CN116836631A - Efficient PMA adhesive for connecting composite material components - Google Patents

Efficient PMA adhesive for connecting composite material components Download PDF

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Publication number
CN116836631A
CN116836631A CN202310901117.6A CN202310901117A CN116836631A CN 116836631 A CN116836631 A CN 116836631A CN 202310901117 A CN202310901117 A CN 202310901117A CN 116836631 A CN116836631 A CN 116836631A
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China
Prior art keywords
parts
adhesive
component
pma
acrylate
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CN202310901117.6A
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Chinese (zh)
Inventor
李勇
朱康
还大军
肖军
胡泽辉
王雪敏
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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Priority to CN202310901117.6A priority Critical patent/CN116836631A/en
Publication of CN116836631A publication Critical patent/CN116836631A/en
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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
    • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
    • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
    • 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
    • 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
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention provides a high-efficiency PMA adhesive for connecting composite material members, which comprises a component A, a component B and a component C, wherein the component A comprises the following components in percentage by mass: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 1.5-15 parts of oxidant; the component B comprises: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.3-3 parts of reducing agent; the component C comprises: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.1-1 part of organic metal compound for regulating and controlling the polymerization rate of the acrylate resin. The adhesive can be hardened at room temperature and has controllable hardening time, has good bonding performance on metal materials and polymer materials, and is particularly suitable for bonding composite honeycomb sandwich structures with thermoplastic resins such as polyacrylate, polylactic acid and the like as matrixes.

Description

Efficient PMA adhesive for connecting composite material components
Technical field:
the invention belongs to the technical field of high polymer materials, and particularly relates to a high-efficiency PMA adhesive for connecting composite material components.
The background technology is as follows:
with the progress of science and technology, composite materials are gradually replacing traditional metal materials, and higher requirements are also put on the physicochemical properties, forming quality and processing performance of the composite materials. The composite material has high specific strength and specific modulus, excellent corrosion resistance, aging resistance and impact resistance, and has wide application prospect in the fields of aerospace, civil construction, automobiles, ships and the like. The connection of the composite material is the key of the forming processing of the composite material, and in the service process of a composite material workpiece, the connection part of the workpiece is always damaged before the composite material body, so that the structural performance of the composite material body is fully exerted, the connection strength of the composite material is improved by adopting a proper method, and the main connection method of the composite material comprises mechanical connection, cementing and welding.
Mechanical connection methods are developed earlier and are one of the most common connection methods in composite material industrial application, however, mechanical connection can cause damage to a composite material body, stress concentration phenomenon occurs at a punching position, and the reliability of component connection is seriously affected. The use of fusion welding and thermosetting structural adhesive bonding to join composite materials, while not causing significant damage to the composite body, still presents several problems: 1) The heated and melted resin can be rapidly cooled and solidified under the condition of heat source withdrawal, so that the welding operation time is short and the difficulty is high; 2) The resin to be bonded is melted in the welding process, so that certain erosion can be caused to the material body, and particularly, the composite material honeycomb interlayer is formed; 3) The cooling process is difficult to control, residual heat stress is easy to generate, so that the connection strength of the components is reduced, and even deformation is generated; 4) Compared with thermosetting resin, the surface energy of the thermoplastic resin is lower, the compatibility of the common thermosetting structural adhesive and the thermoplastic resin is poor, and the bonding strength of the traditional thermosetting structural adhesive to the thermoplastic composite material is lower. Based on the above, the present invention proposes a high-efficiency PMA adhesive for joining composite members to solve the above-mentioned problems.
The invention comprises the following steps:
the invention aims at solving the problems of high connection difficulty, low connection strength, easiness in generating defects and the like of composite material components in the prior art, and provides a high-efficiency Polyacrylate (PMA) adhesive for connecting the composite material components, which has high adhesive strength, excellent comprehensive mechanical properties, adjustable hardening time and wide application range, can bond traditional metal materials and thermosetting composite materials and thermoplastic composite materials, and is particularly suitable for bonding polylactic acid, polyvinyl chloride, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene copolymer, polyacrylate thermoplastic resin and composite material components thereof.
