CN111363123A - Self-repairable epoxy resin and preparation method thereof - Google Patents
Self-repairable epoxy resin and preparation method thereof Download PDFInfo
- Publication number
- CN111363123A CN111363123A CN202010262149.2A CN202010262149A CN111363123A CN 111363123 A CN111363123 A CN 111363123A CN 202010262149 A CN202010262149 A CN 202010262149A CN 111363123 A CN111363123 A CN 111363123A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- self
- ether
- polyamine
- repairable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003822 epoxy resin Substances 0.000 title claims abstract description 81
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 229920000768 polyamine Polymers 0.000 claims abstract description 19
- 239000003085 diluting agent Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 239000012295 chemical reaction liquid Substances 0.000 claims description 14
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- RAFNCPHFRHZCPS-UHFFFAOYSA-N di(imidazol-1-yl)methanethione Chemical compound C1=CN=CN1C(=S)N1C=CN=C1 RAFNCPHFRHZCPS-UHFFFAOYSA-N 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- -1 glycidyl ester Chemical class 0.000 claims description 5
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 3
- 235000013824 polyphenols Nutrition 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 claims description 2
- 125000000623 heterocyclic group Chemical group 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- JIMDQTNPLVRAES-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-(oxetan-3-yl)benzamide Chemical group NCC1=CC(=NC(=C1)C(F)(F)F)OC=1C=C(C(=O)NC2COC2)C=CC=1 JIMDQTNPLVRAES-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000005215 recombination Methods 0.000 abstract description 3
- 230000006798 recombination Effects 0.000 abstract description 3
- 230000008439 repair process Effects 0.000 description 7
- 230000035876 healing Effects 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- IFZOPNLVYZYSMQ-UHFFFAOYSA-N 2-[2-[2-[2-(2-aminoethoxy)ethoxy]ethoxy]ethoxy]ethanamine Chemical compound NCCOCCOCCOCCOCCN IFZOPNLVYZYSMQ-UHFFFAOYSA-N 0.000 description 1
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 description 1
- 238000007306 functionalization reaction Methods 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
- 230000003993 interaction Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- AFEQENGXSMURHA-UHFFFAOYSA-N oxiran-2-ylmethanamine Chemical compound NCC1CO1 AFEQENGXSMURHA-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000005855 radiation Effects 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
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5006—Amines aliphatic
- C08G59/5013—Amines aliphatic containing more than seven carbon atoms, e.g. fatty amines
-
- 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
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
- C08G59/5026—Amines cycloaliphatic
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Epoxy Resins (AREA)
Abstract
The invention discloses a self-repairable epoxy resin and a preparation method thereof. The method comprises the steps of mixing and reacting the diimidazole compound, the polyamine, the diluent and the epoxy resin, introducing hydrogen bond groups such as thiourea group and urea group into a high-molecular chain segment of the epoxy resin, and realizing self-repair of the material by means of the breakage and recombination of hydrogen bonds in molecules or between molecules, so that the epoxy resin material has a good self-repair function. The self-repairable epoxy resin has high self-repairing efficiency, simple preparation process and low cost.
Description
Technical Field
The invention belongs to the field of epoxy resin and preparation thereof, and particularly relates to self-repairable epoxy resin and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The epoxy resin is one of the most widely applied thermosetting resins, and has the characteristics of large binding power, small shrinkage rate, good corrosion resistance, excellent electrical property, good durability, easy modification, easy obtainment of raw materials and the like. With the rapid development of national construction and the continuous emergence of new fields, higher requirements are put forward on the functional development of epoxy resin. In a plurality of epoxy resin modification researches, it can be found that epoxy resin functionalization mainly proceeds around the directions of high temperature resistance, metal corrosion resistance, flame retardance, fire resistance, wear resistance, insulation and the like, and the ultimate purpose of the epoxy resin is to meet the requirements of fields such as aviation, aerospace, automobiles, machinery, buildings, electronics, electrical appliances, transportation and the like on the special performance of the epoxy resin, so that the epoxy resin tends to develop towards the multifunctionalization of bonding, corrosion resistance, radiation resistance, flame retardance, insulation, high conductivity and the like. However, the epoxy resin material is still inevitably vulnerable to external mechanical damage during use, which shortens the service life thereof and greatly increases the repair and replacement costs of the material. To solve this problem, it is an effective solution to make the epoxy resin material have self-repairing capability.
