CN114605944A - Acrylate structural adhesive and preparation method thereof - Google Patents

Acrylate structural adhesive and preparation method thereof Download PDF

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Publication number
CN114605944A
CN114605944A CN202210330000.2A CN202210330000A CN114605944A CN 114605944 A CN114605944 A CN 114605944A CN 202210330000 A CN202210330000 A CN 202210330000A CN 114605944 A CN114605944 A CN 114605944A
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Prior art keywords
component
acrylate
structural adhesive
acrylate structural
parts
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Chinese (zh)
Inventor
金闯
任瑶
高松
梁哲会
蒋晓明
倪建国
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Taicang Sidike New Material Science and Technology Co Ltd
Jiangsu Sidike New Materials Science and Technology Co Ltd
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Taicang Sidike New Material Science and Technology Co Ltd
Jiangsu Sidike New Materials Science and Technology Co Ltd
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Priority to CN202210330000.2A priority Critical patent/CN114605944A/en
Publication of CN114605944A publication Critical patent/CN114605944A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J143/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Adhesives based on derivatives of such polymers
    • C09J143/02Homopolymers or copolymers of monomers containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/20Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02Non-macromolecular additives
    • C09J11/06Non-macromolecular additives organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08Macromolecular additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09JADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04Homopolymers or copolymers of esters
    • C09J133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062Copolymers with monomers not covered by C09J133/06
    • C09J133/066Copolymers with monomers not covered by C09J133/06 containing -OH groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

The invention relates to an acrylate structural adhesive and a preparation method thereof, wherein the acrylate structural adhesive comprises a component A and a component B, wherein the component A comprises an acrylate monomer, a functional monomer, a toughening agent, a stabilizer, a reducing agent, a thixotropic agent and a wax auxiliary agent; the component B comprises an oxidant, a plasticizer and a filler. The invention carries out integral optimization on the component A and the component B in the acrylate structural adhesive, and comprises the steps of adding a functional monomer and a wax auxiliary agent in the component A, adjusting the using amount of a stabilizing agent, and adding a plasticizer in the component B, so that the obtained acrylate structural adhesive becomes the acrylate structural adhesive with high-strength adhesive property on ABS, PC and metal materials. In addition, the acrylate structural adhesive provided by the invention has better shearing performance after aging post-treatment, also meets the waterproof requirement, has good reworking property, and can improve the reuse rate of materials. Meanwhile, the acrylate structural adhesive provided by the invention also has the advantage of fast curing time.

Description

Acrylate structural adhesive and preparation method thereof
Technical Field
The invention belongs to the field of adhesive application, and relates to an acrylate structural adhesive and a preparation method thereof.
Background
The acrylate structural adhesive is a fully-reacted bi-component adhesive, and is mainly used for quickly positioning metals, plastics and composite materials and for assembling and maintaining. The performance of the existing acrylate structural adhesive product is greatly improved, and the acrylate structural adhesive has the advantages of room-temperature rapid curing, adjustable curing speed, good reworkability, high and low temperature resistance, damp and hot aging resistance, short-term storage stability and the like.
The existing acrylate structural adhesive can not give consideration to the bonding effect among metal articles, ABS and PC materials.
Disclosure of Invention
Based on the above, one of the objects of the present invention is to provide an acrylate structural adhesive which can bond ABS, PC and metal materials with high strength.
The above object of the present invention can be achieved by the following means.
One of the purposes of the invention is to provide an acrylate structural adhesive which comprises a component A and a component B, wherein the component A and the component B are calculated by weight parts,
the component A comprises:
Figure BDA0003574913290000011
Figure BDA0003574913290000021
the component B comprises:
20 to 40 portions of an oxidant, namely,
30 to 60 parts of a plasticizer, and
10-30 parts of a filler;
the functional monomer is selected from one or more of hydroxyethyl methacrylate phosphate, methacrylic acid, acrylate, methyl tetrahydrofuran acrylate, dicyclopentadiene acrylate, cyclotrimethylolpropane methylal acrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate and ethoxylated trimethylolpropane triacrylate.
