CN117965120B - High-stability low-heat-release structural adhesive system material and preparation method and application thereof - Google Patents
High-stability low-heat-release structural adhesive system material and preparation method and application thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 26
- 239000007788 liquid Substances 0.000 claims description 21
- 239000010456 wollastonite Substances 0.000 claims description 21
- 229910052882 wollastonite Inorganic materials 0.000 claims description 21
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- 238000012360 testing method Methods 0.000 claims description 17
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
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- 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 description 11
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides a high-stability low-heat-release structural adhesive system material, a preparation method and application thereof, and relates to the technical field of structural adhesives, wherein the mass ratio of a resin part to a curing agent part of the structural adhesive system material is 10 (4-5); the resin part comprises 60-80 parts of bisphenol A type epoxy resin, 2-15 parts of bisphenol F type epoxy resin, 10-20 parts of inorganic reinforcing filler and 3-8 parts of thickening thixotropic agent; the curing agent part comprises 56-115 parts of amine curing agent, 5-20 parts of inorganic reinforcing filler, 5-9 parts of thickening thixotropic agent and 4-60 parts of modified amine rheological aid; the modified amine rheological additive is prepared by pre-reacting an amine substance and a substance capable of carrying out addition reaction with the amine substance at 25-150 ℃. The invention solves the problems of improving the stability of the structural adhesive and ensuring the smoothness and uniformity of heat in the curing exothermic process while meeting the mechanical property requirements.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to a high-stability low-heat-release structural adhesive system material, and a preparation method and application thereof.
Background
Epoxy resins have been widely used in various fields and have become the most important component of wind power blade structural adhesives due to their excellent mechanical properties, adhesive properties, abrasion resistance, chemical resistance and small shrinkage rate during curing. The epoxy resin is a linear or branched low-molecular substance, can not be solidified by itself, and must be reacted with a curing agent under a certain condition to form a cross-linked network structure or a body type structure, so that the epoxy resin and the curing agent are cross-linked into insoluble and infusible structural adhesive, and the epoxy resin has use value in the bonding process of wind power blades. The curing agent plays a quite important role on the epoxy resin, and the type and the amount of the curing agent play an important role on the performance of the cured structural adhesive.
In the production process of the wind generating set blade, the bonding area and bonding strength are required to be ensured when the upper shell and the lower shell are clamped and bonded, the structural adhesive smeared on the bonding surface is required to be filled, and the bonding defects such as adhesive shortage and the like after the clamping are avoided, so that the effective bonding between the shells and the web plate is ensured. Therefore, the structural adhesive is required to have higher shape retention capability on the premise of ensuring better fluidity in the adhesive beating process at normal temperature. Meanwhile, in order to reduce the cost, improve the mechanical property of the product and the dimensional stability in the curing process, wollastonite, ground glass fiber, calcium carbonate and other inorganic reinforcing fillers are generally required to be added, and as the filler density is higher than the resin density, resin liquid precipitation easily occurs in the storage process, and the delamination phenomenon of inorganic filler sedimentation causes the deviation of the mixing proportion in the use of the structural adhesive, so that the ideal curing effect cannot be achieved.
Thixotropic properties and storage stability are important properties of interest in various fields such as adhesives, coatings, cosmetics, foods and the like, as well as wind power structural adhesive products. The conventional method for improving the sedimentation of the filler in the product comprises modifying the surface of the filler to improve the interaction between the filler and the resin, adding a rheological additive for improving the dispersion state of the filler and adding a thickener to improve the viscosity of a continuous phase, but modifying the surface of the filler not only increases the cost of the product, but also hardly ensures the stability of the batch of the product, and the conventional sedimentation-resistant rheological additive is a solvent of polyamide or polyurea and has certain adverse effects on the adhesive property and TVOC of the product.
