CN114231186B - Fast-curing modified dry-hanging adhesive and preparation method and application thereof - Google Patents

Fast-curing modified dry-hanging adhesive and preparation method and application thereof Download PDF

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CN114231186B
CN114231186B CN202111534582.8A CN202111534582A CN114231186B CN 114231186 B CN114231186 B CN 114231186B CN 202111534582 A CN202111534582 A CN 202111534582A CN 114231186 B CN114231186 B CN 114231186B
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stirring
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CN114231186A (en
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杜昆文
杜昆武
王云飞
余琦
叶盛阳
朱本玮
张忠侠
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Jiangsu Hercules Marble Care Materials Co ltd
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Wuhan Keda Marble Protective Materials Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J4/00Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/04Non-macromolecular additives inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Epoxy Resins (AREA)

Abstract

The invention discloses a fast curing modified dry-hanging adhesive as well as a preparation method and application thereof, and the fast curing modified dry-hanging adhesive comprises a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 100 parts of multifunctional acrylate monomer, 10-30 parts of thickening reinforcing agent, 0-30 parts of first thixotropic agent, 1-3 parts of first coupling agent and 50-200 parts of first powder filler; the component B comprises the following raw materials in parts by weight: 80-100 parts of self-made modified amine curing agent, 0.5-5 parts of first accelerator, 2-5 parts of second accelerator, 1-3 parts of second coupling agent, 0-30 parts of second thixotropic agent and 50-250 parts of second powder filler. Compared with the fast epoxy dry-hang glue prepared by other means, the novel fast curing modified dry-hang glue prepared by the invention has the advantages of easily available raw materials, very obvious price advantage and good economic benefit.

Description

Fast-curing modified dry-hanging adhesive and preparation method and application thereof
Technical Field
The invention belongs to the technical field of adhesive curing, and particularly relates to a fast-curing modified dry-hanging adhesive as well as a preparation method and application thereof.
Background
The epoxy dry-hanging adhesive is a well-known normal-temperature high-performance structural adhesive, has high strength, small shrinkage, very good adhesion to most materials, and excellent weather resistance, chemical resistance and other performances, so that the epoxy dry-hanging adhesive is widely applied by people and is often used as a stone structural adhesive.
The epoxy dry-hanging adhesive has the disadvantages that firstly, the viscosity of the epoxy resin in the component A is high, a diluent is often added in the application, secondly, the reaction activity of the epoxy resin is low, the epoxy resin can be cured for a relatively long time to obtain the required strength, and particularly in a low-temperature environment, the viscosity of the epoxy resin is obviously increased, the reaction activity is greatly reduced, even the situation of false curing or no curing occurs, and the practical application is limited by a high temperature.
Aiming at the defects of the epoxy dry-hanging adhesive, in order to effectively solve the problems in the production and formula design of daily enterprises, the following methods are usually adopted:
1. when in use, the dry hanging glue is heated to reduce the viscosity of the product and improve the reactivity. But the operation is comparatively troublesome, and the power consumption is great, and it has certain potential safety hazard to heat at the job site simultaneously.
2. A large amount of diluent is added to reduce the viscosity of the resin and improve the operability, but the diluent has great influence on the strength of the product body. Meanwhile, amine or thiol curing agents with high activity are adopted to improve the reaction activity, but the reaction activity is still greatly influenced by the temperature, the operation is generally required to be carried out at the temperature of more than 5 ℃, and more harmful gases are released and the cost is greatly increased.
Through examining the literature, patent CN201410853728 "a room temperature fast curing low stress transparent epoxy resin adhesive" still adopts epoxy resin as the main body, and acrylate monomers as the diluent, and the principle of fast curing still adopts thiol curing agent to improve the curing activity of epoxy resin.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a quick-curing modified dry-hanging adhesive. The invention starts from the curing reaction activity of the two-component adhesive, adopts the reaction of the high-activity multifunctional acrylate monomer and the organic amine curing agent, has large reaction activity and small influence of temperature, can still quickly react and crosslink and cure at lower temperature (0 ℃), and simultaneously has low viscosity of the acrylate monomer and easy operation at low temperature.