In some of these embodiments, the stabilizer is selected from one or more of hydroquinone, benzoquinone, naphthoquinone, 2-tert-butylhydroquinone, tetraacetic acid, sodium salt of ethylene glycol, and p-hydroxyanisole.
In some of these embodiments, the plasticizer is selected from one or more of dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, dioctyl adipate, and dioctyl sebacate.
In some of these embodiments, the acrylate monomer is selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, butyl methacrylate, and octyl methacrylate.
In some of these embodiments, the toughening agent is selected from one or more of ABS resins, MBS resins, SBS resins, hydroxyl terminated liquid rubbers, carboxylated nitrile rubbers, hydrogenated nitrile rubbers, hydroxyl terminated nitrile rubbers, rosin resins, epoxy modified acrylic resins, urethane modified acrylic resins, styrene butadiene rubbers, and acrylate rubbers.
In some of these embodiments, the reducing agent is selected from one or more of N, N-diethyl-p-toluidine, N-dimethyl-p-toluidine, N-dihydroxyethyl-p-toluidine, tetramethyl thiourea, and vinyl thiourea.
In some of these embodiments, the thixotropic agent is selected from one or more of fumed silica and nano calcium carbonate.
In some of these embodiments, the oxidizing agent is selected from one or more of cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, vanadium pentoxide, and dicumyl peroxide.
In some of these embodiments, the filler is selected from one or more of zinc stearate, talc, and calcium carbonate.
In some of these embodiments, the B component further comprises a pigment.
In some of these embodiments, the weight ratio of the A component to the B component is (8-12): 1.
Another object of the present invention is to provide a method for preparing the acrylate structural adhesive, wherein the method comprises the following steps: respectively preparing the component A and the component B, and mixing to prepare the acrylate structural adhesive;
the preparation method comprises the following steps: respectively preparing the component A and the component B, and mixing to prepare the acrylate structural adhesive;
the step of preparing the A component comprises: mixing the acrylate monomer, the functional monomer, the toughening agent, the stabilizer, the reducing agent, the thixotropic agent and the wax auxiliary agent to prepare the component A;
the step of preparing the B component comprises the following steps: and mixing the oxidant, the plasticizer and the filler to prepare the component B.
Compared with the prior art, the invention has the following beneficial effects:
the invention carries out integral optimization on the component A and the component B in the acrylate structural adhesive, comprises the steps of adding a functional monomer and a wax auxiliary agent in the component A and adjusting the using amount of a stabilizing agent, and adds a plasticizer in the component B, so that the obtained acrylate structural adhesive becomes the acrylate structural adhesive with high-strength bonding performance to ABS, PC and metal materials, can be widely applied to a plurality of fields of intelligent electronic watches, mobile phones, computers, automobiles, sports equipment and the like, and is a structural adhesive product with wide application. In addition, the acrylate structural adhesive provided by the invention has good shearing performance after aging post-treatment, also meets the waterproof requirement (IPX8), has good reworkability, and can improve the reuse rate of materials. Meanwhile, the acrylate structural adhesive provided by the invention also has the advantage of fast curing time.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments and examples. It should be understood that these embodiments and examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention, which is provided for the purpose of making the present disclosure more thorough and complete. It is also understood that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein, and that various changes and modifications may be effected therein by one of ordinary skill in the art without departing from the spirit and scope of the invention and the resulting equivalents are within the scope and range of equivalents of the present application. Furthermore, in the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention, and it is to be understood that the present invention may be practiced without one or more of these details.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments and examples only and is not intended to be limiting of the invention.
