CN111073525A - Low-modulus flexible acrylate adhesive and preparation method thereof - Google Patents
Low-modulus flexible acrylate adhesive and preparation method thereof Download PDFInfo
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- CN111073525A CN111073525A CN201911410097.2A CN201911410097A CN111073525A CN 111073525 A CN111073525 A CN 111073525A CN 201911410097 A CN201911410097 A CN 201911410097A CN 111073525 A CN111073525 A CN 111073525A
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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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
Abstract
The invention relates to the field of polymer chemical industry, in particular to a low-modulus flexible acrylate adhesive and a preparation method thereof. The low modulus flexible acrylate adhesive comprises a component A and a component B; the component A comprises one or a combination of more of acrylate monomer, polyurethane acrylate oligomer, core-shell particles, oxidant, polymerization inhibitor and metal ion complex; the component B comprises one or a combination of more of acrylate monomer, polyurethane acrylate oligomer, core-shell particles, reducing agent, polymerization inhibitor and metal ion complex; the volume ratio of the component A to the component B is 1: (1-20). According to the invention, by regulating and controlling the types and parameters of the added acrylate monomers and other additives, the acrylate adhesive with good flexibility, long operation time and high shear strength after curing and forming is obtained.
Description
Technical Field
The invention relates to the field of polymer chemical industry, in particular to a low-modulus flexible acrylate adhesive and a preparation method thereof.
Background
Methacrylate adhesives are highly attractive high performance engineered structural materials. The adhesive has the characteristics of convenient operation, room-temperature curing, high peel strength, excellent adhesive property, good water resistance, universality of base materials and the like.
The existing methacrylate adhesive in the market is mainly used in the aspects of automobile, electronics, wind power and industrial bonding. Because more monomers with double functional groups or even polyfunctional monomers are added, and a plurality of high molecular elastomers with hard chain segments are used, the fully cured high molecular elastomer has higher crosslinking density, but can cause higher internal stress of the body; meanwhile, the shrinkage rate is over 10 percent, and the existence of higher shrinkage force on the bonded structure causes deformation of the bonded part or structure, which is not favorable for the stability and durability of bonding.
Disclosure of Invention
In order to solve the technical problems, the invention provides a low-modulus flexible acrylate adhesive in a first aspect, which comprises a component A; the component A comprises an acrylate monomer, a polyurethane acrylate oligomer and an oxidant.
As a preferable technical scheme, the component A comprises 10-100 parts by weight of acrylate monomer, 0-50 parts by weight of urethane acrylate oligomer and 5-60 parts by weight of oxidant.
As a preferred embodiment, the acrylate monomer includes a functional monomer.
As a preferable technical scheme, the functional monomer is selected from one or more of hydroxyl acrylate, amino acrylic acid, epoxy acrylate and solid acrylic resin.
As a preferred technical scheme, the hydroxyl acrylic ester is selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl acrylate and 4-hydroxybutyl acrylate.
As a preferred technical solution, the acrylate monomer further comprises a hard monomer.
In a preferred embodiment, the hard monomer is selected from any one or more of methyl methacrylate, methyl acrylate, isopropyl methacrylate, isobornyl methacrylate, methoxyethyl methacrylate, tetrahydrofuryl methacrylate, phenoxyethyl methacrylate, and n-butyl methacrylate.
In a preferred embodiment, the oxidizing agent is selected from the group consisting of oxyhalides, hydroperoxides, organic peroxides, inorganic peracids and salts thereof, organic peracids and salts thereof, halogen molecules, and ozone.
As a preferred technical scheme, the paint also comprises a component B; the component B comprises an acrylate monomer, a polyurethane acrylate oligomer and a reducing agent; the volume ratio of the component A to the component B is 1: (1-20).
The second aspect of the invention provides a preparation method of the low-modulus flexible acrylate adhesive, which at least comprises the following steps:
(1) preparing a component A;
(2) preparing a component B;
(3) mixing the component A and the component B.
Has the advantages that: the acrylic ester adhesive with good flexibility, long operation time and high shear strength after curing and forming is obtained by regulating and controlling the types and parameters of the added acrylic ester monomers and other additives.
Detailed Description
The disclosure may be understood more readily by reference to the following detailed description of preferred embodiments of the invention and the examples included therein. 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. In case of conflict, the present specification, including definitions, will control.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In addition, the indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the stated number clearly indicates that the singular form is intended.
In order to solve the above technical problems, the present invention provides in a first aspect a low modulus flexible acrylate adhesive comprising a component a; the component A comprises an acrylate monomer, a polyurethane acrylate oligomer and an oxidant.
Component A
In a preferred embodiment, the component A comprises 10-100 parts by weight of acrylate monomer, 0-50 parts by weight of urethane acrylate oligomer and 5-60 parts by weight of oxidant.
In a preferred embodiment, the component A comprises 20-80 parts by weight of acrylate monomer, 2-30 parts by weight of urethane acrylate oligomer and 10-40 parts by weight of oxidant.
In a preferred embodiment, the component A comprises 55-70 parts by weight of acrylate monomer, 15 parts by weight of urethane acrylate oligomer and 20-30 parts by weight of oxidant.
Acrylate monomer
In the invention, the acrylic ester refers to a general term of esters of acrylic acid and homologues thereof, can be polymerized or copolymerized with other monomers, and is a monomer for manufacturing adhesives, synthetic resins, special rubbers and plastics.
In one embodiment, the acrylate monomer comprises a functional monomer.
In one embodiment, the functional monomer is selected from one or more of hydroxyl-based acrylates, amino-based acrylics, epoxy-based acrylates, solid acrylics.
In one embodiment, the hydroxyl-based acrylate is selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate.
In a preferred embodiment, the hydroxyl acrylate is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl acrylate, hydroxypropyl methacrylate.
In a preferred embodiment, the hydroxyl-based acrylate is a secondary hydroxyl-based acrylic acid.
In a preferred embodiment, the hydroxyl-based acrylate is hydroxyethyl methacrylate and/or hydroxypropyl methacrylate.
In a more preferred embodiment, the hydroxy-acrylate is hydroxypropyl methacrylate.
In one embodiment, the amino acrylic acid is selected from one or more of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate.
In one embodiment, the epoxy acrylate is selected from one or more of glycidyl methacrylate, glycidyl acrylate, 3, 4-epoxycyclohexyl methacrylate.
