CN111675990A - Polyether amine pre-cured epoxy fast curing adhesive and preparation method thereof - Google Patents
Polyether amine pre-cured epoxy fast curing adhesive and preparation method thereof Download PDFInfo
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
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- C08G14/00—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00
- C08G14/02—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes
- C08G14/04—Condensation polymers of aldehydes or ketones with two or more other monomers covered by at least two of the groups C08G8/00 - C08G12/00 of aldehydes with phenols
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- 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
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- 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
- C08G59/56—Amines together with other curing agents
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- 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
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- 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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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- 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
- C08G59/68—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 catalysts used
- C08G59/687—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 catalysts used containing sulfur
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J11/04—Non-macromolecular additives inorganic
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Abstract
The invention discloses a polyether amine pre-cured epoxy fast curing adhesive which comprises a component A and a component B in parts by weight: the component A comprises 100 parts of polyetheramine-epoxy polymer and 10-25 parts of filler; the component B consists of 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator; when in use, the component A and the component B are mixed uniformly and then can be used; the polyether amine pre-cured epoxy fast curing adhesive disclosed by the invention has excellent adhesion and thixotropy, has higher strength and good toughness after curing, is simple in operation steps during use, can be fast cured at room temperature or even low temperature, realizes adhesion to large devices, and has a good test effect.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a polyether amine pre-cured epoxy fast curing adhesive and a preparation method thereof.
Background
In recent years, the manufacturing industry of high-speed rails, automobiles or mechanical equipment and artificial intelligence devices are rapidly developed, and epoxy resin adhesives are more and more popular due to light weight, high mechanical strength, stress concentration reduction and good sealing performance, but pure epoxy resin has high crosslinking density and has the defects of brittleness, low toughness and poor impact resistance, so that the problem of how to improve the toughness of the epoxy resin is always explored in the field.
At present, the rapid curing epoxy adhesive in the market mostly uses micromolecule mercaptan as a curing agent, although the rapid curing epoxy resin can be realized, the epoxy adhesive cured by the mercaptan has lower bonding strength, poor temperature resistance and large brittleness.
For example, CN110184011 discloses a low-temperature fast curing epoxy glue used in the mobile phone industry, which is prepared by adopting epoxy resin, a mercaptan curing agent, a butyronitrile toughening agent, an accelerant and a silane coupling agent through simple mixing and grinding, needs to be cured for 3 minutes at 95 ℃, and has the initial shearing force of 40N/cm2And is not suitable for the application in the manufacturing industries of high-speed rails, automobiles and mechanical equipment.
CN1640979 discloses a fast curing two-component epoxy adhesive and a preparation method thereof, the invention comprises a component A consisting of epoxy resin, a plasticizer or a toughening agent, wherein the component B is prepared by reacting aliphatic amine, a hydroxyl compound and thiourea at 70-120 ℃ to prepare a compound containing-SH and matching with an accelerant, the gel time is 3-8 minutes at room temperature, the maximum shear strength is 10.8Mpa, and the bonding strength is low. The adhesive obtained by modifying the epoxy resin with the curing agent has low bonding strength and poor temperature resistance, and a toughening agent is required to be additionally used for increasing the toughness.
The polyether amine is a polymer with a main chain of a polyether structure and an amino active functional group at the tail end, can be theoretically used as a high-performance curing agent of epoxy resin and is used for producing high-strength and high-toughness composite materials, particularly after the high-molecular weight polyether amine cures the epoxy resin, but the problem of curing temperature exists when the high-molecular weight polyether amine cures the epoxy resin, namely the curing time of the high-molecular weight polyether amine and the epoxy resin is long at normal temperature and is different from hours to days, the high-molecular weight polyether amine needs to be heated to a certain temperature when curing the epoxy resin, the high-molecular weight polyether amine is difficult to be completely cured at the normal temperature, the strength is low even if the high-molecular weight polyether amine cures the epoxy resin, the strength requirement of an adhesive cannot be met, the high-temperature curing limits the use range of the epoxy resin, and. On the other hand, the prior art using resorcinol-formaldehyde-amine-based polymers as curing agents is less common because resorcinol-formaldehyde-amine-based polymers are too reactive, have high viscosity, and are easily gelled.