Term(s) for
Unless otherwise stated or contradicted, terms or phrases used herein have the following meanings:
the term "and/or", "and/or" as used herein is intended to be inclusive of any one of the two or more items listed in association, and also to include any and all combinations of the items listed in association, including any two or more of the items listed in association, any more of the items listed in association, or all combinations of the items listed in association. It should be noted that when at least three items are connected by at least two conjunctive combinations selected from "and/or", "or" and/or ", it should be understood that in this application, the technical solutions unquestionably include the technical solutions all connected by" logical and ", and also unquestionably include the technical solutions all connected by" logical or ". For example, "A and/or B" includes A, B and A + B. For example, the embodiments of "a, and/or, B, and/or, C, and/or, D" include any of A, B, C, D (i.e., all embodiments using a "logical or" connection), any and all combinations of A, B, C, D, i.e., any two or any three of A, B, C, D, and four combinations of A, B, C, D (i.e., all embodiments using a "logical and" connection).
The present invention relates to "plural", etc., and indicates that it is 2 or more in number, unless otherwise specified. For example, "one or more" means one or two or more.
As used herein, "a combination thereof," "any combination thereof," and the like, includes all suitable combinations of any two or more of the listed items.
In the present specification, the term "suitable" in "a suitable combination, a suitable manner," any suitable manner "and the like shall be construed to mean that the technical solution of the present invention can be implemented, the technical problem of the present invention can be solved, and the technical effect of the present invention can be achieved.
The terms "preferably", "better" and "suitable" are used herein only to describe preferred embodiments or examples, and it should be understood that the scope of the present invention is not limited by these terms.
In the present invention, "further", "still further", "specifically" and the like are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of the present invention.
In the present invention, "optionally", "optional" and "optional" refer to the presence or absence, i.e., to any one of two juxtapositions selected from "present" and "absent". If multiple optional parts appear in one technical scheme, if no special description exists, and no contradiction or mutual constraint relation exists, each optional part is independent.
In the present invention, the terms "first", "second", "third", "fourth", etc. in the terms of "first aspect", "second aspect", "third aspect", "fourth aspect", etc. are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or quantity, nor as implying that importance or quantity indicating the technical feature being indicated. Also, "first," "second," "third," "fourth," etc. are used for non-exhaustive enumeration of description purposes only and should not be construed as a closed limitation to the number.
In the present invention, the technical features described in the open type include a closed technical solution composed of the listed features, and also include an open technical solution including the listed features.
In the present invention, where a range of values (i.e., a numerical range) is recited, unless otherwise specified, alternative distributions of values within the range are considered to be continuous, and include both the numerical endpoints of the range (i.e., the minimum and maximum values), and each numerical value between the numerical endpoints. Unless otherwise specified, when a numerical range refers to integers only within the numerical range, both endpoints of the numerical range and each integer between the two endpoints are included, and in this document, it is equivalent to reciting each integer directly, for example, t is an integer selected from 1 to 10, meaning t is any integer selected from the group of integers consisting of 1, 2, 3, 4, 5, 6, 7, 8, 9 and 10. Further, when multiple range-describing features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, the ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The temperature parameter in the present invention is not particularly limited, and may be a constant temperature treatment or a variation within a certain temperature range. It will be appreciated that the described thermostatic process allows the temperature to fluctuate within the accuracy of the instrument control. Allowing fluctuations in the temperature ranges of, for example, +/-5 deg.C, +/-4 deg.C, +/-3 deg.C, +/-2 deg.C and + -1 deg.C.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. The citation referred to herein is incorporated by reference in its entirety for all purposes unless otherwise in conflict with the present disclosure's objectives and/or technical solutions. Where a citation is referred to herein, the definition of a reference in the document, including features, terms, nouns, phrases, etc., that is relevant, is also incorporated by reference. In the present invention, when the citation is referred to, the cited examples and preferred embodiments of the related art features are also incorporated by reference into the present application, but the present invention is not limited to the embodiments. It should be understood that where the citation conflicts with the description herein, the application will control or be adapted in accordance with the description herein.