In a preferred embodiment, the epoxy acrylate is 3, 4-epoxycyclohexylmethacrylate (CAS number 64630-63-3).
In one embodiment, the acrylate monomer further comprises a hard monomer.
In one embodiment, the hard monomer is selected from any one or combination of methyl methacrylate, methyl acrylate, isopropyl methacrylate, isobornyl methacrylate, methoxyethyl methacrylate, tetrahydrofuryl methacrylate, phenoxyethyl methacrylate, n-butyl methacrylate.
In a preferred embodiment, the hard monomer is an even carbon containing hard monomer.
In a preferred embodiment, the hard monomer is selected from one or more of n-butyl methacrylate, isobornyl methacrylate (CAS number 7534-94-3), 2-phenoxyethyl methacrylate (CAS number 10595-06-9).
In a preferred embodiment, the hard monomer is n-butyl methacrylate and/or 2-phenoxyethyl methacrylate.
In one embodiment, the acrylate monomers further comprise soft monomers.
In one embodiment, the soft monomer is selected from one or more of lauryl methacrylate, isooctyl acrylate, isodecyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-octyl acrylate.
In a preferred embodiment, the hard monomer is a hard monomer having an even number of carbons, and the difference between the number of carbons of the soft monomer and the number of carbons of the hard monomer is 4 to 10.
In a preferred embodiment, the soft monomer is lauryl methacrylate.
In a preferred embodiment, the lauryl methacrylate is 15 to 36% by weight of the total acrylate monomers.
The inventor finds that when the acrylate monomer contains a specific soft monomer, especially lauryl methacrylate, the adhesive disclosed by the invention has low modulus, and the inventor believes that the possible reason is that in the cross-linking process, the cured copolymer has better flexibility, but the molecular chain of the copolymer is even alkyl, the molecular symmetry is good, the polarity is lower, the viscosity of the system is increased due to excessive soft segment number, the cage effect is obvious, and the content of the system is controlled to be less than 36% of the total mass percent of the acrylate monomer. In further studies, the inventors have unexpectedly found that when a specific hard monomer is used, and the number of carbon atoms of the hard monomer is an even number, and the difference between the number of carbon atoms of the soft monomer and the number of carbon atoms of the hard monomer is 4 to 10, not only the modulus is low but also the hardness is not high, i.e., when the soft monomer is lauryl methacrylate and the hard monomer is n-butyl methacrylate or 2-phenoxyethyl methacrylate, the inventors speculate that lauryl methacrylate may be less polar, the structure of the crosslinked specific hard monomer blocks excessive crosslinking between chain segments, and meanwhile, the polarity of the chain segments can be adjusted by adopting the specific hard monomer with carbon atom number, so that the system has proper intermolecular force, the proper miscibility with other monomers is ensured, and the hydrogen bond association of the chain segments is weakened.
In a more preferred embodiment, when the hard monomer is n-butyl methacrylate, the functional monomer comprises 3, 4-epoxycyclohexyl methacrylate or hydroxypropyl methacrylate; and the weight ratio of the n-butyl methacrylate to the 3, 4-epoxycyclohexyl methacrylate or the hydroxypropyl methacrylate is 1: (0.5-1.5).
In a more preferred embodiment, when the hard monomer is n-butyl methacrylate, the functional monomer further comprises a solid acrylic resin; and the weight ratio of the n-butyl methacrylate to the solid acrylic resin is 1: (0.75-2).
In a more preferred embodiment, when the hard monomer is n-butyl methacrylate, the functional monomer is a mixture of solid acrylic resin, 3, 4-epoxycyclohexyl methacrylate or hydroxypropyl methacrylate, and the weight ratio of solid acrylic resin, 3, 4-epoxycyclohexyl methacrylate or hydroxypropyl methacrylate is 1: (0.5-0.75).
In another more preferred embodiment, when the hard monomer is 2-phenoxyethyl methacrylate, the functional monomer comprises hydroxypropyl methacrylate; and the weight ratio of the 2-phenoxyethyl methacrylate to the hydroxypropyl methacrylate is 6: 1.
in another more preferred embodiment, when the hard monomer is 2-phenoxyethyl methacrylate, the functional monomer comprises 3, 4-epoxycyclohexyl methacrylate; and the weight ratio of the 2-phenoxyethyl methacrylate to the 3, 4-epoxycyclohexyl methacrylate is (2-3): 1.
in another most preferred embodiment, when the hard monomer is 2-phenoxyethyl methacrylate, the functional monomer is a mixture of hydroxypropyl methacrylate and 3, 4-epoxycyclohexyl methacrylate; and the weight ratio of the 2-phenoxyethyl methacrylate, the hydroxypropyl methacrylate and the 3, 4-epoxycyclohexyl methacrylate is (2-3): (0.33-0.5): 1.
the invention adopts functional monomers, hard monomers and soft monomers to form a three-dimensional network structure through crosslinking, and improves the bonding strength of the adhesive, but the inventor finds that when the hard monomers are n-butyl methacrylate, the functional monomers are epoxy group acrylic acid or hydroxyl group acrylic acid, wherein the hydroxyl group acrylic acid is a secondary hydroxyl group acrylic acid monomer, the functional monomers not only have lower modulus, but also have proper hardness, while the primary hydroxyl group acrylic acid monomer has poor effect.
Urethane acrylate oligomer
In the invention, the polyurethane acrylate oligomer refers to a modified substance of polyurethane acrylate.
In one embodiment, the urethane acrylate oligomer is purchased from Shadoma Guangzhou chemical company, Inc. under the designation CN-991 NS.
Oxidizing agent
In the present invention, the oxidizing agent contains a substance from which an electron element is easily obtained, i.e., a substance having strong oxidizing properties.
In one embodiment, the oxidizing agent is selected from the group consisting of oxyhalides, hydroperoxides, organic peroxides, inorganic peracids and salts thereof, organic peracids and salts thereof, halogen molecules, ozone, and combinations of one or more thereof.
The halogen oxide refers to a molecule combining one or more halogen atoms and oxygen; the halogen oxide includes but is not limited to NaClO, ClO2、NaClO4Any one of the above.
The halogen molecule refers to a diatomic species from the group of the periodic table beginning with fluorine; the halogen molecule includes but is not limited to F2、Cl2、Br2、I2Any one of the above.
