CN116103003A - High-strength low-viscosity low-temperature moisture-cured two-component epoxy resin adhesive and preparation method and application thereof - Google Patents
High-strength low-viscosity low-temperature moisture-cured two-component epoxy resin adhesive and preparation method and application thereof Download PDFInfo
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- CN116103003A CN116103003A CN202211656438.6A CN202211656438A CN116103003A CN 116103003 A CN116103003 A CN 116103003A CN 202211656438 A CN202211656438 A CN 202211656438A CN 116103003 A CN116103003 A CN 116103003A
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 90
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 90
- 239000000853 adhesive Substances 0.000 title claims abstract description 66
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- 239000003085 diluting agent Substances 0.000 claims abstract description 37
- -1 modified alicyclic amine Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000007822 coupling agent Substances 0.000 claims abstract description 19
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims abstract description 17
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000008439 repair process Effects 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 239000004575 stone Substances 0.000 claims description 26
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 15
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 12
- 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 claims description 11
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 6
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 5
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 2
- 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 abstract description 6
- 238000001723 curing Methods 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 10
- GEQHKFFSPGPGLN-UHFFFAOYSA-N cyclohexane-1,3-diamine Chemical compound NC1CCCC(N)C1 GEQHKFFSPGPGLN-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 4
- 229920006335 epoxy glue Polymers 0.000 description 3
- 238000013035 low temperature curing Methods 0.000 description 3
- 239000012790 adhesive layer Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000013008 moisture curing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
-
- 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
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Epoxy Resins (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention discloses a high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive, and a preparation method and application thereof, wherein the adhesive comprises a component A and a component B, and the component A is prepared from the following raw materials: 50-65% of epoxy resin, 34-50% of diluent A and 1-3% of coupling agent; the raw materials of the component B are as follows: 35-45% of amine curing agent, 48-58% of modified alicyclic amine curing agent, 5-10% of auxiliary agent, the epoxy resin is a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, and the diluent A is trimethylolpropane triacrylate or a compound diluent containing the trimethylolpropane triacrylate. The double-component epoxy resin adhesive has the advantages of higher strength, lower viscosity, capability of realizing effective curing in a low-temperature and humid environment, and the like, is a novel epoxy resin repair adhesive with excellent performance, can be suitable for repair treatment in a low-temperature and humid environment, and has high use value and good application prospect.
Description
Technical Field
The invention relates to a high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive, and a preparation method and application thereof.
Background
In general, the water content of the stone itself is higher than 0.12%, and in particular, in special cases such as rainy days or underwater operations, the water content is higher than 0.12%, which makes the stone glue available on the market not applicable to the coating or repair reinforcement treatment of the stone. Based on this, the inventors of the present application have proposed a low viscosity, hydrophilically curable epoxy stone repair face adhesive, however, the following disadvantages are found to exist during its actual use: (1) The viscosity is still higher than 70 mPa.s/25 ℃, which is not beneficial to the glue solution to quickly permeate into micro cracks, oblique cracks or micro holes of the stone; (2) Curing is difficult to achieve at temperatures below 20 ℃ (particularly below 5 ℃); and (3) the tensile shear strength, the compressive shear strength and the Shore hardness are lower. Therefore, developing a high-strength, low-viscosity, low-temperature and moisture-cured bi-component epoxy resin stone repairing surface adhesive is very necessary, and has important significance for effective repairing of stone.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects of the prior art and providing a high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive as well as a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a high-strength, low-viscosity, low-temperature moisture-cured two-component epoxy resin adhesive comprises a component A and a component B;
the component A comprises the following raw material components in percentage by weight:
50 to 65 percent of epoxy resin,
34 to 50 percent of diluent A,
1-3% of coupling agent, wherein the sum of the weight percentages of the raw materials is 100%;
the component B comprises the following raw material components in percentage by weight:
35 to 45 percent of amine curing agent,
48 to 58 percent of modified alicyclic amine curing agent,
5-10% of auxiliary agent, wherein the sum of the weight percentages of the raw materials is 100%;
the epoxy resin is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin;
the diluent A is trimethylolpropane triacrylate, or the diluent A is a compound diluent containing trimethylolpropane triacrylate.