First aspect of the invention
The invention provides an acrylate structural adhesive, which comprises a component A and a component B, wherein the component A and the component B are calculated by weight parts,
the component A comprises:
Figure BDA0003574913290000071
the component B comprises:
20 to 40 portions of an oxidant, namely,
30 to 60 parts of a plasticizer, and
10-30 parts of a filler;
the functional monomer is selected from one or more of hydroxyethyl methacrylate phosphate, methacrylic acid, acrylate, methyl tetrahydrofuran acrylate, dicyclopentadiene acrylate, cyclotrimethylolpropane methylal acrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate and ethoxylated trimethylolpropane triacrylate.
The acrylate structural adhesive is bi-component, the component A and the component B can be matched in a proper proportion, and the initial positioning time is about five minutes. The acrylate structural adhesive has the advantages of considering the bonding effect of various materials and having better shearing performance after aging post-treatment. As in the examples, the shear strength for ABS is more than 11MPa, the shear strength for SUS is more than 14MPa, and the shear strength for PC is more than 10 MPa. (ii) a And still has better shearing performance after being aged for three days under the conditions of 65 ℃/95 percent or 85 ℃/85 percent.
The acrylate structural adhesive is a bi-component adhesive, and the preferable proportion of the component A to the component B is A: b is 10:1, which has the following characteristics: firstly, the curing speed is fast: the initial fixation can be carried out in about 5 minutes, the strength can reach 80% after 30 minutes, and the maximum strength can be reached after 24 hours; secondly, the strength is high: high adhesion strength to metal articles, ABS, PC, and other materials. And thirdly, the waterproof performance is good (the IPX8 standard is met).
In one example, the stabilizer is selected from one or more of hydroquinone, benzoquinone, naphthoquinone, 2-tert-butylhydroquinone, sodium edetate and p-hydroxyanisole.
In one example, the plasticizer is selected from one or more of dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, dioctyl adipate, and dioctyl sebacate.
In one example, the acrylate monomer is selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, butyl methacrylate, and octyl methacrylate. Preferably, the acrylate monomer is selected from one or more of methyl methacrylate, hydroxypropyl methacrylate, tetrahydrofuran acrylate, butyl methacrylate and octyl methacrylate
In one example, the toughening agent is selected from one or more of ABS resin, MBS resin, SBS resin, hydroxyl terminated liquid rubber, carboxylated nitrile rubber, hydrogenated nitrile rubber, hydroxyl terminated nitrile rubber, rosin resin, epoxy modified acrylic resin, urethane modified acrylic resin, styrene butadiene rubber, and acrylate rubber.
In one example, the reducing agent is selected from one or more of N, N-diethyl-p-toluidine, N-dimethyl-p-toluidine, N-dihydroxyethyl-p-toluidine, tetramethylthiourea, and vinylthiourea.
In one example, the thixotropic agent is selected from one or more of fumed silica and nano calcium carbonate.
In one example, the oxidizing agent is selected from one or more of cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, vanadium pentoxide, and dicumyl peroxide.
In one example, the filler is selected from one or more of zinc stearate, talc and calcium carbonate.
In one example, the B component further comprises a pigment. It is to be understood that the amount of the pigment used in the present invention is not particularly limited, and for example, the B component further contains 0.1 to 1 part of a pigment.
In one example, the weight ratio of the A component to the B component is (8-12): 1. E.g., 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12: 1.
Second aspect of the invention
The invention provides a preparation method of the acrylate structural adhesive, which comprises the following steps: respectively preparing the component A and the component B, and mixing to prepare the acrylate structural adhesive;
the preparation method comprises the following steps: respectively preparing the component A and the component B, and mixing to prepare the acrylate structural adhesive;
the preparation method of the component A comprises the following steps: mixing the acrylate monomer, the functional monomer, the toughening agent, the stabilizing agent, the reducing agent, the thixotropic agent and the wax auxiliary agent to prepare the component A;
the preparation method of the component B comprises the following steps: and mixing the oxidant, the plasticizer and the filler to prepare the component B.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Embodiments of the present invention will be described in detail with reference to examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures for the conditions not specified in the following examples, preferably with reference to the guidelines given in the present invention, may also be performed according to the experimental manual or the conventional conditions in the art, may also be performed according to the conditions suggested by the manufacturer, or may be performed according to the experimental procedures known in the art.