At present, self-repairing epoxy resin materials have been reported. Generally, the introduction of a structural unit with reversible dynamic reversible covalent bond or reversible noncovalent bond interaction in an epoxy resin chain is a main method for constructing a self-repairing epoxy resin. However, the introduction mode of introducing the self-repairing group into the epoxy resin chain segment and the preparation process are complex and tedious and have high cost at present; in addition, most of the existing self-repairing epoxy resins have poor mechanical properties, and some self-repairing epoxy resin materials with better mechanical properties have the problems of long repairing time, low repairing efficiency and the like. These problems limit the wide application of self-healing epoxy materials.
Disclosure of Invention
The invention aims to: provided is a self-repairable epoxy resin which has high self-repairing efficiency.
Another object of the present invention is to: the preparation method of the self-repairable epoxy resin is simple in preparation process and low in cost.
The object of the invention is achieved by:
the self-repairable epoxy resin is characterized by comprising the following raw materials in parts by weight:
epoxy resin 100 parts
1-200 parts of diimidazole compound
1-200 parts of polyamine
0 to 200 parts of diluent
The epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxidized olefin compound, heterocyclic epoxy resin and mixed epoxy resin;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole; the diluent is at least one of an alcohol solvent and an ether solvent;
the polyamine is a polyamine compound having at least 2 primary amino groups in the molecule.
A preparation method of self-repairable epoxy resin is characterized by comprising the following steps: the method comprises the following steps:
(A) mixing a diimidazole compound, polyamine and a diluent, and reacting for 1-12 hours at the temperature of 20-80 ℃ to obtain a pre-reaction solution;
(B) stirring and mixing the pre-reaction liquid and epoxy resin uniformly; stirring and reacting for 5-200 min at 10-100 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin;
the diluent is at least one of an alcohol solvent and an ether solvent;
the alcohol solvent is at least one of ethanol, methanol, isopropanol and n-butanol;
the ether solvent is at least one of diethyl ether, tetrahydrofuran, 1, 4-dioxane, diethylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether and petroleum ether;
the polyamine is at least one of the substances shown in the following structural formula:
wherein m is 1-200; n is 0 to 5; t is 1-5; d is 1 to 16; k is 3 to 500.
In order to realize the self-repairing function of the epoxy resin, the invention comprises the following steps:
the reaction ratio of polyamine and N, N' -thiocarbonyl diimidazole is controlled, and thiourea-containing groups can be introduced into the pre-reaction liquid as shown in the following;
wherein:
represents a polyamine.
The reaction ratio of polyamine and N, N' -carbonyl diimidazole is controlled, and urea-containing groups can be introduced into the pre-reaction liquid, as shown in the following;
wherein:
represents a plurality of elementsAn amine.
The reaction ratio of polyamine, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole is controlled, and urea-containing groups and thiourea groups can be simultaneously introduced into a pre-reaction liquid, as shown in the following;
wherein:
represents a polyamine.
The method comprises the following steps of mixing and reacting a diimidazole compound, polyamine and a diluent to obtain a pre-reaction liquid containing thiourea groups and urea groups, and further reacting the pre-reaction liquid with epoxy resin, so that hydrogen bond groups such as thiourea groups and urea groups are introduced into a high-molecular chain segment of the epoxy resin, and self-repair of the material is realized by means of breakage and recombination of hydrogen bonds in molecules or between molecules, so that the epoxy resin material has a good self-repair function. The principle of the hydrogen bond action inside the epoxy resin material containing the thiourea group, the urea group and other hydrogen bond groups is as follows:
meanwhile, the formed hydrogen bond groups such as thiourea-containing groups, urea groups and the like can also form a hydrogen bond structure with a hydrogen bond donor/acceptor of the epoxy resin, so that the hydrogen bond function of the system is further enhanced.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the method comprises the steps of mixing and reacting the diimidazole compound, the polyamine, the diluent and the epoxy resin, introducing hydrogen bond groups such as thiourea group and urea group into a high-molecular chain segment of the epoxy resin, and realizing self-repair of the material by means of the breakage and recombination of hydrogen bonds in molecules or between molecules, so that the epoxy resin material has a good self-repair function.
2. The self-repairable epoxy resin has high self-repairing efficiency, simple preparation process and low cost.
Drawings
FIG. 1 is a self-healing process diagram of the self-healing epoxy resin of example 1.
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings and examples, but the embodiments of the present invention are not limited thereto.
