CN117843922A - Rapidly-cured vitrimer resin and preparation method thereof - Google Patents
Rapidly-cured vitrimer resin and preparation method thereof Download PDFInfo
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- CN117843922A CN117843922A CN202311720281.3A CN202311720281A CN117843922A CN 117843922 A CN117843922 A CN 117843922A CN 202311720281 A CN202311720281 A CN 202311720281A CN 117843922 A CN117843922 A CN 117843922A
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- 229920005989 resin Polymers 0.000 title claims abstract description 101
- 239000011347 resin Substances 0.000 title claims abstract description 101
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 23
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 8
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 6
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 6
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- VYKYSTWKUAETPR-UHFFFAOYSA-N 3-(2-hydroxyphenyl)-1,1-dimethylurea Chemical compound CN(C)C(=O)NC1=CC=CC=C1O VYKYSTWKUAETPR-UHFFFAOYSA-N 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 3
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000005303 weighing Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 230000006872 improvement Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000008439 repair process Effects 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- 238000012958 reprocessing Methods 0.000 description 3
- 150000003512 tertiary amines Chemical class 0.000 description 3
- 238000005809 transesterification reaction Methods 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- -1 coatings Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 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
- 150000002466 imines Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention provides a fast-curing vitrimer resin and a preparation method thereof, wherein the preparation method comprises the following steps: mixing 10-100 parts of acid curing agent with 100 parts of epoxy resin, stirring and reacting for 20-180 minutes at 60-100 ℃, and cooling to room temperature to obtain pre-cured resin A with fluidity; mixing 0.1-10 parts of amine curing agent, 0.1-10 parts of accelerator and 0.1-5 parts of polymerization inhibitor with the resin A, and stirring for 10-60 minutes at 20-60 ℃ to obtain resin B; pouring the resin B into a mould, and curing for 10-30 minutes under the conditions of the pressure of 1-10MPa and the temperature of 120-160 ℃ to obtain a vitrimer resin cured product. By adopting the technical scheme of the invention, rapid curing can be realized, and the cured resin has self-repairing capability under the heating condition.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a fast-curing vitrimer resin and a preparation method thereof.
Background
Epoxy resins have excellent mechanical properties, electrical insulating properties, adhesive properties, chemical stability, and the like, and are widely used in the fields of composite materials, electronic packaging materials, coatings, adhesives, and the like. But its dense three-dimensional network structure and chemical inertness increase the difficulty of recovering the epoxy resin. By introducing different dynamic bonds into the epoxy resin network, a dynamic cross-linked network is formed in the system, the difficulties in the aspects of reprocessing and recycling of the traditional epoxy resin can be overcome, and the novel material is called vitrimer (glass-like) epoxy.
Vitrimer epoxy combines the advantages of thermosetting property and thermoplasticity, not only has excellent mechanical property, thermal stability and the like, but also can be self-repaired and recycled, and has higher potential application value. Many studies have been made to achieve the preparation of high performance vitrimer epoxy by means of ester, imine, siloxane and disulfide linkages, but most vitrimer epoxy cure times are long, typically requiring several hours.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a fast-curing vitrimer resin and a preparation method thereof, which can realize fast curing, and simultaneously has self-repairing capability and high repairing efficiency.
In this regard, the invention adopts the following technical scheme:
a method for preparing a fast curing vitrimer resin, comprising the steps of:
step S1, mixing 10-100 parts of acid curing agent and 100 parts of epoxy resin, stirring and reacting for 20-180 minutes at 60-100 ℃, and cooling to room temperature to obtain pre-cured resin A with fluidity;
step S2, mixing 0.1-10 parts of amine curing agent, 0.1-10 parts of accelerator and 0.1-5 parts of polymerization inhibitor with the resin A, and stirring for 10-60 minutes at 20-60 ℃ to obtain resin B;
and S3, pouring the resin B into a mould, and curing for 10-30 minutes under the conditions of the pressure of 1-10MPa and the temperature of 120-160 ℃ to obtain a vitrimer resin cured product.