The double-component epoxy resin adhesive is further improved, and the mass ratio of the bisphenol A type epoxy resin to the bisphenol F type epoxy resin is 6-7:3-4.
The double-component epoxy resin adhesive is further improved, wherein the composite diluent comprises trimethylolpropane triacrylate and a diluent B, and the mass ratio of the trimethylolpropane triacrylate to the diluent B is 7-9:11-13; the diluent B is at least one of 1, 4-butanediol diglycidyl ether, benzyl alcohol, isobutanol and ethylene glycol diglycidyl ether.
The two-component epoxy resin adhesive is further improved, and the coupling agent is one of KH560 and KH570 or a mixture thereof.
The two-component epoxy resin adhesive is further improved, and the amine curing agent is one or a mixture of 1, 3-cyclohexanediamine, isophorone diamine and N-aminoethylpiperazine.
The bi-component epoxy resin adhesive is further improved, and the auxiliary agent is benzyl alcohol.
The two-component epoxy resin adhesive is further improved, and the modified alicyclic amine curing agent is prepared by the following method: adding alicyclic amine into a reactor, adjusting the temperature to be 32-38 ℃, dropwise adding 1, 4-butanediol diglycidyl ether, finishing dropwise adding in 2.5-4.0 hours, and continuously reacting for 2.5 hours at the temperature of 38-43 ℃ to obtain a modified alicyclic amine curing agent; the molar ratio of the alicyclic amine to the 1, 4-butanediol diglycidyl ether is 1:1.1-1.5.
The double-component epoxy resin adhesive is further improved, and the weight ratio of the component A to the component B is 1.93-2.07:1.
As a general technical conception, the invention also provides a preparation method of the double-component epoxy resin adhesive, which comprises the following steps:
s1, heating epoxy resin to 75-80 ℃, sequentially adding a diluent and a coupling agent, and stirring to obtain a component A; sequentially adding the modified alicyclic amine curing agent and the auxiliary agent into the amine curing agent, adjusting the temperature to 40-50 ℃, and stirring to obtain a component B;
s2, mixing the component A and the component B to obtain the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive.
The preparation method is further improved, and in the preparation process of the component A, the stirring time is 75-90 min.
The preparation method is further improved, and the stirring time is 75-90 min in the preparation process of the component B.
As a general technical conception, the invention also provides the application of the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive or the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive prepared by the preparation method in stone repairing.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects of relatively high viscosity, difficult low-temperature curing, low strength and the like in the existing double-component epoxy resin adhesive, the invention provides the double-component epoxy resin adhesive with high strength, low viscosity and low-temperature moisture curing, which comprises an A component and a B component, wherein in the A component, the adopted epoxy resin is a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, so that the constructed cured product is more compact, the strength of the repairing adhesive is improved, the adopted diluent A is trimethylolpropane triacrylate or a compound diluent containing the trimethylolpropane triacrylate, and more heat is released in the using process of the trimethylolpropane triacrylate, so that the system temperature can be raised to more than 20 ℃, the adhesive has a self-heating function, the curing can be realized under the moisture condition of lower temperature (such as 5 ℃ or 20 ℃), the performances of low-temperature curing and moisture curing are shown to be more excellent, the used coupling agent has the performance of reacting with trace water and can react with the surface and crack, and the phenomenon of poor curing or incomplete curing of the surface of the stone plate is eliminated; in the component B, the modified alicyclic amine curing agent and the auxiliary agent have amino, secondary amino and phenolic groups, so that the epoxy resin adhesive is better suitable for a wet and water-containing environment, can be used in the wet and water-containing environment, can transfer wet moisture to the surface of a resin system, cannot cause poor curing effect or difficult curing due to the fact that the stone surface is wet or has a small amount of moisture, has good yellowing resistance, and can prevent yellowing. On the basis, the use amount of each raw material in the A/B component is further optimized, so that the double-component epoxy resin adhesive has more excellent performance, such as higher strength, lower viscosity and capability of realizing effective curing in a low-temperature and humid environment, is a novel epoxy resin repairing adhesive with excellent performance, and can be widely used for repairing in the fields of stone and the like, and has high use value and good application prospect.
