CN112745501A - Dendritic toughening curing agent, and preparation method and application thereof - Google Patents
Dendritic toughening curing agent, and preparation method and application thereof Download PDFInfo
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- CN112745501A CN112745501A CN202011601048.XA CN202011601048A CN112745501A CN 112745501 A CN112745501 A CN 112745501A CN 202011601048 A CN202011601048 A CN 202011601048A CN 112745501 A CN112745501 A CN 112745501A
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- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 3
- DGUJJOYLOCXENZ-UHFFFAOYSA-N 4-[2-[4-(oxiran-2-ylmethoxy)phenyl]propan-2-yl]phenol Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C1=CC=C(O)C=C1 DGUJJOYLOCXENZ-UHFFFAOYSA-N 0.000 claims description 3
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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
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
- C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
-
- 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
Abstract
The invention discloses a dendritic toughening curing agent, a preparation method and application thereof, and belongs to the field of curing agents. The technical scheme comprises the step of reacting an epoxy-terminated monomer containing a flexible long chain with a polyethylene polyamine monomer at a certain temperature to generate the dendritic toughening curing agent with an amino-terminated group. The invention is applied to the aspect of curing and toughening of epoxy resin, solves the problems that the existing epoxy resin curing agent can not have dual performances of toughening and curing and has a complex preparation method, has excellent curing performance, can also obviously improve the toughness of the resin, and has the characteristics of simple preparation method and easy realization of industrial production.
Description
Technical Field
The invention belongs to the field of curing agents, and particularly relates to a dendritic toughening curing agent, and a preparation method and application thereof.
Background
As a common matrix resin material, the epoxy resin has the characteristics of strong adhesive force, excellent electrical insulation performance, easiness in processing and forming, good filler combination performance, excellent wear resistance and the like, and is widely applied to the fields of chemical industry, aerospace, medicine, environmental protection and the like. However, the epoxy resin forms a highly crosslinked three-dimensional network structure after being cured, which is characterized by high brittleness, poor impact resistance and insufficient crack expansion resistance, so the epoxy resin is particularly important for toughening in the curing process. The common methods for toughening epoxy resin include: compounding with rubber elastomer, thermoplastic resin, thermotropic liquid crystal polymer and other material with excellent toughness to toughen the second phase; forming a composite material with a semi-penetrating or interpenetrating network structure; and a flexible chain segment is introduced, so that the flexibility of a molecular chain is improved, and the crosslinking density is reduced. However, the curing agent for epoxy resin has not yet been commercialized, which has a toughening effect during the curing process.
Chinese patent CN105131287A discloses a method for synthesizing an amino-terminated epoxy resin toughening type curing agent, which comprises the following steps: adding 2 moles of aromatic diamine containing ether bonds into a three-neck flask, introducing nitrogen into an organic solvent, and stirring at normal temperature until the aromatic diamine is completely dissolved; then adding 1 mol of aromatic dianhydride, controlling the temperature at 30 ℃, and stirring for 5 hours to obtain light yellow transparent liquid; dripping into deionized water, stirring to obtain a white turbid suspension, washing, and performing suction filtration to obtain a white filter cake, namely the terminal amino epoxy resin curing agent. According to the invention, aromatic diamine containing ether bonds and aromatic dianhydride are synthesized into terminal amino polyamic acid in a molar ratio of 2:1, and the amino group of the terminal amino polyamic acid can perform prepolymerization reaction with an epoxy group of epoxy resin to introduce the polyamic acid into a molecular structure of the epoxy resin, so that the toughening effect is achieved, and the impact strength is improved by 20%.
However, the amine-terminated epoxy resin toughening curing agent obtained in the above patent mainly depends on a flexible ether bond, and the polyamic acid is introduced into an epoxy system through the reaction of the amine-terminated group in the polyamic acid and epoxy, so that the curing and toughening effects are not good, the preparation method is solution polymerization, reagents such as a solvent, nitrogen, deionized water and the like are required in the reaction and post-treatment processes, and the post-treatment process requires washing and drying, and the process is complex and the post-treatment process is troublesome.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to solve the technical problems that the existing epoxy resin curing agent cannot have dual performances of toughening and curing and the preparation method is complex, and provides a dendritic toughening curing agent which has excellent curing performance, can obviously improve the toughness of resin, is simple in preparation method and is easy to realize industrial production, and a preparation method and application thereof.