The invention adopts the following technical scheme:
the invention provides a high-efficiency PMA adhesive for connecting composite material members, which comprises a component A, a component B and a component C, wherein the three components A, B, C can be stored for a long time under the conditions of normal temperature and low temperature; the component A comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 1.5-15 parts of oxidant; the component B comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.3-3 parts of reducing agent; the component C comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.1-1 part of organic metal compound.
Further, the weight ratio of the component A to the component B to the component C is (50-80): 50: (0-10).
Further, the weight ratio of the component A to the component B to the component C is (50-80): 50: (1-9).
Further, the organic metal compound is ferrous acetylacetonate, ferric naphthenate, ferrous lactate, alpha-hydroxyethyl ferrocene or ferrocene.
Further, the polyacrylate resin mixture includes one or more combinations of polybutyl acrylate, polymethyl methacrylate, polylactic acid, styrene-butadiene-styrene block copolymer, polystyrene, polybutyl methacrylate, and polymethyl acrylate.
Further, the acrylate mixed monomer comprises methyl methacrylate; or the acrylate mixed monomer comprises methyl methacrylate and simultaneously comprises one or a combination of more of alpha-fluoro methyl acrylate, acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, styrene and butadiene.
Further, the filler is mainly used for improving the comprehensive mechanical properties of the adhesive, and specifically comprises one or more of silicon dioxide, calcium carbonate, aluminum hydroxide, carbon nanotubes, butyl acrylate-styrene-acrylonitrile terpolymer and methyl methacrylate-butadiene-styrene triblock copolymer.
Further, the oxidant is organic peroxide, and specifically is one or a combination of more of methyl ethyl ketone peroxide, dibenzoyl peroxide, cumene hydroperoxide, tert-butyl perbenzoate and cyclohexanone peroxide.
Further, the reducing agent is one or more of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-methyl-N-hydroxyethyl-p-toluidine and N, N-di (2-hydroxyethyl) p-toluidine.
Furthermore, the polymerization reaction of the adhesive can be carried out under the condition of room temperature or at the temperature higher than the room temperature, preferably, the reaction temperature of the adhesive is 25-80 ℃, and the reaction temperature is properly increased, so that the hardening rate of the adhesive can be further accelerated, and the comprehensive mechanical property of the adhesive layer can be further improved.
Furthermore, the hardening time of the adhesive can be controlled to be 5-240 min.
Further, when the mass percentage of the organometallic compound in the redox initiation system is lower than 5%, the polymerization reaction rate is accelerated with the increase of the use amount of the organometallic compound; when the mass percent of the organic metal compound in the redox initiation system is higher than 5%, the polymerization reaction rate is slowed down along with the increase of the use amount of the organic metal compound; the redox initiation system includes an oxidizing agent, a reducing agent, and an organometallic compound.
The invention can greatly reduce the activation energy of active free radical generated by the decomposition of the initiator, so that the polymerization reaction can be carried out at room temperature. Wherein the composite redox initiation system for promoting the polymerization of the acrylate resin comprises three types of organic matters, namely an oxidant, a reducing agent and an organic metal compound. The organic metal compound is used for adjusting the polymerization reaction rate of the acrylic resin, adjusting and controlling the hardening time of the adhesive, and ensuring the sufficient operation time by adjusting the proportion of each component of the adhesive according to the operation time required by the bonding of the composite material components.
The organic metal compound can participate in various chemical reactions of monomers, oxidants and reducing agents, and the action mechanism is as follows: adding a small amount of organic metal compound, wherein the dissociated metal cations in the glue solution can react with peroxide to generate active free radicals with initiating capability, and the reaction product can also react with a reducing agent to generate another active free radical, so that the reaction rate is improved; the addition of an excess of organometallic compound, too high a concentration of metal cations, deactivates a portion of the active radicals and thus reduces the reaction rate.