(2) In the invention, the mass ratio of bisphenol A epoxy resin to bisphenol F epoxy resin is optimized to be 6-7:3-4, so that the viscosity of the system can be reduced, and the comprehensive strength and the compactness of the cured product can be improved.
(3) In the invention, when the diluent A is a composite diluent containing trimethylolpropane triacrylate, the curing rate can be better controlled by optimizing the dosage ratio of the trimethylolpropane triacrylate to other diluents to be 7-9:11-13, and the low-temperature curing effect can be better controlled.
Detailed Description
The invention is further described below in connection with specific preferred embodiments, but it is not intended to limit the scope of the invention.
The materials and instruments used in the examples below are all commercially available; the equipment and the preparation process adopted are conventional equipment and conventional process unless otherwise specified.
Example 1
The high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in percentage by weight:
50% of epoxy resin,
49% of diluent,
1% of a coupling agent;
the component B comprises the following raw material components in percentage by weight:
35 percent of amine curing agent,
55% of modified alicyclic amine curing agent,
10% of an auxiliary agent;
in this embodiment, the epoxy resin is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, and the mass ratio of the two is 63:37.
In the embodiment, the diluent is a mixture of trimethylolpropane triglycidyl ether and ethylene glycol diglycidyl ether, and the mass ratio of the two is 19:31.
In this example, the coupling agent is a mixture of KH560 and KH570, wherein the weight ratio of KH560 to KH570 is 2:1.5.
In this example, the amine curing agent is a mixture of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine, wherein the weight ratio of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine is 9:7:4.
In this example, the modified cycloaliphatic amine curing agent was prepared by the following method: adding an amine curing agent into a reactor, adjusting the temperature to be 32-38 ℃, dropwise adding 1, 4-butanediol diglycidyl ether, finishing dropwise adding in 2.5-4.0 hours, and continuously reacting for 2.5 hours at the temperature of 38-43 ℃ to obtain a self-made modified alicyclic amine curing agent; the molar ratio of the amine curing agent to the 1, 4-butanediol diglycidyl ether is 1:1.1-1.5.
In this embodiment, the auxiliary agent is benzyl alcohol.
In this example, the weight ratio of the component A to the component B was 2:1.
The preparation method of the high-strength, low-viscosity and low-temperature moisture-cured two-component epoxy resin adhesive in the embodiment comprises the following steps of:
50.0g of epoxy resin is heated to 75-80 ℃, added into a reaction flask, stirred, 49.0g of diluent and 1.0g of coupling agent are sequentially added, and stirred for 75 minutes to prepare the component A.
Adding 35g of amine curing agent, 55g of self-made modified alicyclic amine curing agent and 10g of auxiliary agent into a reaction flask in sequence, adjusting the temperature to 45-50 ℃, and stirring for 75 minutes to obtain the component B.
The component A and the component B are mixed according to the weight ratio of 2:1, and the mixture is uniformly mixed to obtain the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive which can be directly used.
Tested: the properties of the high strength, low viscosity, low temperature moisture cured two-part epoxy glue in this example are shown in table 1. In addition, the high-strength, low-viscosity, low-temperature moisture-curable two-component epoxy resin adhesive of this example was applied to the surface of stone material having a moisture content of 0.7%, and cured at a temperature of 5℃and at a temperature of 20℃and at a temperature of 25℃to give the results shown in Table 1. The results show that the performance of the high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive after being cured on the surface of the stone meets the requirements of stone surface adhesive, the brightness is high, and the adhesive permeates into cracks.