The second purpose of the invention is to provide a preparation method of the fast curing modified dry-hang glue, which improves the bonding performance of the system by means of physical and chemical methods.
The third purpose of the invention is to provide the application of the fast curing modified dry-hanging adhesive, when in use, the A component and the B component are uniformly mixed according to a certain proportion, and the fast reaction curing can be realized.
In order to solve the technical problems, the invention is realized by the following technical scheme:
in a first aspect, the invention provides a novel fast-curing modified dry-hanging adhesive, which comprises two components A and B, wherein the component A comprises the following raw materials in parts by weight: 100 parts of multifunctional acrylate monomer, 10-30 parts of thickening reinforcing agent, 0-30 parts of first thixotropic agent, 1-3 parts of first coupling agent and 50-200 parts of first powder filler; the component B comprises the following raw materials in parts by weight: 80-100 parts of self-made modified amine curing agent, 0.5-5 parts of first accelerator, 2-5 parts of second accelerator, 1-3 parts of second coupling agent, 0-30 parts of second thixotropic agent and 50-250 parts of second powder filler.
Preferably, the multifunctional acrylate monomer is selected from trimethylolpropane triacrylate (TMPTA), pentaerythritol tetraacrylate (PET 4A), methoxylated trimethylolpropane triacrylate (TMP 3 EOTA) and ethoxylated pentaerythritol tetraacrylate (PPTTA).
Preferably, the thickening and reinforcing agent is selected from polyacrylate resin and solid bisphenol A type epoxy resin; the first coupling agent is selected from the group consisting of 3- (methacryloyloxy) propyltrimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane.
Preferably, the base amine raw material of the homemade modified amine curing agent is selected from the group consisting of m-xylylenediamine (MXDA), isophoronediamine (IPDA), 1, 3-diaminomethylcyclohexane (1, 3-BAC), methylcyclohexanediamine (HTDA), 4' -diaminodicyclohexylmethane (HMDA), and 1, 2-cyclohexanediamine.
Preferably, the first accelerator is selected from the group consisting of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, o-hydroxybenzyldimethylamine and triethylamine; the second promoter is benzyl alcohol; the second coupling agent is selected from the group consisting of 3-aminopropyltriethoxysilane and 3- (2-aminoethylamino) propyltrimethoxysilane.
Preferably, the first thixotropic agent and the second thixotropic agent are both selected from precipitated silica and fumed silica; the first powder filler and the second powder filler are selected from calcium carbonate, silicon micropowder, barium sulfate and glass beads.
In a second aspect, the invention provides a preparation method for preparing the above fast curing modified dry-hanging adhesive, which comprises the following steps:
preparation of the component A:
weighing raw materials of a multifunctional acrylate monomer, a thickening reinforcing agent, a first thixotropic agent, a first coupling agent and a first powder filler according to the weight part ratio, firstly putting the multifunctional acrylate monomer and the thickening reinforcing agent into a stirrer, heating to 70-80 ℃, fully stirring until the thickening reinforcing agent is completely dissolved at the rotating speed of 50-80 r/min, then adding the first coupling agent, premixing and stirring for 5-15 min, then adding the first thixotropic agent, stirring for 5-15 min until the thickening reinforcing agent is completely uniform, then adding the first powder filler, continuously stirring for 50-60 min until the thickening reinforcing agent is completely uniform, and simultaneously cooling to 50 ℃ and discharging;
b, preparation of a component:
the method comprises the steps of firstly preparing a self-made modified amine curing agent according to a modification method, then weighing the raw materials of the self-made modified amine curing agent, a first accelerator, a second coupling agent, a second thixotropic agent and a second powder filler according to the weight part ratio, then adding the self-made modified amine curing agent, the first accelerator, the second accelerator and the second coupling agent into a stirrer, stirring for 5-15 minutes at a rotating speed of 50-80 r/min, then adding the second thixotropic agent into the stirrer, premixing and stirring for 5-15 minutes till the mixture is completely uniform, then adding the second powder filler, continuously stirring for 50-60 minutes till the mixture is completely uniform, and then discharging.
