CN112980371A - High-toughness glass fiber reinforced plastic adhesive and preparation method thereof - Google Patents
High-toughness glass fiber reinforced plastic adhesive and preparation method thereof Download PDFInfo
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- CN112980371A CN112980371A CN202110374334.5A CN202110374334A CN112980371A CN 112980371 A CN112980371 A CN 112980371A CN 202110374334 A CN202110374334 A CN 202110374334A CN 112980371 A CN112980371 A CN 112980371A
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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
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
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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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a high-toughness glass fiber reinforced plastic adhesive and a preparation method thereof, wherein the adhesive comprises a component A and a component B, and the component A is prepared from the following components in percentage by mass: 100 parts of polyurethane modified epoxy resin (HXR-UE 29), 8-12 parts of reinforcing agent, 8-1 parts of coupling agent KH 5600.5, 20-30 parts of filler and 2-10 parts of change promoter are added into a kneader and stirred uniformly, and then the white thixotropic A component is obtained. B, preparation of a component: adding 18-30 parts of curing agent, 1-2 parts of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 1-1 part of coupling agent KH 5500.5, 1-2 parts of pigment iron oxide green and 15-25 parts of filler into a kneader and stirring uniformly to obtain a green component B with paste. The high-toughness glass fiber reinforced plastic adhesive provided by the invention has the characteristics of high adhesive strength and good toughness.
Description
Technical Field
The invention relates to a glass fiber reinforced plastic adhesive, belonging to the field of composite non-metallic materials.
Background
Glass Fiber Reinforced Plastic (FRP) or GFRP is a non-metallic material compounded from glass fiber and synthetic resin (such as polyester resin and epoxy resin), has excellent properties of low density, high strength, corrosion resistance and the like, and is widely applied in various industries.
The connection of traditional glass steel spare mostly adopts riveted mode, and this connected mode construction is convenient, easy operation. However, the main disadvantages of riveting are that stress concentration of the glass fiber reinforced plastic member is easily caused, and loosening of the rivet and local cracking of the glass fiber reinforced plastic member are easily caused during use.
Disclosure of Invention
In view of the above, the invention aims to design a high-toughness glass fiber reinforced plastic adhesive for self-adhesion and mutual adhesion of glass fiber reinforced plastics and adhesion, filling, sealing, repair and the like of glass fiber reinforced plastics and glass fibers made by mixing various materials.
The invention provides a high-toughness glass fiber reinforced plastic adhesive which comprises a component A and a component B in parts by mass
A number, wherein:
preparation of a component A:
100 parts of polyurethane modified epoxy resin is added,
8-12 parts of a reinforcing agent,
KH 5600.5-1 parts of coupling agent,
20-30 parts of a filler,
adding 2-10 parts of a change promoter into a kneader and uniformly stirring to obtain a white thixotropic component A;
b, preparation of a component:
18-30 parts of a curing agent,
1-2 parts of accelerator 2,4, 6-trisphenol,
KH 5500.5-1 parts of coupling agent,
1-2 parts of pigment iron oxide green,
and adding 15-25 parts of filler into a kneading machine, and uniformly stirring to obtain a green B component with a paste.
Further, the synthesis method of the polyurethane modified epoxy resin in the component A comprises the following steps:
adding diisocyanate into a reaction kettle, introducing nitrogen for protection, starting a stirrer, heating to 70-80 ℃, slowly adding dehydrated polyether glycol, and reacting until isocyanic acid radical reaches a theoretical value to obtain a polyurethane prepolymer for later use;
adding epoxy resin into a reaction kettle, dehydrating, introducing nitrogen for protection, starting a stirrer, heating to 80-90 ℃, adding a polyurethane prepolymer, and reacting until isocyanate disappears to obtain the polyurethane modified epoxy resin.
Further, the reinforcing agent in the component A is one or more of 400-1000 meshes of alumina powder, 400-800 meshes of zinc oxide powder and 325 meshes of mica powder.
