CN112552850A - High-performance adhesive composition for wind power blade and preparation method and application thereof - Google Patents
High-performance adhesive composition for wind power blade and preparation method and application thereof Download PDFInfo
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- CN112552850A CN112552850A CN202011461189.6A CN202011461189A CN112552850A CN 112552850 A CN112552850 A CN 112552850A CN 202011461189 A CN202011461189 A CN 202011461189A CN 112552850 A CN112552850 A CN 112552850A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/62—Alcohols or phenols
- C08G59/621—Phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/66—Mercaptans
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention provides a high-performance adhesive composition for wind power blades, and a preparation method and application thereof, wherein the high-performance adhesive composition for the wind power blades comprises a combination of epoxy resin, graphene, polythiol, tertiary amine, pyrogallol and a filler; the high-performance adhesive composition for the wind power blade is prepared by selecting epoxy resin as a main material and adding graphene, so that the high-performance adhesive composition for the wind power blade has high strength and toughness, and by adding polythiol, tertiary amine and pyrogallol, the high-performance adhesive has short curing time, can quickly generate gel, greatly shortens the operation time in actual application, and is beneficial to improving the production efficiency and yield of the blade when being applied to the wind power generation blade.
Description
Technical Field
The invention belongs to the technical field of wind power generation, and particularly relates to a high-performance adhesive composition for a wind power blade, and a preparation method and application thereof.
Background
Wind power generation has received much attention due to its many advantages of being efficient, clean, and renewable. As a core component of a wind driven generator, the blade has huge market potential, and meanwhile, the efficiency, the service life and the performance of the wind driven generator set are directly influenced by the quality of the blade. The blade of the wind driven generator is mainly prepared from a composite material, and an epoxy resin system for the blade of the composite material is the key for preparing the blade of the wind driven generator.
At present, many studies and reports are made on epoxy resin system adhesives for wind power generation. CN104962225A discloses an epoxy adhesive for manufacturing wind energy blades, which is prepared from a resin part and a curing agent part according to the ratio of 100: 40-50 by weight; the weight ratio of the raw materials of the resin part is as follows: 50-70 parts of bisphenol A epoxy resin, 0-10 parts of bisphenol F epoxy resin, 0-10 parts of 1, 6-hexanediol diglycidyl ether, 10-20 parts of calcium carbonate, 5-10 parts of fumed silica, 0-5 parts of glass fiber and 0.01-1 part of expandable microspheres; the curing agent part comprises the following raw materials in percentage by weight: 20-40 parts of polyetheramine D400, 20-30 parts of isophorone diamine, 20-40 parts of polyamide, 10-20 parts of calcium carbonate, 5-20 parts of fumed silica, 0-5 parts of glass fiber and 0.01-1 part of expandable microspheres. The curing agent part can offset the volume shrinkage of the epoxy adhesive caused by curing, reliably and effectively control the volume shrinkage of the epoxy adhesive, and easily realize zero shrinkage and even moderate expansion of the volume of the epoxy adhesive. However, the wind driven generator blade is large in size and high in required bonding strength, the adhesive prepared from the components is poor in structural strength and toughness, and the technical requirements of high strength and high toughness required by wind power blades, especially megawatt large-scale wind power blades, cannot be met.
CN101851481A discloses an epoxy resin adhesive for manufacturing wind turbine blades and a preparation method thereof, the epoxy resin adhesive is composed of a resin part and a curing agent part, the resin part comprises: epoxy resin, a diluent, a filler, a thixotropic agent and an auxiliary agent; the curing agent part comprises an amine curing agent, a filler and a thixotropic agent; the filler comprises a powdery filler and a fibrous filler. The epoxy resin adhesive prepared by adopting the general epoxy resin has higher strength, particularly, the strength of the material is further improved by adding the fibrous filler, the cracking resistance of the material is improved, the special requirements of the wind driven generator blade above megawatt level on the material are met, the material cost is low, and the economy is good. CN101525439A discloses a modified epoxy resin for a wind power generation blade structural adhesive, which comprises the following components in parts by weight: 10-50 wt% of epoxy resin E-44; 10-50 wt% of epoxy resin E-51; 5-15 wt% of epoxy resin E-20; 10-50 wt% of epoxy resin 830; 0.1 to 1 wt% of an isooctoate; 10-30 wt% of PU prepolymer; 0.1-1 wt% of a tin catalyst; 1000, 5-20 wt% of amine-terminated silicone resin; 1-10 wt% of SP resin; 1-5 wt% of a tetrafunctional epoxy resin; compared with the epoxy resin before modification, the performance of the cured product of the modified epoxy resin is remarkably improved, the breaking strength is improved by 40-60%, the shear strength is improved by 40-80%, and the impact toughness is improved by 150-200%; also has excellent shear fatigue properties and bending fatigue properties: cycle 107 times at 50% shear load. The modified epoxy structural adhesives aim at solving the technical problems of low structural strength and low toughness, however, because the structural strength and the toughness are relatively contradictory material characteristics, the existing modified epoxy structural adhesives for the wind power blades are usually only focused on solving the structural strength or the toughness, and the toughness is reduced along with the improvement of the structural strength. Therefore, the existing epoxy structural adhesive for the wind power blade cannot meet the technical requirements of high strength and high toughness required by the wind power blade, particularly the megawatt large wind power blade, and the existing epoxy resin system adhesive generally needs to have long operable time, namely long gel time, so that the production efficiency is reduced, and the epoxy structural adhesive is not beneficial to large-scale industrial production and use.
