step (1) and the step (2) is an epoxy resin with different structures.
Preferably, in the method for preparing an epoxy thermosetting resin, the amine compound containing disulfide in the step (1) is one of the following structures:
preferably, in the method for preparing an epoxy thermosetting resin, the amine compound containing diselenide in the step (2) is one of the following structures:
preferably, in the above method for preparing an epoxy thermosetting resin, the molar ratio of the epoxy resin to the disulfide-containing amine compound in the step (1) is 1 to 2:1.
preferably, in the above method for preparing an epoxy thermosetting resin, the molar ratio of the epoxy resin to the diselenide-containing amine compound in the step (2) is 1-2: 1.
preferably, in the method for preparing an epoxy thermosetting resin, the solvent in the step (1) and the step (2) is independently one or more of dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol and butanone.
Preferably, in the above method for preparing an epoxy thermosetting resin, the hot pressing pressure in the step (3) is 2 to 10MPa; the hot pressing temperature is 110-150 ℃; the hot pressing time is 12-20 h.
The invention also provides the epoxy thermosetting resin prepared by the preparation method of the epoxy thermosetting resin.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, two different dynamic covalent bonds-S-S-and-Se-Se-are introduced into epoxy resins with different structures, so that the epoxy resins with different structures and different cross-linking agents are prepared, and the-S-Se-cross-linked epoxy thermosetting resin composition is formed through high-temperature solid phase fusion. The preparation method is simple, and the prepared epoxy thermosetting resin composition containing different structures has the same mechanical property as the crosslinked epoxy resin with a single structure, so that the mixing of the thermosetting epoxy resins with different structures is realized, and the composition also has the functions of self-repairing, shape memory and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is a schematic flow chart of P1 prepared by hot pressing P1-1 and P1-2 of example 1.
Detailed Description
The invention provides a preparation method of epoxy thermosetting resin, which comprises the following steps:
(1) Mixing epoxy resin and amine compound containing disulfide, adding solvent, standing in a mould, and standing for 10-14 h at 110-130 ℃ after the solvent is volatilized to obtain disulfide bond exchange-dynamic epoxy network;
(2) Mixing epoxy resin and amine compound containing diselenide, adding solvent, standing in a mould, and standing for 10-14 h at 110-130 ℃ after the solvent is volatilized to obtain diselenide bond exchange-dynamic epoxy network;
(3) Mixing and hot-pressing a disulfide bond exchange-dynamic epoxy network and a diselenide bond exchange-dynamic epoxy network to obtain epoxy thermosetting resin;
wherein, step (1) and step (2) are not limited in order.
In the present invention, the epoxy resin in step (1) and step (2) is independently preferably one or more of ethylene glycol diglycidyl ether, poly (ethylene glycol) diglycidyl ether, poly (propylene glycol) diglycidyl ether, epoxidized vegetable oil, triglycidyl isocyanurate, alicyclic glycidyl ester, bisphenol F diglycidyl ether, bisphenol a diglycidyl ether and bisphenol S diglycidyl ether, and the epoxy resin in step (1) and step (2) is an epoxy resin of a different structure, further preferably one or more of poly (ethylene glycol) diglycidyl ether, epoxidized soybean oil, triglycidyl isocyanurate, alicyclic glycidyl ester, bisphenol F diglycidyl ether and bisphenol S diglycidyl ether, more preferably one or more of epoxidized soybean oil, isocyanuric acid triglycidyl ester and bisphenol F diglycidyl ether.
In the present invention, the disulfide-containing amine compound in step (1) is preferably one of the following structures:
in the present invention, the diselenide-containing amine compound in step (2) is preferably one of the following structures:
in the present invention, the molar ratio of the epoxy resin to the disulfide-containing amine compound in the step (1) is preferably 1 to 2:1, more preferably 1.1 to 1.9:1, more preferably 1.6:1.
in the present invention, the temperature of the standing in the step (1) is preferably 110 to 130 ℃, more preferably 114 to 127 ℃, still more preferably 121 ℃; the time for the standing is preferably 10 to 14 hours, more preferably 10.2 to 13.5 hours, and still more preferably 12 hours.
In the present invention, the molar volume ratio of the epoxy resin and the solvent in the step (1) is preferably 1 to 10mmol:2 to 7mL, more preferably 3 to 9mmol:3 to 6mL, more preferably 7mmol:4mL.
In the present invention, the molar ratio of the epoxy resin to the diselenide-containing amine compound in the step (2) is preferably 1 to 2:1, more preferably 1.2 to 1.8:1, more preferably 1.3:1.
in the present invention, the temperature of the standing in the step (2) is preferably 110 to 130 ℃, more preferably 112 to 128 ℃, still more preferably 125 ℃; the time for the standing is preferably 10 to 14 hours, more preferably 10.6 to 13.2 hours, and still more preferably 12.5 hours.