Example 2
The high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in percentage by weight:
63 percent of epoxy resin,
34% of diluent,
3% of a coupling agent;
the component B comprises the following raw material components in percentage by weight:
43 percent of amine curing agent,
52 percent of modified alicyclic amine curing agent,
5% of auxiliary agent.
In the embodiment, the epoxy resin is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, and the mass ratio of the two is 17:8.
In the embodiment, the diluent is a mixture of trimethylolpropane triacrylate and ethylene glycol diglycidyl ether, and the mass ratio of the two is 11:14.
In this example, the coupling agent is a mixture of KH560 and KH570, wherein the weight ratio of KH560 to KH570 is 2:1.5.
In this example, the amine curing agent is a mixture of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine, wherein the weight ratio of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine is 3:5:2.
In this example, the modified cycloaliphatic amine curing agent was prepared by the following method: adding 30% of 1, 3-cyclohexanedimethylamine, 50% of isophorone diamine and 20% of N-aminoethylpiperazine into a reactor, adjusting the temperature to be 32-38 ℃, dropwise adding 1, 4-butanediol diglycidyl ether for 2.5-4.0 hours, and continuously reacting for 2.5 hours at the temperature of 38-43 ℃ to obtain a self-made modified alicyclic amine curing agent; the molar ratio of the alicyclic amine to the 1, 4-butanediol diglycidyl ether is 1:1.1-1.5.
In this embodiment, the auxiliary agent is benzyl alcohol.
In this example, the weight ratio of the component A to the component B was 2:1.
The preparation method of the high-strength, low-viscosity and low-temperature moisture-cured two-component epoxy resin adhesive in the embodiment comprises the following steps of:
63.0g of epoxy resin is heated to 75-80 ℃, added into a reaction flask, stirred, 34.0g of diluent and 3.0g of coupling agent are sequentially added, and stirred for 75 minutes to obtain the component A.
43g of amine curing agent, 52g of self-made modified alicyclic amine curing agent and 5g of auxiliary agent are sequentially added into a reaction flask, the temperature is regulated to 45-50 ℃, and the mixture is stirred for 75 minutes to obtain the component B.
The component A and the component B are mixed according to the weight ratio of 2:1, and the mixture is uniformly mixed to obtain the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive which can be directly used.
Tested: the properties of the high strength, low viscosity, low temperature moisture cured two-part epoxy glue in this example are shown in table 1. In addition, the high-strength, low-viscosity, low-temperature moisture-curable two-component epoxy resin adhesive of this example was applied to the surface of stone material having a moisture content of 2.2%, and cured at a temperature of 5℃and at a temperature of 20℃and at a temperature of 25℃to give the results shown in Table 1. The results show that the performance of the high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive after being cured on the surface of the stone meets the requirements of stone surface adhesive, the brightness is high, and the adhesive permeates into cracks.
Example 3
The high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in percentage by weight:
56% of epoxy resin,
42 percent of diluent,
2% of a coupling agent;
the component B comprises the following raw material components in percentage by weight:
42.5 percent of amine curing agent,
55% of modified alicyclic amine curing agent,
2.5% of auxiliary agent.
In this embodiment, the epoxy resin is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, and the mass ratio of the two is 13:7.
In the embodiment, the diluent is a mixture of trimethylolpropane triacrylate and ethylene glycol diglycidyl ether, and the mass ratio of the two is 2:3.
In this example, the coupling agent is a mixture of KH560 and KH570, wherein the weight ratio of KH560 to KH570 is 2:1.5.
In this example, the amine curing agent is a mixture of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine, wherein the weight ratio of 1, 3-cyclohexanediamine, isophorone diamine, and N-aminoethylpiperazine is 5:4:1.