For structural adhesives, the main component is an active oligomer. Prior to curing, inert thixotropic agents are commonly used in the related art to increase viscosity and impart optimal workability to the oligomer in order to prevent sagging or slumping. The filler with high specific surface area such as fumed silica, fumed alumina and organic bentonite can obviously improve the zero shear viscosity of the oligomer by adding a small amount, improve the sagging resistance of the paint and the adhesive, adjust the shear thinning behavior of the paint and the adhesive, is an ideal thickening thixotropic agent, and can adsorb continuous phase liquid to prevent the liquid precipitation behavior and the filler sedimentation behavior. However, the inventors found that all the above effects can be achieved by adding such thickening thixotropic agents, and that the key point is to effectively adjust the interactions between filler particles and between the matrix, and further to obtain a flocculated particle network structure, and that the liquid precipitation behavior cannot be thoroughly solved only by changing the surface properties of the filler.
In summary, the problems of the existing structural adhesives in the current markets at home and abroad include cracking during transportation, skinning, caking, filler sedimentation and liquid precipitation during long-term storage, failure to meet the requirements of various shapes and sizes during the sizing stage, and severe heat release during the curing process. Therefore, how to improve the stability of the structural adhesive and ensure the smooth and uniform heat quantity in the curing exothermic process while meeting the mechanical property requirements is an urgent problem to be solved in the field at present.
Therefore, there is a need to develop a high-stability low-heat release structural adhesive system material, and a preparation method and application thereof to solve the above problems.
Disclosure of Invention
The invention aims to provide a high-stability low-heat-release structural adhesive system material, and a preparation method and application thereof, which solve the problems of improving the stability of structural adhesive and ensuring the smoothness and uniformity of heat in the curing heat release process while meeting the mechanical property requirement.
In order to achieve the above object, in a first aspect, the present invention provides a high-stability low-heat release structural adhesive system material, which comprises a resin part and a curing agent part, wherein the mass ratio of the resin part to the curing agent part is 10 (4-5);
the resin part comprises 60-80 parts of bisphenol A type epoxy resin, 2-15 parts of bisphenol F type epoxy resin, 10-20 parts of inorganic reinforcing filler and 3-8 parts of thickening thixotropic agent in parts by mass;
The curing agent part comprises 56-115 parts of an amine curing agent, 5-20 parts of inorganic reinforcing filler, 5-9 parts of thickening thixotropic agent and 4-60 parts of modified amine rheological auxiliary agent, and the liquid leaching rate of the curing agent part is lower than 2.0%; the modified amine rheological additive is prepared by pre-reacting an amine substance and a substance capable of carrying out addition reaction with the amine substance at the temperature of 25-150 ℃, wherein the amine substance comprises at least one of polyetheramine, polyamide and alicyclic amine, and the substance capable of carrying out addition reaction with the amine substance comprises at least one of isocyanate, chain-extended isocyanate, epoxy resin and chain-extended epoxy resin.
Optionally, in the pre-reaction of the modified amine rheological additive, the dosage of the amine substance is 10-40 parts, and the dosage of the substance capable of undergoing addition reaction with the amine substance is 5-15 parts.
Optionally, the amine curing agent comprises 10-40 parts of polyetheramine, 30-40 parts of polyamide and/or alicyclic amine.
Optionally, the curing agent part comprises 40-70 parts of amine curing agent, 5-20 parts of inorganic reinforcing filler, 5-9 parts of thickening thixotropic agent and 4-60 parts of modified amine rheological aid.
Optionally, the inorganic reinforcing filler comprises at least one of ground glass fiber, wollastonite, calcium carbonate, and fused silica.
Optionally, the thickening thixotropic agent comprises at least one of fumed silica, fumed alumina, and organobentonite.
Optionally, the resin part further comprises 2-6 parts of a toughening agent and 0.05-0.2 parts of a defoaming agent.
In a second aspect, the invention provides a method for preparing a high-stability low-heat release structural adhesive system material, which comprises the following steps:
Preparing the resin part: preparing raw materials according to a proportion, and uniformly mixing the raw materials required by the resin part to obtain the resin part;
Preparing the curing agent part: p1, heating and mixing corresponding parts by weight of the amine substances and the substances capable of carrying out addition reaction with the amine substances at 25-150 ℃ for pre-reaction to obtain the modified amine rheological auxiliary agent; p2, taking corresponding parts by weight of the modified amine rheological auxiliary agent, adding the amine curing agent, the inorganic reinforcing filler and the thickening thixotropic agent into the modified amine rheological auxiliary agent according to a proportion, and stirring at room temperature to obtain the curing agent part;
mixing the resin part and the curing agent part according to the mass ratio of 10 (4-5) to obtain the structural adhesive system material, wherein the exothermic peak temperature of the high-stability low-exothermic structural adhesive system material is lower than 70 ℃, the gel time is longer than 220 minutes, and the curing time is longer than 500 minutes.