In order to solve the technical problem, the technical scheme adopted by the invention is as follows:
in one aspect, the invention provides a method for preparing a dendritic toughening curing agent, which comprises the following steps
The flexible long-chain-containing epoxy-terminated monomer reacts with the polyethylene polyamine monomer at a certain temperature to generate the amine-terminated dendritic toughening curing agent.
Preferably, the molar ratio of the flexible long-chain-containing end epoxy group monomer to the polyvinyl polyamine monomer is 1:1-1: 4.
Preferably, the epoxy-terminated monomer containing the flexible long chain reacts with the polyethylene polyamine monomer at a certain temperature, wherein the reaction temperature is 25-100 ℃.
Preferably, the terminal epoxy group monomer containing the flexible long chain is a glycidyl ether monomer.
Preferably, the glycidyl ether monomer is at least one selected from the group consisting of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol a glycidyl ether, glycerol triglycidyl ether, propoxyglycerol triglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol glycidyl ether.
Preferably, the ethylene polyamine monomer is at least one selected from ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine.
On the other hand, the invention provides the dendritic toughening curing agent prepared by the preparation method of the dendritic toughening curing agent in any technical scheme.
Preferably, the dendritic toughening curing agent has a terminal amino group and a flexible long chain segment structure; the terminal amine group comprises at least one of primary amine and secondary amine; the flexible long chain segment comprises an ether structure.
The invention also provides application of the dendritic toughening curing agent in any technical scheme in epoxy resin.
Preferably, the addition mass ratio of the dendritic toughening curing agent to the epoxy resin is 1:10-6: 10.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a dendritic toughening curing agent, which has the characteristics of simple process and capability of realizing industrial production; the dendritic toughening curing agent prepared by the preparation method has the advantages that the flexible long chain segment is introduced into the flexible chain segment, the flexible chain segment also comprises an ether structure, after the flexible chain segment is introduced into the epoxy resin chain segment, the flexible chain segment can reduce stress concentration and prevent crack expansion, so that the toughening effect is achieved, meanwhile, the curing effect is achieved, the product does not contain primary amine and tertiary amine or secondary amine, the curing or curing promoting effect can be achieved in the epoxy curing process, the polyamine and the epoxy group caused by the dendritic structure react, the curing reaction sites are more, the cross-linking structure is improved to a certain extent, and the curing effect is better; the dendritic toughening curing agent is used for the epoxy resin toughening curing agent, can obviously improve the toughening and curing performance of the epoxy resin, and does not reduce other performances of the epoxy resin.
Drawings
FIG. 1 is a schematic diagram of the reaction of an epoxy-terminated monomer containing a flexible long chain and a polyethylene polyamine monomer according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be fully described in detail below. It is obvious that the described embodiments are only some specific embodiments, not all embodiments, of the general technical solution of the present invention. All other embodiments, which can be derived by a person skilled in the art from the general idea of the invention, fall within the scope of protection of the invention.
The invention provides a preparation method of a dendritic toughening curing agent, which comprises the step of reacting an epoxy-terminated monomer containing a flexible long chain with a polyethylene polyamine monomer at a certain temperature to generate the dendritic toughening curing agent containing an amine-terminated group. As shown in FIG. 1, the epoxy group in the glycidyl ether directly reacts with the amino group in the polyethylene polyamine monomer, and the epoxy group opens a ring. The preparation method is simple and is beneficial to realizing industrial production.
In a preferred embodiment, the molar ratio of the flexible long-chain-containing end epoxy group monomer to the polyvinyl polyamine-based monomer is 1:1 to 1: 4. This example defines the molar ratio of the terminal epoxy group monomer containing the flexible long chain to the said polyethylene polyamine monomer, it being understood that the molar ratio may also be 1:2, 1:3 and any point within the range, so defining a molar ratio of the two, since the amount of polyethylene polyamine is greater, since it is ensured that the product synthesized is terminal amine groups. The molar ratio of the flexible long-chain-containing terminal epoxy group monomer to the polyethylene polyamine-based monomer is actually the molar ratio of the epoxy group in the flexible long-chain-containing terminal epoxy group monomer to the polyethylene polyamine-based monomer.