Further, the filler in the component A and the component B is one or more of 400-3000 mesh silica powder and precipitated white carbon black.
Furthermore, the accelerant in the component A is one or the combination of more than one of gas-phase silicon dioxide, organic bentonite and hydrogenated castor oil.
Further, the curing agent in the component B is one or the combination of more than one of polyether amine D230 and m-xylylenediamine.
The preparation method of the high-toughness glass fiber reinforced plastic adhesive comprises a component A and a component B, and comprises the following steps in parts by weight:
S1A component preparation step:
100 parts of polyurethane modified epoxy resin is added,
8-12 parts of a reinforcing agent,
KH 5600.5-1 parts of coupling agent,
20-30 parts of a filler,
adding 2-10 parts of a change promoter into a kneader, uniformly stirring, and vacuumizing to obtain a white thixotropic component A;
preparation of the S2B component:
18-30 parts of a curing agent,
1-2 parts of accelerator 2,4, 6-trisphenol,
KH 5500.5-1 parts of coupling agent,
1-2 parts of pigment iron oxide green,
adding 15-25 parts of filler into a kneading machine, uniformly stirring, and vacuumizing to obtain a green paste-containing component B;
s3, completely pouring the liquid resin A into the liquid resin B, stirring for 1-10min to make the liquid resin A uniform, immediately pouring the glue along one side of the inner wall, and standing still for 10-20 min without moving after the glue is gelled; after 1-2 h, the product can be put into use after being verified to be qualified.
Further, the synthesis method of the polyurethane modified epoxy resin in the component A comprises the following steps:
adding diisocyanate into a reaction kettle, introducing nitrogen for protection, starting a stirrer, heating to 70-80 ℃, slowly adding dehydrated polyether glycol, and reacting until isocyanic acid radical reaches a theoretical value to obtain a polyurethane prepolymer for later use;
adding epoxy resin into a reaction kettle, dehydrating, introducing nitrogen for protection, starting a stirrer, heating to 80-90 ℃, adding a polyurethane prepolymer, and reacting until isocyanate disappears to obtain the polyurethane modified epoxy resin.
The invention has the beneficial effects that: according to the invention, diisocyanate and polyether diol are reacted to obtain a polyurethane prepolymer, and then the polyurethane prepolymer is reacted with epoxy resin to obtain polyurethane modified epoxy HXR-UE29, so that a polyether soft chain is introduced into a side chain of the epoxy resin, and the functionality of the epoxy resin is improved. The high-toughness glass fiber reinforced plastic adhesive prepared by taking the polyurethane modified epoxy resin HXR-UE29 as a base material forms a stable micro or submicroscopic multiphase morphological structure in the curing process, obviously improves the toughness of the material, improves the shear strength, adhesive force, tensile strength, bending strength, wear resistance and the like of an adhesive layer, and has little influence on the modulus and heat resistance of the material.
Therefore, the high-toughness glass fiber reinforced plastic adhesive provided by the invention has the characteristics of high adhesive strength and good toughness.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1:
the high-toughness glass fiber reinforced plastic bonding adhesive comprises a component A and a component B, wherein the mixing ratio of the component A to the component B is A, B according to the mass fraction of 100:33, and the component A is prepared by the following steps: 100 parts of polyurethane modified epoxy resin (HXR-UE 29), 10 parts of reinforcing agent 400-mesh zinc oxide powder, KH 5601 parts of coupling agent, 20 parts of filler 400-mesh silica powder, 12 parts of precipitated white carbon black and 2 parts of thixotropic agent hydrogenated castor oil are added into a kneader to be uniformly stirred, vacuumized and subpackaged to obtain a white thixotropic component A. B, preparation of a component: adding 23020 parts of curing agent polyetheramine D, 2 parts of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), KH 5500.5 parts of coupling agent, 2 parts of pigment iron oxide green, 20 parts of filler 3000-mesh silica powder and 3 parts of thixotropic agent fumed silica into a kneader, uniformly stirring, vacuumizing, and subpackaging to obtain a green component B with a paste.