Optionally, in the step P1: and (3) dropwise adding the substances capable of carrying out addition reaction with the amine substances into the amine substances, and stirring at 100 ℃ for 30min at a rotating speed of 100-2000rpm to obtain the modified amine rheological auxiliary agent.
Optionally, in the step P1: mixing the amine substances, dropwise adding the substances capable of carrying out addition reaction with the amine substances into the amine substances, and stirring at 100 ℃ and a rotating speed of 100-2000rpm for 30min to obtain the modified amine curing agent.
In a third aspect, the invention provides application of a high-stability low-heat-release structural adhesive system material, which is applied to bonding of wind power blades.
Optionally, the application includes: and performing stress scanning test on the curing agent part to obtain a yield transition curve and a yield stress value of the curing agent part, predicting the stability of the curing agent part, wherein when the stress of the curing agent part is higher than the yield stress value, the yield transition curve does not generate mutation, and the curing agent part does not generate cracking behavior.
The beneficial effects of the invention include:
1. the structural adhesive system material prepared by the preparation method improves the stability of the curing agent part in the transportation and storage processes, and does not crack, liquid precipitation and filler sedimentation.
2. The structural adhesive system material prepared by the preparation method reduces the heat release amount generated in the curing process of the resin part and the curing agent part, so that the reaction heat release is gentle and the higher heat release peak is eliminated.
3. The modified amine rheological auxiliary agent prepared by the pre-reaction reduces the curing rate of the resin part and the curing agent part and prolongs the operable time.
4. The stress scanning test shows that even when the stress is higher than the yield stress value, the yield transition curve of the curing agent part does not change suddenly, namely the curing agent part does not crack in the transportation and storage processes.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing a high-stability low-heat-release structural adhesive system material according to an embodiment of the invention;
FIG. 2 is a graph of shear viscosity as a function of stress for various samples of the present invention;
FIG. 3 is a graph of modulus versus time for various samples of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The structural adhesive system material prepared by the preparation method has the advantages of good storage stability, excellent processability, long operation time, mild curing heat release, low heat release peak and excellent mechanical property.
The invention selects the filler with high specific surface area and high cost performance, and then adjusts the polarity of the oligomer matrix by synthesizing the modified amine rheological aid, thereby playing the roles of changing the thixotropic property and yield transformation process of the sample and improving the stability of the product. The polarity of the oligomer matrix can be effectively and customized adjusted by adding the synthesized modified amine rheological auxiliary agent into the amine curing agent, so that the new rheological property of the structural adhesive product is endowed. The modified amine rheological additive is prepared by the synthesis reaction of amine substances and substances which can react with the amine substances in an addition way (such as isocyanate, chain-extended isocyanate, epoxy resin and chain-extended epoxy resin). The modified amine rheological auxiliary agent not only can improve sagging resistance, storage and transportation stability of the product, but also can participate in subsequent curing reaction, and reduces the heat release amount of the curing reaction of the structural adhesive.
The invention provides a high-stability low-heat release structural adhesive system material, which comprises a resin part and a curing agent part, wherein the mass ratio of the resin part to the curing agent part is 10 (4-5);
the resin part comprises 60-80 parts of bisphenol A type epoxy resin, 2-15 parts of bisphenol F type epoxy resin, 10-20 parts of inorganic reinforcing filler and 3-8 parts of thickening thixotropic agent in parts by mass;
The curing agent part comprises 56-115 parts of an amine curing agent, 5-20 parts of inorganic reinforcing filler, 5-9 parts of thickening thixotropic agent and 4-60 parts of modified amine rheological auxiliary agent, and the liquid leaching rate of the curing agent part is lower than 2.0%; the modified amine rheological additive is prepared by pre-reacting an amine substance and a substance capable of carrying out addition reaction with the amine substance at the temperature of 25-150 ℃, wherein the amine substance comprises at least one of polyetheramine, polyamide and alicyclic amine, and the substance capable of carrying out addition reaction with the amine substance comprises at least one of isocyanate, chain-extended isocyanate, epoxy resin and chain-extended epoxy resin.