Disclosure of Invention
The invention aims to solve the problems that epoxy resin is low in toughness, cannot be cured at normal temperature and needs high-temperature curing when being cured by adopting polyether amine, and provides a polyether amine pre-cured epoxy fast curing adhesive and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B in parts by weight: the component A comprises 100 parts of polyetheramine-epoxy polymer and 10-25 parts of filler; the component B consists of 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
precuring bisphenol A epoxy resin and polyetheramine with the molecular weight of 2000-5000 at 145-155 ℃ for 1.5-2.5 hours, and cooling to room temperature to obtain polyetheramine-epoxy polymer;
wherein the mass ratio of the bisphenol A epoxy resin to the polyether amine is 1: 0.5-1;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding resorcinol, aliphatic amine and methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45-50 ℃, then dripping formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dripping, reacting for 1-2 hours at 60-70 ℃ after dripping is finished, then distilling under reduced pressure at 78-82 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain a resorcinol-formaldehyde-amine polymer;
wherein the mol ratio of the resorcinol, the aliphatic amine, the methanol and the formaldehyde is 1: 0.5-0.8: 1-1.5: 0.5-0.8;
the mass ratio of the reaction liquid to the ethanol is 68-72: 28-32;
the aliphatic amine is ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
the filler is one, two or three of nano magnesium oxide, nano calcium carbonate or nano zinc oxide;
the accelerant is 2-mercaptobenzothiazole, DMP-30 or DMP-10.
Preferably, the bisphenol A epoxy resin is one, two or three of epoxy resin E-51, epoxy resin E-54 or epoxy resin E-56.
Preferably, the bisphenol A epoxy resin is obtained by mixing epoxy resin E-51 and epoxy resin E-56 according to the mass ratio of 1: 1.
Preferably, the polyether amine is polyether amine D2000 or polyether amine T5000.
Preferably, the filler is nano zinc oxide.
Preferably, the accelerator is 2-mercaptobenzothiazole.
Preferably, the aliphatic amine is triethylene tetramine.
Preferably, the molar ratio of resorcinol, aliphatic amine, methanol and formaldehyde is 1: 0.6: 1.2: 0.6.
The invention also comprises a preparation method of the polyether amine pre-cured epoxy fast curing adhesive, which comprises the following steps:
preparing a component A:
adding 10-25 parts of filler into 100 parts of polyetheramine-epoxy polymer, and uniformly stirring to obtain a component A;
preparing a component B:
uniformly stirring 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator to obtain a component B;
and thirdly, the component A and the component B are uniformly mixed and used, so that the curing can be quickly carried out.
Compared with the prior art, the invention has the following advantages:
the polyether amine pre-cured epoxy fast curing adhesive disclosed by the invention has excellent adhesion and thixotropy, has higher strength and good toughness after curing, is simple in operation steps during use, can be fast cured at room temperature or even low temperature, realizes adhesion to large devices, and has a good test effect.
Firstly, the polyether amine is subjected to a pre-curing reaction with epoxy resin at a high temperature, the main chain of a reaction product is still epoxy-terminated liquid epoxy resin, and during embedding of the polyether amine into the main chain of the epoxy resin, a large amount of-NH and-OH in the polyether amine molecules are brought into the main chain of the epoxy resin, so that the molecular weight of the polyether amine is increased, and the activity of the polyether amine is greatly improved; secondly, the self-made resorcinol-formaldehyde-amine polymer has high activity, and after the polyether amine is added to pre-cure the epoxy resin, the fast curing effect is achieved under the promotion of the active promoter; on the other hand, the resorcinol-formaldehyde-amine polymer can realize rapid curing of the epoxy resin at low temperature, has high bonding strength after curing, and can be used for rapid processing and manufacturing industries of high-speed rails, automobiles, mechanical equipment, military industry and the like.
Detailed Description
The invention aims to provide a polyetheramine precured epoxy fast curing adhesive and a preparation method thereof, and the preparation method is realized by the following technical scheme:
a polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B in parts by weight: the component A comprises 100 parts of polyetheramine-epoxy polymer and 10-25 parts of filler; the component B consists of 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
precuring bisphenol A epoxy resin and polyetheramine with the molecular weight of 2000-5000 at 145-155 ℃ for 1.5-2.5 hours, and cooling to room temperature to obtain a viscous liquid polyetheramine-epoxy polymer;
wherein the mass ratio of the bisphenol A epoxy resin to the polyether amine is 1: 0.5-1;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding resorcinol, aliphatic amine and methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45-50 ℃, then dripping formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dripping, reacting for 1-2 hours at 60-70 ℃ after dripping is finished, then distilling under reduced pressure at 78-82 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain a resorcinol-formaldehyde-amine polymer; the viscosity of the resorcinol-formaldehyde-amine polymer is generally 2000-3000 Pa.s, the viscosity is moderate, and the use is convenient;
wherein the mol ratio of the resorcinol, the aliphatic amine, the methanol and the formaldehyde is 1: 0.5-0.8: 1-1.5: 0.5-0.8;
the mass ratio of the reaction liquid to the ethanol is 68-72: 28-32;
the aliphatic amine is ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
the filler is one, two or three of nano magnesium oxide, nano calcium carbonate or nano zinc oxide;
the accelerant is 2-mercaptobenzothiazole, DMP-30 or DMP-10.