Therefore, the development of a high-performance adhesive composition for wind turbine blades, which has short curing time and high strength and toughness, is a problem to be solved urgently at present.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a high-performance adhesive composition for a wind power blade and a preparation method and application thereof, wherein the high-performance adhesive composition for the wind power blade is prepared by selecting epoxy resin as a main material and adding graphene, so that the high-performance adhesive composition for the wind power blade has higher strength and toughness; and by adding polythiol, tertiary amine and pyrogallol, the curing time is short while other properties are not influenced, gel can be quickly generated, the operation time is shortened, and when the curing agent is applied to a wind power generation blade, the production efficiency and the yield of the blade are favorably improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a high-performance adhesive composition for wind power blades, which comprises the following raw materials in parts by weight: 60-80 parts of epoxy resin, 0.6-2 parts of graphene, 40-80 parts of polythiol, 20-25 parts of tertiary amine, 10-20 parts of pyrogallol and 15-20 parts of filler.
The epoxy resin may be 62 parts by weight, 64 parts by weight, 66 parts by weight, 68 parts by weight, 70 parts by weight, 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, or the like.
The graphene may be 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, 1.8 parts by weight, or the like.
The polythiol can be 44 parts by weight, 48 parts by weight, 52 parts by weight, 56 parts by weight, 60 parts by weight, 64 parts by weight, 68 parts by weight, 72 parts by weight, 76 parts by weight, or 80 parts by weight, or the like.
The tertiary amine may be 20.5 parts by weight, 21 parts by weight, 21.5 parts by weight, 22 parts by weight, 22.5 parts by weight, 23 parts by weight, 23.5 parts by weight, 24 parts by weight, 24.5 parts by weight, or the like.
The pyrogallol may be 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, or the like.
The filler may be 15.5 parts by weight, 16 parts by weight, 16.5 parts by weight, 17 parts by weight, 17.5 parts by weight, 18 parts by weight, 18.5 parts by weight, 19 parts by weight, 19.5 parts by weight, or the like.
The high-performance adhesive composition for the wind power blade comprises a combination of epoxy resin, graphene, polythiol, tertiary amine, pyrogallol and a filler; on one hand, the graphene is added into the epoxy resin matrix, so that the adhesive composition has excellent structural strength and toughness, the heat-conducting property of the graphene is excellent, and the heat-radiating performance of the adhesive composition can be improved; on the other hand, the combination of polythiol and tertiary amine is used as an accelerator and a curing agent, and pyrogallol is added, so that the reaction activity of the system can be further improved, the high-performance adhesive has shorter curing time while other performances of the high-performance adhesive are not influenced, gel can be quickly generated, the operation time is shortened, and when the high-performance adhesive is applied to a wind power generation blade, the production efficiency and the yield of the blade are favorably improved.
Preferably, the viscosity of the high-performance adhesive composition for wind power blades is 3000 to 25000mPa · s, such as 3500mPa · s, 4000mPa · s, 5000mPa · s, 6000mPa · s, 7000mPa · s, 10000mPa · s, 13000mPa · s, 16000mPa · s, 19000mPa · s, 21000mPa · s, or 24000mPa · s, and specific point values therebetween are limited to space and for the sake of brevity, and the specific point values included in the range are not exhaustive.
Preferably, the epoxy resin includes any one of or a combination of at least two of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, an alicyclic epoxy resin, or a novolac epoxy resin.
Preferably, the tertiary amine comprises any one of triethylamine, benzyldimethylamine or triethanolamine, or a combination of at least two thereof.