Preferably, the modification method of the homemade modified amine curing agent comprises addition modification or Mannich modification;
when the modification method is addition modification, the addition modification method includes:
adding a basic amine raw material into a reaction device, heating to 50-70 ℃ under the stirring condition, adding liquid epoxy resin in batches every 20-30 minutes under continuous stirring, heating to 70-80 ℃ after adding the materials, carrying out heat preservation reaction for 1.5-2 hours, cooling to normal temperature, and discharging to obtain a self-made addition modified amine curing agent; wherein the liquid epoxy resin and the basic amine raw material are added in the following weight ratio: 1:1.5 to 3.5.
When the modification method is a mannich modification, the mannich modification method comprises:
adding basic amine and phenol raw materials into a reaction device, heating to 80-85 ℃ under the stirring condition, adding paraformaldehyde in batches every 20-30 minutes under continuous stirring, heating to 95-105 ℃ after the materials are added, carrying out heat preservation reaction for 3-5 hours, finally controlling the temperature to be 100-105 ℃, removing water in the system through vacuum, collecting through a condensation reflux mode until no water is evaporated, cooling and discharging to obtain the self-made Mannich modified amine curing agent. Wherein the adding weight ratio of phenol to paraformaldehyde and basic amine raw materials is as follows: 1:0.64:3.0 to 4.5.
It is further preferred that the liquid epoxy resin is selected from the group consisting of bisphenol a type epoxy resin and bisphenol F type epoxy resin.
In a third aspect, the invention also provides an application of the novel fast curing modified dry-hanging adhesive, wherein when the component A and the component B are used, the weight ratio of the component A to the component B is 1:1, mixing uniformly, and then realizing rapid reaction and solidification.
The thickening and reinforcing agent disclosed by the invention has the functions of thickening (viscosity increasing) and improving the system strength. The multifunctional acrylate monomer has good solubility in the multifunctional acrylate monomer of the component A, the resin viscosity can be improved by adding the multifunctional acrylate monomer, the sedimentation condition of the multifunctional acrylate monomer is greatly improved after various fillers are added, and meanwhile, an interpenetrating network can be formed with main resin or even cross-linked with amine components during later-stage curing, so that the bulk strength of a cured product is further improved.
The accelerator selected by the invention is a tertiary amine accelerator and benzyl alcohol, the first accelerator is a tertiary amine accelerator which can accelerate the gelling process, and the second accelerator is benzyl alcohol which can improve the post-curing speed of the reaction and further reduce the mixing initial viscosity of the system, so that the operability is improved. The component A is the coupling agent with epoxy group or double bond to ensure the stable coexistence of the system, and the component B is the coupling agent with amido group to ensure the stable coexistence of the system. The invention discloses two modification methods of a self-made modified amine curing agent, which mainly aim to increase a rigid chain segment structure in a curing system through modification so as to improve the strength of a cured product.
Compared with the prior art, the low-temperature fast curing composition prepared by the invention has the following beneficial effects:
the fast curing modified dry-hanging adhesive prepared by the invention has the advantages that the double components have low viscosity at normal temperature, can have good blending hand feeling at low temperature of 0 ℃, are far lower than an epoxy system, are very easy to operate, and are very convenient to operate even at lower temperature in winter. The curing speed is high, the gel time is only a few minutes to more than ten minutes at normal temperature according to different raw materials and formulas, and the gel can be cured in a short time at the low temperature of 0-5 ℃. Meanwhile, compared with the fast epoxy dry-hang glue prepared by other means, the fast curing modified dry-hang glue prepared by the invention has the advantages of easily available raw materials, very obvious price advantage and good economic benefit.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.
The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.