By adopting the technical scheme of the invention, the acid curing agent is firstly adopted to perform pre-curing treatment, chain extension is performed, and then the amine curing agent and the accelerator are adopted to realize rapid curing; in addition, the amine curing agent is converted into tertiary amine in the curing process, and can be used as a catalyst for transesterification reaction, so that the epoxy resin can be converted into a dynamic cross-linked network to realize reprocessing. In addition, a polymerization inhibitor is added in step S2, and the resin B may be stored for a long period of time, and the curing operation of step S3 may be performed again as needed.
As a further improvement of the invention, the epoxy resin is one or a mixture of more than two of bisphenol A epoxy E20, E44, E51 and bisphenol F epoxy.
As a further improvement of the invention, the acid curing agent is one or a mixture of more than two of methyl hexahydrophthalic anhydride, adipic acid, cyclopentanetetra-acid dianhydride and diphenyl ether tetra-acid dianhydride.
As a further improvement of the invention, the amine curing agent is one or a mixture of more than two of dicyandiamide, xylylenediamine, ethylenediamine and m-phenylenediamine.
As a further improvement of the invention, the promoter is one or a mixture of more than two of triethylamine, benzyl dimethylamine, N- (2-hydroxy-4-nitrobenzene) -N ', N' -dimethyl urea, N- (2-hydroxyphenyl) -N ', N' -dimethyl urea, resorcinol and 2-methylimidazole.
As a further improvement of the invention, the polymerization inhibitor is one or a mixture of more than two of hydroquinone, p-benzoquinone and p-hydroxyanisole.
As a further improvement of the present invention, the viscosity of the resin A is less than 10000 mPas at 70 ℃.
The invention also discloses a fast-curing vitrimer resin, which is prepared by adopting the preparation method of the fast-curing vitrimer resin.
Compared with the prior art, the invention has the beneficial effects that:
firstly, by adopting the technical scheme of the invention, the epoxy resin is subjected to pre-curing treatment by using the acid curing agent, and the epoxy resin which is chain-extended but has no net-shaped cross-linked structure is obtained by controlling the reaction time, and at the moment, the epoxy resin also has better fluidity and processability. Then adding proper amount of amine curing agent and accelerator, mixing uniformly, and realizing the quick curing of the epoxy resin at the process temperature, wherein the cured resin has self-repairing capability under the heating condition. And the intermediate product resin B can be stored for a long time with the help of a polymerization inhibitor so as to be convenient to take along with use and finally solidify as required.
Secondly, by adopting the technical scheme of the invention, the amine curing agent can be used as a catalyst for transesterification to catalyze ester bonds in an epoxy crosslinking network in the curing process of the amine curing agent and the epoxy resin, so that the epoxy resin can be subjected to the conversion of a dynamic crosslinking network to realize reprocessing. And the catalyst is fixed in the crosslinked network through chemical reaction, so that the problems of ageing and precipitation of the catalyst can be avoided. In addition, the repair efficiency and the curing speed of the epoxy resin can be controlled by changing the proportion of the amine curing agent and the acid curing agent, so that the vitrimer epoxy meeting different use requirements is obtained.
Thirdly, the preparation process of the resin in the technical scheme of the invention does not involve a complex synthesis process and harmful chemical reagents, is environment-friendly, and is suitable for industrial mass production.
Drawings
FIG. 1 is a scratch repair picture of the resin cured product obtained in examples and comparative examples of the present invention; wherein (a) - (d) are each C 1 -C 4 Initial scratches on the resin, (e) - (h) are C respectively 1 -C 4 Scratch after heating at 160℃for 2 hours.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
A method for preparing a fast curing vitrimer epoxy resin, comprising the steps of:
step 1: weighing 10-100 parts of acid curing agent and 100 parts of epoxy resin, mixing, stirring and reacting for 20-180 minutes under the oil bath condition of 60-100 ℃, and cooling to room temperature after the reaction is finished to obtain pre-cured resin A with fluidity;
step 2: weighing 1-10 parts of amine curing agent, 0.1-10 parts of accelerator and 0.1-5 parts of polymerization inhibitor, mixing with the resin A, and stirring for 10-60 minutes under the oil bath condition of 20-60 ℃ to obtain resin B;
step 3: pouring the resin B into a mould, placing the mould on a hot press for heating, curing for 10-30 minutes at 120-160 ℃, controlling the pressure to be 1-10MPa, and taking out the cured virmer resin after hot pressing is finished to obtain the cured virmer resin.
