CN115595096A - Anaerobic adhesive and preparation method thereof - Google Patents

Anaerobic adhesive and preparation method thereof Download PDF

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CN115595096A
CN115595096A CN202210926795.3A CN202210926795A CN115595096A CN 115595096 A CN115595096 A CN 115595096A CN 202210926795 A CN202210926795 A CN 202210926795A CN 115595096 A CN115595096 A CN 115595096A
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monomer
methacrylic acid
monomers
anaerobic adhesive
accelerator
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CN115595096B (en
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杨梦云
蔡玉婷
曹建强
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Dikma New Material Technology Suzhou Co ltd
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/14—Polycondensates modified by chemical after-treatment
    • C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
    • C08G59/1438—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds containing oxygen
    • C08G59/1455—Monocarboxylic acids, anhydrides, halides, or low-molecular-weight esters thereof
    • C08G59/1461—Unsaturated monoacids
    • C08G59/1466—Acrylic or methacrylic acids
    • 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
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/10—Epoxy resins modified by unsaturated compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2170/00—Compositions for adhesives
    • C08G2170/20—Compositions for hot melt adhesives

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

Abstract

The application discloses an anaerobic adhesive and a preparation method thereof. The anaerobic adhesive comprises a monomer-polymerization inhibitor mixture; an initiator selected from one or more of organic peroxides; the first accelerator and the second accelerator are respectively selected from one or more of first amine, hydrazine and derivatives thereof or first organic dibasic acid; and a co-promoter selected from one or more of a saccharinate or a second organic diacid; wherein the mass ratio of the monomer-polymerization inhibitor mixture, the initiator, the first accelerator, the second accelerator and the auxiliary accelerator is 100:0.4-0.5:1.8-2.0:0.005-0.006:0.4-0.5.

Description

Anaerobic adhesive and preparation method thereof
Technical Field
The application relates to the field of chemistry, in particular to anaerobic adhesive and a preparation method thereof.
Background
Anaerobic adhesives are adhesives that do not cure when exposed to air or oxygen and remain in liquid form for long periods of time, but cure rapidly in the absence of air or oxygen. With the rapid promotion of global industrialization in recent years, the anaerobic adhesive technology is rapidly developed, novel anaerobic adhesives continuously appear, and the application field also covers industries such as aviation, automobiles, machinery, ships, chemical pipelines and the like. With the continuous and deep industrialization, the need for anaerobic adhesive with continuously improved technical indexes such as high temperature resistance, high strength and radiation resistance is more urgent.
Disclosure of Invention
In order to solve the problems, the application provides an anaerobic adhesive and a preparation method thereof. The anaerobic adhesive is high temperature resistant and high in shear strength.
In one aspect, the present application provides an anaerobic adhesive comprising a monomer-polymerization inhibitor mixture; an initiator selected from one or more of organic peroxides; the first accelerator and the second accelerator are respectively selected from one or more of first amine, hydrazine and derivatives thereof or first organic dibasic acid; and a co-promoter selected from one or more of a saccharinate or a second organic diacid; wherein the mass ratio of the monomer-polymerization inhibitor mixture, the initiator, the first accelerator, the second accelerator and the auxiliary accelerator is 100:0.4-0.5:1.8-2.0:0.005-0.006:0.4-0.5.
In some embodiments, the monomers in the monomer-polymerization inhibitor mixture include methacrylic acid monomers including one or more of methacrylic acid, bis-methacrylic acid polyethylene glycol ester monomers, bisphenol a dimethacrylate epoxy resin monomers, tetrahydrofurfuryl methacrylate monomers, methacrylic acid aliphatic epoxy monomers, hydantoin epoxy resin monomers, methacrylic acid silicone epoxy resin monomers, organic titanium methacrylate epoxy resin monomers, methacrylic acid trimellitic anhydride-triethylene glycol di-monomers.
In some embodiments, the methacrylic acid monomer at least comprises a methacrylic acid organic titanium epoxy resin monomer, and the mass ratio of the methacrylic acid organic titanium epoxy resin monomer is 20-100%.
