CN115181272B - Preparation method of modified MQ resin and acrylate adhesive prepared by using preparation method - Google Patents

Preparation method of modified MQ resin and acrylate adhesive prepared by using preparation method Download PDF

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CN115181272B
CN115181272B CN202211006578.9A CN202211006578A CN115181272B CN 115181272 B CN115181272 B CN 115181272B CN 202211006578 A CN202211006578 A CN 202211006578A CN 115181272 B CN115181272 B CN 115181272B
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parts
resin
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modified
acrylate
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CN115181272A (en
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李岳
王勃
魏莉
孔宪志
孙东洲
于国良
吕虎
孙禹
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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Institute of Petrochemistry of Heilongjiang Academy of Sciences
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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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • 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
    • C09J155/00—Adhesives based on homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C09J123/00 - C09J153/00
    • C09J155/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A preparation method of modified MQ resin and an acrylate adhesive prepared by using the same relate to a preparation method of MQ resin and an acrylate adhesive prepared by using the same. The invention aims to solve the problem that the existing acrylate adhesive can not have better adhesive property on various materials. The preparation method of the modified MQ resin comprises the following steps: stirring and dissolving methyl MQ resin, methyl methacrylate and a stabilizer to obtain a reaction system, adding aminopropyl triethoxysilane and a catalyst, stirring for reaction, then adding acryloyloxy trimethoxysilane, stirring for reaction, and cooling to room temperature. An acrylate adhesive prepared with a modified MQ resin, which is composed of a first component and a second component packaged separately. The invention relates to a preparation method for modified MQ resin and an acrylate adhesive prepared by using the same.

Description

Preparation method of modified MQ resin and acrylate adhesive prepared by using preparation method
Technical Field
The invention relates to a preparation method of MQ resin and an acrylate adhesive prepared by using the same.
Background
The reactive acrylate adhesive is also called a second-generation acrylate adhesive (SGA), is a room-temperature curing bi-component adhesive based on acrylate free radical graft copolymerization, is invented by DuPont company in 1975 in the United states, and is introduced into a novel redox system for formally putting into the market in the next year. Following the development and improvement of Germany, japan, and England, etc., sgAs have been rapidly developed. SGA is mainly composed of acrylic ester monomer, elastomer toughening polymer, initiator, accelerator, stabilizer and the like, and the package is double-component and can be glued manually or mechanically. Other auxiliary agents such as adhesion promoters, thixotropic agents, pigments and the like can also be added according to different requirements. The acrylic polymer has good stability and good tolerance to heat, oxidative decomposition and photochemistry; the acrylate monomer is easy to copolymerize with vinyl-containing elastomer, oligomer and the like, and can improve the physical and chemical properties of the polymer such as mechanical property, environmental resistance and the like, so the acrylate monomer has wider application as an adhesive. The ester group of the acrylic ester has stronger polarity and has stronger bonding capability with hydrogen bonds; the adhesive has the advantages of quick solidification, high strength and the like, is convenient to use, is suitable for bonding various materials, and is an ideal adhesive. With the development of electronics and aviation industry, the adhesive is developed to the fields of automatic gluing and special structure bonding, and is particularly used for bonding difficult-to-bond materials such as aircraft titanium alloy, composite materials and the like. In recent years, the adhesive has the characteristics of rapid solidification at normal temperature, high strength, good adhesion performance to various materials, convenience for automatic gluing and the like, and is widely applied to the electronic and aviation industries.
The curing reaction of SGA is a free radical polymerization reaction initiated by a redox system, which forms free radical active species through internal electron transfer (ISET) and initiates polymerization of monomers at lower temperatures. The redox initiation system can not only shorten the induction period, but also improve the polymerization rate. SGA is susceptible to polymerization and usually requires the addition of stabilizers.
The main varieties of acrylate monomers (including monofunctional monomers and polyfunctional monomers) are as follows: (1) common monomers such as Methyl Methacrylate (MMA), butyl Acrylate (BA) and the like; (2) low volatility monomers such as hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, and the like; (3) diester monomers such as ethylene glycol methacrylate, diester methacrylate, and the like; (4) acrylic oligomers, which provide basic properties of adhesives (e.g., hardness, chemical resistance, flexibility, etc.); (5) commonly used modifying monomers such as epoxy acrylates, urethane acrylates, silicone acrylates, and the like.