Example 1
(A) Mixing 30g of N, N' -thiocarbonyldiimidazole, 10g of 1, 2-bis (2-aminoethoxy) ethane and 20g of ethanol, and reacting at 40 ℃ for 4 hours to obtain a pre-reaction solution;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (glycidyl ester type epoxy resin); stirring and reacting for 100 min at 50 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The resulting self-repairable epoxy was broken and re-contacted as shown in figure 1, and the material healed within 2 minutes. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Example 2
(A) Mixing 40g of N, N' -thiocarbonyldiimidazole, 10g of triethylene glycol bis (2-aminoethyl) ether and 5g of methanol, and reacting for 4 hours at the temperature of 60 ℃ to obtain a pre-reaction liquid;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (bisphenol A epoxy resin); stirring and reacting for 80 min at 40 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The obtained self-repairable epoxy resin is disconnected and contacted again, and the material can be healed and repaired within 1 minute. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Example 3
(A) Mixing 10g of N, N' -thiocarbonyldiimidazole, 2g of ethylene glycol mono (2-aminoethyl) ether and 10g of N-butanol, and reacting at 40 ℃ for 3 hours to obtain a pre-reaction solution;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (bisphenol F type epoxy resin); stirring and reacting for 120 min at the temperature of 60 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The obtained self-repairable epoxy resin is disconnected and contacted again, and the material can be healed and repaired within 4 minutes. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Example 4
(A) Mixing 50g of N, N' -carbonyldiimidazole, 2g of polyamine and 100g of tetrahydrofuran, and reacting at 50 ℃ for 6 hours to obtain a pre-reaction solution;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (aliphatic glycidyl ether epoxy resin); stirring and reacting for 100 min at 70 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The obtained self-repairable epoxy resin is disconnected and contacted again, and the material can be healed and repaired within 1 minute. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Example 5
(A) Mixing 1g of N, N' -carbonyldiimidazole and 1g of amino-terminated polyethylene glycol (average molecular weight is about 2000 g/mol), and reacting at 20 ℃ for 12 hours to obtain a pre-reaction solution;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (polyphenol type glycidyl ether epoxy resin); stirring and reacting for 5 min at the temperature of 100 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The obtained self-repairable epoxy resin is disconnected and contacted again, and the material can be healed and repaired within 10 minutes. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
Example 6
(A) Mixing 200g of N, N' -carbonyldiimidazole, 100g of isophorone diamine, 100g of ethanol and 100g of diethylene glycol monomethyl ether, and reacting at 80 ℃ for 1h to obtain a pre-reaction solution;
(B) uniformly stirring and mixing the pre-reaction liquid and 100g of epoxy resin (glycidyl amine type epoxy resin); stirring and reacting for 200 min at the temperature of 10 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin.
The obtained self-repairable epoxy resin is disconnected and contacted again, and the material can be healed and repaired within 5 minutes. Therefore, after the contact at room temperature in a short time, efficient healing and repair can be realized.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (2)
1. The self-repairable epoxy resin is characterized by comprising the following raw materials in parts by weight:
epoxy resin 100 parts
1-200 parts of diimidazole compound
1-200 parts of polyamine
0 to 200 parts of diluent
The epoxy resin comprises at least one of bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, epoxidized olefin compound, heterocyclic epoxy resin and mixed epoxy resin;
the diimidazole compound is at least one of N, N '-carbonyl diimidazole and N, N' -thiocarbonyl diimidazole;
the diluent is at least one of an alcohol solvent and an ether solvent;
the polyamine is a polyamine compound having at least 2 primary amino groups in the molecule.