Wherein the epoxy resin is one or a mixture of bisphenol A epoxy E20, E44, E51, bisphenol F epoxy and the like.
The acid curing agent is one or a mixture of more of methyl hexahydrophthalic anhydride, adipic acid, cyclopentanetetra acid dianhydride, diphenyl ether tetracarboxylic dianhydride and the like.
The amine curing agent is one or a mixture of more of dicyandiamide, xylylenediamine, ethylenediamine, m-phenylenediamine and the like.
The promoter is one or more of triethylamine, benzyl dimethylamine, N- (2-hydroxy-4-nitrobenzene) -N ', N' -dimethyl urea, N- (2-hydroxyphenyl) -N ', N' -dimethyl urea, resorcinol, 2-methylimidazole and the like.
The polymerization inhibitor is one or a mixture of hydroquinone, p-benzoquinone, p-hydroxyanisole and the like.
The viscosity of the resin A is less than 10000 mPa.s at 70 ℃.
The following description is made in connection with specific preferred embodiments.
Example 1
A method for preparing a fast curing vitrimer resin, comprising the steps of:
step 1: 40 parts of adipic acid and 100 parts of epoxy resin E51 are weighed and mixed, stirred and reacted for 60 minutes under the oil bath condition of 80 ℃, and air-cooled to room temperature after the reaction is finished, so as to obtain the pre-cured resin A with fluidity 1 ；
Step 2: 1 part dicyandiamide, 0.1 part of 2-methylimidazole, 0.1 part of hydroquinone and resin A are weighed 1 Mixing, stirring at 60deg.C for 30 min to obtain resin B 1 ；
Step 3: resin is subjected toB 1 Pouring into a mold, heating in a hot press, curing at 140deg.C for 20min under 2MPa, and taking out to obtain cured resin C 1 。
Example 2
A method for preparing a fast curing vitrimer resin, comprising the steps of:
step 1: weighing 45 parts of methyl hexahydrophthalic anhydride and 100 parts of epoxy resin E51, mixing, stirring and reacting for 60 minutes under the oil bath condition of 80 ℃, and cooling to room temperature after the reaction is finished to obtain the pre-cured resin with fluidity;
step 2: 1 part of dicyandiamide, 0.1 part of 2-methylimidazole and 0.1 part of hydroquinone are weighed and mixed with the resin obtained in the step 1, and stirred for 30 minutes under the oil bath condition of 60 ℃ to obtain the resin;
step 3: pouring the resin obtained in the step 2 into a die, placing the die on a hot press for heating, curing at 140 ℃ for 20 minutes, controlling the pressure to be 2MPa, and taking out the cured resin after the hot pressing is finished to obtain a cured resin.
Example 3
A method for preparing a fast curing vitrimer resin, comprising the steps of:
step 1: weighing 45 parts of methyl hexahydrophthalic anhydride and 100 parts of epoxy resin E51, mixing, stirring and reacting for 60 minutes under the oil bath condition of 80 ℃, and cooling to room temperature after the reaction is finished to obtain the pre-cured resin with fluidity;
step 2: weighing 1.5 parts of dicyandiamide, 0.5 part of 2-methylimidazole and 0.5 part of hydroquinone, mixing with the resin obtained in the step 1, and stirring for 30 minutes under the oil bath condition at 60 ℃ to obtain the resin;
step 3: pouring the resin obtained in the step 2 into a die, placing the die on a hot press for heating, curing at 160 ℃ for 10 minutes, controlling the pressure to be 2MPa, and taking out the cured resin after the hot pressing is finished to obtain a cured resin.