The elastomer in SGA (in the process of free radical polymerization of glue solution, some of the elastomer participates in reaction to generate graft copolymer, and some of the elastomer forms a sea-island structure), so that the impact resistance, peeling resistance, fatigue resistance, durability and bonding strength of the adhesive can be effectively improved, and meanwhile, the viscosity of the adhesive can be regulated, and the curing shrinkage rate can be reduced. Therefore, it is very important to select an elastomer compatible with the monomer. The elastomers which are generally added are acrylate rubber, chlorosulfonated polyethylene, chloroprene rubber, nitrile rubber, ABS (acrylonitrile-butadiene-styrene plastic), MBS (methyl methacrylate-butadiene-styrene) and the like.
The initiator has oxidability, the accelerator has reducibility, and the initiator and the accelerator generate oxidation-reduction reaction (the reaction generates active free radicals to trigger the monomer and the elastomer to generate chain growth reaction to form a graft copolymer of the monomer and the elastomer) at room temperature when the glue solution is mixed, so that the glue solution has excellent quick curing performance. The oxidant generally adopts peroxide: hydroperoxides, such as t-Butyl Hydroperoxide (BHP); diacyl peroxides such as Benzoyl Peroxide (BPO); ketone peroxides, such as Methyl Ethyl Ketone Peroxide (MEKP); peroxyesters. Cumene hydroperoxide is favored because of its excellent performance and low cost. Typical accelerators are N, N-dimethylaniline, amine butyraldehyde condensate, tetramethylthiourea, vinylthiourea, ascorbic acid and the like. The initiator and the accelerator can be used independently or in a plurality of ways, and when in use, the initiator and the accelerator are respectively placed in the two components, and the mass ratio of the initiator and the accelerator is generally 0.04-4% of that of the main agent.
Since the components of SGA are susceptible to polymerization, a certain amount of stabilizer (e.g., hydroquinone methyl ether, p-methoxyphenol, 2, 6-di-t-butyl-p-cresol, etc.) is added to prevent them from curing by initiating polymerization during storage. Since the stabilizer has an adverse effect on the curing rate of the glue solution, the stabilizer should be carefully selected and used in proper amount according to practical situations. Other auxiliary agents can be added in the actual use process so as to further improve the performance of the adhesive. A small amount of paraffin is added into the glue solution, so that the polymerization inhibition effect of air can be reduced, and the volatilization of low-boiling monomers can be reduced; the liquid cement can be thixotropic by introducing the fumed silica; the curing of the unsaturated polyester and the methacrylic acid diester can be accelerated by adding a proper amount of the unsaturated polyester and the methacrylic acid diester.
The polysiloxane and the acrylic ester are grafted and copolymerized, so that the surface tension, the water absorption and the stain resistance of the polyacrylate can be obviously reduced, and the high and low temperature resistance of the polyacrylate can be improved. Because of the characteristics of the molecular structure, the compatibility of the acrylic resin and the organosilicon is poor, and the acrylic resin and the organosilicon are well mixed, the organosilicon and the acrylic resin graft copolymer or various silane coupling agents can be used as compatibilizers, or the organosilicon is used for modifying the acrylic resin, so that the organosiloxane is introduced onto an acrylic ester molecular chain, and the compatibility of the acrylic resin and the organosilicon is improved.
With the application of new materials in the high-end fields of aviation, aerospace and microelectronics, the matched adhesive needs to simultaneously meet the requirement of bonding materials such as aluminum alloy, titanium alloy, stainless steel, resin-based carbon fiber reinforced composite materials, engineering plastics and the like. Most of the existing acrylate adhesives in the market have higher bonding strength to metal materials such as aluminum alloy, carbon steel and the like, but have lower bonding strength to non-metal materials such as titanium alloy, stainless steel, metallic nickel and the like which are difficult to bond, carbon fiber reinforced composite materials, engineering plastics and the like.
Disclosure of Invention
The invention aims to solve the problem that the existing acrylate adhesive can not have better adhesive property on various materials. Further provides a preparation method of the modified MQ resin and an acrylate adhesive prepared by using the modified MQ resin.
The preparation method of the modified MQ resin comprises the following steps:
1. weighing 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate, 0.1-0.5 part of stabilizer, 15-50 parts of aminopropyl triethoxysilane, 0.1-0.5 part of catalyst and 15-50 parts of acryloyloxy trimethoxysilane according to parts by mass;
2. stirring and dissolving 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate and 0.1-0.5 part of stabilizer to obtain a reaction system, heating the reaction system to 80-90 ℃, condensing and refluxing, adding 15-50 parts of aminopropyl triethoxysilane and 0.1-0.5 part of catalyst, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, then adding 15-50 parts of acryloyloxy trimethoxysilane, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, and cooling to room temperature to obtain the modified MQ resin.