The invention has the beneficial effects that:
1) The adhesive provided by the invention does not damage the body configuration of the member to be bonded, is suitable for bonding between a composite material panel and a sandwich layer with a honeycomb and other complex configurations in a thermoplastic composite material sandwich structure, and avoids erosion damage to materials caused by a traditional thermoplastic composite material welding method;
2) Compared with a solvent type adhesive method and an induction welding method, the adhesive provided by the invention can not generate release matters and impurity residues in the reaction process, and can further improve the adhesive strength;
3) The adhesive provided by the invention can dissolve or swell thermoplastic resins such as polyacrylate, polylactic acid, polyvinyl chloride, polystyrene, acrylonitrile-butadiene-styrene copolymer and the like, promote entanglement of a glue layer and a resin molecular chain on the surface of an object to be adhered, and further improve the adhesive strength, so that the adhesive is particularly suitable for adhering a composite sandwich structure taking the thermoplastic resin as a matrix, particularly a honeycomb sandwich structure, and can still ensure higher adhesive quality under the condition of smaller adhesive area;
4) The reaction time of the adhesive is adjustable, so that the requirements of various sizes of bonding faces on operation time are met while the rapid polymerization is ensured;
5) The polymerization reaction of the adhesive does not depend on heating equipment such as an oven and the like, can be completed at room temperature, and avoids residual thermal stress possibly generated in the welding and high-temperature curing structural adhesive connection process;
6) The adhesive provided by the invention has proper viscosity, can be easily extruded from a rubber tube and uniformly mixed at a lower temperature, is easy to spread on the surface of an object to be adhered, and has easily controlled thickness;
7) The adhesive provided by the invention has high polarity, so that the adhesive has high adhesive force.
Description of the drawings:
FIG. 1 is a schematic diagram of adhesive compounding and mixing;
FIG. 2 is a schematic illustration of the application of an adhesive to the to-be-bonded face of a composite sandwich structure;
FIG. 3 is a schematic view showing the hardening formation of an adhesive under pressure with the surfaces to be bonded in phase;
FIG. 4 is a schematic view of the composite part after bonding is completed;
the marks in the drawings are:
1. dividing and loading the adhesive into tubes; 2. a stirring rod; 3. an adhesive component A; 4. an adhesive component B; 5. an adhesive component C; 6. an adhesive is uniformly mixed; 7. the composite material workpiece 1 to be bonded; 8. a glue spreading brush; 9. the composite article 2 is to be bonded.
The specific embodiment is as follows:
for the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. 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 invention provides a high-efficiency PMA adhesive for connecting composite material members, which comprises a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is (50-80): 50: (0-10); the component A comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 1.5-15 parts of oxidant; the component B comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.3-3 parts of reducing agent; the component C comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.1-1 part of organic metal compound.
In the invention, the organic metal compound is ferrous acetylacetonate, ferric naphthenate, ferrous lactate, alpha-hydroxyethyl ferrocene or ferrocene; the polyacrylate resin mixture comprises one or more of polybutyl acrylate, polymethyl methacrylate, polylactic acid, styrene-butadiene-styrene block copolymer, polystyrene, polybutyl methacrylate and polymethyl acrylate; the acrylate mixed monomer comprises methyl methacrylate and simultaneously comprises one or a combination of more of alpha-fluoro methyl acrylate, acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, styrene and butadiene; the filler comprises one or more of silica, calcium carbonate, aluminum hydroxide, carbon nanotubes, butyl acrylate-styrene-acrylonitrile terpolymer and methyl methacrylate-butadiene-styrene terpolymer; the oxidant is one or a combination of more of methyl ethyl ketone peroxide, dibenzoyl peroxide, cumene hydroperoxide, tert-butyl perbenzoate and cyclohexanone peroxide; the reducing agent is one or a combination of more of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-methyl-N-hydroxyethyl-p-toluidine and N, N-di (2-hydroxyethyl) p-toluidine.