The invention relates to a fast curing modified dry-hanging adhesive which comprises two components A and B, wherein the component A comprises 100 parts of multifunctional acrylate monomer, 10-30 parts of thickening reinforcing agent, 1-3 parts of first coupling agent, 0-30 parts of first thixotropic agent and 50-200 parts of first powder filler; the component B comprises 80-100 parts of self-made modified amine curing agent, 0.5-5 parts of first accelerator, 2-5 parts of second accelerator, 1-3 parts of second coupling agent, 0-30 parts of second thixotropic agent and 50-250 parts of second powder filler.
A fast curing modified dry-hanging adhesive is prepared by the following preparation process:
the preparation method of the component A comprises the following steps:
weighing raw materials of a multifunctional acrylate monomer, a thickening reinforcing agent, a first thixotropic agent, a first coupling agent and a first powder filler according to the weight part ratio, firstly putting the multifunctional acrylate monomer and the thickening reinforcing agent into a stirrer, heating to 70-80 ℃, fully stirring until the thickening reinforcing agent is completely dissolved at the rotating speed of 50-80 r/min, then adding the first coupling agent, premixing and stirring for 5-15 min, then adding the first thixotropic agent, stirring for 5-15 min until the thickening reinforcing agent is completely uniform, then adding the first powder filler, continuously stirring for 50-60 min until the thickening reinforcing agent is completely uniform, and simultaneously cooling to 50 ℃ and discharging.
The preparation method of the component B comprises the following steps:
firstly, self-made modified amine curing agent is prepared by two modification methods, specifically:
the first method, the addition modification method:
adding a basic amine raw material into a reaction device, heating to 50-70 ℃ under stirring, adding liquid epoxy resin in batches every 20-30 minutes under continuous stirring, heating to 70-80 ℃ after adding the materials, carrying out heat preservation reaction for 1.5-2 hours, cooling to normal temperature, and discharging to obtain a self-made addition modified amine curing agent; the liquid epoxy resin is selected from bisphenol A type epoxy resin and bisphenol F type epoxy resin. Wherein the liquid epoxy resin and the basic amine raw material are added in the following weight ratio: 1:1.5 to 3.5.
Second method, mannich modification method:
adding basic amine and phenol raw materials into reaction equipment, heating to 80-85 ℃ under the stirring condition, adding paraformaldehyde in batches every 20-30 minutes under continuous stirring, heating to 95-105 ℃ after adding the materials, carrying out heat preservation reaction for 3-5 hours, finally controlling the temperature to be 100-105 ℃, removing water in the system through vacuum, collecting through a condensation reflux mode until no water is evaporated, cooling and discharging to obtain the self-made Mannich modified amine curing agent. Wherein the adding weight ratio of phenol to paraformaldehyde and basic amine raw materials is as follows: 1:0.64:3.0 to 4.5.
And then, after the self-made modified amine curing agent is synthesized, weighing the raw materials of the self-made modified amine curing agent, a first accelerator, a second coupling agent, a second thixotropic agent and a second powder filler according to the weight part ratio, then adding the self-made modified amine curing agent, the first accelerator, the second accelerator and the second coupling agent into a stirrer at the rotating speed of 50-80 r/min, stirring for 5-15 min, then adding the second thixotropic agent, premixing and stirring for 5-15 min to be completely uniform, then adding the second powder filler, continuously stirring for 50-60 min to be completely uniform, and discharging.
A modified fast-curing dry-hanging adhesive comprises the following specific embodiments:
step one, self-preparing a modified amine curing agent, wherein the specific method comprises the following steps of:
table I self-made modified amine curing agent raw material and proportion
Examples of self-made modified amine curing agents Raw material feeding weight ratio
Self-made modified amine curing agent 1 Epoxy 128: m-xylylenediamine =1:2
Self-made modified amine curing agent 2 And (3) epoxy 170: methylcyclohexanediamine =1:1.88
Self-made modified amine curing agent 3 And (3) epoxy 170: HMDA =1:3.5
Self-made modified amine curing agent 4 Epoxy 128:1, 2-cyclohexanediamine=1:1.5
Self-made modified amine curing agent 5 Phenol: paraformaldehyde: isophorone diamine =1:0.64:4.52
Self-made modified amine curing agent 6 Phenol: paraformaldehyde: 1,3-BAC =1:0.64:3.56
Self-made modified amine curing agent 7 Phenol: paraformaldehyde: methylcyclohexanediamine =1:0.64:3.4
Self-made modified amine curing agent 8 Phenol: paraformaldehyde: 1, 2-cyclohexanediamine =1:0.64:3.03
Note: the homemade modified amine curing agent is illustrated as part of the invention, wherein the effects of the un-illustrated components are basically equivalent to the effects of the illustrated components. Wherein epoxy 128 is a commercial grade of bisphenol a type liquid epoxy and epoxy 170 is a commercial grade of bisphenol F type liquid epoxy.
