CN113372277A - Epoxy resin latent curing agent and preparation method thereof - Google Patents
Epoxy resin latent curing agent and preparation method thereof Download PDFInfo
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- CN113372277A CN113372277A CN202110636904.3A CN202110636904A CN113372277A CN 113372277 A CN113372277 A CN 113372277A CN 202110636904 A CN202110636904 A CN 202110636904A CN 113372277 A CN113372277 A CN 113372277A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 58
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 58
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title abstract description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 74
- -1 imidazole compound Chemical class 0.000 claims abstract description 18
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 11
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 125000002883 imidazolyl group Chemical group 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 150000002460 imidazoles Chemical class 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000003746 solid phase reaction Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 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 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 150000007519 polyprotic acids Polymers 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 5
- 239000011347 resin Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004132 cross linking Methods 0.000 abstract description 3
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000003860 storage Methods 0.000 description 5
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 4
- YDSWCNNOKPMOTP-UHFFFAOYSA-N mellitic acid Chemical compound OC(=O)C1=C(C(O)=O)C(C(O)=O)=C(C(O)=O)C(C(O)=O)=C1C(O)=O YDSWCNNOKPMOTP-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 description 3
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 description 1
- PQAMFDRRWURCFQ-UHFFFAOYSA-N 2-ethyl-1h-imidazole Chemical compound CCC1=NC=CN1 PQAMFDRRWURCFQ-UHFFFAOYSA-N 0.000 description 1
- LYWVNPSVLAFTFX-UHFFFAOYSA-N 4-methylbenzenesulfonate;morpholin-4-ium Chemical compound C1COCCN1.CC1=CC=C(S(O)(=O)=O)C=C1 LYWVNPSVLAFTFX-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- 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
- C08G59/5046—Amines heterocyclic
- C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
- C08G59/5073—Amines heterocyclic containing only nitrogen as a heteroatom having two nitrogen atoms in the ring
Abstract
The invention discloses an epoxy resin latent curing agent and a preparation method thereof. The invention takes polybasic carboxylic acid containing benzene ring and imidazole compound as raw materials to form carboxylic acid imidazole salt structure at a certain temperature. As a latent curing agent, the epoxy resin can initiate ring-opening polymerization at medium temperature, and has good thermal reaction activity and latent heat performance. The cross-linking density of the resin can be improved and the resin performance can be enhanced by introducing alkyl and benzene ring groups, and the epoxy resin has wide research potential and application background in an epoxy resin system.
Description
Technical Field
The invention relates to the field of epoxy resin curing agents, in particular to an epoxy resin latent curing agent and a preparation method thereof.
Background
Epoxy resins are a class of thermosetting resins that are widely used in composite board, aerospace, building processing and electronics, and are commonly made into adhesives, coatings and fiber-based composites. However, the epoxy resin belongs to thermoplastic materials, has no practical value, and can be used only by being crosslinked with polyamine curing agents, acid anhydrides curing agents and tertiary amine curing agents. Once the curing agent is mixed with the resin, the curing agent must be used in a short time, otherwise the curing agent cannot be used after gelation, waste and pollution are caused, and the efficiency is low because each batching process is complicated. To solve this problem, latent curing agents are introduced into epoxy resin systems:
namely, after the epoxy resin is mixed, the epoxy resin does not react at room temperature, and can generate crosslinking reaction at a certain temperature or other external conditions.
The existing latent curing agents include dicyandiamide and modified dicyandiamide, hydrazide, boramine and the like. Among these curing agents: dicyandiamide, the energy consumption is too large; boron amine has poor electrical property, and has respective advantages and disadvantages.
Imidazole curing agents are commonly used as curing agents for epoxy resins, and can be used in small amounts to react at relatively low temperatures and relatively fast rates, and also as accelerators for other epoxy resin curing agents such as anhydrides, dicyandiamide, and the like. However, the single-component system of imidazole and epoxy resin has low bonding strength, low curing temperature and short storage period, and the related application of imidazole and epoxy resin in the epoxy resin system is limited. Therefore, the limitation or blocking of the imidazole reactivity under normal temperature conditions is often achieved by various methods, such as modification, encapsulation, and the like.