The acrylate adhesive prepared by utilizing the modified MQ resin consists of a first component and a second component which are packaged independently; the volume ratio of the first component to the second component is (7-10) 1;
the first component consists of 55 to 70 parts by mass of propylene, 15 to 25 parts by mass of elastomer toughening agent, 3 to 15 parts by mass of modified MQ resin, 0.5 to 6 parts by mass of accelerator and 0.02 to 0.5 part by mass of stabilizer; the propylene is one or two of acrylic acid and acrylic ester monomers;
the second component consists of 30 to 45 parts of acrylic ester monomer, 15 to 25 parts of elastomer toughening agent, 30 to 50 parts of initiator and 0.01 to 0.5 part of stabilizer according to the mass parts.
The beneficial effects of the invention are as follows:
1. the invention uses aminopropyl triethoxy silane and acryloyloxy trimethoxy silane to end-cap the hydroxyl of methyl MQ resin, the modified MQ resin has alkoxy, aminopropyl and acryloyloxy, the introduction of acryloyloxy leads the compatibility of the modified MQ resin and an acrylate adhesive system to be better, and the aminopropyl and alkoxy groups can increase the adhesive strength of the adhesive to metal materials and nonmetallic materials, such as aluminum alloy, titanium alloy, high-temperature alloy, composite materials, corrosion resistant steel and other materials, and have good adhesive property. The room temperature shear strength of the adhesive bonding metal material is larger than 30MPa, the room temperature shear strength of the bonding carbon fiber reinforced composite material is larger than 25MPa, and the room temperature shear strength of the bonding PEI is larger than 15MPa.
2. The invention directly adopts methyl methacrylate as the solvent of methyl MQ resin, does not need to be separated after synthesis, and can be directly used for preparing acrylate adhesive.
3. According to the MQ resin modified acrylic acid ester adhesive, the modified methyl MQ resin is added into an acrylic acid ester adhesive system, so that the high and low temperature resistance and the environmental resistance of the adhesive can be improved.
The MQ resin modified acrylate adhesive prepared by the method is mainly applied to the adhesive field and is used for bonding rigid structural parts in the fields of aviation, aerospace and microelectronics.
The invention is used for a preparation method of modified MQ resin and an acrylate adhesive prepared by using the same.
Drawings
FIG. 1 is an infrared spectrum of a methyl methacrylate solution of an MQ resin;
FIG. 2 is an infrared spectrum of a modified MQ resin prepared in example one.
Detailed Description
The first embodiment is as follows: the preparation method of the modified MQ resin comprises the following steps:
1. weighing 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate, 0.1-0.5 part of stabilizer, 15-50 parts of aminopropyl triethoxysilane, 0.1-0.5 part of catalyst and 15-50 parts of acryloyloxy trimethoxysilane according to parts by mass;
2. stirring and dissolving 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate and 0.1-0.5 part of stabilizer to obtain a reaction system, heating the reaction system to 80-90 ℃, condensing and refluxing, adding 15-50 parts of aminopropyl triethoxysilane and 0.1-0.5 part of catalyst, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, then adding 15-50 parts of acryloyloxy trimethoxysilane, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, and cooling to room temperature to obtain the modified MQ resin.
The molecular formula of the modified MQ resin is as follows:
wherein the MQ is specifically
According to the embodiment, the modified MQ resin is prepared, so that the bonding performance of the MQ resin modified acrylate adhesive to various materials is simultaneously satisfied.
The beneficial effects of this embodiment are:
1. in the embodiment, the hydroxy groups of the methyl MQ resin are respectively blocked by aminopropyl triethoxy silane and acryloyloxy trimethoxy silane, the modified MQ resin is provided with alkoxy groups, aminopropyl groups and acryloyloxy groups, the introduction of the acryloyloxy groups enables the modified MQ resin to have better compatibility with an acrylate adhesive system, and the aminopropyl groups and the alkoxy groups can increase the adhesive strength of the adhesive to metal materials and nonmetallic materials, such as aluminum alloy, titanium alloy, superalloy, composite materials, corrosion resistant steel and other materials, and have good adhesive properties. The room temperature shear strength of the adhesive bonding metal material is larger than 30MPa, the room temperature shear strength of the bonding carbon fiber reinforced composite material is larger than 25MPa, and the room temperature shear strength of the bonding PEI is larger than 15MPa.