Example 4
A method for preparing a fast curing vitrimer resin, comprising the steps of:
step 1: weighing 45 parts of methyl hexahydrophthalic anhydride, mixing with 50 parts of epoxy resin E44 and 50 parts of epoxy resin E51, stirring and reacting for 60 minutes under the oil bath condition of 80 ℃, and cooling to room temperature after the reaction is finished to obtain the pre-cured resin with fluidity;
step 2: weighing 3 parts of m-phenylenediamine, 0.2 part of N- (2-hydroxyphenyl) -N ', N' -dimethylurea and 0.3 part of p-benzoquinone, mixing with the resin obtained in the step 1, and stirring for 30 minutes under the oil bath condition at 60 ℃ to obtain the resin;
step 3: pouring the resin obtained in the step 2 into a die, placing the die on a hot press for heating, curing at 120 ℃ for 30 minutes, controlling the pressure to be 2MPa, and taking out the cured resin after the hot pressing is finished to obtain a cured resin.
Comparative example 1
A method for preparing a resin, comprising the steps of:
step 1: 40 parts of adipic acid and 100 parts of epoxy resin E51 are weighed and mixed, stirred and reacted for 240 minutes under the oil bath condition of 80 ℃, and air-cooled to room temperature after the reaction is finished, so as to obtain the pre-cured resin A with fluidity 2 ；
Step 2: weighing 2 parts of dicyandiamide, 0.1 part of 2-methylimidazole, 0.1 part of hydroquinone and resin A 2 Mixing, stirring at 60deg.C for 30 min to obtain resin B 2 ；
Step 3: resin B 2 Pouring into a mold, heating in a hot press, curing at 140deg.C for 20min under 2MPa, and taking out to obtain cured resin C 2 。
Comparative example 2
A method for preparing a resin, comprising the steps of:
step 1: 40 parts of adipic acid and 100 parts of epoxy resin E51 are weighed and mixed, stirred and reacted for 60 minutes under the oil bath condition of 80 ℃, and air-cooled to room temperature after the reaction is finished, so as to obtain the pre-cured resin A with fluidity 3 ；
Step 2: weighing 12 parts of dicyandiamide, 0.1 part of 2-methylimidazole, 0.1 part of hydroquinone and resin A 3 Mixing, atStirring for 30 minutes at 60 ℃ under the oil bath condition to obtain resin B 3 ；
Step 3: resin B 3 Pouring into a mold, heating in a hot press, curing at 140deg.C for 20min under 2MPa, and taking out to obtain cured resin C 3 。
Comparative example 3
A method for preparing a resin, comprising the steps of:
step 1: 40 parts of adipic acid, 10 parts of zinc acetylacetonate and 100 parts of epoxy resin E51 are weighed and mixed, and stirred and dispersed for 20 minutes at room temperature to obtain resin B 4 Then resin B 4 Pouring into a mold, heating in a hot press, curing at 80deg.C for 60 min, 100deg.C for 60 min, and 140deg.C for 120 min, controlling pressure to 2MPa, and taking out to obtain cured resin C 4 。
Resin cured product C obtained by using the above examples and comparative examples 1 -C 4 The repair efficiency of the resin cured product was judged by performing scratch damage on the surface thereof, then heating at 160 ℃ and observing the change of the scratch repair condition thereof with time. As a result, as shown in FIG. 1, it can be seen that the resin cured product C 1 、C 4 After heating, the scratch width gradually decreases, indicating successful construction of the dynamic cross-linked network in the resin. However, the resin cured product C of comparative example 3 4 The curing time required for (2) was as long as 4 hours, whereas the curing time step S3 of example 1 was only 20 minutes, plus the pre-curing of step S1 was also much less than 4 hours.