Preferably, the filler comprises any one or a combination of at least two of talc, aluminium hydroxide, calcium carbonate, calcium silicate or silica.
Preferably, the high-performance adhesive composition for the wind power blade further comprises a thixotropic agent and/or an antifoaming agent.
Preferably, the thixotropic agent is contained in the high-performance adhesive composition for wind turbine blades in an amount of 3 to 8 parts by weight, for example, 3.3 parts by weight, 3.6 parts by weight, 3.9 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, 5.2 parts by weight, 5.6 parts by weight, 5.9 parts by weight, 6.5 parts by weight, 7 parts by weight, or 7.5 parts by weight, and specific points therebetween are limited by space and for brevity, and the specific points included in the range are not exhaustive.
Preferably, the thixotropic agent comprises an organobentonite and/or hydrogenated castor oil.
Preferably, the amount of the foaming agent in the high performance adhesive composition for wind turbine blades is 0.01 to 0.1 parts by weight, such as 0.02 part by weight, 0.03 part by weight, 0.04 part by weight, 0.05 part by weight, 0.06 part by weight, 0.07 part by weight, 0.08 part by weight or 0.09 part by weight, and specific values therebetween are limited by space and for brevity, and the specific values included in the range are not exhaustive.
In a second aspect, the invention provides a preparation method of the high-performance adhesive composition for the wind turbine blade in the first aspect, and the preparation method comprises the following steps:
(1) mixing an epoxy resin, graphene, a filler, optionally a defoamer, and optionally a thixotropic agent to obtain a first mixture; reacting polythiol, tertiary amine and pyrogallol to obtain a second mixture;
(2) and (2) mixing the first mixture and the second mixture obtained in the step (1) to obtain the high-performance adhesive composition for the wind power blade.
Preferably, the temperature of the mixing in step (1) is 25-40 ℃, such as 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃ or 39 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the mixing time in step (1) is 1.5-3 h, such as 1.7h, 1.9h, 2.1h, 2.3h, 2.5h, 2.7h or 2.9h, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the range for brevity and conciseness.
Preferably, the reaction temperature in step (1) is 25-40 ℃, such as 27 ℃, 29 ℃, 31 ℃, 33 ℃, 35 ℃, 37 ℃ or 39 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not intended to be exhaustive of the specific values included in the range.
Preferably, the reaction time in step (1) is 1.5 to 3 hours, such as 1.7 hours, 1.9 hours, 2.1 hours, 2.3 hours, 2.5 hours, 2.7 hours or 2.9 hours, and the specific values therebetween are not limited by the space and for the sake of brevity, and the invention is not exhaustive.
Preferably, the mixing time in step (2) is 0.5-1.5 h, such as 0.7h, 0.9h, 1.1h, 1.3h, 1.4h or 1.5h, and the specific values therebetween, which are limited by space and for the sake of brevity, the present invention is not exhaustive list of the specific values included in the range.
Preferably, the mixing in the step (2) is carried out under stirring conditions, and more preferably under stirring conditions at a rotation speed of 300-500 r/min (320r/min, 340r/min, 360r/min, 380r/min, 400r/min, 420r/min, 440r/min, 460r/min or 480r/min, etc.).
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing epoxy resin, graphene, a filler, an optional defoaming agent and an optional thixotropic agent at 25-40 ℃ for 1.5-3 h to obtain a first mixture; reacting polythiol, tertiary amine and pyrogallol at 25-40 ℃ for 1.5-3 h to obtain a second mixture;
(2) and (2) mixing the first mixture and the second mixture obtained in the step (1) for 0.5-1.5 h under the stirring condition that the rotating speed is 300-500 r/min, so as to obtain the high-performance adhesive composition for the wind power blade.
In a third aspect, the invention provides a high-performance adhesive composition for wind power blades as described in the first aspect, and the high-performance adhesive composition is applied to wind power generation equipment.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the high-performance adhesive composition for the wind power blade, provided by the invention, the epoxy resin is selected as a main material, and the graphene is added, so that the high-performance adhesive composition for the wind power blade has high strength and toughness, and particularly, the tensile strength of the high-performance adhesive composition for the wind power blade is 86-90 MPa, and the impact strength of the high-performance adhesive composition for the wind power blade is 51-54 kJ/m2。
(2) By adding polythiol, tertiary amine and pyrogallol, the high-performance adhesive has shorter curing time and can quickly generate gel, the curing time of the high-performance adhesive composition for the wind power blade is only 37-40 min, the operation time in actual application is greatly shortened, and when the high-performance adhesive composition is applied to a wind power generation blade, the production efficiency and the yield of the blade are favorably improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 5
The high-performance adhesive composition for the wind power blade has the viscosity of 10000mPa & s, and the specific components are shown in Table 1, wherein the dosage unit of each component is 'part by weight'.