2. In the embodiment, methyl methacrylate is directly adopted as a solvent of methyl MQ resin, separation is not needed after synthesis, and the method can be directly used for preparing acrylate adhesives.
3. According to the MQ resin modified acrylic acid ester adhesive, modified methyl MQ resin is added into an acrylic acid ester adhesive system, so that the high and low temperature resistance and the environmental resistance of the adhesive can be improved.
The MQ resin modified acrylate adhesive prepared by the method is mainly applied to the adhesive field and is used for bonding rigid structural parts in the fields of aviation, aerospace and microelectronics.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: the stabilizer in the first step is one or a mixture of more of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, ferrous sulfate and cuprous oxide. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from one or both of the embodiments in that: the catalyst in the first step is one or a mixture of several of acetic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and cyclohexanone oxime. The other is the same as the first or second embodiment.
The specific embodiment IV is as follows: the acrylate adhesive prepared by utilizing the modified MQ resin in the embodiment consists of a first component and a second component which are packaged independently; the volume ratio of the first component to the second component is (7-10) 1;
the first component consists of 55 to 70 parts by mass of propylene, 15 to 25 parts by mass of elastomer toughening agent, 3 to 15 parts by mass of modified MQ resin, 0.5 to 6 parts by mass of accelerator and 0.02 to 0.5 part by mass of stabilizer; the propylene is one or two of acrylic acid and acrylic ester monomers;
the second component consists of 30 to 45 parts of acrylic ester monomer, 15 to 25 parts of elastomer toughening agent, 30 to 50 parts of initiator and 0.01 to 0.5 part of stabilizer according to the mass parts.
Fifth embodiment: the fifth difference between this embodiment and the third embodiment is that: the acrylic acid in the first component is one or a mixture of two of methacrylic acid and acrylic acid. The other is the same as in the fifth embodiment.
Specific embodiment six: this embodiment differs from the fourth or fifth embodiment in that: the acrylic ester monomers in the first component and the second component are one or a mixture of a plurality of methyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, hydroxy vinyl methacrylate, hydroxy propylene methacrylate, hydroxy vinyl acrylate, hydroxy propylene acrylate, ethylene glycol (methyl) acrylate, triethylene glycol di (methyl) acrylate and tetraethylene glycol di (methyl) acrylate. The others are the same as those of the fourth or fifth embodiment.
Seventh embodiment: the present embodiment differs from one of the fourth to sixth embodiments in that: the elastomer toughening agent in the first component is one or a mixture of a plurality of acrylonitrile-butadiene-styrene copolymer, nitrile rubber, carboxylated nitrile rubber, chlorosulfonated polyethylene and acrylate rubber; the elastomeric toughening agent in the second component is an acrylonitrile-butadiene-styrene copolymer. The others are the same as those of the fourth to sixth embodiments.
Eighth embodiment: the present embodiment differs from one of the fourth to seventh embodiments in that: the accelerator in the first component is one or a mixture of more of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, tetramethylthiourea, triphenylphosphine, triethylamine and vanadium acetylacetonate. The others are the same as in the fourth to seventh embodiments.
Detailed description nine: the present embodiment differs from one of the fourth to eighth embodiments in that: the stabilizer in the first component and the second component is one or a mixture of more of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, ferrous sulfate and cuprous oxide. The others are the same as in embodiments four to eight.
Detailed description ten: this embodiment differs from one of the fourth to ninth embodiments in that: the initiator in the second component is one or a mixture of more of benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide. The others are the same as in the fourth to ninth embodiments.
The following examples are used to verify the benefits of the present invention:
embodiment one:
the preparation method of the modified MQ resin comprises the following steps:
1. weighing 100 parts of methyl MQ resin (MQ 102), 100 parts of methyl methacrylate, 0.2 part of stabilizer, 25 parts of aminopropyl triethoxysilane, 0.2 part of catalyst and 25 parts of acryloxy trimethoxy silane according to parts by weight;
2. stirring and dissolving 100 parts of methyl MQ resin, 100 parts of methyl methacrylate and 0.2 part of stabilizer to obtain a reaction system, heating the reaction system to 80 ℃, condensing and refluxing, adding 25 parts of aminopropyl triethoxysilane and 0.2 part of catalyst, stirring and reacting for 2 hours at the temperature of 80 ℃, then adding 25 parts of acryloyloxy trimethoxysilane, stirring and reacting for 2 hours at the temperature of 80 ℃, and cooling to room temperature to obtain the modified MQ resin.