In a preferred embodiment, the epoxy-terminated monomer containing the flexible long chain is reacted with the polyethylene polyamine monomer at a temperature of 25-100 ℃. This example specifically defines the reaction temperature, and it is understood that the reaction temperature may also be 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃ and any value within the range thereof.
In a preferred embodiment, the terminal epoxy group monomer containing a flexible long chain is a glycidyl ether monomer. Specifically, the glycidyl ether monomer is at least one selected from ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol a glycidyl ether, glycerol triglycidyl ether, propoxyglycerol triglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, and sorbitol glycidyl ether. This example specifically defines the kind of glycidyl ether monomer, and it is understood that the glycidyl ether monomer may be other substances reasonably selected in the art by those skilled in the art in combination with common general knowledge in the art.
In a preferred embodiment, the ethylene polyamine monomer is selected from at least one of ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine. This example defines the type of ethylene polyamine monomer in particular, it being understood that it may also be other materials reasonably selected in the art by a person skilled in the art in combination with the general knowledge in the art.
On the other hand, the invention provides the dendritic toughening curing agent prepared by the preparation method of the dendritic toughening curing agent in any technical scheme. Specifically, the dendritic toughening curing agent has a terminal amino group and a flexible long chain segment structure; the terminal amine group comprises at least one of primary amine and secondary amine; the flexible long chain segment comprises an ether structure. Flexible long chain segment has been introduced in this dendritic toughening curing agent, the ether structure has been included again in the flexible chain segment, back in the epoxy resin chain segment was introduced to the flexible chain segment, the flexible chain segment can reduce stress concentration, prevent the extension of crack, thereby reach the effect of toughening, the solidification effect has simultaneously, it has primary amine not bare in the product, secondary amine in addition, can both play the effect of solidification or promotion solidification in the epoxy curing process, and the polyamine that dendritic structure brought and the reaction of epoxy group, the solidification reaction site is more, improve crosslinked structure to a certain extent, thereby the curing effect is better.
The invention also provides application of the dendritic toughening curing agent in any technical scheme in epoxy resin. The dendritic toughening curing agent is used for the epoxy resin curing toughening agent, so that the toughening and curing properties of the epoxy resin can be obviously improved, and other properties of the epoxy resin are not reduced. Specifically, the dendritic toughening curing agent can reduce the viscosity of the epoxy resin, is convenient to process, reduces the cost, improves the tensile shear strength and the adhesive force, and is light in color, so that the color of a product after the resin is cured is basically not influenced. It should be noted that, the conventional curing agent can only cure the epoxy resin, and the toughening agent needs to be added additionally for toughening. Specifically, the conventional curing agent can only cure the epoxy resin simply, and a toughening agent is required to be added for toughening. Early studies have improved the toughness of epoxy resins by reducing their crosslink density by adding non-stoichiometric hardeners, using epoxy resins of different relative molecular masses, incomplete curing, etc., but this approach severely affects the tensile and flexural strength of the epoxy resin. At present, in order to achieve the purpose of toughening, liquid rubber, thermoplastic plastics, nano materials, shell-core structure polymer particles, liquid crystal polymers, block copolymer micelles and other hard particles are mostly added into epoxy resin in the industry as a second phase, so that although the toughness and the modulus of the epoxy resin are improved, the glass transition temperature and the thermal stability of the epoxy resin are influenced, and the processing performance is influenced due to the increase of the viscosity of the epoxy resin.