In this example, the modified cycloaliphatic amine curing agent was prepared by the following method: adding 50% of 1, 3-cyclohexanediamine, 40% of isophorone diamine and 10% of N-aminoethylpiperazine into a reactor, adjusting the temperature to be 32-38 ℃, dropwise adding 1, 4-butanediol diglycidyl ether for 2.5-4.0 hours, and continuously reacting for 2.5 hours at the temperature of 38-43 ℃ to obtain a self-made modified alicyclic amine curing agent; the mol ratio of 50% of 1, 3-cyclohexanediamine, 40% of isophorone diamine, 10% of N-aminoethylpiperazine and 1, 4-butanediol diglycidyl ether is 1:1.1-1.5.
In this embodiment, the auxiliary agent is benzyl alcohol.
In the embodiment, the weight ratio of the component A to the component B is 2:1.
the preparation method of the high-strength, low-viscosity and low-temperature moisture-cured two-component epoxy resin adhesive in the embodiment comprises the following steps of:
56.0g of epoxy resin is heated to 75-80 ℃, added into a reaction flask, stirred, then 42.0g of diluent and 2.0g of coupling agent are added in sequence, and stirred for 90 minutes to obtain the component A.
Adding 42.5g of amine curing agent, 55g of self-made modified alicyclic amine curing agent and 2.5g of auxiliary agent into a reaction flask in sequence, adjusting the temperature to 45-50 ℃, and stirring for 90 minutes to obtain the component B.
The component A and the component B are mixed according to the weight ratio of 2:1, and the mixture is uniformly mixed to obtain the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive which can be directly used.
Tested: the properties of the high strength, low viscosity, low temperature moisture cured two-part epoxy glue in this example are shown in table 1. In addition, the high-strength, low-viscosity, low-temperature moisture-curable two-component epoxy resin adhesive of this example was applied to the surface of stone material having a moisture content of 1.4%, and cured at a temperature of 5℃and at a temperature of 20℃and at a temperature of 25℃to give the results shown in Table 1. The results show that the performance of the high-strength low-viscosity low-temperature moisture-cured double-component epoxy resin adhesive after being cured on the surface of the stone meets the requirements of stone surface adhesive, the brightness is high, and the adhesive permeates into cracks.
Comparative example 1
The double-component epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in percentage by weight:
46% of epoxy resin,
52% of diluent,
2% of a coupling agent;
the component B comprises the following raw material components in percentage by weight:
32.5 percent of amine curing agent,
65% of modified alicyclic amine curing agent,
2.5% of auxiliary agent;
in comparative example 1, the conditions were the same as in example 3 except that the amounts of the respective raw materials were different.
Tested: the properties of the two-component epoxy resin adhesive in comparative example 1 are shown in Table 1. In addition, the two-component epoxy resin adhesive of comparative example 1 was applied to the surface of stone material having a water content of 1.4%, and cured at a temperature of 5℃and at a temperature of 20℃and at a temperature of 25℃to give the results shown in Table 1. The results show that the two-component epoxy resin adhesive in comparative example 1 has the performance after the stone surface is cured: the adhesive layer is soft and cannot be polished, and the Shore hardness of the adhesive layer cannot be 70D.
Comparative example 2
The double-component epoxy resin adhesive comprises a component A and a component B, wherein the component A comprises the following raw material components in percentage by weight:
68% of epoxy resin,
30% of diluent,
2% of a coupling agent;
the component B comprises the following raw material components in percentage by weight:
55% of amine curing agent,
42 percent of modified alicyclic amine curing agent,
3% of an auxiliary agent;
in comparative example 2, the conditions were the same as in example 3 except that the amounts of the respective raw materials were different.
Tested: the properties of the two-component epoxy resin adhesive in comparative example 2 are shown in Table 1. In addition, the two-component epoxy resin adhesive of comparative example 2 was applied to the surface of stone material having a water content of 1.4%, and cured at a temperature of 5℃and at a temperature of 20℃and at a temperature of 25℃to give the results shown in Table 1. The results show that the two-component epoxy resin adhesive in comparative example 2 has the performance after the stone surface is cured: the Shore hardness is higher than 80D, and the polishing is difficult (too hard).