In the invention, when the mass percent of the organic metal compound in the redox initiation system is lower than 5%, the polymerization reaction rate is accelerated along with the increase of the use amount of the organic metal compound; when the mass percent of the organometallic compound in the redox initiation system is higher than 5%, the polymerization reaction rate is retarded as the amount of the organometallic compound increases. The hardening time of the adhesive can be controlled to be 5-240 min, and when the mass percentage of the organic metal compound in the redox initiation system is 5%, the hardening time of the adhesive is the shortest, namely 5min.
The specific implementation steps of the efficient PMA adhesive for connecting composite material components are as follows:
firstly, weighing raw materials according to a given proportion, uniformly mixing to obtain an adhesive component A, a component B and a component C respectively, and sealing and storing;
secondly, designing the proportion of each component of the adhesive according to the bonding area and the bonding operation time, and estimating the use amount of the adhesive;
thirdly, mixing the adhesive component A, the component B and the component C according to a set proportion, and fully and uniformly mixing, as shown in figure 1;
fourthly, uniformly coating the uniformly mixed adhesive on the surface to be bonded of the composite material, as shown in figure 2;
fifthly, the surfaces to be bonded of the components are combined, the relative positions are adjusted and then fixed, and certain compressive stress is applied, as shown in fig. 3;
sixthly, placing the composite material component coated with the adhesive at the temperature of 25-80 ℃ for reaction;
and seventhly, after the adhesive layer is hardened, relieving the compressive stress to obtain the bonded composite material component.
Example 1
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A and a component B, wherein the weight ratio of the component A to the component B is 50:50;
the component A comprises: 30g of polymethyl methacrylate, 40g of methyl methacrylate, 10g of acrylonitrile, 10g of aluminum hydroxide and 1.5g of dibenzoyl peroxide;
the component B comprises: 30g of polymethyl methacrylate, 40g of methyl methacrylate, 10g of acrylonitrile, 10g of aluminum hydroxide and 0.3g of N, N-dimethyl-p-toluidine.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B according to a weight ratio of 50:50, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting the relative positions, fixing to prevent dislocation of the surfaces to be bonded, and then applying certain forming stress on the bonding surface of the composite material, so that the adhesive solution completes polymerization reaction at room temperature until the adhesive layer is completely hardened, and bonding of composite material components is completed. In this example, the curing time of the adhesive was 240 minutes.
Example 2
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 50:50:1;
the component A comprises: 30g of polylactic acid, 40g of methyl methacrylate, 10g of butyl acrylate-styrene-acrylonitrile terpolymer and 1.5g of cumene hydroperoxide;
the component B comprises: 30g of polylactic acid, 40g of methyl methacrylate, 10g of butyl acrylate-styrene-acrylonitrile terpolymer and 0.3g of N, N-dimethylaniline;
the component C comprises: 30g of polylactic acid, 40g of methyl methacrylate, 10g of butyl acrylate-styrene-acrylonitrile terpolymer and 0.1g of alpha-hydroxyethyl ferrocene.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B and C according to a weight ratio of 50:50:1, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting relative positions, fixing to prevent dislocation of the surfaces to be bonded, then applying a certain forming stress on the bonding surface of the composite material, and allowing the adhesive solution to complete polymerization reaction at room temperature until the adhesive layer is completely hardened, thus completing bonding of the composite material components. In this example, the adhesive hardening time was 150 minutes.