The organic peracid refers to a polycarbonic organic compound in which-OH in the acid group is substituted by-OOH group, such as compounds of the general formula RCO-OOH; the organic peracid includes, but is not limited to, any one of peracetic acid, perbenzoic acid, m-chloroperoxybenzoic acid.
The inorganic peracid refers to a sulfur, phosphorus or carbon compound in which-OH in the acid group is substituted by-OOH group; the inorganic peracid includes, but is not limited to, any one of peroxydiphosphoric acid, peroxydisulfuric acid, sodium percarbonate, sodium peroxydisulfate, potassium peroxydisulfate, ammonium peroxydisulfate.
In a preferred embodiment, the oxidizing agent is selected from one or more of hydrogen peroxide, sodium peroxide, urea peroxide, alkyl peroxides, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, diacyl peroxide, lauroyl peroxide, cumene hydroperoxide, dicumyl peroxide, peroxy salts, persulfates, perborates, sodium percarbonate.
In a preferred embodiment, the oxidizing agent is one or more of diacyl peroxide, benzoyl peroxide, lauroyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide and dicumyl peroxide.
In a more preferred embodiment, the oxidizing agent is cumene hydroperoxide (CAS number 80-15-9).
In one embodiment, the a component further comprises core shell particles; the weight portion of the core-shell particles is 0-70.
In a preferred embodiment, the weight parts of the core-shell particles are 0 to 50 parts.
In a more preferred embodiment, the weight parts of the core-shell particles are 0 to 15 parts.
Core-shell particles
In the invention, the core-shell particles are particles of a nanoscale orderly assembly structure formed by coating one nano material with another nano material through chemical bonds or other acting forces.
In one embodiment, the core-shell particles have a brand selected from one or more of MX125, EPS-125, and P52, all purchased from shenzhen clock source technologies, ltd.
In a preferred embodiment, the core-shell particles have the designation MX 125.
In one embodiment, the a component further comprises an adjuvant.
Auxiliary agent
In one embodiment, the auxiliary comprises 0.1-10 parts of polymerization inhibitor and 0-0.5 part of metal ion complex by weight.
In a preferred embodiment, the auxiliary comprises 0.1-5 parts of polymerization inhibitor and 0-0.1 part of metal ion complex by weight.
In a preferred embodiment, the auxiliary comprises 1-4 parts of polymerization inhibitor and 0-0.1 part of metal ion complex by weight.
(polymerization inhibitor)
In the present invention, the polymerization inhibitor is an industrial assistant, and is generally used for preventing the progress of polymerization. The inhibitor molecules react with the chain radicals to form non-radical species or low reactive radicals that cannot initiate, thereby terminating the polymerization.
In one embodiment, the polymerization inhibitor is selected from one or more of a phenolic polymerization inhibitor, a quinone polymerization inhibitor, an aromatic nitro compound polymerization inhibitor, and an inorganic compound polymerization inhibitor.
The phenolic polymerization inhibitor includes, but is not limited to, any one of hydroquinone, t-butyl p-phenol, methyl hydroquinone, p-t-butyl catechol, p-hydroxyanisole, 2-t-butyl hydroquinone, 2, 5-di-t-butyl hydroquinone, 2, 6-di-t-butyl-4-methylphenol, 4' -dihydroxybiphenyl, pyrogallol and bisphenol A.
The quinone polymerization inhibitor includes, but is not limited to, any one of tetrachlorobenzoquinone, l, 4-naphthoquinone, and p-benzoquinone.
The inorganic compound polymerization inhibitor includes, but is not limited to, any one of ferric chloride, cuprous chloride, cupric sulfate, titanium trichloride, titanium chloride, sodium sulfate, sodium sulfide, and ammonium thiocyanate.
In a preferred embodiment, the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, dibutyl hydroxy toluene, 1, 4-naphthoquinone, 2, 6-di-tert-butyl-4-methylphenol, catechol, 2, 6-di-tert-butylphenol, and p-methoxyphenol.
In a more preferred embodiment, the polymerization inhibitor is dibutylhydroxytoluene (CAS number 128-37-0).
(Metal ion Complex)
In the present invention, the metal ion complex is a substance capable of forming a coordination with a metal ion.
In one embodiment, the metal ion complex is one or more of ethylenediaminetetraacetic acid disodium salt, ethylenediaminetetraacetic acid diammonium salt, ethylenediaminetetraacetic acid tetrasodium salt, and ethylenediaminetetraacetic acid tetraammonium salt.
In a preferred embodiment, the metal ion complex is ethylenediaminetetraacetic acid tetrasodium salt; the ethylene diamine tetraacetic acid tetrasodium salt is EDTA-4 Na.
In one embodiment, the a component further comprises fumed silica.
Fumed silica
In the invention, the fumed silica has small particle size, large specific surface area, strong surface adsorption force and good dispersion performance.
In one embodiment, the fumed silica is purchased from the avastin reagent.
In one embodiment, the mass ratio of fumed silica to urethane acrylate oligomer is 1: (2-5).
In a preferred embodiment, the mass ratio of the fumed silica to the urethane acrylate oligomer is 1: 3.5.
in subsequent studies, the inventors have found that when the hard monomer is 2-phenoxyethyl methacrylate, the shrinkage greatly varies and the hardness is low when epoxyacrylic acid or secondary hydroxyl acrylic acid is used alone; the inventors have surprisingly found that the performance is very good when epoxy acrylic acid and secondary hydroxyl acrylic acid are used together. The inventor speculates that the secondary hydroxyl acrylic acid has bifunctional groups which are not easy to form a body-type cross-linking structure, and can be fully cross-linked with the epoxy acrylic acid to form a sea-island structure, and at the moment, the hard monomer methacrylic acid-2-phenoxyethyl ester can be used as a stress concentration center to ensure that the shearing strength is better; but at the same time, the curing reaction degree is low and the adhesive shrinkage is large due to the high functionality, and the inventor unexpectedly finds that when the core-shell particles and the fumed silica of the invention are used for reacting with other reactants, the shrinkage is reduced, the inventor speculates that the inventor thinks that when the system is cured, phase separation can occur between the polyurethane acrylate oligomer and a newly generated crosslinking structure to offset partial shrinkage, and in addition, the core-shell particles and the fumed silica can be used as a bridge, the benzene ring in the hard monomer can receive lone pair electrons of the fumed silica to form a reversible three-dimensional network structure, so that the shrinkage is also inhibited while the phase separation is reduced, and active functional groups on the core-shell particles can participate in the reaction to react with the fumed silica to introduce metal ions into a sea-island structure finally formed in the hard segment.