In some embodiments of the present invention, in the pre-reaction of the modified amine rheological additive, the amine substance is used in an amount of 10-40 parts, and the substance capable of undergoing an addition reaction with the amine substance is used in an amount of 5-15 parts.
In some embodiments of the invention, the amine curing agent comprises 10-40 parts polyetheramine, 30-40 parts polyamide and/or alicyclic amine.
In some embodiments of the present invention, the curative portion comprises 40-70 parts of an amine curative, 5-20 parts of an inorganic reinforcing filler, 5-9 parts of a thickening thixotropic agent, and 4-60 parts of a modified amine rheology aid.
In some embodiments of the invention, the inorganic reinforcing filler comprises at least one of ground glass fiber, wollastonite, calcium carbonate, and fused silica.
In some embodiments of the invention, the thickening thixotropic agent comprises at least one of fumed silica, fumed alumina, and organobentonite.
In some embodiments of the invention, the resin portion further comprises 2-6 parts of a toughening agent and 0.05-0.2 parts of a defoamer.
The invention provides a preparation method of a high-stability low-heat release structural adhesive system material, which comprises the following steps of:
S1: preparing the resin part: preparing raw materials according to a proportion, and uniformly mixing the raw materials required by the resin part to obtain the resin part;
s2: preparing the curing agent part: p1, heating and mixing corresponding parts by weight of the amine substances and the substances capable of carrying out addition reaction with the amine substances at 25-150 ℃ for pre-reaction to obtain the modified amine rheological auxiliary agent; p2, taking corresponding parts by weight of the modified amine rheological auxiliary agent, adding the amine curing agent, the inorganic reinforcing filler and the thickening thixotropic agent into the modified amine rheological auxiliary agent according to a proportion, and stirring at room temperature to obtain the curing agent part;
S3: mixing the resin part and the curing agent part according to the mass ratio of 10 (4-5) to obtain the structural adhesive system material, wherein the exothermic peak temperature of the high-stability low-exothermic structural adhesive system material is lower than 70 ℃, the gel time is longer than 230 minutes, and the curing time is longer than 500 minutes.
In some embodiments of the invention, the pre-reaction time is 30-90 minutes.
In some embodiments of the invention, in the step P1: and (3) dropwise adding the substances capable of carrying out addition reaction with the amine substances into the amine substances, and stirring at 100 ℃ for 30min at a rotating speed of 100-2000rpm to obtain the modified amine rheological auxiliary agent.
In some embodiments of the invention, in the step P1: firstly mixing the amine substances, then adding the substances capable of carrying out addition reaction with the amine substances into the amine substances dropwise, and stirring at 100 ℃ and a rotating speed of 100-2000rpm for 30min to obtain the modified amine rheological auxiliary agent.
The invention provides an application of a high-stability low-heat-release structural adhesive system material, which is applied to bonding of wind power blades.
Some embodiments of the invention, the application comprising: and performing stress scanning test on the curing agent part to obtain a yield transition curve and a yield stress value of the curing agent part, predicting the stability of the curing agent part, wherein when the stress of the curing agent part is higher than the yield stress value, the yield transition curve does not generate mutation, and the curing agent part does not generate cracking behavior.
In other embodiments of the present invention, the toughening agent and the defoamer are commercially available and will not be described in detail herein.
In some embodiments of the invention, the alicyclic amine comprises isophorone diamine.
According to some embodiments of the invention, the method can be used for guiding the formula optimization of the curing agent part by judging whether the curing agent part is cracked or not, so that the formula and the optimization process of the curing agent part can be adjusted according to the states of the curing agent part at different test temperatures and defect improvement degrees in the test process.