The stabilizer in the first step is hydroquinone. The catalyst cyclohexanone oxime described in step one.
The acrylate adhesive prepared by utilizing the modified MQ resin consists of a first component and a second component which are packaged independently; the volume ratio of the first component to the second component is 10:1;
the first component consists of 68.9 parts by mass of propylene, 24 parts by mass of elastomer toughening agent, 3.9 parts by mass of modified MQ resin, 3.5 parts by mass of accelerator and 0.1 part by mass of stabilizer; the propylene in the first component is 3.9 parts of methacrylic acid and 65 parts of methyl methacrylate; the elastomer toughening agent in the first component is 12 parts of acrylonitrile-butadiene-styrene copolymer and 12 parts of nitrile rubber; the accelerator in the first component is 1 part of N, N-dimethyl-p-toluidine and 2.5 parts of tetramethylthiourea; the stabilizer in the first component is hydroquinone;
the preparation method of the first component comprises the following steps: adding nitrile rubber and acrylonitrile-butadiene-styrene copolymer into methyl methacrylate and methacrylic acid, stirring until the nitrile rubber and the acrylonitrile-butadiene-styrene copolymer are completely dissolved, then adding modified MQ resin, N-dimethyl-p-toluidine, tetramethylthiourea and hydroquinone, and continuously stirring until the nitrile rubber and the acrylonitrile-butadiene-styrene copolymer are completely mixed uniformly.
The second component consists of 40 parts of acrylic ester monomer, 20 parts of elastomer toughening agent, 40 parts of initiator and 0.5 part of stabilizer in parts by mass; the acrylic ester monomer in the second component is methyl methacrylate; the elastomer toughening agent in the second component is an acrylonitrile-butadiene-styrene copolymer; the stabilizer in the second component is hydroquinone; the initiator in the second component is benzoyl peroxide;
the preparation method of the second component comprises the following steps: adding the acrylonitrile-butadiene-styrene copolymer into methyl methacrylate, stirring until the copolymer is completely dissolved, then adding benzoyl peroxide and hydroquinone, and continuously stirring until the copolymer is completely and uniformly mixed.
The first component is detailed in Table 1:
TABLE 1
The second component is detailed in Table 2:
TABLE 2
Comparison experiment: the first difference between this comparative experiment and the example is: 72.9 parts of propylene in the first component; the propylene in the first component is 3.9 parts of methacrylic acid and 69 parts of methyl methacrylate; the addition of the modified MQ resin was canceled. The other is the same as in the first embodiment.
The acrylate adhesive prepared in the first example and the comparative experiment is tested, the tensile shear strength is tested at 23+/-2 ℃ according to GB/T7124-2008 standard, the tensile shear strength is tested at 100+/-2 ℃ according to GJB 444-1988 standard, and the 90 DEG peel strength is tested at 23+/-2 ℃ according to GJB 446-1988 standard, and the test results are shown in Table 3.
TABLE 3 Table 3
Note that in the table, the aluminum alloy is LY12CZ, the titanium alloy is TC4, the superalloy is a286, the corrosion resistant steel is 304 stainless steel, and the composite material is 5224/CF3052/42 epoxy resin based carbon fiber reinforced composite material (prepreg provided by beijing 621, manufactured by baoding 550 factories).
The acrylate adhesive prepared in the first embodiment is used for bonding aluminum alloy-aluminum alloy and carrying out an environmental aging resistance test, and the performance data are as follows:
TABLE 4 Table 4
Mixing 100 parts by weight of methyl MQ resin (MQ 102) and 100 parts by weight of methyl methacrylate to obtain a methyl methacrylate solution of the MQ resin, wherein FIG. 1 is an infrared spectrogram of the methyl methacrylate solution of the MQ resin; FIG. 2 is an infrared spectrum of a modified MQ resin prepared in example one; as can be seen from the figure, 3467.53cm after the reaction -1 The absorption peak disappears, and the hydroxyl in the system participates in the reaction, so that the hydroxyl substitution end capping of the methyl MQ resin is realized. 3366.04cm -1 And 1638.22cm -1 The absorption peak is obviously enhanced, and amino groups are introduced into a visible system.