Imidazole compounds are modified by a variety of methods, and commonly used modifying compounds include halides, unsaturated double bond compounds, alcohols, epoxides, aldehydes or ketones, carboxylic acids, carboxylic esters, metal salts, and the like. The producer can select proper compound according to different purposes of the epoxy resin to obtain the corresponding modified imidazole compound.
In the process of generating carboxylic acid imidazolium salt by carboxylic acid and imidazole, the carboxylic acid can block the reactivity of N at the third position of imidazole, so that the reaction temperature of epoxy resin and imidazole is increased, and the service life of imidazole is prolonged. Meanwhile, the carboxylic acid and the epoxy resin can participate in the reaction and participate in the epoxy resin cross-linked network, so that the stability of an epoxy resin curing system is not influenced. However, in the process of modifying imidazole to reduce its reactivity, organic reagents are generally selected as solvents, which often causes great pollution.
Therefore, the technical problem to be solved by the technical personnel in the field is to provide the imidazole group-containing epoxy resin latent curing agent prepared by a solid-phase synthesis method.
Disclosure of Invention
In view of the above, the invention provides an epoxy resin latent curing agent and a green preparation method thereof, and the preparation method is simple and pollution-free and does not select any organic solvent. Meanwhile, the epoxy resin latent curing agent prepared by the invention is easy to disperse, has excellent storage stability, can be rapidly cured at medium temperature, and can be widely popularized and used in the existing epoxy resin curing system.
In order to achieve the purpose, the invention adopts the following technical scheme:
the epoxy resin latent curing agent comprises an imidazole compound and polycarboxylic acid, wherein the mass ratio of the imidazole compound to the polycarboxylic acid is 0.15-0.60: 1.
Further, the azole compound is an imidazole compound containing active N-H bonds.
Further, the imidazole compound containing active N-H bonds has the following structure:
wherein R1 is any one of a hydrogen proton, a saturated alkyl group and a phenyl group, and R2 is any one of a hydrogen proton, a saturated alkyl group and a phenyl group.
The imidazole compound is preferably imidazole, 2-methylimidazole and 2-ethylimidazole.
The beneficial effect of adopting the further scheme is that: the imidazole compound adopted by the invention has good reaction with carboxylic acid.
Further the polycarboxylic acid contains at least three carboxyl groups.
Further, the polybasic acid is an organic acid having a benzene ring group.
The polycarboxylic acid is preferably trimesic acid, pyromellitic acid, mellitic acid.
The beneficial effect of adopting the further scheme is that: the carboxylic acid has symmetrical and stable structure and is easy to dissolve and form salt.
Furthermore, the position N3 of the imidazole ring in the imidazole compound is connected with polybasic acid.
The beneficial effect of adopting the further scheme is that: imidazole activity is well inhibited.
The invention also provides a preparation method of the epoxy resin latent curing agent containing the imidazole group, which comprises the following steps:
(1) weighing the raw materials according to the mass ratio;
(2) mixing imidazole compounds and polycarboxylic acid uniformly, and putting the mixture into a ball mill for ball milling to obtain powder;
(3) cooling the powder to room temperature, taking out the powder, stirring, and then putting the powder into an oven for constant-temperature solid-phase reaction;
(4) and taking out the reaction product, cooling to room temperature, grinding in a grinder, and stirring to obtain the epoxy resin latent curing agent containing imidazole groups.
Further, the ball milling rotation speed in the step (2) is 3000-4500r/min, and the ball milling time is 2-4 h.
Further, in the step (3), the stirring speed is 50-120r/min, and the stirring time is 0.5-1 h.
Furthermore, the solid phase reaction temperature in the step (3) is 90-190 ℃, and the reaction time is 2-10 h.
The beneficial effect of adopting the further scheme is that: ensuring sufficient reaction time.
Further, the grinding rotation speed in the step (4) is 1500-; the stirring speed is 50-120r/min, and the stirring time is 0.5-0.75 h.