And step two, preparing the component A and the component B, wherein the specific preparation methods are respectively carried out according to the preparation methods of the component A and the component B as described above, and the weight parts of the relevant examples are as follows:
table two examples a component raw material parts table
Figure BDA0003412133610000061
Continuation table two
Figure BDA0003412133610000062
Figure BDA0003412133610000071
Table three examples ingredient parts of B component
Figure BDA0003412133610000072
Continued table III
Figure BDA0003412133610000081
In the above step, KH-550 is a commercial brand of 3-aminopropyltriethoxysilane, KH-560 is a commercial brand of 3- (2, 3-glycidoxy) propyltrimethoxysilane, KH-570 is a commercial brand of 3- (methacryloyloxy) propyltrimethoxysilane, KH-792 is a commercial brand of 3- (2-aminoethylamino) propyltrimethoxysilane, and DMP-30 is a commercial brand of 2,4, 6-tris (dimethylaminomethyl) phenol.
Thirdly, mixing the components A and B according to the weight ratio of 1:1, testing the mechanical property, and simultaneously comparing the mechanical property with the mechanical property of the epoxy dry-hanging adhesive on the market, wherein the specific data are as follows: TABLE four examples mechanical Property test data
Figure BDA0003412133610000091
Table four
Figure BDA0003412133610000092
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Figure BDA0003412133610000101
Note: in the detection method, the harmonicity is judged by the manual stirring comparison of professional technicians, and the working life, the compression-shear strength, the tensile-shear strength, the bending elastic modulus and the impact strength are detected at the temperature of 23 ℃ by referring to a standard JC 887-2001, namely epoxy adhesive for dry hanging stone curtain walls. The index of the applicable period can be determined by negotiation according to market requirements, so that no index requirement is added.
The novel fast curing modified dry-hanging adhesive related by the invention has various performances related to factors such as structural design of a self-made curing agent, selection of resin and powder, design of solid-liquid ratio, blending of a formula and the like, and can not be complained completely in space. From the performance data of the above examples, it can be seen that example 7 is the best example of this patent.
From the performance data, the novel fast curing modified dry-hang adhesive has excellent harmonious property and particularly shows obvious hand feeling advantage at low temperature because the viscosity of the acrylate monomer is extremely low, so that the two components have lower harmonious viscosity after being mixed. Meanwhile, the curing activity is high, and the gel speed is obviously higher than that of the epoxy system dry-hanging adhesive, so that the epoxy resin has certain convenience in construction. In addition, in terms of mechanical properties, the impact strength is obviously higher than that of the epoxy system dry-hanging adhesive, namely the toughness of the system is obviously better than that of the epoxy system, which is very rare in building adhesives, and other strength indexes can reach the corresponding level of the epoxy dry-hanging adhesive and further exceed the technical indexes of national standard requirements. Therefore, the novel fast curing modified dry-hang adhesive has obvious advantages in practical application and can completely replace epoxy dry-hang adhesive for application.
In conclusion of all the technical indexes, the novel fast-curing modified dry-hang glue disclosed by the invention is excellent in performance of all performance indexes, is a novel dry-hang glue variety with strong applicability, and has good creativity and practical application value.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and should be considered to be within the scope of the invention.