Example 3
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 50:50:3;
the component A comprises: 10g of polybutyl acrylate, 40g of polylactic acid, 30g of methyl methacrylate, 20g of alpha-fluoro methyl acrylate, 10g of calcium carbonate, 0.5g of cumene hydroperoxide and 1g of dibenzoyl peroxide;
the component B comprises: 10g of polybutyl acrylate, 40g of polylactic acid, 30g of methyl methacrylate, 20g of alpha-fluoro methyl acrylate, 10g of calcium carbonate and 0.3g of N-methyl-N-hydroxyethyl-p-toluidine;
the component C comprises: 10g of polybutyl acrylate, 40g of polylactic acid, 30g of methyl methacrylate, 20g of alpha-fluoro methyl acrylate, 10g of calcium carbonate and 0.1g of ferrocene.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B and C according to a weight ratio of 50:50:3, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting relative positions, fixing to prevent dislocation of the surfaces to be bonded, then applying a certain forming stress on the bonding surface of the composite material, and allowing the adhesive solution to complete polymerization reaction at room temperature until the adhesive layer is completely hardened, thus completing bonding of the composite material components. In this example, the curing time of the adhesive was 20 minutes.
Example 4
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 50:50:5;
the component A comprises: 25g of polymethyl methacrylate, 5g of polystyrene, 30g of methyl methacrylate, 20g of styrene, 10g of silicon dioxide, 0.5g of methyl ethyl ketone peroxide and 1g of dibenzoyl peroxide;
the component B comprises: 25g of polymethyl methacrylate, 5g of polystyrene, 30g of methyl methacrylate, 20g of styrene, 10g of silicon dioxide, 0.2g of N, N-dimethylaniline and 0.1g of N, N-bis (2-hydroxyethyl) p-toluidine;
the component C comprises: 25g of polymethyl methacrylate, 5g of polystyrene, 30g of methyl methacrylate, 20g of styrene, 10g of silicon dioxide and 0.1g of iron naphthenate.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B and C according to a weight ratio of 50:50:5, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting relative positions, fixing to prevent dislocation of the surfaces to be bonded, then applying a certain forming stress on the bonding surface of the composite material, and allowing the adhesive solution to complete polymerization reaction at room temperature until the adhesive layer is completely hardened, thus completing bonding of the composite material components. In this example, the adhesive hardening time was 5 minutes.
Example 5
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 50:50:7;
the component A comprises: 25g of polymethyl methacrylate, 5g of polybutyl methacrylate, 50g of methyl methacrylate, 10g of carbon nano tube, 1g of dibenzoyl peroxide and 0.5g of tert-butyl perbenzoate;
the component B comprises: 25g of polymethyl methacrylate, 5g of polybutyl methacrylate, 50g of methyl methacrylate, 10g of carbon nano tube, 0.15g of N, N-dimethyl-p-toluidine and 0.15g of N-methyl-N-hydroxyethyl-p-toluidine;
the component C comprises: 25g of polymethyl methacrylate, 5g of polybutyl methacrylate, 50g of methyl methacrylate, 10g of carbon nano tube and 0.1g of iron naphthenate.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B and C according to a weight ratio of 50:50:7, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting relative positions, fixing to prevent dislocation of the surfaces to be bonded, then applying a certain forming stress on the bonding surface of the composite material, and allowing the adhesive solution to complete polymerization reaction at room temperature until the adhesive layer is completely hardened, thus completing bonding of the composite material components. In this example, the adhesive hardening time was 15 minutes.
Example 6
The embodiment of the invention provides a high-efficiency PMA adhesive for connecting composite material members, which is prepared by uniformly mixing a component A, a component B and a component C, wherein the weight ratio of the component A to the component B to the component C is 50:50:9;
the component A comprises: 10g of polymethyl methacrylate, 10g of polylactic acid, 10g of polymethyl acrylate, 40g of methyl methacrylate, 10g of styrene, 10g of methyl methacrylate-butadiene-styrene ternary block copolymer and 1.5g of cyclohexanone peroxide;
the component B comprises: 10g of polymethyl methacrylate, 10g of polylactic acid, 10g of polymethyl acrylate, 40g of methyl methacrylate, 10g of styrene, 10g of methyl methacrylate-butadiene-styrene ternary block copolymer, 0.15g of N, N-dimethylaniline and 0.15g of N, N-dimethyl-p-toluidine;
the component C comprises: 10g of polymethyl methacrylate, 10g of polylactic acid, 10g of polymethyl acrylate, 40g of methyl methacrylate, 10g of styrene, 10g of methyl methacrylate-butadiene-styrene ternary block copolymer and 0.1g of iron naphthenate.