In some embodiments, the organic peroxide comprises one or more of di-t-butyl peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate.
In some embodiments, the anaerobic glue of claim 4, wherein the organic peroxide is cumene hydroperoxide.
In some embodiments, the first amine comprises one or more of triethylamine, N-dimethylaniline, N-diethyl-p-toluidine, 1, 2-propanediamine, triethanolamine, dimethylamide.
In some embodiments, the first amine is triethylamine or N, N-dimethylaniline, the hydrazine and derivatives thereof are phenylhydrazine, and the first organic diacid is oxalic acid.
In some embodiments, the saccharinate salt comprises one or more of a SQ salt, a STQ salt, a SMQ salt, a SQA salt.
In some embodiments, the saccharinate salt is a SQ salt and the second organic diacid is maleic acid.
In some embodiments, the anaerobic adhesive further comprises a polymerization inhibitor selected from the group consisting of phenols, quinones, or second amines; the phenol is hydroquinone or p-tert-butyl catechol, the quinone is p-benzoquinone, and the second amine is N-nitrosodiphenylamine or vulcanized diphenylamine.
In some embodiments, the anaerobic adhesive further comprises a solvent, wherein the solvent is methacrylic acid or acrylic acid.
In another aspect, the present application provides a method for preparing the above anaerobic adhesive, the method comprising: obtaining one or more monomer-polymerization inhibitor mixtures based on the preparation process of one or more monomers, respectively; mixing the one or more monomer-polymerization inhibitor mixtures in a reaction vessel under agitation; adding an initiator, an accelerator and an auxiliary accelerator into the reaction container at the reaction temperature, and uniformly stirring; and adding a solvent into the reaction container, and uniformly stirring to obtain the anaerobic adhesive.
Detailed Description
As used in this application and the appended claims, the terms "a," "an," "the," and/or "the" are not intended to be inclusive in the singular, but rather are intended to be inclusive in the plural unless the context clearly dictates otherwise. In general, the terms "comprises" and "comprising" merely indicate that steps and elements are included which are explicitly identified, that the steps and elements do not form an exclusive list, and that a method or apparatus may include other steps or elements. The numerical ranges used in this application are intended to convey in conciseness each and every value included in the range.
Some embodiments of the present application disclose an anaerobic adhesive comprising a monomer-inhibitor mixture, an initiator, an accelerator, and a co-accelerator.
The monomer may be a component of the anaerobic adhesive for achieving adhesive properties (e.g., anaerobic curing), which may be polymerizable. After the anaerobic gel is cured, the monomer can form a polymer of a lamellar network. For example, the monomer may be a polymerizable or an oligomeric compound containing an unsaturated bond. In some embodiments of the present application, exemplary monomers may include methacrylic monomers including, but not limited to, one or any combination of methacrylic acid, polymethacrylic acid, bis-methacrylic acid polyethylene glycol ester monomers, bisphenol a dimethacrylate type epoxy monomers, tetrahydrofurfuryl methacrylate monomers, methacrylic acid aliphatic epoxy monomers, hydantoin epoxy monomers, silicone methacrylate epoxy monomers, organotitanium methacrylate epoxy monomers, methacrylic acid-trimellitic anhydride-triethylene glycol monomers, methacrylic acid polyethylene glycol ester monomers, epoxy methacrylate monomers, polyurethane type methacrylate monomers, hydroxyethyl methacrylate monomers, hydroxypropyl methacrylate monomers, trimethylolpropane methacrylate monomers, alcohol methacrylate monomers, polyethylene glycol dimethacrylate monomers, diethylene glycol dimethacrylate monomers, triethylene glycol dimethacrylate monomers, tetraethylene glycol dimethacrylate monomers, hydroxyethyl methacrylate monomers, hydroxypropyl methacrylate monomers, and the like. Alternatively or preferably, the monomer may include one or more of methacrylic acid, a bis-methacrylic acid polyethylene glycol ester monomer, a dimethyl acrylic acid bisphenol a type epoxy resin monomer, a methacrylic acid tetrahydrofurfuryl alcohol monomer, a methacrylic acid aliphatic epoxy compound monomer, a methacrylic acid hydantoin epoxy resin monomer, a methacrylic acid silicone epoxy resin monomer, a methacrylic acid organic titanium epoxy resin monomer, a methacrylic acid-trimellitic anhydride-triethylene glycol monomer. Alternatively or preferably, the monomer can be formed by mixing methacrylic acid organic titanium epoxy resin monomer, methacrylic acid tetrahydrofurfuryl alcohol monomer and methacrylic acid-trimellitic anhydride-triethylene glycol monomer. Alternatively or preferably, the monomer may be an organo-titanium methacrylate epoxy monomer.