In addition, C 2 After the same time of heating, the repair efficiency of the scratch is about 40 percent and is lower than C 1 The repair efficiency of (about 70%) is due to C 2 The reaction time in the synthesis process of the step 1 is too long, and the resin A 2 The tertiary amine has a network structure, the tertiary amine obtained by the subsequent reaction of dicyandiamide and epoxy groups has larger steric hindrance with ester bonds, and the transesterification reaction is difficult to catalyze. And C is 3 Even after heating, the scratch width did not change, indicating that the resin did not have self-healing efficiency becauseAdipic acid and dicyandiamide are added in excess, and no reaction sites are used for dynamic bond exchange.
Resin B obtained by the above examples and homogeneously mixed with a curing agent 1 、B 4 The gel time was measured at 140 ℃. The results are shown in Table 1, B 1 Gel times far less than B 4 Indicating B 1 The reaction rate of (C) is obviously faster than that of B 4 The time required for complete curing is also less than B 4 Belongs to fast curing resin. But also in examples 2 to 4, the complete curing of the resin was completed within 30 minutes and the self-repairing ability was exhibited.
TABLE 1 gel time of resins at 140℃
| Resin composition | Gel time |
| B 1 | 4 minutes 53 seconds |
| B 4 | 42 minutes 2 seconds |
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (8)
1. A method for preparing a fast curing vitrimer resin, which is characterized by comprising the following steps: the method comprises the following steps:
step S1, mixing 10-100 parts of acid curing agent and 100 parts of epoxy resin, stirring and reacting for 20-180 minutes at 60-100 ℃, and cooling to room temperature to obtain pre-cured resin A with fluidity;
step S2, mixing 0.1-10 parts of amine curing agent, 0.1-10 parts of accelerator and 0.1-5 parts of polymerization inhibitor with the resin A, and stirring for 10-60 minutes at 20-60 ℃ to obtain resin B;
and S3, pouring the resin B into a mould, and curing for 10-30 minutes under the conditions of the pressure of 1-10MPa and the temperature of 120-160 ℃ to obtain a vitrimer resin cured product.
2. The method of preparing a fast curing vitrimer resin of claim 1, wherein: the epoxy resin is one or more than two of bisphenol A epoxy E20, E44, E51 and bisphenol F epoxy.
3. The method of preparing a fast curing vitrimer resin of claim 2, wherein: the acid curing agent is one or a mixture of more than two of methyl hexahydrophthalic anhydride, adipic acid, cyclopentanetetra acid dianhydride and diphenyl ether tetracarboxylic acid dianhydride.
4. A method of preparing a fast curing vitrimer resin of claim 3, wherein: the amine curing agent is one or a mixture of more than two of dicyandiamide, xylylenediamine, ethylenediamine and m-phenylenediamine.
5. The method of preparing a fast curing vitrimer resin of claim 4, wherein: the promoter is one or more of triethylamine, benzyl dimethylamine, N- (2-hydroxy-4-nitrobenzene) -N ', N' -dimethyl urea, N- (2-hydroxyphenyl) -N ', N' -dimethyl urea, resorcinol and 2-methylimidazole.
6. The method of preparing a fast curing vitrimer resin of claim 5, wherein: the polymerization inhibitor is one or more than two of hydroquinone, p-benzoquinone and p-hydroxyanisole.
7. The method for preparing a fast curing vitrimer resin according to any one of claims 1 to 6, wherein: the viscosity of the resin A is less than 10000 mPa.s at 70 ℃.
8. A fast curing vitrimer resin, characterized by: a method of preparing a fast curing vitrimer resin of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311720281.3A CN117843922A (en) | 2023-12-14 | 2023-12-14 | Rapidly-cured vitrimer resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311720281.3A CN117843922A (en) | 2023-12-14 | 2023-12-14 | Rapidly-cured vitrimer resin and preparation method thereof |
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| Publication Number | Publication Date |
|---|---|
| CN117843922A true CN117843922A (en) | 2024-04-09 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311720281.3A Pending CN117843922A (en) | 2023-12-14 | 2023-12-14 | Rapidly-cured vitrimer resin and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117843922A (en) |
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2023
- 2023-12-14 CN CN202311720281.3A patent/CN117843922A/en active Pending
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