CN111925756A - Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof - Google Patents
Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof Download PDFInfo
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- CN111925756A CN111925756A CN201910421024.7A CN201910421024A CN111925756A CN 111925756 A CN111925756 A CN 111925756A CN 201910421024 A CN201910421024 A CN 201910421024A CN 111925756 A CN111925756 A CN 111925756A
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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
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/28—Oxygen or compounds releasing free oxygen
- C08F4/32—Organic compounds
- C08F4/34—Per-compounds with one peroxy-radical
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Abstract
The invention provides an anaerobic adhesive initiator composition, which adopts onium salt formed by nitrogen-containing heterocyclic compounds as an accelerator. The invention also relates to an anaerobic adhesive containing the initiator composition, which comprises a signed initiator composition, acrylate or methacrylate monomer/oligomer and polymerization inhibitor and stabilizer in a certain proportion. The initiator composition can quickly cure the anaerobic adhesive during application, and the obtained anaerobic adhesive has practical strength and has the outstanding advantages of neutral and stable pH value, no volatile irritation and convenient use of single components compared with the conventional hydrazide and amine combined amine accelerator.
Description
Technical Field
The invention relates to an initiator composition for anaerobic adhesive, anaerobic adhesive containing the same and a preparation method thereof.
Background
The anaerobic adhesive is an adhesive prepared by mixing and reacting (methyl) acrylate serving as a main component and raw materials such as an accelerator, an auxiliary accelerator, an integrating agent, a filler, an initiator and the like, is not cured when being in contact with air or oxygen, can keep a liquid state for a long time, and is rapidly cured under the condition of being isolated from the air or the oxygen. The anaerobic adhesive has the characteristics of quick curing, high strength, simple process, convenient use, small pollution and the like, is widely applied to industries such as aviation, automobiles, machinery, ships, chemical pipelines and the like, and mainly plays roles in thread locking, structural bonding, plane sealing, cylindrical part fixing and the like.
Generally, the main components of the anaerobic adhesive comprise an initiator system consisting of an initiator, an accelerator and a co-accelerator, a polymerization inhibitor, an integrating agent and other modifiers such as a thickening agent, a filler, a dye, an odor masking agent and the like besides the acrylate. The initiator system is crucial to ensure that the anaerobic adhesive has the stability of long-term storage and the performance of quick curing.
The anaerobic adhesive reaction mechanism is an oxidation-reduction reaction pair formed by an accelerant and organic peroxide, wherein an oxidant, a reducing agent and oxygen (which can be regarded as an oxidant) dissolved in the adhesive liquid in the anaerobic adhesive are in dynamic equilibrium of continuous reaction, and the anaerobic adhesive can be kept stable in a storage period by the equilibrium reaction. When the equilibrium is broken after the exclusion of oxygen, the non-inhibited oxidizing agent decomposes active radicals, which combine with unsaturated functional groups in the anaerobic adhesive resin monomer, initiate a chain extension reaction and eventually cure.
Based on this specificity of anaerobic gel initiators, few anaerobic gel initiator systems can be successfully used. The current representative anaerobic adhesive initiator technology mainly comprises two main systems, namely two initiator systems consisting of peroxide-organic substituted hydrazine-saccharin (the representative composition of the peroxide-organic substituted hydrazine-saccharin is cumene hydroperoxide-acetyl phenylhydrazine-saccharin), or peroxide-tertiary amine-saccharin (the representative composition of the peroxide-tertiary amine-saccharin is cumene hydroperoxide-dialkyl substituted toluidine-saccharin). The initiator system is two representative initiator systems which are successfully applied to the past and have excellent performance in the 70 th 20 th century, particularly a Cumene Hydroperoxide (CHP) -Acetyl Phenylhydrazine (APH) -saccharin system, and is more commonly used by anaerobic glue manufacturers at home and abroad at present.