Table 1 comparison of the Performance of different two-component epoxy resin gums
The results show that the two-component epoxy resin adhesive provided by the invention has more excellent performances, such as higher strength, lower viscosity and capability of realizing effective curing in a low-temperature and humid environment, is a novel epoxy resin repairing adhesive with excellent performances, can be widely used for repairing in the fields of stone and the like, and is particularly suitable for repairing in the low-temperature and humid environment, and has high use value and good application prospect.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (10)
1. A high-strength, low-viscosity and low-temperature moisture-cured two-component epoxy resin adhesive is characterized by comprising a component A and a component B;
the component A comprises the following raw material components in percentage by weight:
50 to 65 percent of epoxy resin,
34 to 50 percent of diluent A,
1-3% of coupling agent, wherein the sum of the weight percentages of the raw materials is 100%;
the component B comprises the following raw material components in percentage by weight:
35 to 45 percent of amine curing agent,
48 to 58 percent of modified alicyclic amine curing agent,
5-10% of auxiliary agent, wherein the sum of the weight percentages of the raw materials is 100%;
the epoxy resin is a mixture of bisphenol A epoxy resin and bisphenol F epoxy resin;
the diluent A is trimethylolpropane triacrylate, or the diluent A is a compound diluent containing trimethylolpropane triacrylate.
2. The two-component epoxy resin adhesive according to claim 1, wherein the mass ratio of bisphenol a type epoxy resin to bisphenol F type epoxy resin is 6-7:3-4.
3. The two-component epoxy resin adhesive according to claim 1, wherein the composite diluent comprises trimethylolpropane triacrylate and a diluent B, and the mass ratio of the trimethylolpropane triacrylate to the diluent B is 7-9:11-13; the diluent B is at least one of 1, 4-butanediol diglycidyl ether, benzyl alcohol, isobutanol and ethylene glycol diglycidyl ether.
4. A two-component epoxy resin glue according to any one of claims 1 to 3, characterized in that the coupling agent is one of KH560, KH570 or a mixture thereof.
5. A two-component epoxy resin glue according to any one of claims 1 to 3, wherein the amine curing agent is one of 1, 3-cyclohexanedimethylamine, isophoronediamine, N-aminoethylpiperazine or a mixture thereof;
the auxiliary agent is benzyl alcohol.
6. A two-component epoxy resin glue according to any one of claims 1 to 3, wherein the modified alicyclic amine curing agent is prepared by the following method: adding alicyclic amine into a reactor, adjusting the temperature to be 32-38 ℃, dropwise adding 1, 4-butanediol diglycidyl ether, finishing dropwise adding in 2.5-4.0 hours, and continuously reacting for 2.5 hours at the temperature of 38-43 ℃ to obtain a modified alicyclic amine curing agent; the molar ratio of the alicyclic amine to the 1, 4-butanediol diglycidyl ether is 1:1.1-1.5.
7. A two-component epoxy resin adhesive according to any one of claims 1 to 3, wherein the weight ratio of the a component and the B component is 1.93-2.07:1.
8. A method for preparing the two-component epoxy resin adhesive as claimed in any one of claims 1 to 7, comprising the steps of:
s1, heating epoxy resin to 75-80 ℃, sequentially adding a diluent and a coupling agent, and stirring to obtain a component A; sequentially adding the modified alicyclic amine curing agent and the auxiliary agent into the amine curing agent, adjusting the temperature to 40-50 ℃, and stirring to obtain a component B;
s2, mixing the component A and the component B to obtain the high-strength, low-viscosity and low-temperature moisture-cured double-component epoxy resin adhesive.
9. The preparation method according to claim 8, wherein the stirring time is 75-90 min during the preparation of the component A;
in the preparation process of the component B, the stirring time is 75-90 min.
10. Use of a high strength, low viscosity, low temperature moisture cured two-part epoxy resin glue as defined in any one of claims 1 to 7 or a high strength, low viscosity, low temperature moisture cured two-part epoxy resin glue as defined in claim 8 or 9 in stone repair.
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