The beneficial effect of adopting the further scheme is that: the agglomerated portion of the reaction product is redispersed.
The invention has the beneficial effects that:
1. the invention provides a green and environment-friendly preparation reaction method of a latent curing agent containing imidazole groups, which is a solid-phase reaction method, and can select various carboxylic acids to modify imidazole compounds, in particular to reaction modification of polycarboxylic acid containing benzene rings on 2-methylimidazole.
2. The synthetic method has the advantages of simple process, easy realization of conditions, environmental friendliness and environmental protection. Most importantly, no by-products such as waste liquid and the like are generated in the preparation process, waste liquid treatment is not needed, and the cost is low.
3. The addition of the polycarboxylic acid containing benzene rings effectively reduces the reaction activity of the imidazole curing agent and improves the storage capacity. Meanwhile, the addition of benzene ring and carboxyl structure improves the crosslinking density and modulus of the resin.
4. After the imidazole is modified, the normal temperature stability of an epoxy resin curing system is greatly improved, so that the epoxy resin mixed material has wider use scenes and more convenient transportation and storage conditions.
Drawings
FIG. 1 is a DSC curve of curing agent A versus epoxy resin in example 1 of the present invention;
FIG. 2 is a DSC curve of curing agent B against epoxy resin in example 2 of the present invention;
FIG. 3 is a DSC curve of curing agent C versus epoxy resin in example 3 of the present invention;
FIG. 4 is a graph showing the results of an infrared test of curing agent B in example 2 of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Weighing 21.2g of 1,3, 5-benzene tricarboxylic acid and 41.0g of dimethyl imidazole;
(2) mixing imidazole compounds and polycarboxylic acid uniformly, and putting the mixture into a ball mill for ball milling for 2 hours at 3000r/min to obtain powder;
(3) cooling the powder to room temperature, taking out the powder at 50r/min, stirring for 0.5h, and then putting the powder into an oven for solid-phase reaction at the constant temperature of 90 ℃ for 2 h;
(4) taking out the reaction product, cooling, putting the reaction product into a grinder, grinding for 1h at 4000r/min, and then stirring for 0.75h at 50r/min to obtain the epoxy resin latent curing agent (number: A) containing imidazole groups;
(5) 14g of the modified imidazole curing agent is added into 80gE-51 type epoxy resin at 40 ℃ and uniformly mixed to obtain a latent medium-temperature epoxy resin system A, and DSC is carried out at a heating rate of 10K/min, and the result is shown in figure 1.
Example 2
(1) Weighing 25.4g of 1,2,4, 5-benzenetetracarboxylic acid and 82g of dimethyl imidazole;
(2) uniformly stirring and mixing the imidazole compound and the polycarboxylic acid, and putting the mixture into a ball mill for ball milling for 2 hours at 3500r/min to obtain powder;
(3) cooling the powder to room temperature, taking out the powder, stirring for 0.5h at 120r/min, and then putting the powder into an oven for constant-temperature solid-phase reaction at 160 ℃ for 2 h;
(4) taking out the reaction product, cooling, putting the reaction product into a grinding machine, grinding for 2h at 3500r/min, and stirring for 0.5h at 120r/min to obtain the epoxy resin latent curing agent (number: B) containing imidazole groups;
(5) 10g of the modified imidazole curing agent is added into 100g of E-51 type epoxy resin at 60 ℃ and uniformly mixed to obtain a latent medium-temperature epoxy resin system B, and DSC tests at a heating rate of 10K/min to obtain the result shown in 2.
Example 3
(1) Weighing 34.2g of mellitic acid and 61.5g of dimethyl imidazole;
(2) mixing imidazole compounds and polycarboxylic acid uniformly, and putting the mixture into a ball mill for ball milling for 4 hours at 4500r/min to obtain powder;
(3) cooling the powder to room temperature, taking out the powder at 80r/min, stirring for 0.1h, and then putting the powder into an oven for solid-phase reaction at the constant temperature of 190 ℃ for 10 h;
(4) taking out the reaction product, cooling, grinding for 1.5h at 3000r/min in a grinder, and stirring for 0.5h at 80r/min to obtain the epoxy resin latent curing agent (number: C) containing imidazole groups;
(5) 22g of the modified imidazole curing agent is added into 80gE-51 type epoxy resin at 60 ℃ and uniformly mixed to obtain a latent medium-temperature epoxy resin system C, and DSC tests are carried out at a heating rate of 10K/min, and the result is shown in figure 3.