In addition to the two main initiator systems mentioned above, several new initiator systems have appeared in recent years, for example WO03078537A2 reports the use of phenylenediamine as an accelerator. CN100463924C reports a new initiator system consisting of peroxides, tautomers, organic acids. US6958368 uses sulfimides and sulfonamides as accelerators, obtaining an anaerobic gel initiator composition free of saccharin. US6897277 uses Phenylglycine (Phenylglycine) and its derivatives as a component of an accelerator. CN1328103A uses hydroxyl peroxide, alkyl peroxide, organic substituted hydrazine and tertiary amine to compound, so as to obtain the anaerobic adhesive with quick curing and long storage period. CN1355831A added a weak acidic salt to expect an increased cure rate.
Disclosure of Invention
The invention provides an anaerobic adhesive initiator composition which can enable anaerobic adhesives to be cured quickly and has high storage stability.
An initiator composition for anaerobic adhesives comprising: initiator, accelerator, auxiliary accelerator and chelating agent, wherein the accelerator is onium salt containing nitrogen heterocycle.
The initiator composition comprises the following components in parts by mass: initiator: 0.1-5 parts of accelerator: 0.05-5 parts of auxiliary accelerator: 0.1-3 parts of a chelating agent: 0.01 to 0.5 portion.
The invention uses peroxide as initiator and onium salt as promoter to form a new initiator composition, which can make anaerobic adhesive quickly solidify. In addition, the initiating system is mixed with acrylate or methacrylate monomer and/or oligomer and polymerization inhibitor in certain proportion to obtain anaerobic adhesive, so as to reach the aim of the present invention.
The onium salt is added into the anaerobic adhesive composition provided by the invention, so that the initial curing time of the anaerobic adhesive can be reduced, and meanwhile, the onium salt is a neutral component, so that the anaerobic adhesive composition has higher stability compared with the conventional amine and hydrazine accelerators, has no volatilization or irritant gas release, and can greatly reduce the harm to human bodies.
The invention provides an anaerobic adhesive, which comprises: acrylate or methacrylate monomers and/or oligomers, and an initiator composition as described above.
The acrylate or methacrylate monomer and oligomer is at least one selected from the group consisting of polyethylene glycol methacrylate, epoxy methacrylate, polyurethane methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane methacrylate, alcohol methacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
The acrylate or methacrylate monomer and/or oligomer can be unsaturated bond-containing polymerizable monomer and oligomer which are widely used in anaerobic adhesive at present. The acrylate or methacrylate monomer may be selected from at least one of monoacrylates, diacrylates, polyacrylates, monomethacrylates, dimethacrylates, and polymethacrylates; the oligomer may be selected from at least one of bisphenol a epoxy acrylate, bisphenol a epoxy methacrylate, novolac epoxy acrylate, novolac epoxy methacrylate, propylene glycol acetate polyester acrylate, propylene glycol acetate polyester methacrylate, urethane acrylate, and urethane methacrylate.
The initiator is organic peroxide and is at least one selected from dicumyl peroxide, 1, 4-di-tert-butylperoxyisopropyl benzene, tert-butyl peroxypivalate, tert-butyl peroxyisopropyl benzene, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, 2, 5-dimethyl-2, 5- (di-tert-butylperoxy) hexane and cyclohexylidene diperoxide.
The accelerator is used for controlling the activation performance of the initiator, can reduce the decomposition activation energy of the initiator, improves the initiated decomposition rate and the conversion rate of the initiator, and can prevent the colloid from being stored and solidified due to overhigh activity of an initiating system by properly controlling the dosage of the accelerator and matching with the chelating agent. The onium salt is a heterocyclic compound which has a cyclic structure, wherein cyclic atoms contain nitrogen atoms besides carbon atoms, and the heterocyclic compound can be combined with a peroxide bond on peroxide to greatly reduce decomposition activation energy of a peroxide initiator so as to promote initiation.
The accelerant is an onium salt containing a nitrogen heterocycle, and the accelerant is selected from at least one of 1-methyl-1, 2, 3, 4-tetrahydroisoquinoline hydrochloride, pyridine hydrobromide, 1H-pyrazole-3-acetic acid hydrochloride, 1, 2, 3, 4-tetrahydroquinoline hydrochloride, pyridinium tribromide, 4, 5, 6, 7-tetrahydrothiophene pyridine hydrochloride and 6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline sulfate.