In the present invention, the molar volume ratio of the epoxy resin and the solvent in the step (2) is preferably 1 to 10mmol:2 to 7mL, more preferably 4 to 9mmol:4 to 6mL, more preferably 8mmol:5mL.
In the present invention, the solvent in step (1) and step (2) is independently preferably one or more of dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol and butanone, more preferably one or more of dichloromethane, tetrahydrofuran, methanol, ethanol and butanone, and still more preferably one or more of tetrahydrofuran, methanol and butanone.
In the present invention, the pressure of the hot pressing in the step (3) is preferably 2 to 10MPa, more preferably 3 to 9MPa, still more preferably 6MPa; the hot-pressing temperature is preferably 110 to 150 ℃, more preferably 117 to 143 ℃, and even more preferably 136 ℃; the time for hot pressing is preferably 12 to 20 hours, more preferably 13 to 19 hours, and still more preferably 14 hours.
The invention also provides the epoxy thermosetting resin prepared by the preparation method of the epoxy thermosetting resin.
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides an epoxy thermosetting resin, and the preparation method thereof comprises the following steps:
(1) Mixing 8mmol of bisphenol F diglycidyl ether and 4mmol of cystamine, adding 5mL of tetrahydrofuran, uniformly stirring, placing in a polytetrafluoroethylene membrane with 50mm x 2mm, standing for 12h at 120 ℃ after the solvent is volatilized, and obtaining a disulfide bond exchange-dynamic epoxy network, which is marked as P1-1;
mixing 8mmol of bisphenol A diglycidyl ether and 4mmol of selenocysteine, adding 5mL of tetrahydrofuran, uniformly stirring, placing in a polytetrafluoroethylene film with the thickness of 50mm and 2mm, standing for 12h at 120 ℃ after the solvent is volatilized, and obtaining a diselenide bond exchange-dynamic epoxy network, which is marked as P1-2;
the reaction process is as follows:
(2) A schematic flow chart of the hot pressing preparation of P1 by P1-1 and P1-2 prepared in the step (1) is shown in FIG. 1: shearing and mixing 0.5g of P1-1 and 0.5g of P1-2, and hot-pressing for 12 hours at the temperature of 110 ℃ under the pressure of 3MPa to obtain an epoxy thermosetting resin film with a flat surface, which is denoted as P1;
the reaction process is as follows:
example 2
The embodiment provides an epoxy thermosetting resin, and the preparation method thereof comprises the following steps:
(1) Mixing 4mmol of poly (ethylene glycol) diglycidyl ether and 2mmol of 2,2' -dithiodiphenylamine, adding 6mL of dichloromethane, uniformly stirring, placing in a polytetrafluoroethylene membrane with the thickness of 50mm and 2mm, standing for 10 hours at 120 ℃ after the solvent is volatilized, and obtaining a disulfide bond exchange-dynamic epoxy network, which is marked as P2-1;
mixing 4mmol of bisphenol F diglycidyl ether and 2mmol of bis (2-aminophenyl) diselenide, adding 6mL of dichloromethane, uniformly stirring, placing in a polytetrafluoroethylene film with the thickness of 50mm and 2mm, standing for 10 hours at 120 ℃ after the solvent is volatilized, and obtaining a diselenide bond exchange-dynamic epoxy network, which is marked as P2-2;
the reaction process is as follows:
(2) Shearing and mixing 0.5g of P2-1 and 0.5g of P2-2, and hot-pressing for 16 hours at the temperature of 120 ℃ under the pressure of 3.5MPa to obtain an epoxy thermosetting resin film with a flat surface, which is denoted as P2;
the reaction process is as follows:
example 3
The embodiment provides an epoxy thermosetting resin, and the preparation method thereof comprises the following steps:
(1) Mixing 2mmol of epoxidized soybean oil and 2mmol of L-cystine dimethyl ester, adding 5mL of ethanol, uniformly stirring, placing in a polytetrafluoroethylene membrane with the thickness of 50mm and 2mm, standing for 13h at 120 ℃ after the solvent is volatilized, and obtaining a disulfide bond exchange-dynamic epoxy network, which is marked as P3-1;
mixing 4mmol of poly (ethylene glycol) diglycidyl ether and 2mmol of bis (4-aminophenyl) dibenzyl diselenide, adding 5mL of ethanol, uniformly stirring, placing in a 50 mm-2 mm polytetrafluoroethylene film, standing for 13h at 120 ℃ after the solvent is volatilized, and obtaining a diselenide bond exchange-dynamic epoxy network, which is marked as P3-2;
the reaction process is as follows:
(2) Shearing and mixing 0.5g of P3-1 and 0.5g of P3-2, and hot-pressing for 15h at the temperature of 140 ℃ under the pressure of 8MPa to obtain an epoxy thermosetting resin film with a flat surface, which is denoted as P3;
the reaction process is as follows:
example 4
The embodiment provides an epoxy thermosetting resin, and the preparation method thereof comprises the following steps:
(1) Mixing 4mmol of bisphenol A diglycidyl ether and 2mmol of 4, 4-dithiodiphenylamine, adding 4mL of methanol, uniformly stirring, placing in a polytetrafluoroethylene membrane with the thickness of 50mm and 2mm, standing for 14h at 120 ℃ after the solvent is volatilized, and obtaining a disulfide bond exchange-dynamic epoxy network, which is marked as P4-1;
mixing 4mmol of bisphenol F diglycidyl ether and 2mmol of bis (4-aminophenyl) diselenide, adding 4mL of methanol, uniformly stirring, placing in a polytetrafluoroethylene membrane with the thickness of 50mm being 2mm, standing for 14h at 120 ℃ after the solvent is volatilized, and obtaining a diselenide bond exchange-dynamic epoxy network, which is marked as P4-2;
the reaction process is as follows:
(2) Shearing and mixing 0.5g of P4-1 and 0.5g of P4-2, and hot-pressing for 20 hours at the temperature of 150 ℃ under the pressure of 10MPa to obtain an epoxy thermosetting resin film with a flat surface, which is denoted as P4;
the reaction process is as follows:
the epoxy thermosetting resin films, disulfide bond exchange-dynamic epoxy networks and diselenide bond exchange-dynamic epoxy networks of examples 1 to 4 were subjected to performance tests, and specifically include: tensile strength, elongation at break, solids content, DSC and DMA, the results are shown in Table 1.
Table 1 results of performance tests of examples 1 to 4
As can be seen from table 1, the properties of the samples after the mixed hot pressing of the epoxy thermosetting resin films of examples 1 to 4 tended to be intermediate values of the properties of the two epoxy network samples before hot pressing. In example 1, the tensile strength, elongation at break and solids content of the P1 sample were similar to those of P1-1 and P1-2, T of P1 g Intermediate between P1-1 and P1-2.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The preparation method of the epoxy thermosetting resin is characterized by comprising the following steps of:
(1) Mixing epoxy resin, amine compound containing disulfide and solvent, standing, volatilizing the solvent, and standing for 10-14 h at 110-130 ℃ to obtain disulfide bond exchange-dynamic epoxy network;
(2) Mixing epoxy resin, amine compound containing diselenide and solvent, standing, volatilizing the solvent, and standing for 10-14 h at 110-130 ℃ to obtain diselenide bond exchange-dynamic epoxy network;
(3) Mixing and hot-pressing a disulfide bond exchange-dynamic epoxy network and a diselenide bond exchange-dynamic epoxy network to obtain epoxy thermosetting resin;
wherein, step (1) and step (2) are not limited in order;
the epoxy resin in the step (1) and the step (2) is independently one of poly (ethylene glycol) diglycidyl ether, epoxidized soybean oil, bisphenol F diglycidyl ether and bisphenol A diglycidyl ether, and the epoxy resins in the step (1) and the step (2) are epoxy resins with different structures;
the disulfide-containing amine compound in the step (1) is one of the following structures:
the amine compound containing diselenide in the step (2) is one of the following structures:
2. the method for preparing an epoxy thermosetting resin according to claim 1, wherein the molar ratio of the epoxy resin to the disulfide-containing amine compound in the step (1) is 1 to 2:1.
3. the method for preparing epoxy thermosetting resin according to claim 1, wherein the molar ratio of epoxy resin to diselenide-containing amine compound in the step (2) is 1-2: 1.
4. the method for preparing epoxy thermosetting resin according to claim 2, wherein the solvent in the step (1) and the step (2) is independently one or more of dichloromethane, chloroform, tetrahydrofuran, acetone, methanol, ethanol and butanone.
5. The method for producing an epoxy thermosetting resin according to claim 1 or 4, wherein the hot pressing pressure in the step (3) is 2 to 10MPa; the hot pressing temperature is 110-150 ℃; the hot pressing time is 12-20 h.
6. An epoxy thermosetting resin produced by the process for producing an epoxy thermosetting resin according to any one of claims 1 to 5.
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| CN202210198913.3A CN114350116B (en) | 2022-03-01 | 2022-03-01 | Epoxy thermosetting resin and preparation method thereof |
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| CN116655888B (en) * | 2023-08-01 | 2023-10-31 | 南京海关工业产品检测中心 | Self-repairing material and preparation and recycling methods thereof |
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