2. The method for preparing a self-repairable epoxy resin according to claim 1, wherein: the method comprises the following steps:
(A) mixing a diimidazole compound, polyamine and a diluent, and reacting for 1-12 hours at the temperature of 20-80 ℃ to obtain a pre-reaction solution;
(B) stirring and mixing the pre-reaction liquid and epoxy resin uniformly; stirring and reacting for 5-200 min at 10-100 ℃, and then carrying out vacuum defoaming to obtain the self-repairable epoxy resin;
the diluent is at least one of an alcohol solvent and an ether solvent;
the alcohol solvent is at least one of ethanol, methanol, isopropanol and n-butanol;
the ether solvent is at least one of diethyl ether, tetrahydrofuran, 1, 4-dioxane, diethylene glycol monomethyl ether, propylene glycol methyl ether, dipropylene glycol dimethyl ether and petroleum ether;
the polyamine is at least one of the substances shown in the following structural formula:
wherein m is 1-200; n is 0 to 5; t is 1-5; d is 1 to 16; k is 3 to 500.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262149.2A CN111363123A (en) | 2020-04-06 | 2020-04-06 | Self-repairable epoxy resin and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010262149.2A CN111363123A (en) | 2020-04-06 | 2020-04-06 | Self-repairable epoxy resin and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111363123A true CN111363123A (en) | 2020-07-03 |
Family
ID=71203023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010262149.2A Pending CN111363123A (en) | 2020-04-06 | 2020-04-06 | Self-repairable epoxy resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111363123A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280056A (en) * | 2020-11-06 | 2021-01-29 | 湖南科技大学 | Preparation method of repairable graphene oxide material based on hydrogen bond effect |
| CN113480727A (en) * | 2021-06-08 | 2021-10-08 | 华南理工大学 | Preparation method of modified polyether amine epoxy resin curing agent |
| CN114230749A (en) * | 2021-11-29 | 2022-03-25 | 西安交通大学 | Epoxy resin cured material capable of being quickly self-repaired, preparation method and application |
-
2020
- 2020-04-06 CN CN202010262149.2A patent/CN111363123A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280056A (en) * | 2020-11-06 | 2021-01-29 | 湖南科技大学 | Preparation method of repairable graphene oxide material based on hydrogen bond effect |
| CN113480727A (en) * | 2021-06-08 | 2021-10-08 | 华南理工大学 | Preparation method of modified polyether amine epoxy resin curing agent |
| CN114230749A (en) * | 2021-11-29 | 2022-03-25 | 西安交通大学 | Epoxy resin cured material capable of being quickly self-repaired, preparation method and application |
| CN114230749B (en) * | 2021-11-29 | 2023-03-17 | 西安交通大学 | Epoxy resin cured material capable of being quickly self-repaired, preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111363123A (en) | Self-repairable epoxy resin and preparation method thereof | |
| CN101475685B (en) | Preparation of hyperbranched polymer and hyperbranched epoxy resin | |
| CN109503812B (en) | Epoxy resin material and preparation method and application thereof | |
| CN100513411C (en) | Double-ring cage shape substituted silsesquioxane and its preparation method and uses | |
| CN108250382B (en) | Biomass diphenolic acid-furfuryl amine type benzoxazine resin and preparation method thereof | |
| CN102924690A (en) | Epoxy resin material used for toughening and reinforcing of hyperbranched polyether type epoxy resin and preparation method thereof | |
| CN102803334A (en) | Thermosettable composition containing a half ester of a cycloaliphatic diol and a thermoset product therefrom | |
| CN111825829B (en) | Triazine ring structure-containing bio-based epoxy resin and preparation method thereof | |
| CN104693409A (en) | Flexibility-adjustable core adding type hyper-branched urethane acrylate resin and preparing method | |
| Zhang et al. | Multifunctional tannin extract-based epoxy derived from waste bark as a highly toughening and strengthening agent for epoxy resin | |
| CN109233571B (en) | Solvent-free self-repairing epoxy resin and preparation method thereof | |
| US20200062888A1 (en) | Biomass-based epoxy resin and preparation method thereof | |
| CN102884101A (en) | Novel curing agents | |
| CN108299341A (en) | A kind of castor oil-base epoxy resin and preparation method thereof | |
| CN111019111B (en) | Ionic liquid catalyst for synthesizing bio-based polycarbonate and method for synthesizing bio-based polycarbonate | |
| CN115678204A (en) | Epoxy fiber composite material for wind power blade and preparation method thereof | |
| Monteserin et al. | Sustainable biobased epoxy thermosets with covalent dynamic imine bonds for green composite development | |
| CN109535387B (en) | Method for preparing polyurethane foam plastic from TGIC (triglycidyl isocyanurate) by-product | |
| GB2101605A (en) | Lactone-modified epoxy resin and composition containing such resin | |
| CN101440087B (en) | Phthalimide diglycidyl ether and preparation thereof | |
| CN111423561A (en) | Flame-retardant epoxy resin curing agent, flame-retardant epoxy resin containing curing agent and method for preparing curing agent | |
| CN102504211B (en) | preparation method of thermoset imide resin modified silazane and its composite material | |
| CN117164817B (en) | Autocatalysis type cardanol-based self-repairing and recyclable polymer and preparation method thereof | |
| CN115028824B (en) | Preparation method of carbon dioxide-based polycarbonate polyol product | |
| CN114591490B (en) | Synthesis method of glycidylamine epoxy resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200703 |