In one embodiment, the method for preparing the a component comprises the steps of:
(1) stirring acrylate monomers, polyurethane acrylate oligomers and core-shell particles for 1-3 h;
(2) adding oxidant, polymerization inhibitor, metal ion complex and fumed silica, stirring for 5-20min, vacuumizing, stirring for 5-20min, and discharging to obtain the component A;
the stirring temperature is 25-45 ℃.
In a preferred embodiment, the preparation method of the A component comprises the following steps:
(1) stirring acrylate monomers, polyurethane acrylate oligomers and core-shell particles for 2 hours;
(2) adding an oxidant, a polymerization inhibitor, a metal ion complex and fumed silica, stirring for 10min, vacuumizing and stirring for 10min, and discharging to obtain the component A;
the temperature of the stirring was 45 ℃.
In another embodiment, the component a may be prepared without the addition of metal ion complexes and core-shell particles.
In a preferred embodiment, the low modulus flexible acrylate adhesive further comprises a B component; the component B comprises an acrylate monomer, a polyurethane acrylate oligomer and a reducing agent.
B component
In one embodiment, the volume ratio of the a component to the B component is 1: (1-20).
In a preferred embodiment, the volume ratio of the a component to the B component is 1: (3-15).
In a preferred embodiment, the volume ratio of the a component to the B component is 1: (4-8).
In a preferred embodiment, the volume ratio of the a component to the B component is 1: 6.
in a preferred embodiment, the component B comprises 10 to 100 parts by weight of acrylate monomer, 0 to 50 parts by weight of urethane acrylate oligomer and 0.01 to 10 parts by weight of reducing agent.
In a preferred embodiment, the component B comprises 20 to 80 parts by weight of acrylate monomer, 2 to 30 parts by weight of urethane acrylate oligomer and 0.05 to 5 parts by weight of reducing agent.
In a more preferred embodiment, the component B comprises 65-75 parts by weight of acrylate monomer, 10-20 parts by weight of urethane acrylate oligomer and 2-5 parts by weight of reducing agent.
Acrylate monomer
The acrylate monomer in the component B is the same as the acrylate monomer in the component A.
Urethane acrylate oligomer
The polyurethane acrylate oligomer in the component B is the same as the polyurethane acrylate oligomer in the component A.
Reducing agent
In the present invention, the reducing agent is a substance that loses electrons or deviates electrons in a redox reaction.
In one embodiment, the reducing agent is selected from one or more of sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium sulfite, iron bisulfite, formic acid, oxalic acid, sodium borohydride, potassium borohydride, lithium borohydride, borane, vanadyl acetylacetonate, copper octoate, iron hexanoate, iron propionate, vanadium acetylacetonate, triethylamine, tetramethylthiourea, N-dimethylaniline, N-dimethyl-p-toluidine, N-diethylaniline.
In a preferred embodiment, the reducing agent is a combination of one or more of vanadyl acetylacetonate, copper octoate, iron hexanoate, iron propionate, vanadium acetylacetonate, triethylamine, tetramethylthiourea, N-dimethylaniline, N-dimethyl-p-toluidine, N-diethylaniline.
In a more preferred embodiment, the reducing agent is vanadyl acetylacetonate (CAS number 3153-26-2) or vanadium acetylacetonate (CAS number 13476-99-8).
In one embodiment, the B component further comprises core shell particles; the weight portion of the core-shell particles is 0-70.
In a preferred embodiment, the weight parts of the core-shell particles are 0 to 50 parts.
In a more preferred embodiment, the weight parts of the core-shell particles are 0 to 20 parts.
Core-shell particles
The core-shell particles in the component B are the same as the core-shell particles in the component A.
In one embodiment, the B component further comprises an auxiliary agent.
Auxiliary agent
In one embodiment, the auxiliary comprises 0.1-10 parts of polymerization inhibitor and 0-0.5 part of metal ion complex by weight.
In a preferred embodiment, the auxiliary comprises 0.1-5 parts of polymerization inhibitor and 0-0.1 part of metal ion complex by weight.
In a preferred embodiment, the auxiliary comprises 0.5-1 part of polymerization inhibitor and 0-0.03 part of metal ion complex by weight.
(polymerization inhibitor)
The polymerization inhibitor in the component B is the same as that in the component A.
(Metal ion Complex)
The metal ion complex in the component B is the same as the metal ion complex in the component A.
In one embodiment, the B component further comprises fumed silica.
Fumed silica
The fumed silica in the component B is the same as the fumed silica in the component A.
In one embodiment, the B component further comprises 0 to 10 parts by weight of a phosphate ester.
In a preferred embodiment, the B component further comprises 0 to 5 parts by weight of a phosphate ester.
Phosphoric acid esters
In the present invention, the phosphoric acid ester is an ester derivative of phosphoric acid.
In one embodiment, the phosphate is selected from one or more of lauryl phosphate, hydroxyethyl methacrylate phosphate, polyethylene glycol methacrylate phosphate, 2-ethylhexyl phosphate, and methacrylate phosphate.
In one embodiment, the phosphate ester is a methacrylate phosphate ester (CAS number 52628-03-2).
In one embodiment, the method for preparing the B-component comprises the following steps:
(1) stirring acrylate monomers, polyurethane acrylate oligomers and core-shell particles for 1-3 h;
(2) adding a reducing agent, a polymerization inhibitor, a metal ion complex and fumed silica, stirring for 5-20min, then vacuumizing and stirring for 5-20min, and discharging to obtain the component B;
the stirring temperature is 25-45 ℃.
In a preferred embodiment, the preparation method of the B component comprises the following steps:
(1) stirring acrylate monomers, polyurethane acrylate oligomers and core-shell particles for 2 hours;
(2) adding oxidant, polymerization inhibitor, metal ion complex and fumed silica, stirring for 10min, vacuumizing, stirring for 10min, and discharging to obtain the component B;
the temperature of the stirring was 45 ℃.
In another embodiment, the B component may be prepared without the addition of metal ion complexes and core-shell particles.