The monomer may include at least an organic titanium epoxy methacrylate monomer. By way of example, the monomer may be entirely composed of a methacrylic acid organotitanium epoxy monomer. As another example, the monomer may be composed of a methacrylic acid organotitanium epoxy monomer and one or more other monomers. For example, the monomer may be composed of an organic titanium epoxy methacrylate monomer and a tetrahydrofurfuryl methacrylate monomer and/or a methacrylic acid-trimellitic anhydride-triethylene glycol monomer.
Polymerization inhibitors, which may also be referred to as stabilizers, may be used to prevent polymerization of the monomers during non-use (e.g., purification, storage, and/or transportation) overfilling, thereby affecting the performance of the anaerobic adhesive. It is known that although oxygen can play a role in inhibiting polymerization to some extent, it cannot guarantee good storage stability of the anaerobic adhesive. Therefore, the polymerization inhibitor is added to further prevent the monomer from polymerizing, so as to achieve the purpose of long-term storage. In some embodiments, the polymerization inhibitor may be selected from one or more of a phenol, a quinone, or an amine (which may be referred to as a second amine in some embodiments). Exemplary phenols include phenol, halophenols, nitrophenols, hydrocarbylphenols, benzenediols, halophenols, hydrocarbylbenzenediols, benzenetriols, naphthols, naphthalenediols, and the like. Alternatively or preferably, the phenol may be hydroquinone or p-tert-butylcatechol. Exemplary quinones can include benzoquinones (e.g., ortho-benzoquinone and para-benzoquinone), as well as naphthoquinones, anthraquinones, phenanthraquinones, and the like. Alternatively or preferably, the quinone may be benzoquinone. Exemplary second amines may include one or more of aliphatic amines, aromatic amines or halogenated, hydrocarbon-based or thio compounds thereof. Alternatively or preferably, the second amine may be N-nitrosodiphenylamine or thiodiphenylamine (which may also be referred to as phenothiazine).
In some embodiments, the monomer-polymerization inhibitor mixture may be obtained by uniformly mixing the monomer and the polymerization inhibitor. In some embodiments, the polymerization inhibitor may be added into the reaction system during the monomer synthesis process, and is retained after reaction and post-treatment without participating in the monomer synthesis. The monomer-inhibitor mixture can finally be obtained after the end of the monomer synthesis. The amount of the polymerization inhibitor added is very small and the mass thereof can be omitted compared to the monomer. Reference may be made to the examples section of this application for further description of the monomer-polymerization inhibitor.
The initiator may be a component for initiating polymerization of the monomer. Upon exclusion of air, the initiator may generate free radicals, thereby causing the monomers to polymerize. During the storage process, the free radicals generated by the initiator are continuously consumed under the action of oxygen and a polymerization inhibitor (stabilizer), so that the anaerobic adhesive is ineffective after being placed for polymerization. In some embodiments herein, the initiator may be selected from organic peroxides. <xnotran> (, , , , , , , ( ) , ), (,2,5- -2,5- ( ) -3, 2,5- -2,5- , , ), (, , 3,5,5- , ), (, ,2,2- ( ) ,1,1- ( ) ,1,1- -3,3,5- ,3,6,9- -3,6,9- -1,4,7- ), (, , , , -2- , , -2- , , ,4,4- ( ) , , (2- ) , </xnotran> Bis (4-t-butylcyclohexyl) peroxydicarbonate, t-butyl peroxyacetate, t-butylperoxy-3, 5-trimethylhexanoate, t-butylperoxyisobutyrate, t-butyl peroxy-2-ethylhexanoate, t-amyl peroxy-2-ethylhexanoate, t-butyl peroxypivalate, t-amyl peroxypivalate, cumyl peroxyneodecanoate, t-butyl peroxyneodecanoate, etc.), peroxydicarbonate (e.g., dicetyl peroxydicarbonate, ditetradecyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, bis- (2-ethylhexyl) peroxydicarbonate, etc.), etc. Alternatively or preferably, the initiator may be one or more selected from the group consisting of di-t-butyl peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate. Alternatively or preferably, the initiator may be cumene hydroperoxide.