In the following specific examples, the measurement parameters relating to the components of the raw materials, if not specified otherwise, may be subject to slight deviations within the accuracy of the weighing. Temperature and time parameters are involved to allow for acceptable deviation due to instrument test accuracy or operational accuracy.
Example 1:
preparation of component A: firstly, adding 20 parts of methyl methacrylate, 7 parts of methyl tetrahydrofuran acrylate, 3 parts of acrylate and 4 parts of methacrylic acid, mixing, and mixing for 5 minutes by using a double-planet stirrer at 800 r/min; adding 60 parts of acrylate rubber and 4 parts of trimethylolpropane trimethacrylate, mixing at 800r/min, and dissolving at 2000 r/min; and finally, adding 0.5 part of wax, 1.5 parts of naphthoquinone, 2 parts of fumed silica, 1.5 parts of hydroxyethyl methacrylate phosphate and 1 part of tetramethyl thiourea, premixing for 5 minutes at 800r/min, and dissolving at 2000r/min to obtain the component A.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
The weight ratio of the component A to the component B is 10: 1.
Example 2:
preparation of component A: firstly, adding 45 parts of methyl methacrylate, 7 parts of methyl tetrahydrofuran acrylate, 3 parts of acrylate and 4 parts of methacrylic acid, mixing, and mixing for 5 minutes by using a double-planet stirrer at 800 r/min; adding 30 parts of acrylate rubber and 4 parts of trimethylolpropane trimethacrylate, mixing at 800r/min, and dissolving at 2000 r/min; and finally, adding 0.5 part of wax, 1.5 parts of naphthoquinone, 2 parts of fumed silica, 1.5 parts of hydroxyethyl methacrylate phosphate and 1 part of tetramethyl thiourea, premixing for 5 minutes at 800r/min, and dissolving at 2000r/min to obtain the component A.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
The weight ratio of the component A to the component B is 10: 1.
Example 3:
preparation of component A: on the basis of example 2, 30 parts of methyl methacrylate, 1 part of acrylate, 48 parts of acrylate rubber and the like were changed, and mixing was performed according to the relevant process of example 2 to obtain a component a.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
The weight ratio of the component A to the component B is 10: 1.
Example 4:
preparation of component A: on the basis of example 3, the amount of methyl methacrylate added was changed to 31 parts, acrylic acid ester was changed to 3 parts, the amount of methacrylic acid was changed to 1 part, and the other materials were not changed, and mixing was performed according to the procedure of example 2 to obtain a component a.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
The weight ratio of the component A to the component B is 10: 1.
Example 5:
preparation of component A: on the basis of example 2, the methyl methacrylate was changed to 28 parts, the amount of hydroxyethyl methacrylate phosphate was changed to 1 part, the acrylate rubber was changed to 50 parts, and the other materials were changed, and mixing was performed according to the relevant process of example 2 to obtain a component a.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
The weight ratio of the component A to the component B is 10: 1.
Example 6:
preparation of component A: on the basis of example 2, 27 parts of methyl methacrylate, 48 parts of acrylate rubber and the like were changed, and mixing was carried out according to the relevant process of example 2 to obtain a component A.
The material proportion of the component B is as follows: 25 parts of cumene hydroperoxide, 54 parts of bisphenol A epoxy resin, 20 parts of zinc stearate and 1 part of pigment.
Example 7:
the acrylate structural adhesive comprises a component A and a component B, and the components are calculated by weight parts,
the component A comprises: 60 parts of acrylate monomer (hydroxypropyl methacrylate), 1 part of functional monomer (dicyclopentadiene acrylate), 20 parts of toughening agent (rosin resin), 0.5 part of stabilizing agent (hydroquinone), 2 parts of reducing agent (N, N-diethyl-p-toluidine), 0.1 part of thixotropic agent (nano calcium carbonate) and 1 part of wax assistant;
the component B comprises: 20 parts of oxidizing agent (cumene hydroperoxide), 60 parts of plasticizer (dipropylene glycol dibenzoate), 0.1 part of pigment and 10 parts of filler (zinc stearate). The preparation method can refer to example 1.