In another embodiment, a phosphate ester is added to the preparation method of the B component.
The second aspect of the invention provides a preparation method of the low-modulus flexible acrylate adhesive, which at least comprises the following steps:
(1) preparing a component A;
(4) preparing a component B;
(3) mixing the component A and the component B.
The present invention will be specifically described below by way of examples. It should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention, and that the insubstantial modifications and adaptations of the present invention by those skilled in the art based on the above disclosure are still within the scope of the present invention.
In addition, the starting materials used are all commercially available, unless otherwise specified.
Examples
Example 1
Embodiment 1 provides a low modulus flexible acrylate adhesive comprising an a-component and a B-component; the volume ratio of the component A to the component B is 1: 3;
the component A comprises 65 parts of acrylate monomer, 15 parts of urethane acrylate oligomer, 20 parts of oxidant, 1 part of polymerization inhibitor and 7.5 parts of fumed silica in parts by weight;
the component B comprises 65 parts of acrylate monomer, 10 parts of urethane acrylate oligomer, 5 parts of reducing agent, 1 part of polymerization inhibitor and 5 parts of fumed silica in parts by weight;
the acrylic ester monomer in the component A comprises, by weight, 20 parts of n-butyl methacrylate, 15 parts of solid acrylic resin, 20 parts of lauryl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate;
the polyurethane acrylate oligomer is available under the brand name CN-991NS and is purchased from Shadoma Guangzhou chemical Co., Ltd;
the oxidant is cumene hydroperoxide (CAS number 80-15-9);
the polymerization inhibitor is dibutyl hydroxy toluene (CAS number is 128-37-0);
the fumed silica was purchased from alatin reagent;
the acrylate monomer in the component B comprises, by weight, 20 parts of n-butyl methacrylate, 20 parts of solid acrylic resin, 10 parts of lauryl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate;
the reducing agent is vanadium acetylacetonate (CAS number 13476-99-8).
The preparation method of the low-modulus flexible acrylate adhesive comprises the following steps:
(1) preparation of component A: mixing and stirring n-butyl methacrylate, solid acrylic resin, lauryl methacrylate, 3, 4-epoxy cyclohexyl methacrylate and polyurethane acrylate oligomer for 2h, adding cumene hydroperoxide, adding dibutyl hydroxy toluene, adding fumed silica, heating to 25 ℃, stirring for 10min, vacuumizing, stirring for 30min, and discharging to obtain a component A;
(2) preparation of the component B: mixing n-butyl methacrylate, solid acrylic resin, lauryl methacrylate, 3, 4-epoxy cyclohexyl methacrylate and urethane acrylate oligomer, heating to 25 ℃, stirring for 2 hours, adding vanadium acetylacetonate and dibutyl hydroxy toluene, stirring for 30 minutes, adding fumed silica, stirring for 30 minutes, vacuumizing, stirring for 20 minutes, and discharging to obtain a component B;
(3) and mixing the component A and the component B in proportion to obtain the low-modulus flexible acrylate adhesive.
Example 2
Embodiment 2 provides a low modulus flexible acrylate adhesive comprising a component a and a component B; the volume ratio of the component A to the component B is 1: 15;
the component A comprises, by weight, 70 parts of acrylate monomer, 15 parts of urethane acrylate oligomer, 30 parts of oxidant, 4 parts of polymerization inhibitor and 3 parts of fumed silica;
the component B comprises, by weight, 75 parts of acrylate monomer, 10 parts of urethane acrylate oligomer, 4 parts of reducing agent, 0.5 part of polymerization inhibitor and 3 parts of fumed silica;
the acrylic ester monomer in the component A comprises, by weight, 10 parts of n-butyl methacrylate, 25 parts of lauryl methacrylate, 15 parts of hydroxypropyl methacrylate and 20 parts of solid acrylic resin;
the polyurethane acrylate oligomer is available under the brand name CN-991NS and is purchased from Shadoma Guangzhou chemical Co., Ltd;
the oxidant is cumene hydroperoxide (CAS number 80-15-9);
the polymerization inhibitor is dibutyl hydroxy toluene (CAS number is 128-37-0);
the fumed silica was purchased from alatin reagent;
the acrylate monomer in the component B comprises, by weight, 20 parts of n-butyl methacrylate, 25 parts of lauryl methacrylate, 10 parts of hydroxypropyl methacrylate and 20 parts of solid acrylic resin;
the reducing agent is vanadyl acetylacetonate (CAS number 3153-26-2).
The preparation method of the low-modulus flexible acrylate adhesive comprises the following steps:
(1) preparation of component A: mixing n-butyl methacrylate, lauryl methacrylate, hydroxypropyl methacrylate, polyurethane acrylate oligomer and solid acrylic resin, heating to 35 ℃, stirring for 1.5h, adding cumene hydroperoxide, adding dibutyl hydroxy toluene, then adding fumed silica, stirring for 10min, vacuumizing, stirring for 20min, and discharging to obtain a component A;
(2) preparation of the component B: mixing n-butyl methacrylate, lauryl methacrylate, hydroxypropyl methacrylate, polyurethane acrylate oligomer and solid acrylic resin, heating to 35 ℃, stirring for 2h, adding vanadyl acetylacetonate, adding dibutyl hydroxy toluene, stirring for 30min, then adding fumed silica, stirring for 10min, vacuumizing, stirring for 20min, and discharging to obtain a component B;
(3) and mixing the component A and the component B in proportion to obtain the low-modulus flexible acrylate adhesive.
Example 3
Embodiment 3 provides a low modulus flexible acrylate adhesive comprising an a component and a B component; the volume ratio of the component A to the component B is 1: 8;
the component A comprises, by weight, 55 parts of acrylate monomer, 15 parts of polyurethane acrylate oligomer, 15 parts of core-shell particles, 25 parts of oxidant, 3 parts of polymerization inhibitor, 0.03 part of metal ion complex and 4.3 parts of fumed silica;
the component B comprises, by weight, 70 parts of acrylate monomer, 15 parts of urethane acrylate oligomer, 20 parts of core-shell particles, 5 parts of reducing agent, 0.5 part of polymerization inhibitor, 0.03 part of metal ion complex and 4.3 parts of fumed silica;
the acrylate monomer in the component A comprises, by weight, 10 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate, 5 parts of hydroxypropyl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate;
the polyurethane acrylate oligomer is available under the brand name CN-991NS and is purchased from Shadoma Guangzhou chemical Co., Ltd;
the brand of the core-shell particles is MX125, and the core-shell particles are purchased from Shenzhen clock source science and technology Limited;
the oxidant is cumene hydroperoxide (CAS number 80-15-9);
the polymerization inhibitor is dibutyl hydroxy toluene (CAS number is 128-37-0);
the metal ion complex is EDTA-4 Na;
the fumed silica was purchased from alatin reagent;
the acrylate monomer in the component B comprises, by weight, 20 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate, 5 parts of hydroxypropyl methacrylate and 15 parts of 3, 4-epoxy cyclohexyl methacrylate;
the reducing agent is vanadyl acetylacetonate (CAS number 3153-26-2).