Claims (8)

1. The fast curing modified dry-hang glue is characterized by comprising a component A and a component B, wherein the component A comprises the following raw materials in parts by weight: 100 parts of multifunctional acrylate monomer, 10-30 parts of thickening reinforcing agent, 0-30 parts of first thixotropic agent, 1-3 parts of first coupling agent and 50-200 parts of first powder filler; the component B comprises the following raw materials in parts by weight: 80-100 parts of self-made modified amine curing agent, 0.5-5 parts of first accelerator, 2-5 parts of second accelerator, 1-3 parts of second coupling agent, 0-30 parts of second thixotropic agent and 50-250 parts of second powder filler; the basic amine raw material of the self-made modified amine curing agent is selected from m-xylylenediamine, isophorone diamine, 1, 3-diaminomethylcyclohexane, methylcyclohexanediamine, 4' -diaminodicyclohexylmethane and 1, 2-cyclohexanediamine;
the modification method of the self-made modified amine curing agent comprises addition modification or Mannich modification;
when the modification method is addition modification, the addition modification method includes:
adding a basic amine raw material into a reaction device, heating to 50-70 ℃ under stirring, adding liquid epoxy resin in batches every 20-30 minutes under continuous stirring, heating to 70-80 ℃ after adding the materials, carrying out heat preservation reaction for 1.5-2 hours, cooling to normal temperature, and discharging to obtain a self-made addition modified amine curing agent; wherein the liquid epoxy resin and the basic amine raw material are added in the following weight ratio: 1:1.5 to 3.5;
when the modification method is a mannich modification, the mannich modification method comprises:
adding basic amine and phenol raw materials into a reaction device, heating to 80-85 ℃ under the stirring condition, adding paraformaldehyde in batches every 20-30 minutes under continuous stirring, heating to 95-105 ℃ after adding the materials, carrying out heat preservation reaction for 3-5 hours, finally controlling the temperature to be 100-105 ℃, removing water in the system through vacuum, collecting through a condensation reflux mode until no water is evaporated, cooling and discharging to obtain the self-made Mannich modified amine curing agent; wherein the adding weight ratio of the phenol to the paraformaldehyde and the basic amine raw materials is as follows: 1:0.64:3.0 to 4.5.
2. The fast curing modified xerogel according to claim 1 wherein the multifunctional acrylate monomer is selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol tetraacrylate, methoxylated trimethylolpropane triacrylate and ethoxylated pentaerythritol tetraacrylate.
3. The fast curing modified xerogel according to claim 1 wherein the thickening and strengthening agent is selected from polyacrylate resin and solid bisphenol a epoxy resin; the first coupling agent is selected from the group consisting of 3- (methacryloyloxy) propyltrimethoxysilane and 3- (2, 3-glycidoxy) propyltrimethoxysilane.
4. The fast curing modified xerogel of claim 1 wherein the first accelerator is selected from the group consisting of 2,4, 6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, o-hydroxybenzyldimethylamine, and triethylamine; the second promoter is benzyl alcohol; the second coupling agent is selected from the group consisting of 3-aminopropyltriethoxysilane and 3- (2-aminoethylamino) propyltrimethoxysilane.
5. The fast-curing modified dry-hang glue of claim 1, wherein the first thixotropic agent and the second thixotropic agent are both selected from precipitated silica and fumed silica; the first powder filler and the second powder filler are selected from calcium carbonate, silicon micropowder, barium sulfate and glass beads.