Claims (8)

1. The acrylate adhesive prepared by utilizing the modified MQ resin is characterized by comprising a first component and a second component which are packaged independently; the volume ratio of the first component to the second component is (7-10) 1;
the first component consists of 55-70 parts by mass of propylene, 15-25 parts by mass of elastomer toughening agent, 3-15 parts by mass of modified MQ resin, 0.5-6 parts by mass of accelerator and 0.02-0.5 part by mass of stabilizer; the propylene is one or two of acrylic acid and acrylic ester monomers;
the second component consists of, by mass, 30-45 parts of acrylic ester monomers, 15-25 parts of elastomer toughening agents, 30-50 parts of initiators and 0.01-0.5 part of stabilizers;
the modified MQ resin is prepared according to the following steps:
1. weighing 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate, 0.1-0.5 part of stabilizer, 15-50 parts of aminopropyl triethoxysilane, 0.1-0.5 part of catalyst and 15-50 parts of acryloyloxy trimethoxysilane according to parts by mass;
the catalyst is one or a mixture of several of acetic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid and cyclohexanone oxime;
2. stirring and dissolving 100 parts of methyl MQ resin, 50-100 parts of methyl methacrylate and 0.1-0.5 part of stabilizer to obtain a reaction system, heating the reaction system to 80-90 ℃, condensing and refluxing, adding 15-50 parts of aminopropyl triethoxysilane and 0.1-0.5 part of catalyst, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, then adding 15-50 parts of acryloyloxy trimethoxysilane, stirring and reacting for 1-2 h at the temperature of 80-90 ℃, and cooling to room temperature to obtain the modified MQ resin.
2. The acrylic acid ester adhesive prepared by the modified MQ resin according to claim 1, wherein the stabilizer in the first step is one or a mixture of more of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, ferrous sulfate and cuprous oxide.
3. The acrylate adhesive prepared with modified MQ resin of claim 1, wherein the acrylic acid in the first component is one or a mixture of methacrylic acid and acrylic acid.
4. The acrylate adhesive prepared by using the modified MQ resin according to claim 1, wherein the acrylate monomers in the first component and the second component are one or a mixture of several of methyl methacrylate, isobutyl methacrylate, cyclohexyl methacrylate, ethylene glycol (meth) acrylate, triethylene glycol di (meth) acrylate and tetraethylene glycol di (meth) acrylate.
5. The acrylate adhesive prepared by using modified MQ resin according to claim 1, wherein the elastomer toughening agent in the first component is one or a mixture of several of acrylonitrile-butadiene-styrene copolymer, nitrile rubber, carboxylated nitrile rubber, chlorosulfonated polyethylene and acrylate rubber; the elastomeric toughening agent in the second component is an acrylonitrile-butadiene-styrene copolymer.
6. The acrylate adhesive prepared by using modified MQ resin according to claim 1, wherein the accelerator in the first component is one or a mixture of several of N, N-dimethyl-p-toluidine, N-diethyl-p-toluidine, tetramethylthiourea, triphenylphosphine, triethylamine and vanadium acetylacetonate.
7. The acrylate adhesive prepared by using modified MQ resin according to claim 1, wherein the stabilizer in the first component and the second component is one or a mixture of more of hydroquinone, 2, 6-di-tert-butyl-4-methylphenol, ferrous sulfate and cuprous oxide.
8. The acrylate adhesive prepared with the modified MQ resin of claim 1, wherein the initiator in the second component is one or a mixture of more of benzoyl peroxide, lauroyl peroxide and cumene hydroperoxide.
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CN102329574A (en) * 2011-08-12 2012-01-25 上海邦中高分子材料有限公司 Tackiness agent for automobile tank
CN103087329A (en) * 2013-01-28 2013-05-08 中科院广州化学有限公司 Silicone-modified methacrylic resin as well as preparation method and application thereof
CN109207115A (en) * 2018-08-31 2019-01-15 东莞市新懿电子材料技术有限公司 A kind of one pack system anaerobic adhesive and preparation method thereof quickly fixed for chip
CN110964444A (en) * 2019-12-09 2020-04-07 南京金世家新材料科技有限公司 Low-temperature fast-curing high-strength high-temperature-resistant acrylic adhesive and preparation method and application thereof
CN112430329A (en) * 2020-11-27 2021-03-02 成都博达爱福科技有限公司 Method for synthesizing acryloxy MQ silicon resin

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CN101979454A (en) * 2010-10-27 2011-02-23 黑龙江省科学院石油化学研究院 Method for preparing high-strength heat-resistant silicon resin modified acrylic ester pressure-sensitive adhesive
CN102329574A (en) * 2011-08-12 2012-01-25 上海邦中高分子材料有限公司 Tackiness agent for automobile tank
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