According to some embodiments of the invention, a constant temperature curing curve of the structural adhesive system material is measured through a rheometer, curing rates of different structural adhesive system materials are compared, and mechanical properties of the structural adhesive system material after curing are evaluated.
In some embodiments of the invention, the bisphenol a epoxy resin has an epoxy equivalent weight of 170-240; the epoxy equivalent of the bisphenol F type epoxy resin is 160-180.
The manufacturer and model or make of the instruments used in the examples of the present invention are shown in table 1.
Table 1 instrument manufacturer and model or make thereof
The sources, acronyms and CAS numbers of the chemical reagents applied in the examples of the present invention are shown in table 2.
TABLE 2 Source of chemical reagents, english abbreviation and CAS number
| Chemical reagent | Source(s) | English abbreviation | CAS number |
| Bisphenol A type epoxy resin | Insulating material for Laizhou market | -- | 25036-25-3 |
| Bisphenol F type epoxy resin | Hubei Shiteng chemical technology Co.Ltd | -- | -- |
| Isophorone diisocyanate | Vanhua chemical group Co., ltd | IPDI | -- |
| Wollastonite | Shanghai sugarcane chemical Co., ltd | -- | 13983-17-0 |
| Calcium carbonate | Shanghai Source leaf Biotechnology Co Ltd | -- | 471-34-1 |
| Toughening agent | Pandek (Shanghai) International trade Limited | -- | 143106-82-5 |
| Defoaming agent | Fine chemical engineering | -- | -- |
| Isophorone diamine | Shanghai sugarcane chemical Co., ltd | IPDA | 2855-13-2 |
| Polyamide 350A | Nanjing Dishi import and export trade Limited company | -- | -- |
| Polyetheramine D230 | Shanghai Jizhu Biochemical technology Co.Ltd | -- | 9046-10-0 |
| Polyetheramine D400 | Chuzhou Hui Cheng electronic materials Co Ltd | -- | 9046-10-0 |
| Hydrophobic fumed silica | Shanghai Source leaf Biotechnology Co Ltd | -- | 7631-86-9 |
| Ground glass fiber | Shanghai Source leaf Biotechnology Co Ltd | -- | 65997-17-3 |
Note that: in the table "-" indicates none.
Example 1
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
preparation of modified amine rheological auxiliary agent: dropwise adding 10 parts of bisphenol A epoxy resin into 10 parts of isophorone diamine, and stirring at 50 ℃ and 200rpm for 30 minutes to obtain a modified amine rheological aid;
Preparation of the curing agent part: adding 10 parts of polyether amine D230, 30 parts of polyether amine D400, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 2:1 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 2
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: dropwise adding 10 parts of bisphenol A epoxy resin into 10 parts of isophorone diamine, and stirring at 100 ℃ and 500rpm for 30 minutes to obtain a modified amine rheological aid;
Preparation of the curing agent part: adding 10 parts of polyether amine D230, 30 parts of polyether amine D400, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 2:1 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 3
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: dropwise adding 10 parts of bisphenol A epoxy resin into 30 parts of polyamide 350A, and stirring at 100 ℃ and 2000rpm for 60 minutes to obtain a modified amine rheological aid;
Preparation of the curing agent part: adding 10 parts of isophorone diamine, 10 parts of polyether amine D230, 30 parts of polyether amine D400, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 5:2 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 4
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: dropwise adding 15 parts of bisphenol A epoxy resin into 30 parts of polyether amine D400, and stirring for 90 minutes at 120 ℃ and 1000rpm to obtain a modified amine rheological additive;
preparation of the curing agent part: adding 10 parts of isophorone diamine, 10 parts of polyether amine D230, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 2:1 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 5
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: 15 parts of IPDI is added into 30 parts of polyetheramine D400 drop by drop, and stirred for 60 minutes at 90 ℃ and 1000rpm to obtain a modified amine rheological additive;
preparation of the curing agent part: adding 10 parts of isophorone diamine, 10 parts of polyether amine D230, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 5:2 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 6
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: dropwise adding 5 parts of bisphenol A epoxy resin into 10 parts of isophorone diamine, stirring at 100 ℃ and 500rpm for 30 minutes to obtain a first modified amine rheological additive, dropwise adding 10 parts of bisphenol A epoxy resin into 30 parts of polyether amine D400, stirring at 100 ℃ and 500rpm for 30 minutes to obtain a second modified amine rheological additive, and uniformly mixing the first modified amine rheological additive and the second modified amine rheological additive at normal temperature to obtain a modified amine rheological additive;
preparation of the curing agent part: adding 10 parts of polyether amine D230, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 2:1 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
Example 7
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of modified amine rheological auxiliary agent: mixing 10 parts of isophorone diamine and 30 parts of polyetheramine D400 to obtain a first mixture, dropwise adding 15 parts of bisphenol A type epoxy resin into the first mixture, and stirring at 100 ℃ and 500rpm for 30 minutes to obtain a modified amine rheological aid;
preparation of the curing agent part: adding 10 parts of polyether amine D230, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fiber and 5 parts of wollastonite into the modified amine rheological auxiliary agent, and uniformly stirring at room temperature to obtain a curing agent part;
and mixing the resin part and the curing agent part according to the mass ratio of 5:2 at the rotating speed of 2000rpm to obtain a structural adhesive system material sample.