Example 4
Qualitative test of latent curing agent containing imidazole group
The powdery modified imidazole curing agent (No. B) obtained in example 2 was subjected to an infrared test, and the result is shown in FIG. 4 at 1428cm-1And 1621cm-1The presence of characteristic peaks ascribed to imidazole carboxylate, respectively ascribed to stretching vibration of-COO-and-NH+The deformation shock absorption peak of C confirmed that the obtained product was a reaction product of carboxylic acid and imidazole.
Example 5
And (3) testing the stability of the latent curing agent containing the imidazole group.
Firstly, the latent intermediate-temperature epoxy resin curing system of the embodiment 2 is subjected to gelation time measurement at different temperatures;
setting constant temperature spaces with different temperatures, putting the latent medium-temperature epoxy resin curing system B and the pure imidazole epoxy resin curing epoxy resin system into the constant temperature spaces, and determining that the activity of the carboxylic acid modified imidazole is far lower than that of the pure imidazole and the storage stability is obviously improved according to the comparison result of the gel time shown in table 1.
TABLE 1
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The epoxy resin latent curing agent is characterized by comprising an imidazole compound and polycarboxylic acid, wherein the mass ratio of the imidazole compound to the polycarboxylic acid is 0.15-0.60: 1.
2. The latent epoxy resin curing agent according to claim 1, wherein the azole compound is an imidazole compound having an active N-H bond.
3. The latent epoxy resin curing agent of claim 2, wherein the imidazole-based compound having an active N-H bond has the following structure:
wherein R1 is any one of a hydrogen proton, a saturated alkyl group and a phenyl group, and R2 is any one of a hydrogen proton, a saturated alkyl group and a phenyl group.
4. The latent curing agent for epoxy resins according to claim 1, wherein the polycarboxylic acid contains at least three carboxyl groups.
5. The latent curing agent for epoxy resins according to claim 4, wherein the polybasic acid is an organic acid containing a benzene ring group.
6. The method for preparing the latent curing agent for epoxy resin according to claim 1, comprising the steps of:
(1) weighing the raw materials according to the mass ratio of any one of claims 1 to 5;
(2) mixing imidazole compounds and polycarboxylic acid uniformly, and putting the mixture into a ball mill for ball milling to obtain powder;
(3) cooling the powder to room temperature, taking out the powder, stirring, and then putting the powder into an oven for constant-temperature solid-phase reaction;
(4) and taking out the reaction product, cooling to room temperature, grinding in a grinder, and stirring to obtain the epoxy resin latent curing agent containing imidazole groups.
7. The method for preparing the latent epoxy resin curing agent as claimed in claim 6, wherein the ball milling speed in step (2) is 3000-4500r/min, and the ball milling time is 2-4 h.
8. The method for preparing a latent curing agent for epoxy resin according to claim 6, wherein the stirring speed in the step (3) is 50 to 120r/min, and the stirring time is 0.5 to 1 hour.
9. The method for preparing a latent curing agent for epoxy resin according to claim 6, wherein the solid phase reaction temperature in the step (3) is 90-190 ℃ and the reaction time is 2-10 hours.
10. The method for preparing the latent curing agent according to claim 6, wherein the grinding speed in step (4) is 1500-; the stirring speed is 50-120r/min, and the stirring time is 0.5-0.75 h.
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| CN114409874A (en) * | 2022-01-19 | 2022-04-29 | 浙江博菲电气股份有限公司 | Epoxy resin curing agent and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114409874A (en) * | 2022-01-19 | 2022-04-29 | 浙江博菲电气股份有限公司 | Epoxy resin curing agent and preparation method thereof |
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