Preferably, the bisphenol A epoxy resin is one, two or three of epoxy resin E-51, epoxy resin E-54 or epoxy resin E-56. The preferred bisphenol a epoxy resins are selected for their relatively high epoxy value, low viscosity, and the polyetheramines form viscous epoxy terminated polymers after pre-curing.
Preferably, the bisphenol A epoxy resin is obtained by mixing epoxy resin E-51 and epoxy resin E-56 according to the mass ratio of 1: 1.
Preferably, the polyether amine is polyether amine D2000 or polyether amine T5000; the preferable polyether amine is amine-terminated polyether, and a large amount of terminal-NH and-OH can be brought into the main chain of the epoxy resin in the pre-cured epoxy resin, so that the molecular weight of the epoxy resin is increased, the activity of the epoxy resin is greatly improved, and the epoxy resin plays a role of a toughening agent;
preferably, the filler is nano zinc oxide; the nano-grade filler selected by the application can be well dispersed in the binder, can be well mixed with other components, and plays a role in synergy;
preferably, the accelerator is 2-mercaptobenzothiazole. The preferable accelerator 2-mercaptobenzothiazole has an electron orbit which is empty on the outer layer of a sulfur atom in the accelerator 2-mercaptobenzothiazole or can generate a positron which has electrophilic tendency, and the accelerator is an electrophilic accelerator which attacks an oxygen atom of an epoxy group to form a hydrogen bond, so that the ring opening of the epoxy group is promoted to react with active hydrogen of an amino group, and the good curing acceleration effect is achieved.
Preferably, the aliphatic amine is triethylene tetramine. The preferable aliphatic amine has moderate number of active hydrogen and moderate molecular chain, and can well react with resorcinol and formaldehyde resin to prepare an epoxy resin curing agent with moderate viscosity and high activity;
preferably, the molar ratio of resorcinol, aliphatic amine, methanol and formaldehyde is 1: 0.6: 1.2: 0.6.
The invention also comprises a preparation method of the polyether amine pre-cured epoxy fast curing adhesive, which comprises the following steps:
preparing a component A:
adding 10-25 parts of filler into 100 parts of polyetheramine-epoxy polymer, and uniformly stirring to obtain a component A;
preparing a component B:
uniformly stirring 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator to obtain a component B;
and thirdly, uniformly mixing the component A and the component B for use.
The invention is further described with reference to specific examples.
Example 1
A polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 10kg of filler; the component B consists of 30kg of resorcinol-formaldehyde-amine polymer and 1kg of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
precuring 100kg of bisphenol A epoxy resin and 50kg of polyetheramine with molecular weight of 2000 at 145 ℃ for 1.5 hours, and cooling to room temperature to obtain polyetheramine-epoxy polymer;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding 55kg of resorcinol, 15kg of aliphatic amine and 16kg of methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45 ℃, then dripping 7.5kg of formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dripping, reacting at 60 ℃ for 2 hours after dripping is finished, then distilling under reduced pressure at 78 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain the resorcinol-formaldehyde-amine polymer;
wherein the mass ratio of the reaction liquid to the ethanol is 68: 32;
the aliphatic amine is ethylenediamine;
the filler is nano magnesium oxide;
the accelerant is 2-mercaptobenzothiazole.
Example 2
A polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 25kg of filler; the component B consists of 45kg of resorcinol-formaldehyde-amine polymer and 5kg of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
50kg of bisphenol A epoxy resin and 50kg of polyetheramine with the molecular weight of 5000 are subjected to pre-curing reaction at 155 ℃ for 2.5 hours, and the temperature is reduced to room temperature, so that polyetheramine-epoxy polymer is obtained;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding 55kg of resorcinol, 41.2kg of aliphatic amine and 24kg of methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45-50 ℃, then dropping 12kg of formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dropping, reacting for 1 hour at 70 ℃ after dropping is finished, then distilling under reduced pressure at 78-82 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain a resorcinol-formaldehyde-amine polymer;
wherein the mass ratio of the reaction liquid to the ethanol is 72: 28;
the fatty amine is diethylenetriamine;
the filler is nano calcium carbonate;
the accelerant is DMP-30.