The preparation method of the low-modulus flexible acrylate adhesive comprises the following steps:
(1) preparation of component A: heating lauryl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, polyurethane acrylate oligomer and core-shell particles to 45 ℃, stirring for 2 hours, adding cumene hydroperoxide, adding dibutyl hydroxy toluene, adding EDTA-4Na, adding fumed silica, stirring for 10 minutes, starting vacuum, stirring for 20 minutes, and discharging to obtain a component A;
(2) preparation of the component B: mixing lauryl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, polyurethane acrylate oligomer and core-shell particles, heating to 45 ℃, stirring for 2 hours, adding vanadyl acetylacetonate, dibutyl hydroxy toluene, EDTA-4Na, adding fumed silica, stirring for 10 minutes, vacuumizing, stirring for 20 minutes, and discharging to obtain a component B;
(3) and mixing the component A and the component B in proportion to obtain the low-modulus flexible acrylate adhesive.
Example 4
Embodiment 4 provides a low modulus flexible acrylate adhesive comprising an a component and a B component; the volume ratio of the component A to the component B is 1: 6;
the component A comprises 65 parts of acrylate monomer, 15 parts of polyurethane acrylate oligomer, 15 parts of core-shell particles, 25 parts of oxidant, 2.5 parts of polymerization inhibitor, 0.1 part of metal ion complex and 4.3 parts of fumed silica in parts by weight;
the component B comprises, by weight, 70 parts of acrylate monomer, 20 parts of urethane acrylate oligomer, 15 parts of core-shell particles, 2 parts of reducing agent, 0.5 part of polymerization inhibitor, 5 parts of phosphate and 5.7 parts of fumed silica;
the acrylate monomer in the component A comprises, by weight, 20 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate, 5 parts of hydroxypropyl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate;
the polyurethane acrylate oligomer is available under the brand name CN-991NS and is purchased from Shadoma Guangzhou chemical Co., Ltd;
the brand of the core-shell particles is MX125, and the core-shell particles are purchased from Shenzhen clock source science and technology Limited;
the oxidant is cumene hydroperoxide (CAS number 80-15-9);
the polymerization inhibitor is dibutyl hydroxy toluene (CAS number is 128-37-0);
the metal ion complex is EDTA-4 Na;
the fumed silica was purchased from alatin reagent;
the acrylate monomer in the component B comprises, by weight, 20 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate, 5 parts of hydroxypropyl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate;
the reducing agent is vanadyl acetylacetonate (CAS number 3153-26-2);
the phosphate is methacrylic acid phosphate (CAS number 52628-03-2).
The preparation method of the low-modulus flexible acrylate adhesive comprises the following steps:
(1) preparation of component A: heating lauryl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, polyurethane acrylate oligomer and core-shell particles to 45 ℃, stirring for 2 hours, adding cumene hydroperoxide, adding dibutyl hydroxy toluene, adding EDTA-4Na, adding fumed silica, stirring for 10 minutes, vacuumizing, stirring for 20 minutes, and discharging to obtain a component A;
(2) preparation of the component B: mixing lauryl methacrylate, methoxyethyl methacrylate, hydroxypropyl methacrylate, 3, 4-epoxycyclohexyl methacrylate, polyurethane acrylate oligomer and core-shell particles, heating to 45 ℃, stirring for 2 hours, adding vanadyl acetylacetonate, adding phosphate methacrylate and dibutyl hydroxy toluene, adding fumed silica, stirring for 10 minutes, vacuumizing, stirring for 20 minutes, and discharging to obtain a component B;
(3) and mixing the component A and the component B in proportion to obtain the low-modulus flexible acrylate adhesive.
Example 5
Embodiment 5 provides a low modulus flexible acrylate adhesive comprising an a-side and a B-side; the volume ratio of the component A to the component B is 1: 4;
the component A comprises, by weight, 60 parts of acrylate monomer, 20 parts of polyurethane acrylate oligomer, 30 parts of core-shell particles, 15 parts of oxidant and 2 parts of polymerization inhibitor;
the component B comprises 64 parts of acrylate monomer, 20 parts of polyurethane acrylate oligomer, 30 parts of core-shell particles, 4 parts of reducing agent, 0.5 part of polymerization inhibitor, 10 parts of phosphate and 5.7 parts of fumed silica in parts by weight;
the acrylate monomer in the component A comprises 20 parts of isobornyl methacrylate, 20 parts of 2-phenoxyethyl methacrylate and 20 parts of tetrahydrofurfuryl methacrylate in parts by weight;
the polyurethane acrylate oligomer is available under the brand name CN-991NS and is purchased from Shadoma Guangzhou chemical Co., Ltd;
the brand of the core-shell particles is MX125, and the core-shell particles are purchased from Shenzhen clock source science and technology Limited;
the oxidant is cumene hydroperoxide (CAS number 80-15-9);
the polymerization inhibitor is dibutyl hydroxy toluene (CAS number is 128-37-0);
the fumed silica was purchased from alatin reagent;
the acrylate monomer in the component B comprises, by weight, 20 parts of isobornyl methacrylate, 20 parts of 2-phenoxyethyl methacrylate, 20 parts of tetrahydrofurfuryl methacrylate, 3 parts of hydroxyethyl methacrylate and 1 part of pentaerythritol trimethacrylate;
the reducing agent is vanadium acetylacetonate (CAS number 13476-99-8);
the phosphate is methacrylic acid phosphate (CAS number 52628-03-2).