The components and their contents in examples 1 to 7 are shown in Table 3.
Table 3 Components and contents of examples
Comparative example 1
Preparation of the resin fraction: taking 65 parts of bisphenol A type epoxy resin, 10 parts of bisphenol F type epoxy resin, 15 parts of wollastonite, 5 parts of calcium carbonate, 5 parts of toughening agent and 0.2 part of defoamer, mixing the above components and uniformly stirring at room temperature to obtain a resin part;
Preparation of the curing agent part: mixing 10 parts of isophorone diamine, 10 parts of polyetheramine D230, 30 parts of polyetheramine D400, 30 parts of polyamide 350A, 5 parts of hydrophobic fumed silica, 10 parts of ground glass fibers and 5 parts of wollastonite, and uniformly stirring at room temperature to obtain a curing agent part;
the resin part and the hardener part were mixed in a mass ratio of 2:1 and at 2000rpm, and a comparative sample was obtained.
The curing agent portions of examples 1 to 7 and comparative example 1 were subjected to stress sweep test to obtain the yield transition process and yield stress value of the curing agent portion, and referring to fig. 2, the rheology test results of the curing agent portions of examples 1 to 7 and comparative example 1 revealed that the curing agent portion of comparative example 1 had a sudden change in shear viscosity (discontinuous change process) when the stress was higher than the yield stress value, and thus it could be judged that the curing agent portion of comparative example 1 had cracking behavior when the stress (surface force per unit area) was higher than the yield stress value or the strain was higher than the critical strain value during transportation; although the yield transition behavior of example 1 was more gradual than that of comparative example 1, in extreme cases, the transport cracking behavior was also likely to occur, and the yield transition processes of examples 2-7 were all relatively continuous, with no transport cracking behavior occurring.
The samples of the structural adhesive system materials of examples 1 to 7 and the comparative sample of comparative example 1 were subjected to modulus test, and referring to fig. 3, the curves of the changes with time of the samples of the structural adhesive system materials of examples 1 to 7 and the comparative sample of comparative example 1 were shown in table 4, the solid curves in fig. 3 represent storage modulus of the samples or comparative samples, the hollow curves represent loss modulus of the samples or comparative samples, the same color curves represent the same samples or comparative samples, the gel point of the comparative sample of comparative example 1 appears at 180min, the gel point of the structural adhesive system materials of examples 1 to 7 appears after 225min, the gel time to reach the gel point is shown in table 4, and the high-stability low-heat-release structural adhesive system materials of examples 1 to 7 of the present application reduce the curing rate of the resin part and the curing agent part, and prolong the operable time.
For the system materials of examples 1-7 and comparative example 1, the example body was not inferior to the comparative example in mechanical properties, and referring to Table 4, the body tensile strength of examples 1-7 tested according to ISO527-2 was slightly higher than that of comparative example 1.