Example 3
A polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 15kg of filler; the component B consists of 40kg of resorcinol-formaldehyde-amine polymer and 2kg of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
pre-curing 100kg of bisphenol A epoxy resin E54 and 60kg of polyetheramine with the molecular weight of 3000 at 150 ℃ for 2.0 hours, and cooling to room temperature to obtain polyetheramine-epoxy polymer;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding 55kg of resorcinol, 43.8kg of aliphatic amine and 19.2kg of methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 48 ℃, then dripping 10.5kg of formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ when dripping, reacting for 1.5 hours at 65 ℃ after dripping is finished, then distilling under reduced pressure at 80 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, stirring uniformly, and discharging to obtain a resorcinol-formaldehyde-amine polymer;
wherein the mass ratio of the reaction liquid to the ethanol is 70: 30;
the aliphatic amine is triethylene tetramine;
the filler is obtained by mixing nano calcium carbonate and nano zinc oxide according to the mass ratio of 1: 2;
the accelerant is DMP-10.
Example 4
A polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B in parts by weight: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 20kg of filler; the component B consists of 35kg of resorcinol-formaldehyde-amine polymer and 4kg of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
precuring 100kg of bisphenol A epoxy resin E-51 and 80kg of polyetheramine D2000 at 148 ℃ for 2.0 hours, and cooling to room temperature to obtain polyetheramine-epoxy polymer;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding 55kg of resorcinol, 66.15kg of aliphatic amine and 17.6kg of methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45 ℃, then dropping 9kg of formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dropping, reacting for 1.5 hours at 65 ℃ after dropping is finished, then distilling under reduced pressure at 80 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain the resorcinol-formaldehyde-amine polymer;
wherein the mass ratio of the reaction solution to the ethanol is 68: 30;
the aliphatic amine is tetraethylenepentamine;
the filler is obtained by mixing nano magnesium oxide and nano calcium carbonate according to the ratio of 1: 1;
the accelerant is 2-mercaptobenzothiazole.
Example 5
A polyether amine pre-cured epoxy fast curing adhesive comprises a component A and a component B in parts by weight: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 14kg of filler; the component B consists of 42kg of resorcinol-formaldehyde-amine polymer and 3kg of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
50kg of bisphenol A epoxy resin E-51, 50kg of bisphenol A epoxy resin E-56 and 80kg of polyetheramine T5000 are subjected to pre-curing reaction at 150 ℃ for 2.0 hours, and the temperature is reduced to room temperature to obtain polyetheramine-epoxy polymer;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding 55kg of resorcinol, 43.8kg of aliphatic amine and 19.2kg of methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 46 ℃, then dropping 9kg of formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dropping, reacting for 1.5 hours at 65 ℃ after dropping is finished, then distilling under reduced pressure at 80 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain the resorcinol-formaldehyde-amine polymer;
the mass ratio of the reaction liquid to the ethanol is 70: 30;
the aliphatic amine is triethylene tetramine;
the filler is nano zinc oxide;
the accelerant is 2-mercaptobenzothiazole.
The accelerator of example 5 was 2-mercaptobenzothiazole to DMP-30, and the remaining components and experimental procedures were unchanged to provide new example 6.
The accelerator of example 5 was 2-mercaptobenzothiazole to DMP-10, and the remaining components and experimental procedures were unchanged to provide new example 7.
Comparative example
The polyether amine pre-cured epoxy adhesive comprises a component A and a component B in parts by weight: wherein the component A consists of 100kg of polyetheramine-epoxy polymer and 14kg of filler; the component B consists of polythiol fast epoxy curing agent GH-80042kg and accelerator 3 kg;
the polyether amine-epoxy polymer is prepared by the following steps:
50kg of bisphenol A epoxy resin E-51, 50kg of bisphenol A epoxy resin E-56 and 80kg of polyetheramine T5000 are subjected to precuring reaction at 150 ℃ for 2.0 hours, and the temperature is reduced to room temperature, so that the polyetheramine-epoxy polymer is obtained.
When in use, the component A and the component B are mixed according to the proportion and then are used.
When in use, the component A and the component B in the embodiment 1-7 are uniformly mixed according to the proportion and then are used.
The performance tests were performed on the polyetheramine precured epoxy fast curing adhesives of examples 1 to 7 and the comparative polyetheramine precured epoxy adhesive, wherein the gel time was measured according to GB/T12007.7-1989 method for measuring gel time of epoxy resin, the test temperatures were-5 ℃ and 25 ℃, the shear strength was measured according to GB/T7124-2008 method for measuring tensile shear strength of adhesive for rigid material versus rigid material, the test temperatures were set to-5 ℃ and 25 ℃, the peel strength was measured according to GB/T2791-1995 method for testing peel strength of adhesive for flexible material versus flexible material, and the test temperatures were set to-5 ℃ and 25 ℃. The results are shown in Table 1.