The PMA adhesive of the embodiment is used for connecting composite materials, and the application method comprises the following steps: firstly, uniformly mixing adhesive components A, B and C according to a weight ratio of 50:50:9, then uniformly coating the uniformly mixed adhesive solution on a surface to be bonded of the composite material, then combining the surfaces to be bonded of the composite material, adjusting relative positions, fixing to prevent dislocation of the surfaces to be bonded, then applying a certain forming stress on the bonding surface of the composite material, and allowing the adhesive solution to complete polymerization reaction at room temperature until the adhesive layer is completely hardened, thus completing bonding of the composite material components. In this example, the adhesive hardening time was 60 minutes.
The foregoing is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, but all technical solutions falling under the concept of the present invention fall within the scope of the present invention, and it should be noted that, for those skilled in the art, several modifications and adaptations without departing from the principles of the present invention should and are intended to be regarded as the scope of the present invention.

Claims (10)

1. A high-efficiency PMA adhesive for connecting composite material components is characterized in that,
comprises a component A, a component B and a component C;
the component A comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 1.5-15 parts of oxidant;
the component B comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.3-3 parts of reducing agent;
the component C comprises the following components in parts by weight: 30-50 parts of polyacrylate resin mixture, 30-50 parts of acrylate mixed monomer, 10-20 parts of filler and 0.1-1 part of organic metal compound.
2. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the weight ratio of the component A to the component B to the component C is (50-80): 50: (0-10).
3. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the organic metal compound is ferrous acetylacetonate, ferric naphthenate, ferrous lactate, alpha-hydroxyethyl ferrocene or ferrocene.
4. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the polyacrylate resin blend includes a combination of one or more of polybutyl acrylate, polymethyl methacrylate, polylactic acid, styrene-butadiene-styrene block copolymer, polystyrene, polybutyl methacrylate, and polymethyl acrylate.
5. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the acrylate mixed monomer comprises methyl methacrylate and also comprises one or a combination of more of alpha-fluoro methyl acrylate, acrylic acid, methacrylic acid, methyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile, styrene and butadiene.
6. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the filler comprises one or more combinations of silica, calcium carbonate, aluminum hydroxide, carbon nanotubes, butyl acrylate-styrene-acrylonitrile terpolymer, and methyl methacrylate-butadiene-styrene terpolymer.
7. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the oxidant is one or a combination of more of methyl ethyl ketone peroxide, dibenzoyl peroxide, cumene hydroperoxide, tert-butyl perbenzoate and cyclohexanone peroxide.
8. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the reducing agent is one or a combination of more of N, N-dimethyl-p-toluidine, N-dimethylaniline, N-methyl-N-hydroxyethyl-p-toluidine and N, N-di (2-hydroxyethyl) p-toluidine.
9. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
the reaction temperature of the adhesive is 25-80 ℃, and the hardening time of the adhesive is 5-240 min.
10. The efficient PMA adhesive for composite member attachment according to claim 1, where in,
when the mass percent of the organic metal compound in the redox initiation system is lower than 5%, the polymerization reaction rate is accelerated along with the increase of the use amount of the organic metal compound; when the mass percent of the organic metal compound in the redox initiation system is higher than 5%, the polymerization reaction rate is slowed down along with the increase of the use amount of the organic metal compound;
the redox initiation system includes an oxidizing agent, a reducing agent, and an organometallic compound.
CN202310901117.6A 2023-07-20 2023-07-20 Efficient PMA adhesive for connecting composite material components Pending CN116836631A (en)

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CN116836631A true CN116836631A (en) 2023-10-03

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