Example 2:
the high-toughness glass fiber reinforced plastic bonding adhesive comprises a component A and a component B, wherein the mixing ratio of the component A to the component B is A, B according to the mass fraction of 100:33, and the component A is prepared by the following steps: 100 parts of polyurethane modified epoxy resin (HXR-UE 29), 12 parts of reinforcing agent 800-mesh alumina powder, KH 5601 parts of coupling agent, 10 parts of filler 3000-mesh silica powder, 20 parts of 800-mesh silica powder and 4 parts of thixotropic agent fumed silica are added into a kneader to be uniformly stirred, vacuumized and subpackaged to obtain a white thixotropic component A. B, preparation of a component: adding 23016 parts of curing agent polyether amine D, 3 parts of m-xylylenediamine, 1 part of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 5500.5 parts of coupling agent KH, 2 parts of pigment iron oxide green, 22 parts of filler 3000-mesh silica micropowder and 2.5 parts of thixotropic agent fumed silica into a kneader, uniformly stirring, vacuumizing, and subpackaging to obtain a green component B with a paste.
Example 3:
the high-toughness glass fiber reinforced plastic bonding adhesive comprises a component A and a component B, wherein the mixing ratio of the component A to the component B is A, B according to the mass fraction of 100:33, and the component A is prepared by the following steps: 100 parts of polyurethane modified epoxy resin (HXR-UE 29), 12 parts of reinforcing agent 800-mesh zinc oxide powder, KH 5601 parts of coupling agent, 20 parts of filler 3000-mesh silica powder, 10 parts of 800-mesh silica powder and 4 parts of thixotropic agent fumed silica are added into a kneader to be uniformly stirred, vacuumized and subpackaged to obtain a white thixotropic component A. B, preparation of a component: adding 23018 parts of curing agent polyether amine D, 4 parts of aminoethyl piperazine, 1 part of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 5500.5 parts of coupling agent KH, 2 parts of pigment iron oxide green, 22 parts of filler 3000-mesh silica powder and 2 parts of thixotropic agent fumed silica into a kneader, uniformly stirring, vacuumizing, and subpackaging to obtain a green component B with a paste.
Comparative example 1:
the glass fiber reinforced plastic adhesive prepared by the method of adding the toughening agent comprises a component A and a component B, wherein the A, B component is mixed according to the mass fraction of 100:50, and the component A is prepared by the following steps: respectively adding 50 parts and 40 parts of epoxy resin E51 and E44, 10 parts of reactive epoxy toughening agent QS-BE, 12 parts of reinforcing agent 800-mesh alumina powder, 5601 parts of coupling agent KH, 10 parts of filler 3000-mesh silica powder, 20 parts of 800-mesh silica powder and 5 parts of thixotropic agent fumed silica into a kneader, uniformly stirring, vacuumizing, and subpackaging to obtain a white component A with thixotropy. B, preparation of a component: 2 parts of curing agent polyether amine D23028, 2 parts of accelerator 2,4, 6-tris (dimethylaminomethyl) phenol (DMP-30), 2 parts of coupling agent KH 5500.5, 2 parts of pigment iron oxide green, 20 parts of filler 3000-mesh silica powder, 20 parts of 800-mesh silica powder and 3 parts of thixotropic agent fumed silica are added into a kneader and uniformly stirred, vacuumized and then subpackaged to obtain the green component B with paste.
The results of the performance tests of the above examples are shown in table 1 below:
table 1 shows the performance test of the products of examples
From the data in the above table, the example products are superior to the comparative products in terms of stack height, tensile strength, elongation at break, steel-to-steel shear resistance, and glass fiber reinforced plastic-to-glass fiber reinforced plastic shear resistance, and exhibit glass fiber reinforced plastic failure, particularly when the bonded glass fiber reinforced plastic is subjected to a shear test. The glass fiber reinforced plastic adhesive prepared by adopting the polyurethane modified epoxy as the main resin effectively improves the elongation at break of a cured product, simultaneously keeps higher mechanical property and has excellent performance on adhering glass fiber reinforced plastic.