The invention takes peroxide as an initiator, onium salt as an accelerator and hydrazine and amine compounds can be further added to form a novel initiator composition, wherein the hydrazine and/or amine compounds are selected from at least one of acetyl phenylhydrazine, benzoyl peroxide, triethylamine, N-dimethyl-p-toluidine, tri-N-butylamine and triethanolamine.
In the present invention, the auxiliary accelerator is at least one selected from saccharin, acrylic acid, methacrylic acid, maleic acid, ascorbic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid.
The chelating agent is at least one selected from sodium ethylenediaminetetraacetate and oxalic acid.
The anaerobic adhesive of the invention can further comprise a polymerization inhibitor, and the polymerization inhibitor is selected from at least one of hydroquinone, p-benzoquinone and p-methoxyphenol.
The anaerobic adhesive of the present invention may also further comprise an inorganic filler selected from at least one of silica, calcium oxide, carbon black, magnesium hydroxide and kaolin.
The anaerobic adhesive comprises the following components in parts by mass: acrylate or methacrylate monomers and/or oligomers: 70-130 parts of a solvent; initiator: 0.1-5 parts; accelerator (b): 0.05-5 parts; auxiliary accelerator: 0.1-3 parts; chelating agent: 0.01 to 0.5 portion.
The invention provides an anaerobic adhesive taking onium salt as an accelerator, which comprises the following components:
30-60 parts of an acrylate monomer;
40-70 parts of acrylate oligomer;
initiator: 0.1-5 parts;
accelerator (b): 0.05-5 parts;
auxiliary accelerator: 0.1-3 parts;
an integrating agent: 0.01-0.5 part;
polymerization inhibitor: 0.01-1 part; and
filling: 0.1-5 parts.
The invention also provides a preparation method of the anaerobic adhesive, which comprises the following steps:
(a) adding acrylate or methacrylate monomer and/or oligomer into a reaction kettle according to the mass part ratio, and heating and stirring uniformly;
(b) adding a chelating agent into the reaction kettle, controlling the temperature to be 50-70 ℃, and reacting for 3-5 h;
(c) then controlling the temperature to be 40-50 ℃, adding an accelerant and an auxiliary accelerant, and stirring for 0.5-2 hours;
(d) controlling the temperature to be lower than 40 ℃, then adding an initiator, and uniformly mixing to obtain the anaerobic adhesive.
According to the above preparation method of the anaerobic adhesive, an inorganic filler selected from at least one of silica, calcium oxide, carbon black, magnesium hydroxide and kaolin may be further added in the step (a); in the step (b), a polymerization inhibitor can be further added, and the polymerization inhibitor is selected from at least one of hydroquinone, p-benzoquinone and p-methoxyphenol.
Or the preparation method comprises the following step (b) adding a chelating agent into a reaction kettle, controlling the temperature to be 50-60 ℃, and reacting for 3-5 hours.
Or according to the preparation method of the invention, wherein (d) the temperature is controlled to be 20-40 ℃, then the initiator is added, and the mixture is uniformly mixed to obtain the anaerobic adhesive.
Compared with the conventional accelerator containing hydrazide and amine, the accelerator used in the invention has the outstanding advantages of neutral and stable pH value, no volatile irritation and convenient use of single component. Compared with the prior art, the invention uses the nitrogenous heterocyclic onium salt or the compounding of the nitrogenous heterocyclic onium salt with organic amines and hydrazine compounds as the accelerator, so that the anaerobic adhesive has the performance of quick curing and good storage stability, has higher activity after long-time storage, has the strength which is not obviously reduced along with the lengthening of the storage time, and has no volatilization or release of irritant gas, thereby greatly reducing the harm to human bodies.
Detailed Description
The present invention will be described in detail with reference to the following embodiments in order to make the aforementioned objects, features and advantages of the invention more comprehensible.
The invention develops a new anaerobic adhesive initiator system by using onium salt formed by nitrogen heterocyclic organic matters and organic/inorganic acid as an accelerator, and the initiator system can quickly cure anaerobic adhesive. Another object was to develop an anaerobic adhesive containing such an accelerator initiation system, the contents of which are further illustrated in the following examples, which should not be construed as limiting the invention.