The resin part and the curing agent part of examples 1 to 7 and comparative example 1 were subjected to storage stability test, and the liquid separation rate was measured according to the test method described in patent CN 116359450B: and placing the resin part and the curing agent part in a high-temperature high-pressure reaction kettle for high-temperature high-pressure test, taking out the resin part and the curing agent part subjected to the high-temperature high-pressure test, and evaluating the liquid precipitation behavior of the resin part and the curing agent part according to the liquid precipitation condition of the resin part and the curing agent part subjected to the high-temperature high-pressure test. The pressure of the high-temperature high-pressure test is 0.2-6 megapascals, the temperature of the high-temperature high-pressure test is 25-100 ℃, and the time of the high-temperature high-pressure test is 4-96 hours. The liquid precipitation rate of the resin part and the curing agent part, namely the calculation mode of the proportion of precipitated liquid is as follows: The heat release of the structural adhesive system material samples of examples 1-7 and the comparative sample of comparative example 1 during curing was monitored and a constant temperature curing test was performed using a rheometer, with y being the weight of the precipitated liquid, g being the weight of the sample to be evaluated, and w being g, and the test results being shown in Table 4.
TABLE 4 Table 4
| Sample of | Stability of resin part (6 months) | Partial stability of curing agent (6 months) | Exothermic peak temperature/o C | Gel time/min | Curing time/min | Tensile Strength/MPa |
| Example 1 | Stabilization | The liquid separation rate is 1.6 percent | 68 | 225 | 520 | 55 |
| Example 2 | Stabilization | The liquid separation rate is 1.1% | 65 | 238 | 640 | 57 |
| Example 3 | Stabilization | The liquid separation rate is 1.3 percent | 60 | 240 | 635 | 61 |
| Example 4 | Stabilization | Stabilization | 53 | 237 | 665 | 57 |
| Example 5 | Stabilization | Stabilization | 55 | 245 | 650 | 55 |
| Example 6 | Stabilization | Stabilization | 50 | 250 | 670 | 57 |
| Example 7 | Stabilization | Stabilization | 53 | 232 | 655 | 58 |
| Comparative example 1 | Stabilization | Liquid separation rate is 7.1% | 118 | 180 | 330 | 52 |
As can be seen from Table 4, the resin portions of examples and comparative example 1 are both good in storage stability, while the curing agent portions of examples 4 to 7 are good in stability, and the curing agent portion of comparative example 1 is severe in liquid precipitation behavior, so that it can be judged that the occurrence of the pre-reaction changes the structure of the molecular chain and affects the interaction of the curing agent portion with the fumed silica, thereby avoiding the occurrence of liquid precipitation behavior; the curing temperatures of examples 1-7 were significantly lower than the exothermic temperature of comparative example 1, indicating that pre-reacting the curative portion significantly reduced the amount of exotherm generated during post-mixing curing; and the gelation time and the curing time of the examples 1-7 are obviously longer than those of the comparative example 1, which shows that the curing rate of the structural adhesive system material is obviously reduced and the operable time is prolonged by designing the pre-reaction process.
While embodiments of the present invention have been described in detail hereinabove, it will be apparent to those skilled in the art that various modifications and variations can be made to these embodiments. It is to be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the following claims. Moreover, the invention described herein is capable of other embodiments and of being practiced or of being carried out in various ways.
Claims (10)
1. The high-stability low-heat-release structural adhesive system material is characterized by comprising a resin part and a curing agent part, wherein the mass ratio of the resin part to the curing agent part is 10 (4-5);
the resin part comprises 60-80 parts of bisphenol A type epoxy resin, 2-15 parts of bisphenol F type epoxy resin, 10-20 parts of inorganic reinforcing filler and 3-8 parts of thickening thixotropic agent in parts by mass;
The curing agent part comprises 40-70 parts of amine curing agent, 5-20 parts of inorganic reinforcing filler, 5-9 parts of thickening thixotropic agent and 4-60 parts of modified amine rheological aid, wherein the modified amine rheological aid is obtained by pre-reacting amine substances with substances capable of undergoing addition reaction with the amine substances, the amine substances comprise at least one of polyether amine, polyamide and alicyclic amine, and the substances capable of undergoing addition reaction with the amine substances comprise isocyanate;
The curing agent part is prepared by the following steps: p1, heating and mixing 10-40 parts of the amine substance and 5-15 parts of the substance capable of undergoing addition reaction with the amine substance at 25-150 ℃ for pre-reaction to obtain the modified amine rheological auxiliary agent; p2, taking corresponding parts by weight of the modified amine rheological auxiliary agent, adding the amine curing agent, the inorganic reinforcing filler and the thickening thixotropic agent into the modified amine rheological auxiliary agent according to a proportion, and stirring at room temperature to obtain the curing agent part;
the liquid precipitation rate of the curing agent part is lower than 2.0%;
Mixing the resin part and the curing agent part according to the mass ratio of 10 (4-5) to obtain the high-stability low-heat-release structural adhesive system material, wherein the heat release peak temperature of the high-stability low-heat-release structural adhesive system material is lower than 70 ℃, the gel time is longer than 230 minutes, and the curing time is longer than 500 minutes.