The embodiment 3 is the best embodiment, the embodiment adopts 800-mesh zinc oxide powder with higher reinforcing performance, the component B curing agent adopts polyether amine and aminoethyl piperazine for compounding, the aminoethyl piperazine is both a curing agent and an accelerant and has good promoting effect on the polyether amine, the glass fiber reinforced plastic adhesive is more fully cured by matching with the accelerant DMP-30, and the tensile strength, the elongation at break, the steel-steel shear strength and the glass fiber reinforced plastic-glass fiber reinforced plastic shear strength are more outstanding in the performance test shown in the table 1.
The use method of the high-toughness glass fiber reinforced plastic bonding glue comprises the following steps: is a set of A, B two cans which are measured in advance, and the weight ratio of A to B is 1:1-5 (optimally 1: 2). And (3) completely pouring the liquid resin in the tank A into the tank B, stirring the liquid resin by using a clean wood chip or a metal rod for 1 to 10min (optimally 3 to 5 min) to be uniform, immediately pouring the glue along one side of the inner wall, and standing the glue in a vertical state for 10 to 20min after the glue is gelled without moving. After 1-2 h, the glue cast by the glue can be put into use after loading is finished and the verification is qualified.
Claims (9)
1. The high-toughness glass fiber reinforced plastic adhesive is characterized by comprising a component A and a component B according to mass
A number, wherein:
preparation of a component A:
100 parts of polyurethane modified epoxy resin is added,
8-12 parts of a reinforcing agent,
KH 5600.5-1 parts of coupling agent,
20-30 parts of a filler,
adding 2-10 parts of a change promoter into a kneader and uniformly stirring to obtain a white thixotropic component A;
b, preparation of a component:
18-30 parts of a curing agent,
1-2 parts of accelerator 2,4, 6-trisphenol,
KH 5500.5-1 parts of coupling agent,
1-2 parts of pigment iron oxide green,
and adding 15-25 parts of filler into a kneading machine, and uniformly stirring to obtain a green B component with a paste.
2. The high-toughness glass fiber reinforced plastic bonding adhesive according to claim 1, wherein the polyurethane modified epoxy resin in the component A is synthesized by a method comprising the following steps:
adding diisocyanate into a reaction kettle, introducing nitrogen for protection, starting a stirrer, heating to 70-80 ℃, slowly adding dehydrated polyether glycol, and reacting until isocyanic acid radical reaches a theoretical value to obtain a polyurethane prepolymer for later use;
adding epoxy resin into a reaction kettle, dehydrating, introducing nitrogen for protection, starting a stirrer, heating to 80-90 ℃, adding a polyurethane prepolymer, and reacting until isocyanate disappears to obtain the polyurethane modified epoxy resin.
3. The high-toughness glass fiber reinforced plastic adhesive according to claim 1, wherein the reinforcing agent in the component A is one or more of 400-1000 mesh alumina powder, 400-800 mesh zinc oxide powder and 325 mesh mica powder.
4. The high-toughness glass fiber reinforced plastic bonding adhesive according to claim 1, wherein the filler in the component A and the component B is one or more of 400-3000 mesh silica powder and precipitated silica.
5. The high-toughness glass fiber reinforced plastic adhesive according to claim 1, wherein the change promoter in the component A is one or more of fumed silica, organic bentonite and hydrogenated castor oil.
6. The high-toughness glass fiber reinforced plastic adhesive according to claim 1, wherein the curing agent in the component B is one or a combination of more than one of polyetheramine D230 and m-xylylenediamine.