Example 1
The anaerobic adhesive is prepared from the following components in parts by mass:
the method for preparing the anaerobic adhesive comprises the steps of adding bisphenol A epoxy methacrylate, hydroxypropyl methacrylate, diethylene glycol dimethacrylate and pentaerythritol triacrylate into a reaction kettle according to the mass ratio, heating and stirring uniformly, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt, oxalic acid and hydroquinone into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 h; controlling the material temperature at 40-50 ℃, sequentially adding methyl-1, 2, 3, 4-tetrahydroisoquinoline hydrochloride and saccharin, and stirring for 0.5-2 h; and finally adding cumene hydroperoxide at the temperature of 30-40 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
Example 2
The anaerobic adhesive is prepared from the following components in parts by mass:
the preparation method of the anaerobic adhesive comprises the steps of adding ethylene glycol diacrylate, hydroxypropyl methacrylate and acrylic acid into a reaction kettle according to the mass ratio, heating and stirring uniformly, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt, oxalic acid and hydroquinone into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 h; controlling the material temperature at 40-50 ℃, sequentially adding 6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline hydrochloride and saccharin, and stirring for 0.5-2 h; and finally adding cumene hydroperoxide at the temperature of 20-30 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
Example 3
Adding polyurethane methacrylate, hydroxyethyl methacrylate and pentaerythritol triacrylate into a reaction kettle according to the mass ratio, heating and uniformly stirring, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt, oxalic acid and p-benzoquinone into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 hours; controlling the material temperature at 40-50 ℃, sequentially adding 1, 2, 3, 4-tetrahydroquinoline hydrochloride and saccharin, and stirring for 0.5-2 h; and finally, adding 1, 4-di-tert-butylperoxyisopropyl benzene at the temperature of 20-40 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
Example 4
The method for preparing the anaerobic adhesive comprises the steps of adding bisphenol A epoxy methacrylate, hydroxypropyl methacrylate, acrylic acid and pentaerythritol triacrylate into a reaction kettle according to the mass ratio, heating and uniformly stirring, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt, oxalic acid and p-benzoquinone into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 hours; controlling the material temperature at 40-50 ℃, sequentially adding pyridinium tribromide and saccharin, and stirring for 0.5-2 h; and finally adding cumene hydroperoxide at the temperature of 20-40 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
Comparative example 1
The anaerobic adhesive of comparative example 1 is prepared, and the formula is as follows according to the mass part ratio:
the method for preparing the anaerobic adhesive of the comparative example 1 comprises the steps of adding bisphenol A epoxy methacrylate, diethylene glycol dimethacrylate and acrylic acid into a reaction kettle according to the mass part ratio, heating and stirring uniformly, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt and hydroquinone into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 hours; controlling the material temperature at 40-50 ℃, sequentially adding N, N-dimethyl-p-toluidine, triethylamine and saccharin, and stirring for 0.5-2 h; and finally adding cumene hydroperoxide at the temperature of 20-40 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
Comparative example 2
The anaerobic adhesive of comparative example 2 is prepared according to the mass part ratio, and the formula is as follows:
the method for preparing the anaerobic adhesive of the comparative example 2 comprises the steps of adding bisphenol A epoxy methacrylate, hydroxypropyl methacrylate and acrylic acid into a reaction kettle according to the mass portion ratio, heating and stirring uniformly, adding fumed silica, stirring and dispersing until the fumed silica is completely dissolved; sequentially adding ethylene diamine tetraacetic acid disodium salt, 1, 4-naphthoquinone and 2, 6-di-tert-butyl-p-cresol into a reaction kettle, controlling the material temperature at 50-60 ℃, and reacting for 3-5 h; controlling the material temperature at 40-50 ℃, sequentially adding N-benzyldiethylamine, triethylamine, acetyl phenylhydrazine and saccharin, and stirring for 0.5-2 h; and finally adding cumene hydroperoxide at the temperature of 20-40 ℃, stirring for 0.5-2 h, and uniformly mixing to obtain the anaerobic adhesive.