The accelerator may be a component for accelerating the curing reaction. The accelerator, when air excluded, can promote rapid polymerization of the initiated monomer (e.g., the monomer from which polymerization is initiated). The initiator does not affect the storage period and the bonding strength of the anaerobic adhesive while realizing the initiation function. In some embodiments of the present application, the anaerobic adhesive includes a first accelerator and a second accelerator. The first accelerator and the second accelerator may be selected from one or more of amines (which may be referred to herein in some embodiments as first amines), hydrazine and derivatives thereof, or organic diacids (which may be referred to herein in some embodiments as first organic diacids). Exemplary first amines may include one or more of aliphatic amines, aromatic amines or halogenated, hydrocarbon-based or thio compounds thereof. Alternatively or preferably, the first amine may be one or more selected from triethylamine, N-dimethylaniline, N-diethyl-p-toluidine, 1, 2-propanediamine, triethanolamine, and dimethylamide. Alternatively or preferably, the first amine may be triethylamine or N, N-dimethylaniline. Exemplary hydrazines and derivatives thereof include hydrazine, phenylhydrazine, substituted phenylhydrazines, hydrazides, substituted hydrazides, and the like. Alternatively or preferably, the hydrazine and derivatives thereof may be phenylhydrazine. Exemplary first organic diacids can include aliphatic diacids (e.g., alkane diacids such as oxalic acid, malonic acid, succinic acid, and the like, alkene diacids such as butenedioic acid, hexadiene diacid, and the like), aromatic diacids (e.g., phenyl diacids such as phthalic acid, phenyl diacetic acid, phenyl dipropionic acid, and the like). Alternatively or preferably, the first organic diacid may be oxalic acid. In some embodiments herein, the first promoter may be N, N-dimethylaniline and the second promoter may be oxalic acid.
The co-accelerator may be a component for enhancing the effect of the accelerator, which does not have a significant accelerating effect when used alone, and can significantly enhance the effect of the accelerator when used together with the accelerator. In some embodiments of the present application, the co-promoter may be selected from a saccharinate or a second organic diacid. The saccharin salt can be the salt formed by the reaction of saccharin (chemical name of o-benzoylsulfonimide) and other substances. Illustratively, the saccharin salts can include SQ salts (salifying saccharin with an amine), STQ salts (salifying saccharin with 1,2,3, 4-tetrahydroquinoline), SMQ salts (salifying saccharin with 6-methyl-1, 2,3, 4-tetrahydroquinoline), SQA salts (salifying saccharin with 1,2,3, 4-tetrahydroquinoline), and the like. Alternatively or preferably, the saccharinate salt may be a SQ salt. The second organic diacid can also include, in the same or similar manner, aliphatic diacids (e.g., alkane diacids such as oxalic acid, malonic acid, succinic acid, etc., alkene diacids such as butenedioic acid, adipic acid, etc.), aromatic diacids (e.g., phenyl diacids such as phthalic acid, phenylenediacetic acid, phenylenedipropionic acid, etc.) as compared to the first organic diacid. Alternatively or preferably, the second organic diacid may be maleic acid.
In some embodiments of the present application, the anaerobic adhesive may further include a solvent. The solvent may include acrylic acid or methacrylic acid. Alternatively or preferably, the solvent may be methacrylic acid.