7. The high-toughness glass fiber reinforced plastic adhesive is characterized by comprising a component A and a component B, wherein the mixing ratio of the component A, B is 100:33 according to mass fraction, and the component A is prepared by the following steps: adding 100 parts of polyurethane modified epoxy resin, 12 parts of reinforcing agent 800-mesh zinc oxide powder, KH 5601 parts of coupling agent, 20 parts of filler 3000-mesh silica powder, 10 parts of 800-mesh silica powder and 4 parts of thixotropic agent fumed silica into a kneading machine, uniformly stirring, vacuumizing, and subpackaging to obtain a white component A with thixotropy;
b, preparation of a component: adding 23018 parts of curing agent polyetheramine, 4 parts of aminoethyl piperazine, 1 part of accelerator 2,4, 6-trisphenol, 5500.5 parts of coupling agent KH, 2 parts of pigment iron oxide green, 22 parts of filler 3000-mesh silica powder and 2 parts of thixotropic agent fumed silica into a kneader, uniformly stirring, vacuumizing, and subpackaging to obtain a green component B with a paste.
8. The preparation method of the high-toughness glass fiber reinforced plastic adhesive is characterized by comprising a component A and a component B, and comprises the following steps in parts by weight:
S1A component preparation step:
100 parts of polyurethane modified epoxy resin is added,
8-12 parts of a reinforcing agent,
KH 5600.5-1 parts of coupling agent,
20-30 parts of a filler,
adding 2-10 parts of a change promoter into a kneader, uniformly stirring, and vacuumizing to obtain a white thixotropic component A;
preparation of the S2B component:
18-30 parts of a curing agent,
1-2 parts of accelerator 2,4, 6-trisphenol,
KH 5500.5-1 parts of coupling agent,
1-2 parts of pigment iron oxide green,
adding 15-25 parts of filler into a kneading machine, uniformly stirring, and vacuumizing to obtain a green paste-containing component B;
s3, completely pouring the liquid resin A into the liquid resin B, stirring for 1-10min to make the liquid resin A uniform, immediately pouring the glue along one side of the inner wall, and standing still for 10-20 min without moving after the glue is gelled; after 1-2 h, the product can be put into use after being verified to be qualified.
9. The preparation method of the high-toughness glass fiber reinforced plastic bonding adhesive according to claim 7, wherein the polyurethane modified epoxy resin in the component A is synthesized by the method comprising the following steps:
adding diisocyanate into a reaction kettle, introducing nitrogen for protection, starting a stirrer, heating to 70-80 ℃, slowly adding dehydrated polyether glycol, and reacting until isocyanic acid radical reaches a theoretical value to obtain a polyurethane prepolymer for later use;
adding epoxy resin into a reaction kettle, dehydrating, introducing nitrogen for protection, starting a stirrer, heating to 80-90 ℃, adding a polyurethane prepolymer, and reacting until isocyanate disappears to obtain the polyurethane modified epoxy resin.
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| CN113462337A (en) * | 2021-07-09 | 2021-10-01 | 武汉梓强生态科技有限公司 | Grouting type high-molecular binder crack repairing adhesive |
| CN114921214A (en) * | 2021-12-09 | 2022-08-19 | 湖北海星瑞新材料科技有限公司 | Low-density insulating heat-conducting electronic pouring sealant and preparation method thereof |
| CN115074068A (en) * | 2022-07-22 | 2022-09-20 | 北京高盟新材料股份有限公司 | Double-component epoxy adhesive and preparation method thereof |
| CN116042150A (en) * | 2022-12-30 | 2023-05-02 | 浙江抟原复合材料有限公司 | Low-temperature epoxy resin for LNG ship containment system and preparation method thereof |
| GB2613001A (en) * | 2021-11-19 | 2023-05-24 | Gurit Uk Ltd | Epoxy resin adhesives |
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| CN116042150A (en) * | 2022-12-30 | 2023-05-02 | 浙江抟原复合材料有限公司 | Low-temperature epoxy resin for LNG ship containment system and preparation method thereof |
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