The preparation method of the low-modulus flexible acrylate adhesive comprises the following steps:
(1) preparation of component A: mixing isobornyl methacrylate, methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate and core-shell particles, heating to 45 ℃, stirring for 2 hours, adding urethane acrylate oligomer, adding cumene hydroperoxide, adding dibutyl hydroxy toluene, vacuumizing, stirring for 30min, and discharging to obtain a component A;
(2) preparation of the component B: mixing isobornyl methacrylate, methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate and core-shell particles, heating to 45 ℃, stirring for 2 hours, adding urethane acrylate oligomer, adding vanadium acetylacetonate, adding phosphate methacrylate, adding hydroxyethyl methacrylate, adding pentaerythritol trimethacrylate, adding fumed silica, stirring for 10 minutes, vacuumizing, stirring for 30 minutes, and discharging to obtain a component B;
(3) and mixing the component A and the component B in proportion to obtain the low-modulus flexible acrylate adhesive.
Example 6
Example 6 provides a low modulus flexible acrylate adhesive, similar to example 1, except that the acrylate monomers in the a component include, by weight, 10 parts of n-butyl methacrylate, 5 parts of solid acrylic resin, 40 parts of lauryl methacrylate, and 10 parts of 3, 4-epoxycyclohexyl methacrylate;
the acrylate monomer in the component B comprises, by weight, 10 parts of n-butyl methacrylate, 5 parts of solid acrylic resin, 40 parts of lauryl methacrylate and 5 parts of 3, 4-epoxy cyclohexyl methacrylate.
Example 7
Example 7 provides a low modulus flexible acrylate adhesive, similar to example 1, except that the acrylate monomers in the a component include, by weight, 20 parts of methyl methacrylate, 15 parts of solid acrylic resin, 20 parts of lauryl methacrylate, 10 parts of 3, 4-epoxycyclohexyl methacrylate;
the acrylate monomer in the component B comprises, by weight, 20 parts of methyl methacrylate, 20 parts of solid acrylic resin, 10 parts of lauryl methacrylate and 10 parts of 3, 4-epoxy cyclohexyl methacrylate.
Example 8
Example 8 provides a low modulus flexible acrylate adhesive, similar to example 2, except that the acrylate monomers in the a component include, by weight, 10 parts of n-butyl methacrylate, 25 parts of lauryl methacrylate, 15 parts of hydroxypropyl acrylate, and 20 parts of solid acrylic resin;
the acrylate monomer in the component B comprises, by weight, 20 parts of n-butyl methacrylate, 25 parts of lauryl methacrylate, 10 parts of hydroxypropyl acrylate and 20 parts of solid acrylic resin.
Example 9
Example 9 provides a low modulus flexible acrylate adhesive, similar to example 1, except that the acrylate monomers in the a component include, by weight, 20 parts of n-butyl methacrylate, 15 parts of solid acrylic resin, 20 parts of lauryl methacrylate, and 10 parts of dimethylaminoethyl acrylate;
the acrylate monomer in the component B comprises, by weight, 20 parts of n-butyl methacrylate, 20 parts of solid acrylic resin, 10 parts of lauryl methacrylate and 10 parts of dimethylaminoethyl acrylate;
the CAS number of the dimethylamine ethyl acrylate is 2439-35-2.
Example 10
Example 10 provides a low modulus flexible acrylate adhesive, similar to example 2, except that the acrylate monomers in the a component comprise, by weight, 10 parts of n-butyl methacrylate, 25 parts of isooctyl acrylate, 15 parts of hydroxypropyl methacrylate, and 20 parts of solid acrylic resin;
the acrylate monomer in the component B comprises, by weight, 20 parts of n-butyl methacrylate, 25 parts of isooctyl acrylate, 10 parts of hydroxypropyl methacrylate and 20 parts of solid acrylic resin.
Example 11
Example 11 provides a low modulus flexible acrylate adhesive, similar to example 3, except that the acrylate monomers in the a component include, by weight, 10 parts of lauryl methacrylate, 40 parts of 2-phenoxyethyl methacrylate, and 5 parts of hydroxypropyl methacrylate;
the acrylate monomer in the component B comprises, by weight, 20 parts of lauryl methacrylate, 45 parts of 2-phenoxyethyl methacrylate and 5 parts of hydroxypropyl methacrylate.
Example 12
Example 12 provides a low modulus flexible acrylate adhesive, similar to example 3, except that the acrylate monomers in the a component include, by weight, 10 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate, and 15 parts of 3, 4-epoxycyclohexyl methacrylate;
the acrylate monomer in the component B comprises, by weight, 20 parts of lauryl methacrylate, 30 parts of 2-phenoxyethyl methacrylate and 20 parts of 3, 4-epoxy cyclohexyl methacrylate.
Example 13
Example 13 provides a low modulus flexible acrylate adhesive, similar to example 3, except that there is no fumed silica.
Example 14
Example 14 provides a low modulus flexible acrylate adhesive, similar to example 3, except that 2-phenoxyethyl methacrylate is absent.
Performance testing
The low modulus flexible acrylate adhesives described in examples 1-14 were allowed to sit for 24 hours and tested for tensile modulus, tensile hardness, and related data.
1. Modulus: the low modulus flexible acrylate adhesives described in examples 1-14 were subjected to modulus testing with reference to ISO 527-2.
2. Hardness: the low modulus flexible acrylate adhesives described in examples 1-14 were tested for hardness with reference to ISO 7619 standards.
3. Shrinkage rate: by adopting the Archimedes buoyancy principle and the glue curing shrinkage tester YT-220SD Shenzhen warrior, the shrinkage of the low-modulus flexible acrylate adhesive described in the examples 1-14 can be directly calculated by measuring the specific gravity values before and after the low-modulus flexible acrylate adhesive described in the examples 1-14 is cured.
4. Tensile shear strength: the low modulus flexible acrylate adhesives described in examples 1-14 were tested for tensile shear strength against the ISO 4587 standard.
Table 1 results of performance testing
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (10)
1. A low modulus flexible acrylate adhesive is characterized by comprising a component A; the component A comprises an acrylate monomer, a polyurethane acrylate oligomer and an oxidant.
2. The low-modulus flexible acrylate adhesive according to claim 1, wherein the component A comprises 10-100 parts by weight of acrylate monomer, 0-50 parts by weight of urethane acrylate oligomer and 5-60 parts by weight of oxidant.