Example 8:
the acrylate structural adhesive comprises a component A and a component B, and the components are calculated by weight parts,
the component A comprises: 60 parts of acrylate monomer (butyl methacrylate), 20 parts of functional monomer (trimethylolpropane trimethacrylate), 20 parts of flexibilizer (ABS resin), 2 parts of stabilizer (p-hydroxyanisole), 1.5 parts of reducing agent (N, N-dihydroxyethyl p-toluidine), 5 parts of thixotropic agent (fumed silica) and 0.01 part of wax assistant;
the component B comprises: 10 parts of an oxidant (vanadium pentoxide), 30 parts of a plasticizer (dipropylene glycol dibenzoate), 0.1 part of a pigment and 30 parts of a filler (zinc stearate).
The preparation method can refer to example 1.
Comparative example 1:
this comparative example 1 is a comparative example to example 1, and the difference with respect to example 1 is mainly that isobornyl methacrylate is used for the a component instead of the methyl methacrylate monomer.
Comparative example 2:
this comparative example 2 is a comparative example to example 1, and the difference with respect to example 1 is mainly that the a-component stabilizer is 0.3 parts.
Comparative example 3:
this comparative example 3 is a comparative example to example 1, the difference with respect to example 1 being mainly that no wax adjuvant was added to the a component.
Comparative example 4:
this comparative example 4 is a comparative example to example 1, and the difference with respect to example 1 is mainly that no plasticizer is added to the B component.
Summary of the formulations of acrylate structural adhesives provided in Table 1, examples and comparative examples
Figure BDA0003574913290000131
Figure BDA0003574913290000141
The acrylate structural adhesives prepared in the above examples and comparative examples were subjected to the related performance tests, and the results are shown in the following table; relevant shear strength test reference: ASTM D1002; waterproof performance test reference: IPX 8.
The performance test results of the epoxy acrylate structural adhesive prepared in the embodiment and the comparative acrylate structural adhesive are as follows:
TABLE 2
Figure BDA0003574913290000151
TABLE 3
Figure BDA0003574913290000152
Figure BDA0003574913290000161
As can be seen from the above table, the shear strength of example 1 for each base material is better, and the shear strength of the base material after aging is slightly reduced, but still has better shear strength; example 2 compared with example 1, the amounts of acrylate rubber and methyl methacrylate are adjusted, epoxy acrylate structural adhesive with high shear strength to ABS, PC and SUS is also obtained, and the change of the shear strength to different materials is not obvious after aging; example 3 a small amount of methyl methacrylate was added to example 2 and the amount of acrylic acid was adjusted to obtain an epoxy acrylate structural adhesive having high shear strength for ABS, PC and SUS; example 5 epoxy acrylate structural adhesives with good shear strength for PC, ABS and SUS materials were also obtained by adjusting the amount of hydroxyethyl methacrylate phosphate, acrylate rubber and methyl methacrylate relative to example 2.
In comparative example 1, when methyl methacrylate was changed to isobornyl methacrylate, the adhesion to ABS, PC and metal materials was reduced. In comparative example 2, when the amount of the stabilizer is reduced, the reaction speed is increased, so that bubbles appear in the cured glue to influence the bonding strength of the material. As can be seen from comparative example 3, the absence of addition of a wax adjuvant leads to a sticky gel after curing. Comparative example 4 can conclude that the adhesive property is degraded when no plasticizer is added.
According to the invention, the formula of the epoxy acrylate structural adhesive is adjusted to obtain the adhesive with better adhesive property to ABS, PC and SUS.