When the dendritic toughening curing agent is applied to epoxy resin, the aim of curing and toughening the epoxy resin can be achieved by only adding the dendritic toughening curing agent, and meanwhile, the toughening curing agent with other performances is not reduced, so that the dendritic toughening curing agent has important significance. The flexibility of the polymer chain segment is mainly based on the long chain structure and the free rotation property of each chain in the chain, the flexible chain segment is combined with the epoxy resin through the bonding effect, a microphase separation structure is generated in the curing process, a dense and loose alternate network structure is generated, and the stress is dispersed, so that the toughening effect is achieved. Dendritic polymers also differ greatly in structure from linear polymers. The linear polymer has most linear parts, few branch points, easily entangled molecular chains and rapidly increased viscosity with the increase of relative molecular mass. The dendritic polymer molecules have a compact structure similar to a sphere, a plurality of branch points, small hydrodynamic radius of gyration and less molecular chain entanglement, so that the influence on viscosity caused by the increase of relative molecular mass is small, and the molecules are provided with a plurality of functional end groups, and the compatibility of the molecules in various systems can be improved or functional materials can be obtained by modifying the molecules. The structural characteristics of the dendritic polymer make it very promising for improving the physical properties of the blend, such as flowability, processability, crystallization behavior, mechanical properties, etc. The dendritic polymer is added with a flexible chain segment, and the end group is modified into an amino-terminated group, and the curing performance is achieved. The dendritic epoxy curing agent is added into the epoxy resin, so that the free volume of the material is increased, the motion capability of a chain segment is improved, and the approximately circular structure of the dendritic epoxy curing agent can absorb impact energy from all directions; a toughening mechanism similar to rubber exists in the system, so that the cured resin generates a strong stress field and a shear band, and can generate shear yield and passivate cracks more quickly when being stretched or impacted; the cross-linking density around the uniformly dispersed dendritic curing agent particles is higher than that around other regions, and the cross-linking network has certain pressure on the particles, so that the yield of the material is promoted, and the toughness is improved.
In a preferred embodiment, the addition mass ratio of the dendritic toughening curing agent to the epoxy resin is 1:10-6: 10. This example specifically defines the addition ratio of the dendritic toughening curing agent to the epoxy resin, it being understood that the ratio may also be 2:10, 3:10, 4:10, 5:10, and any point ratio within the range thereof.
In order to more clearly and specifically describe the preparation method and the application of the dendritic epoxy toughening curing agent provided by the embodiment of the present invention, the following description will be made with reference to specific embodiments.
Example 1
Dropwise adding ethylene glycol diglycidyl ether into diethylenetriamine, feeding according to the molar ratio of the number of epoxy groups to the diethylenetriamine of 1:1, and reacting for 5 hours at 40 ℃ to obtain the terminal amino dendritic toughening curing agent 1.
And (3) blending the dendritic toughening curing agent 1 with epoxy resin, curing for 2h at 60 ℃, and testing the application performance of the dendritic toughening curing agent.
Example 2
And (3) dropwise adding polyethylene glycol diglycidyl ether into triethylene tetramine, feeding according to the molar ratio of the number of epoxy groups to the triethylene tetramine of 1:1.5, and reacting for 8 hours at the temperature of 60 ℃ to obtain the terminal amino dendritic toughening curing agent 2.
And (3) blending the dendritic toughening curing agent 2 with epoxy resin, curing for 2h at 60 ℃, and testing the application performance of the mixture.
Example 3
And (2) dropwise adding the castor oil triglycidyl ether into tetraethylenepentamine, feeding according to the molar ratio of 1:3 of the number of epoxy groups to the tetraethylenepentamine, and reacting for 5 hours at 40 ℃ to obtain the amino-terminated dendritic toughening curing agent 3.
And (3) blending the dendritic toughening curing agent 3 with epoxy resin, curing for 2h at 60 ℃, and testing the application performance of the mixture.
Example 4
And (2) dropwise adding trimethylolpropane triglycidyl ether into diethylenetriamine, feeding according to the molar ratio of the number of epoxy groups to the diethylenetriamine of 1:3.5, and reacting for 5 hours at 50 ℃ to obtain the amino-terminated dendritic toughening curing agent 4.
And (3) blending the dendritic toughening curing agent 4 with epoxy resin, curing for 2h at 60 ℃, and testing the application performance of the mixture.
Example 5
And (3) dripping pentaerythritol tetraglycidyl ether into triethylene tetramine, feeding according to the molar ratio of the number of epoxy groups to the triethylene tetramine of 1:4, and reacting for 2 hours at 100 ℃ to obtain the terminal amino dendritic toughening curing agent 5.
And (3) blending the dendritic toughening curing agent 5 with epoxy resin, curing for 2h at 60 ℃, and testing the application performance of the mixture.