3. The low modulus, flexible acrylate adhesive of claim 1 wherein the acrylate monomer comprises a functional monomer.
4. The low modulus flexible acrylate adhesive of claim 3 wherein the functional monomer is selected from one or more of hydroxyl based acrylates, amino based acrylics, epoxy based acrylates, solid acrylics.
5. The low modulus flexible acrylate adhesive of claim 4 wherein the hydroxyl-based acrylate is selected from one or more of 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate.
6. The low modulus, flexible acrylate adhesive of claim 1 wherein the acrylate monomer further comprises a hard monomer.
7. The low modulus flexible acrylate adhesive of claim 6 wherein the hard monomer is selected from the group consisting of any one or more of methyl methacrylate, methyl acrylate, isopropyl methacrylate, isobornyl methacrylate, methoxyethyl methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, n-butyl methacrylate.
8. The low modulus flexible acrylate adhesive of any of claims 1-7 wherein the oxidizing agent is selected from the group consisting of oxyhalides, hydroperoxides, organic peroxides, inorganic peracids and salts thereof, organic peracids and salts thereof, halogen molecules, ozone, and combinations of one or more thereof.
9. The low modulus, flexible acrylate adhesive of claim 1 further comprising a B-component; the component B comprises an acrylate monomer, a polyurethane acrylate oligomer and a reducing agent; the volume ratio of the component A to the component B is 1: (1-20).
10. A method of preparing the low modulus flexible acrylate adhesive of claim 9 comprising at least the steps of:
(1) preparing a component A;
(2) preparing a component B;
(3) mixing the component A and the component B.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3932964A1 (en) * | 2020-06-30 | 2022-01-05 | Dongguan NVT Technology Limited | Composite phase change material, application method of composite phase change material, and battery |
| CN114752342A (en) * | 2021-05-19 | 2022-07-15 | 道生天合材料科技(上海)股份有限公司 | Acrylate adhesive and preparation method thereof |
| WO2022191071A1 (en) * | 2021-03-09 | 2022-09-15 | 三菱鉛筆株式会社 | Reducing particle dispersion and aqueous ink composition for writing tool containing same |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539099A2 (en) * | 1991-10-25 | 1993-04-28 | Optical Coating Laboratory, Inc. | Repositionable optical cover for monitors |
| CN102850973A (en) * | 2012-10-12 | 2013-01-02 | 北京海斯迪克新材料有限公司 | Low-water-absorptivity acrylate structural adhesive and preparation method thereof |
| CN103725205A (en) * | 2013-12-17 | 2014-04-16 | 广东三和化工科技有限公司 | Anaerobic adhesive and preparation method thereof |
| CN104356964A (en) * | 2014-12-02 | 2015-02-18 | 北京天山新材料技术有限公司 | Preparation of low-odor and environment-friendly acrylate structural glue |
| US20150361317A1 (en) * | 2013-01-28 | 2015-12-17 | Lucite International Uk Limited | Hot melt adhesive |
| CN105482747A (en) * | 2015-12-28 | 2016-04-13 | 倪协照 | High-strength impact-resistance acrylate adhesive and preparation method thereof |
| CN106366224A (en) * | 2015-12-31 | 2017-02-01 | 长兴材料工业股份有限公司 | Thermally polymerizable composition, liquid composition formed therefrom, and use thereof |
| CN106893381A (en) * | 2017-03-31 | 2017-06-27 | 辽宁三环树脂有限公司 | A kind of methacrylate modified reactive resin |
| KR20170115227A (en) * | 2016-04-06 | 2017-10-17 | 주식회사 엘지화학 | Adhesive composition for optical use and the adhesive film for optical use |
| CN108473840A (en) * | 2015-10-07 | 2018-08-31 | 伊利诺斯工具制品有限公司 | Adhesive composition with reparation-reprocessing ability |
-
2019
- 2019-12-31 CN CN201911410097.2A patent/CN111073525B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0539099A2 (en) * | 1991-10-25 | 1993-04-28 | Optical Coating Laboratory, Inc. | Repositionable optical cover for monitors |
| CN102850973A (en) * | 2012-10-12 | 2013-01-02 | 北京海斯迪克新材料有限公司 | Low-water-absorptivity acrylate structural adhesive and preparation method thereof |
| US20150361317A1 (en) * | 2013-01-28 | 2015-12-17 | Lucite International Uk Limited | Hot melt adhesive |
| CN103725205A (en) * | 2013-12-17 | 2014-04-16 | 广东三和化工科技有限公司 | Anaerobic adhesive and preparation method thereof |
| CN104356964A (en) * | 2014-12-02 | 2015-02-18 | 北京天山新材料技术有限公司 | Preparation of low-odor and environment-friendly acrylate structural glue |
| CN108473840A (en) * | 2015-10-07 | 2018-08-31 | 伊利诺斯工具制品有限公司 | Adhesive composition with reparation-reprocessing ability |
| CN105482747A (en) * | 2015-12-28 | 2016-04-13 | 倪协照 | High-strength impact-resistance acrylate adhesive and preparation method thereof |
| CN106366224A (en) * | 2015-12-31 | 2017-02-01 | 长兴材料工业股份有限公司 | Thermally polymerizable composition, liquid composition formed therefrom, and use thereof |
| KR20170115227A (en) * | 2016-04-06 | 2017-10-17 | 주식회사 엘지화학 | Adhesive composition for optical use and the adhesive film for optical use |
| CN106893381A (en) * | 2017-03-31 | 2017-06-27 | 辽宁三环树脂有限公司 | A kind of methacrylate modified reactive resin |
Non-Patent Citations (2)
| Title |
|---|
| 夏文干 等: "《胶接手册》", 28 February 1989, 国防工业出版社 * |
| 李红强: "《胶粘原理、技术及应用》", 31 January 2014, 华南理工大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3932964A1 (en) * | 2020-06-30 | 2022-01-05 | Dongguan NVT Technology Limited | Composite phase change material, application method of composite phase change material, and battery |
| WO2022191071A1 (en) * | 2021-03-09 | 2022-09-15 | 三菱鉛筆株式会社 | Reducing particle dispersion and aqueous ink composition for writing tool containing same |
| CN114752342A (en) * | 2021-05-19 | 2022-07-15 | 道生天合材料科技(上海)股份有限公司 | Acrylate adhesive and preparation method thereof |
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