And (3) testing the curing speed: the steel M10 standard bolt and nut was cleaned with acetone and dried. The anaerobic adhesives of the above examples 1 to 4 and comparative examples 1 to 2 were coated on the bolts, nuts were assembled, and the bolts were left to cure at 23 ℃ with a relative humidity of 50%, and the curing speed was measured as the time required for the bolts to be immobilized by hand.
Breaking torque/average breakout torque test: testing according to GB/T18747.1-2002.
Heat storage stability test: 40g of the anaerobic adhesive of examples 1 to 5 and comparative examples 1 to 2 was weighed into a 100ml low density polyethylene bottle, and the bottle was placed in an environment at 80 ℃ to record the time required for the gel to form from the adhesive solution. The longer the time required for the glue solution to gel, the longer the shelf life of the anaerobic glue at normal temperature.
The results of the performance test on the anaerobic adhesive obtained in examples 1 to 5 and comparative examples 1 to 2 are shown in the following table 1:
TABLE 1
The above examples 1 to 5 and comparative examples 1 to 2 were stored at 23 ℃ for 12 months and then tested for their relevant properties, and the results are shown in the following Table 2:
TABLE 2
| Item | Speed of curing (min) | Breaking torque (N. M) | Mean disassembly torque (N.M) |
| Example 1 | 60 | 32 | 30 |
| Example 2 | 55 | 30 | 26 |
| Example 3 | 40 | 26 | 25 |
| Example 4 | 65 | 41 | 38 |
| Comparative example 1 | 100 | 32 | 30 |
| Comparative example 2 | 90 | 30 | 28 |
In conclusion, the comparison between the above examples and comparative examples shows that the anaerobic adhesive of the present invention has the advantages of fast curing and long-term storage stability, and the anaerobic adhesive containing the accelerator can still maintain high activity after long-term storage, and the strength is not greatly reduced by the longer storage time.
Claims (15)
1. An initiator composition for anaerobic adhesives comprising: initiator, accelerator, auxiliary accelerator and chelating agent, wherein the accelerator is onium salt containing nitrogen heterocycle.
2. The initiator composition according to claim 1, wherein the initiator: 0.1-5 parts of accelerator: 0.05-5 parts of auxiliary accelerator: 0.1-3 parts of a chelating agent: 0.01 to 0.5 portion.
3. An anaerobic adhesive comprising: acrylate or methacrylate monomers and/or oligomers, and the initiator composition according to claim 1.
4. The anaerobic adhesive as claimed in claim 3, wherein the acrylate or methacrylate monomer and oligomer is at least one selected from the group consisting of polyethylene glycol methacrylate, epoxy methacrylate, urethane methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, trimethylolpropane methacrylate, alcohol methacrylate, ethoxylated bisphenol A dimethacrylate, polyethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
5. The anaerobic adhesive according to claim 3, wherein the initiator is an organic peroxide selected from at least one of dicumyl peroxide, 1, 4-di-tert-butylperoxyisopropyl benzene, tert-butyl peroxypivalate, tert-butyl peroxyisopropyl benzene, cumene hydroperoxide, tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, 2, 5-dimethyl-2, 5- (di-tert-butylperoxy) hexane, cyclohexylidene diperoxide.
6. The anaerobic adhesive according to claim 3, wherein the accelerator is an onium salt containing a nitrogen heterocycle, and the accelerator is at least one selected from the group consisting of 1-methyl-1, 2, 3, 4-tetrahydroisoquinoline hydrochloride, pyridine hydrobromide, 1H-pyrazole-3-acetic acid hydrochloride, 1, 2, 3, 4-tetrahydroquinoline hydrochloride, pyridinium tribromide, 4, 5, 6, 7-tetrahydrothiophene pyridine hydrochloride, and 6, 7-dimethoxy-1, 2, 3, 4-tetrahydroisoquinoline sulfate.
7. The anaerobic adhesive as claimed in claim 3, wherein the accelerator further comprises a hydrazine and/or amine compound selected from at least one of acetophenylhydrazine, benzoyl chloride, triethylamine, N-dimethyl-p-toluidine, tri-N-butylamine, and triethanolamine.