Performance testing
After the dendritic toughening curing agent prepared in the embodiment 1 and the embodiment 2 is blended with epoxy resin, the tensile shear strength, impact property, hardness and adhesion force of the cured epoxy resin are tested on a steel plate and a PC plate, wherein the curing temperature on the steel plate and the PC plate is 60 ℃. The results are shown in Table 1.
TABLE 1 Performance testing of dendritic toughening hardeners
The dendritic toughening curing agents obtained in examples 1 to 5 were blended with epoxy resin, and a commercially available toughening curing agent, a commercially available curing agent and epoxy resin, and performance tests were performed as shown in table 2.
TABLE 2 Performance testing after blending with epoxy resins
As shown in table 2, after the epoxy resin is cured by the dendritic toughening curing agent, compared with the commercially available toughening curing agent, the tensile strength and the adhesive force of the material can be obviously improved, and the better curing can be realized through the hardness, and meanwhile, the dendritic toughening curing agent has higher impact property, namely toughness, and has the functions of curing and toughening, and the addition amount is less than that of the conventional curing agent. Meanwhile, the performance of the dendritic toughening curing agent is better than that of a conventional curing agent sold in the market.
Claims (10)
1. A preparation method of a dendritic toughening curing agent is characterized by comprising
The flexible long-chain-containing epoxy-terminated monomer reacts with the polyethylene polyamine monomer at a certain temperature to generate the amine-terminated dendritic toughening curing agent.
2. The preparation method of the dendritic toughening curing agent according to claim 1, wherein the molar ratio of the flexible long-chain-containing epoxy-terminated monomer to the polyvinyl polyamine-based monomer is 1:1-1: 4.
3. The preparation method of the dendritic toughening curing agent according to claim 1, wherein the epoxy-terminated monomer containing the flexible long chain is reacted with the polyethylene polyamine monomer at a temperature of 25-100 ℃.
4. The preparation method of the dendritic toughening curing agent according to claim 1, wherein the epoxy group-terminated monomer containing the flexible long chain is a glycidyl ether monomer.
5. The method of claim 4, wherein the glycidyl ether monomer is selected from the group consisting of ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 1, 2-cyclohexanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, flexible bisphenol A glycidyl ether, glycerol triglycidyl ether, propoxyglycerol triglycidyl ether, trimethylolpropane triglycidyl ether, castor oil triglycidyl ether, pentaerythritol tetraglycidyl ether, and mixtures thereof, At least one of sorbitol glycidyl ethers.
6. The method for preparing a dendritic toughening curing agent according to claim 1, wherein the ethylene polyamine monomer is at least one selected from the group consisting of ethylenediamine, diethylenetriamine, triethylenetetramine and tetraethylenepentamine.
7. The dendritic toughening curing agent prepared by the preparation method of the dendritic toughening curing agent according to any one of claims 1 to 6.
8. The dendritic toughening curing agent of claim 7, wherein the dendritic toughening curing agent has a terminal amine group and a flexible long-chain segment structure; the terminal amine group comprises at least one of primary amine and secondary amine; the flexible long chain segment comprises an ether structure.