TABLE 1 Performance test results of the polyetheramine precured epoxy fast curing adhesive of examples 1 to 7
The data in table 1 show that the gel time of the polyetheramine pre-cured epoxy fast-curing adhesive obtained by the method is 5.5-8.0 minutes at room temperature (25 ℃), and the adhesive can gel within 30 minutes even at low temperature (-10 ℃), so that the adhesive can be fast cured, can be fast cured even at low temperature, and expands the application range of epoxy resin; the data in Table 1 also show that the polyether amine pre-cured epoxy fast curing adhesive obtained by the method of the invention has the shear strength of more than 25MPa after 6 hours, the shear strength of more than 36MPa after 24 hours, the peel strength of more than 72N/cm, fast curing and high bonding performance.
Whereas the comparative example employed the existing curing agent: although the 5-minute polythiol fast epoxy curing agent GH-800 can be rapidly cured in 5.5 minutes at room temperature, the complete curing at low temperature requires a long time, and the shear strength and peel strength after curing are obviously low, so that the resorcinol-formaldehyde-amine compound prepared by the invention has high activity, high bonding strength at low temperature and high bonding strength after curing.
Claims (9)
1. A polyether amine pre-cured epoxy fast curing adhesive is characterized in that: the paint consists of a component A and a component B in parts by weight: the component A comprises 100 parts of polyetheramine-epoxy polymer and 10-25 parts of filler; the component B consists of 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator;
the polyether amine-epoxy polymer is prepared by the following steps:
precuring bisphenol A epoxy resin and polyetheramine with the molecular weight of 2000-5000 at 145-155 ℃ for 1.5-2.5 hours, and cooling to room temperature to obtain polyetheramine-epoxy polymer;
wherein the mass ratio of the bisphenol A epoxy resin to the polyether amine is 1: 0.5-1;
the resorcinol-formaldehyde-amine polymer is prepared by the following steps:
adding resorcinol, aliphatic amine and methanol into a reaction kettle with a reflux condenser and a stirrer to obtain a mixed solution, starting stirring, heating to 45-50 ℃, then dripping formaldehyde into the reaction kettle, controlling the temperature of the mixed solution not to exceed 60 ℃ during dripping, reacting for 1-2 hours at 60-70 ℃ after dripping is finished, then distilling under reduced pressure at 78-82 ℃ to remove water and methanol, then adding ethanol into the reaction kettle, uniformly stirring and discharging to obtain a resorcinol-formaldehyde-amine polymer;
wherein the mol ratio of the resorcinol, the aliphatic amine, the methanol and the formaldehyde is 1: 0.5-0.8: 1-1.5: 0.5-0.8;
the mass ratio of the reaction liquid to the ethanol is 68-72: 28-32;
the aliphatic amine is ethylenediamine, diethylenetriamine, triethylene tetramine or tetraethylene pentamine;
the filler is one, two or three of nano magnesium oxide, nano calcium carbonate or nano zinc oxide;
the accelerant is 2-mercaptobenzothiazole, DMP-30 or DMP-10.
2. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the bisphenol A epoxy resin is one, two or three of epoxy resin E-51, epoxy resin E-54 or epoxy resin E-56.
3. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 2, wherein: the bisphenol A epoxy resin is obtained by mixing epoxy resin E-51 and epoxy resin E-56 according to the mass ratio of 1: 1.
4. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the polyether amine is polyether amine D2000 or polyether amine T5000.
5. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the filler is nano zinc oxide.
6. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the accelerant is 2-mercaptobenzothiazole.
7. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the aliphatic amine is triethylene tetramine.
8. The polyetheramine precured epoxy fast curing adhesive as claimed in claim 1, wherein: the mol ratio of the resorcinol, the aliphatic amine, the methanol and the formaldehyde is 1: 0.6: 1.2: 0.6.
9. The preparation method of the polyether amine precured epoxy fast curing adhesive as claimed in claim 1, which is characterized in that: the method comprises the following steps:
preparing a component A:
adding 10-25 parts of filler into 100 parts of polyetheramine-epoxy polymer, and uniformly stirring to obtain a component A;
preparing a component B:
uniformly stirring 30-45 parts of resorcinol-formaldehyde-amine polymer and 1-5 parts of accelerator to obtain a component B;
and thirdly, uniformly mixing the component A and the component B for use.
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