8. The anaerobic adhesive according to claim 3, wherein the auxiliary accelerator is at least one selected from saccharin, acrylic acid, methacrylic acid, maleic acid, ascorbic acid, chloroacetic acid, dichloroacetic acid, and trichloroacetic acid.
9. The anaerobic adhesive according to claim 3, wherein the chelating agent is at least one selected from the group consisting of ethylenediaminetetraacetic acid sodium salt and oxalic acid.
10. An anaerobic glue according to any one of claims 3 to 9, characterized in that the anaerobic glue further comprises a polymerization inhibitor selected from at least one of hydroquinone, p-benzoquinone and p-methoxyphenol.
11. An anaerobic glue according to any one of claims 3 to 9, characterized in that the anaerobic glue further comprises an inorganic filler selected from at least one of silica, calcium oxide, carbon black, magnesium hydroxide and kaolin.
12. The anaerobic adhesive according to any one of claims 3 to 9, wherein the mass parts of the acrylate or methacrylate monomer and/or oligomer: 70-130 parts of a solvent; initiator: 0.1-5 parts; accelerator (b): 0.05-5 parts; auxiliary accelerator: 0.1-3 parts; chelating agent: 0.01 to 0.5 portion.
13. A method for preparing the anaerobic adhesive according to claim 12, comprising the following steps:
(a) adding acrylate or methacrylate monomer and/or oligomer into a reaction kettle according to the mass part ratio, and heating and stirring uniformly;
(b) adding a chelating agent into the reaction kettle, controlling the temperature to be 50-70 ℃, and reacting for 3-5 h;
(c) then controlling the temperature to be 40-50 ℃, adding an accelerant and an auxiliary accelerant, and stirring for 0.5-2 hours;
(d) controlling the temperature to be lower than 40 ℃, then adding an initiator, and uniformly mixing to obtain the anaerobic adhesive.
14. The method for preparing anaerobic adhesive according to claim 13, wherein an inorganic filler is further added in the step (a), and the inorganic filler is selected from at least one of silica, calcium oxide, carbon black, magnesium hydroxide and kaolin; and (b) further adding a polymerization inhibitor, wherein the polymerization inhibitor is selected from at least one of hydroquinone, p-benzoquinone and p-methoxyphenol.
15. The preparation method of the anaerobic adhesive according to claim 13, wherein (d) the temperature is controlled to be 20-40 ℃, then the initiator is added and mixed uniformly to obtain the anaerobic adhesive.
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| CN115595096A (en) * | 2022-08-03 | 2023-01-13 | 迪马新材料科技（苏州）有限公司（Cn） | Anaerobic adhesive and preparation method thereof |
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| US20030217808A1 (en) * | 2000-05-18 | 2003-11-27 | John Woods | Adhesive compositions for bonding passive substrates |
| CN1328103A (en) * | 2001-06-29 | 2001-12-26 | 中国科学院广州化学研究所 | Trigger used for anaerobic adhesive and its anaerobic adhesive |
| CN101735734A (en) * | 2008-11-04 | 2010-06-16 | 广东恒大新材料科技有限公司 | Anaerobic adhesive initiator composite and anaerobic adhesive containing initiator |
| CN107722842A (en) * | 2017-11-07 | 2018-02-23 | 广东三和控股有限公司 | A kind of quick-drying, high stability anaerobic adhesive and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115595096A (en) * | 2022-08-03 | 2023-01-13 | 迪马新材料科技（苏州）有限公司（Cn） | Anaerobic adhesive and preparation method thereof |
| CN115595096B (en) * | 2022-08-03 | 2024-03-12 | 迪马新材料科技（苏州）有限公司 | Anaerobic adhesive and preparation method thereof |
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| CN111925756B (en) | 2022-10-21 |
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Denomination of invention: Composition of initiator for anaerobic adhesive, anaerobic adhesive and its preparation method Effective date of registration: 20230412 Granted publication date: 20221021 Pledgee: South Taihu New Area sub branch of Huzhou Wuxing Rural Commercial Bank Co.,Ltd. Pledgor: HUZHOU OCHEM CHEMICAL CO.,LTD. Registration number: Y2023980037916 |