The technical features of the embodiments and examples described above can be combined in any suitable manner, and for the sake of brevity, all possible combinations of the technical features of the embodiments and examples described above are not described, but should be considered within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, so as to understand the technical solutions of the present invention specifically and in detail, but not to be understood as the limitation of the protection scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Furthermore, it should be understood that after reading the above teachings of the present invention, various changes or modifications may be made to the invention by those skilled in the art, and equivalents may be obtained and still fall within the scope of the present application. It should also be understood that the technical solutions provided by the present invention, which are obtained by logical analysis, reasoning or limited experiments, are within the scope of the present invention as set forth in the appended claims. Therefore, the protection scope of the patent of the invention is subject to the content of the appended claims, and the description can be used for explaining the content of the claims.

Claims (10)

1. The acrylate structural adhesive is characterized by comprising a component A and a component B in parts by weight,
the component A comprises:
Figure FDA0003574913280000011
the component B comprises:
20 to 40 portions of an oxidant, namely,
30 to 60 parts of a plasticizer, and
10-30 parts of a filler;
the functional monomer is selected from one or more of hydroxyethyl methacrylate phosphate, methacrylic acid, acrylate, methyl tetrahydrofuran acrylate, dicyclopentadiene acrylate, cyclotrimethylolpropane methylal acrylate, trimethylolpropane trimethacrylate, dipentaerythritol pentaacrylate and ethoxylated trimethylolpropane triacrylate.
2. The acrylate structural adhesive of claim 1, wherein the stabilizer is one or more selected from hydroquinone, benzoquinone, naphthoquinone, 2-tert-butylhydroquinone, tetraacetic acid, sodium salt of ethylene glycol, and p-hydroxyanisole.
3. The acrylate structural adhesive of claim 1 wherein said plasticizer is selected from one or more of dipropylene glycol dibenzoate, diethylene glycol dibenzoate, dipropylene glycol dibenzoate, dioctyl adipate, and dioctyl sebacate.
4. The acrylate structural adhesive of any one of claims 1 to 3, wherein the acrylate monomer is selected from one or more of methyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, tetrahydrofurfuryl acrylate, cyclohexyl acrylate, butyl methacrylate and octyl methacrylate.
5. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the toughening agent is selected from one or more of ABS resin, MBS resin, SBS resin, hydroxyl-terminated liquid rubber, carboxyl nitrile rubber, hydrogenated nitrile rubber, hydroxyl-terminated nitrile rubber, rosin resin, epoxy modified acrylic resin, urethane modified acrylic resin, styrene-butadiene rubber and acrylate rubber.
6. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the reducing agent is selected from one or more of N, N-diethyl-p-toluidine, N-dimethyl-p-toluidine, N-dihydroxyethyl-p-toluidine, tetramethylthiourea and vinylthiourea.
7. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the thixotropic agent is selected from one or more of fumed silica and nano calcium carbonate; and/or the first and/or second light sources,
the oxidant is selected from one or more of cumene hydroperoxide, benzoyl peroxide, tert-butyl hydroperoxide, vanadium pentoxide and dicumyl peroxide; and/or the first and/or second light sources,
the filler is selected from one or more of zinc stearate, talcum powder and calcium carbonate.
8. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the B component further comprises a pigment.
9. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the weight ratio of the A component and the B component is (8-12): 1.
10. The method for preparing the acrylate structural adhesive according to any one of claims 1 to 9, wherein the method comprises the following steps: respectively preparing the component A and the component B, and mixing to prepare the acrylate structural adhesive;
the step of preparing the A component comprises: mixing the acrylate monomer, the functional monomer, the toughening agent, the stabilizer, the reducing agent, the thixotropic agent and the wax auxiliary agent to prepare the component A;
the step of preparing the B component comprises the following steps: and mixing the oxidant, the plasticizer and the filler to prepare the component B.
CN202210330000.2A 2022-03-31 2022-03-31 Acrylate structural adhesive and preparation method thereof Pending CN114605944A (en)

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