TABLE 2
| Name (R) | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Bisphenol F type epoxy resin | 70 | 60 | 80 | 70 | 70 |
| Graphene | 1.3 | 0.6 | 2 | 1.3 | 1.3 |
| Polythiols | 60 | 40 | 80 | 62 | 57 |
| Triethylamine | 22 | 20 | 25 | 20 | 25 |
| Pyrogallol | 15 | 10 | 20 | 15 | 15 |
| Calcium carbonate | 17 | 15 | 20 | 17 | 17 |
| Antifoaming agent ST-560 | 0.05 | 0.01 | 0.1 | 0.05 | 0.05 |
| Organic bentonite | 6 | 3 | 8 | 6 | 6 |
The preparation method comprises the following steps:
(1) mixing bisphenol F type epoxy resin (YD-170, national chemical Co., Ltd.), graphene (Henan Taiji chemical products Co., Ltd.), calcium carbonate, a defoaming agent ST-560 and organic bentonite at 30 ℃ for 2h to obtain a first mixture; reacting polythiol, tertiary amine and pyrogallol at 30 ℃ for 2h to obtain a second mixture;
(2) and (2) mixing the first mixture and the second mixture obtained in the step (1) for 1h under the stirring condition that the rotating speed is 400r/min to obtain the high-performance adhesive composition for the wind power blade.
Comparative example 1
The high-performance adhesive composition for the wind power blade is different from that in example 1 only in that graphene is not added, and other components, the using amount and the preparation method are the same as those in example 1.
Comparative example 2
The high-performance adhesive composition for the wind power blade is different from the high-performance adhesive composition in example 1 only in that no pyrogallol is added, and other components, the using amount and the preparation method are the same as those in example 1.
Comparative example 3
The high-performance adhesive composition for the wind power blade is different from that in example 1 only in that the addition amount of triethylamine is 15 parts by weight, the addition amount of polythiol is 67 parts by weight, and other components, the use amounts and the preparation method are the same as those in example 1.
Comparative example 4
The high-performance adhesive composition for the wind power blade is different from that in example 1 only in that the addition amount of triethylamine is 30 parts by weight, the addition amount of polythiol is 62 parts by weight, and other components, the use amounts and the preparation method are the same as those in example 1.
And (3) performance testing:
the high-performance adhesive composition for the wind power blade obtained in the examples 1-5 and the comparative examples 1-4 is cured at room temperature for 24 hours and then cured at 70 ℃ for 8 hours.
(1) Gel time: the test was carried out according to GB 12007.7-1989 method for measuring gel time of epoxy resins.
(2) Tensile strength: the tests were carried out according to ISO 527 general principle for tensile Properties of plastics and composites.
(3) Impact strength: the test was carried out according to ISO 179-1-2010, determination of the pendulum impact behavior of plastics.
The cured samples of the high-performance adhesive composition for the wind power blade obtained in the embodiments 1 to 5 and the comparative examples 1 to 4 were tested according to the test method, and the test results are shown in table 2:
TABLE 2
| Gel time (min) | Tensile Strength (MPa) | Impact Strength (kJ/m)2) | |
| Example 1 | 38 | 90 | 53 |
| Example 2 | 37 | 87 | 52 |
| Example 3 | 39 | 86 | 54 |
| Example 4 | 40 | 89 | 52 |
| Example 5 | 38 | 88 | 51 |
| Comparative example 1 | 38 | 67 | 34 |
| Comparative example 2 | 55 | 68 | 30 |
| Comparative example 3 | 49 | 80 | 49 |
| Comparative example 4 | 48 | 82 | 48 |
According to the data in the table 2, the high-performance adhesive composition for the wind power blade has excellent tensile property and toughness, is short in gel time, and can shorten the curing time in construction.