2. The high stability low heat release structural adhesive system of claim 1, wherein the amine curing agent comprises 10-40 parts polyetheramine, 30-40 parts polyamide and/or cycloaliphatic amine.
3. The high stability low exotherm structural adhesive system of claim 1, wherein the inorganic reinforcing filler comprises at least one of ground glass fiber, wollastonite, calcium carbonate, and fused silica.
4. The high stability low exotherm structural adhesive system of claim 1, wherein the thickening thixotropic agent comprises at least one of fumed silica, fumed alumina, and organobentonite.
5. The high stability low exotherm structural adhesive system of claim 1, wherein the resin portion further comprises 2-6 parts of a toughening agent and 0.05-0.2 parts of a defoamer.
6. A method of preparing a high stability low exotherm structural adhesive system according to any one of claims 1-5, comprising the steps of:
Preparing the resin part: preparing raw materials according to a proportion, and uniformly mixing the raw materials required by the resin part to obtain the resin part;
Preparing the curing agent part: p1, heating and mixing corresponding parts by weight of the amine substances and the substances capable of carrying out addition reaction with the amine substances at 25-150 ℃ for pre-reaction to obtain the modified amine rheological auxiliary agent; p2, taking corresponding parts by weight of the modified amine rheological auxiliary agent, adding the amine curing agent, the inorganic reinforcing filler and the thickening thixotropic agent into the modified amine rheological auxiliary agent according to a proportion, and stirring at room temperature to obtain the curing agent part;
Mixing the resin part and the curing agent part according to the mass ratio of 10 (4-5) to obtain the high-stability low-heat-release structural adhesive system material, wherein the heat release peak temperature of the high-stability low-heat-release structural adhesive system material is lower than 70 ℃, the gel time is longer than 230 minutes, and the curing time is longer than 500 minutes.
7. The method for preparing the high-stability low-heat-release structural adhesive system material according to claim 6, wherein in the step P1: and (3) dropwise adding the substances capable of carrying out addition reaction with the amine substances into the amine substances, and stirring at 100 ℃ for 30min at a rotating speed of 100-2000rpm to obtain the modified amine rheological auxiliary agent.
8. The method for preparing the high-stability low-heat-release structural adhesive system material according to claim 6, wherein in the step P1: firstly mixing the amine substances, then adding the substances capable of carrying out addition reaction with the amine substances into the amine substances dropwise, and stirring at 100 ℃ and a rotating speed of 100-2000rpm for 30min to obtain the modified amine rheological auxiliary agent.
9. The use of a high stability low heat release structural adhesive system according to any one of claims 1 to 5, wherein the structural adhesive system is used for bonding wind power blades.
10. The use of a high stability low heat release structural adhesive system according to claim 9, comprising: and performing stress scanning test on the curing agent part to obtain a yield transition curve and a yield stress value of the curing agent part, predicting the stability of the curing agent part, wherein when the stress of the curing agent part is higher than the yield stress value, the yield transition curve does not generate mutation, and the curing agent part does not generate cracking behavior.
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| CN102627930A (en) * | 2012-03-23 | 2012-08-08 | 烟台德邦科技有限公司 | Epoxy structural adhesive for wind wheel blades and its preparation method |
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