9. Use of a dendritic toughening curing agent according to any one of claims 7 to 8 in an epoxy resin.
10. The use according to claim 9, wherein the addition mass ratio of the dendritic toughening curing agent to the epoxy resin is 1:10 to 6: 10.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785870A (en) * | 2022-12-16 | 2023-03-14 | 威海晨源分子新材料有限公司 | Implanted tendon anchoring adhesive and preparation method thereof |
| CN116285811A (en) * | 2023-02-22 | 2023-06-23 | 威海光威复合材料股份有限公司 | Room-temperature curing epoxy adhesive for composite material and preparation method thereof |
| CN116515362A (en) * | 2023-03-25 | 2023-08-01 | 中电建十一局工程有限公司 | Repair material suitable for concrete surface turtle cracks and construction method thereof |
| CN116987365A (en) * | 2023-05-19 | 2023-11-03 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB961891A (en) * | 1962-01-25 | 1964-06-24 | Dow Chemical Co | Polyglycol epoxide-amine condensate |
| US3634327A (en) * | 1969-10-31 | 1972-01-11 | Dow Chemical Co | Process for preparing improved epoxy resin adhesives containing minor amount of a urethane modifier and a bisphenol type coupling agent |
| CN101624385A (en) * | 2009-06-23 | 2010-01-13 | 中国科学院广州化学研究所 | Non-ionic self-emulsifying aqueous epoxy hardener and preparation method and application thereof |
| CN103555091A (en) * | 2013-10-12 | 2014-02-05 | 山西凌云聚氨酯有限公司 | Epoxy resin modified VAE composite waterproof material and preparation method thereof |
| CN107353397A (en) * | 2017-07-27 | 2017-11-17 | 江苏丰彩新型建材有限公司 | A kind of graphene water-base epoxy high dispersive system and its synthetic method |
| CN107916086A (en) * | 2017-12-12 | 2018-04-17 | 山西省交通科学研究院 | A kind of toughening type aqueous epoxy resin systems and preparation method thereof |
| CN108084720A (en) * | 2017-12-12 | 2018-05-29 | 山西省交通科学研究院 | A kind of embedded antiskid water proof type mist sealing and preparation method thereof |
| CN110105546A (en) * | 2019-06-10 | 2019-08-09 | 威海晨源分子新材料有限公司 | Epoxy curing agent, preparation method and application |
| CN110746578A (en) * | 2019-10-21 | 2020-02-04 | 华南理工大学 | Water-based epoxy curing agent based on castor oil triglycidyl ether and preparation method thereof |
-
2020
- 2020-12-29 CN CN202011601048.XA patent/CN112745501A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB961891A (en) * | 1962-01-25 | 1964-06-24 | Dow Chemical Co | Polyglycol epoxide-amine condensate |
| US3634327A (en) * | 1969-10-31 | 1972-01-11 | Dow Chemical Co | Process for preparing improved epoxy resin adhesives containing minor amount of a urethane modifier and a bisphenol type coupling agent |
| CN101624385A (en) * | 2009-06-23 | 2010-01-13 | 中国科学院广州化学研究所 | Non-ionic self-emulsifying aqueous epoxy hardener and preparation method and application thereof |
| CN103555091A (en) * | 2013-10-12 | 2014-02-05 | 山西凌云聚氨酯有限公司 | Epoxy resin modified VAE composite waterproof material and preparation method thereof |
| CN107353397A (en) * | 2017-07-27 | 2017-11-17 | 江苏丰彩新型建材有限公司 | A kind of graphene water-base epoxy high dispersive system and its synthetic method |
| CN107916086A (en) * | 2017-12-12 | 2018-04-17 | 山西省交通科学研究院 | A kind of toughening type aqueous epoxy resin systems and preparation method thereof |
| CN108084720A (en) * | 2017-12-12 | 2018-05-29 | 山西省交通科学研究院 | A kind of embedded antiskid water proof type mist sealing and preparation method thereof |
| CN110105546A (en) * | 2019-06-10 | 2019-08-09 | 威海晨源分子新材料有限公司 | Epoxy curing agent, preparation method and application |
| CN110746578A (en) * | 2019-10-21 | 2020-02-04 | 华南理工大学 | Water-based epoxy curing agent based on castor oil triglycidyl ether and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115785870A (en) * | 2022-12-16 | 2023-03-14 | 威海晨源分子新材料有限公司 | Implanted tendon anchoring adhesive and preparation method thereof |
| CN116285811A (en) * | 2023-02-22 | 2023-06-23 | 威海光威复合材料股份有限公司 | Room-temperature curing epoxy adhesive for composite material and preparation method thereof |
| CN116515362A (en) * | 2023-03-25 | 2023-08-01 | 中电建十一局工程有限公司 | Repair material suitable for concrete surface turtle cracks and construction method thereof |
| CN116515362B (en) * | 2023-03-25 | 2024-04-05 | 中电建十一局工程有限公司 | Repair material suitable for concrete surface turtle cracks and construction method thereof |
| CN116987365A (en) * | 2023-05-19 | 2023-11-03 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
| CN116987365B (en) * | 2023-05-19 | 2024-04-30 | 广州聚佳新材料科技有限公司 | Low-temperature-resistant resin material and preparation process thereof |
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