6. A method for preparing the fast curing modified xerogel according to any one of claims 1 to 5, comprising:
preparation of a component A:
weighing raw materials including a multifunctional acrylate monomer, a thickening reinforcing agent, a first thixotropic agent, a first coupling agent and a first powder filler according to the weight part ratio, firstly putting the multifunctional acrylate monomer and the thickening reinforcing agent into a stirrer, heating to 70-80 ℃, fully stirring at a rotating speed of 50-80 rpm until the thickening reinforcing agent is completely dissolved, then adding the first coupling agent, premixing and stirring for 5-15 minutes, then adding the first thixotropic agent, stirring for 5-15 minutes until the thickening reinforcing agent is completely uniform, then adding the first powder filler, continuously stirring for 50-60 minutes until the thickening reinforcing agent is completely uniform, and simultaneously cooling to 50 ℃ and then discharging;
b, preparation of a component:
the method comprises the steps of firstly preparing a self-made modified amine curing agent according to a modification method, then weighing the raw materials of the self-made modified amine curing agent, a first accelerator, a second coupling agent, a second thixotropic agent and a second powder filler according to the weight part ratio, then adding the self-made modified amine curing agent, the first accelerator, the second accelerator and the second coupling agent into a stirrer, stirring for 5-15 minutes at a rotating speed of 50-80 r/min, then adding the second thixotropic agent into the stirrer, premixing and stirring for 5-15 minutes till the mixture is completely uniform, then adding the second powder filler, continuously stirring for 50-60 minutes till the mixture is completely uniform, and then discharging.
7. The method for preparing the fast curing modified xerogel according to claim 6, wherein the liquid epoxy resin is selected from bisphenol A epoxy resin and bisphenol F epoxy resin.
8. The use of the fast curing modified dry-hang glue according to any one of claims 1 to 5, wherein the components A and B are mixed according to a weight ratio of 1:1, mixing uniformly, and then realizing rapid reaction and solidification.
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Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4051195A (en) * 1975-12-15 1977-09-27 Celanese Polymer Specialties Company Polyepoxide-polyacrylate ester compositions
DE19520888A1 (en) * 1995-06-08 1996-12-12 Basf Ag Radiation-curable compositions containing multifunctional acrylates and blocked amines
AU711287B2 (en) * 1996-05-16 1999-10-07 Minnesota Mining And Manufacturing Company Adhesive compositions and methods of use
JP4004467B2 (en) * 2001-08-28 2007-11-07 レゾリユーシヨン・リサーチ・ネダーラント・ベー・フエー Epoxy resin low viscosity curing agent composition for low temperature curing
US7244793B2 (en) * 2003-09-26 2007-07-17 Illinois Tool Works Inc. Adhesive compositions
CN101186744B (en) * 2007-08-29 2011-04-06 上纬企业股份有限公司 Epoxy resin and use thereof
US8729197B2 (en) * 2010-08-10 2014-05-20 3M Innovative Properties Company Epoxy structural adhesive
CN103409090B (en) * 2013-06-05 2015-01-14 武汉市科达云石护理材料有限公司 Epoxy caulk compound used in humid environment
CN104673163A (en) * 2015-03-23 2015-06-03 广州市白云化工实业有限公司 Epoxy stone dry hanging adhesive rapidly solidified at normal temperature and preparation method of epoxy stone dry hanging adhesive
CN105037297B (en) * 2015-06-23 2017-10-10 广东博兴新材料科技有限公司 It is a kind of containing carboxy-modified polycyclic amines and preparation method thereof and its application in polyfunctional acrylic ester
CN108003800B (en) * 2017-12-15 2020-12-01 长春永固科技有限公司 Acrylate adhesive capable of being rapidly cured at low temperature and low in warpage and preparation method thereof
CN111019093B (en) * 2019-12-10 2022-05-03 武汉市科达云石护理材料有限公司 Room-temperature rapid epoxy curing agent and application thereof in preparation of epoxy dry-hanging adhesive
CN111087958A (en) * 2019-12-20 2020-05-01 北京高盟新材料股份有限公司 Room-temperature fast-curing epoxy adhesive and preparation method thereof
CN111073526A (en) * 2019-12-23 2020-04-28 烟台信友新材料有限公司 Fast-positioning two-component acrylate structural adhesive and preparation and use methods thereof
CN111057474A (en) * 2019-12-24 2020-04-24 合肥乐凯科技产业有限公司 Adhesive for UV (ultraviolet) anti-adhesive film and UV anti-adhesive film thereof
CN113337235B (en) * 2021-07-09 2023-03-17 成都硅宝科技股份有限公司 Fast-curing epoxy true porcelain adhesive for interior decoration and preparation method thereof

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