Specifically, the curing time of the high-performance adhesive composition for the wind power blade obtained in the embodiment 1 to 5 is 37 to 40min, the tensile strength is 86 to 90MPa, and the impact strength is 51 to 54kJ/m2(ii) a Compared with the high-performance adhesive composition for the wind power blade obtained in the comparative examples 2-4, the curing time is greatly shortened, which shows that the gel time of the high-performance adhesive is favorably prolonged by adding pyrogallol and controlling the dosage ratio of triethylamine to polythiol; compared with the high-performance adhesive composition for the wind power blade, which is not added with graphene in the comparative example 1, the tensile strength and the impact strength are both greatly improved; further, it can be found by comparing example 1 and comparative example 2 that the high performance adhesive composition for wind turbine blade obtained without adding pyrogallol (comparative example 1) has longer gel time and reduced tensile strength and impact strength because the pyrogallol can improve the compatibility of graphene and matrix in addition to being used as a reaction activity promoterAnd the tensile strength and the impact strength of the high-performance adhesive composition for the wind power blade are further improved.
The applicant states that the preparation method and application of the high-performance adhesive composition for the wind turbine blade are illustrated by the above embodiments, but the invention is not limited to the above embodiments, that is, the invention is not limited to the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The high-performance adhesive composition for the wind power blade is characterized by comprising the following raw materials in parts by weight: 60-80 parts of epoxy resin, 0.6-2 parts of graphene, 40-80 parts of polythiol, 20-25 parts of tertiary amine, 10-20 parts of pyrogallol and 15-20 parts of filler.
2. The high-performance adhesive composition for the wind power blade as claimed in claim 1, wherein the viscosity of the high-performance adhesive composition for the wind power blade is 3000-25000 mPa-s.
3. The high-performance adhesive composition for wind blades according to claim 1 or 2, wherein the epoxy resin comprises any one of or a combination of at least two of bisphenol a type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin or novolac epoxy resin.
4. The high-performance adhesive composition for wind power blades according to any one of claims 1 to 3, wherein the tertiary amine comprises any one of triethylamine, benzyl dimethylamine or triethanolamine or a combination of at least two of them.
5. The high-performance adhesive composition for wind turbine blades as claimed in any one of claims 1 to 4, wherein the filler comprises any one or a combination of at least two of talc powder, aluminum hydroxide, calcium carbonate, calcium silicate and silica.
6. The high-performance adhesive composition for the wind power blade as claimed in any one of claims 1 to 5, wherein the high-performance adhesive composition for the wind power blade further comprises a thixotropic agent and/or an antifoaming agent;
preferably, the content of the thixotropic agent in the high-performance adhesive composition for the wind power blade is 3-8 parts by weight;
preferably, the thixotropic agent comprises organobentonite and/or hydrogenated castor oil;
preferably, the content of the defoaming agent in the high-performance adhesive composition for the wind power blade is 0.01-0.1 part by weight.
7. A preparation method of the high-performance adhesive composition for the wind power blade as described in any one of claims 1 to 6, wherein the preparation method comprises the following steps:
(1) mixing an epoxy resin, graphene, a filler, optionally a defoamer, and optionally a thixotropic agent to obtain a first mixture; reacting polythiol, tertiary amine and pyrogallol to obtain a second mixture;
(2) and (2) mixing the first mixture and the second mixture obtained in the step (1) to obtain the high-performance adhesive composition for the wind power blade.
8. The method according to claim 7, wherein the temperature of the mixing in the step (1) is 25 to 40 ℃;
preferably, the mixing time in the step (1) is 1.5-3 h;
preferably, the reaction temperature in the step (1) is 25-40 ℃;
preferably, the reaction time in the step (1) is 1.5-3 h;
preferably, the mixing time in the step (2) is 0.5-1.5 h;
preferably, the mixing in the step (2) is carried out under the condition of stirring, and more preferably under the condition of stirring at the rotating speed of 300-500 r/min.
9. The method according to claim 7 or 8, characterized in that it comprises the steps of:
(1) mixing epoxy resin, graphene, a filler, an optional defoaming agent and an optional thixotropic agent at 25-40 ℃ for 1.5-3 h to obtain a first mixture; reacting polythiol, tertiary amine and pyrogallol at 25-40 ℃ for 1.5-3 h to obtain a second mixture;
(2) and (2) mixing the first mixture and the second mixture obtained in the step (1) for 0.5-1.5 h under the stirring condition that the rotating speed is 300-500 r/min, so as to obtain the high-performance adhesive composition for the wind power blade.
10. Use of the high-performance adhesive composition for wind turbine blades as defined in any one of claims 1 to 6 in wind power generation equipment.
Priority Applications (1)
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| CN115820186A (en) * | 2022-11-29 | 2023-03-21 | 无锡荷雨新能源科技有限公司 | Preparation method of novel spray glue for wind power blade |
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Application publication date: 20210326 |