In some embodiments of the present application, the mass ratio (in parts by weight) of the components constituting the anaerobic adhesive, that is, the monomer-polymerization inhibitor mixture, the initiator, the first accelerator, the second accelerator, and the auxiliary accelerator is 100:0.4-0.5:1.8-2.0:0.005-0.006:0.4-0.5.
In some embodiments, the mass fraction of the organotitanium methacrylate epoxy monomer in the monomer-inhibitor mixture is from 20% to 100%. When all the monomers in the monomer-polymerization inhibitor mixture are methacrylic acid organic titanium epoxy resin monomers, the mass ratio is 100%. When the monomer in the monomer-polymerization inhibitor mixture is a mixture of methacrylic acid organic titanium epoxy resin monomer, methacrylic acid tetrahydrofurfuryl alcohol monomer and methacrylic acid-trimellitic anhydride-triethylene glycol monomer, the mass ratio of the methacrylic acid tetrahydrofurfuryl alcohol monomer to the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 0-40%. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 20. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 33.33. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 40. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 45. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 50. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 60. Alternatively or preferably, the mass ratio of the methacrylic acid organic titanium epoxy resin monomer, the methacrylic acid tetrahydrofurfuryl alcohol monomer and the methacrylic acid-trimellitic anhydride-triethylene glycol monomer is 100.
Alternatively or preferably, the mass fraction of the initiator in the anaerobic adhesive may be 0.4, 0.45, 0.5, etc. The mass portion of the first accelerant in the anaerobic adhesive can be 1.8, 2.0 and the like. The mass portion of the second accelerant in the anaerobic adhesive can be 0.005 or 0.006. The mass portion of the auxiliary accelerator in the anaerobic adhesive can be 0.4 or 0.5.
Some embodiments of the application disclose a preparation method of the anaerobic adhesive. The preparation method comprises the following steps. In a first step, one or more monomer-inhibitor mixtures are obtained, each based on the preparation of one or more monomers. The polymerization inhibitor may be added to the reaction system during the preparation of the monomer, but does not participate in the reaction. After the post-treatment, a monomer-retarder mixture is obtained. In a second step, the one or more monomer-polymerization inhibitor mixtures are mixed in a reaction vessel under agitation. The reaction vessel may be a reaction kettle or a beaker, flask, etc. The one or more monomer-polymerization inhibitor mixtures may be added to the reaction vessel simultaneously and stirred, or one may be added first, then the second one is added under stirring, then the third one is added under stirring, and so on. And thirdly, adding an initiator, a first promoter, a second promoter and an auxiliary promoter into the reaction container at the reaction temperature, and uniformly stirring. The reaction temperature may be room temperature or may be changed depending on the actual conditions. For example, 20 ℃ and 30 ℃. The addition of the initiator, the first accelerator, the second accelerator and the co-accelerator may be performed sequentially. For example, the first accelerator or the second accelerator may be added first, and after stirring for a certain period of time, the second accelerator or the first accelerator and the co-accelerator may be added. After stirring for another period of time, the initiator is added and stirring is continued for another period of time. And fourthly, adding a solvent into the reaction container, and uniformly stirring to obtain the anaerobic adhesive.
Examples
The present application is further illustrated by the following examples. The application is not limited by these examples.
EXAMPLE 1 preparation of tetrahydrofurfuryl methacrylate monomer-Polymer mixture
The reactants were obtained based on the following formulation:
Figure BDA0003779973490000091
adding 100g of tetrahydrofurfuryl alcohol, 164g of toluene and 0.037g of polymerization inhibitor into a flask, adding 90.36g of methacrylic acid into the flask at a temperature of between 58 and 62 ℃, slowly dropwise adding 2.86mL of concentrated sulfuric acid when the internal temperature reaches 100 ℃, ensuring the effluent temperature to be about 108 ℃, ensuring the internal temperature to be no more than 127 ℃ when the reaction is finished, ensuring the theoretical effluent amount to be 17.6g, cooling, and adding 10 percent (NH) 4 ) 2 SO 4 And (4) washing with an aqueous solution. And finally, discharging lower layer acid water, distilling toluene at low pressure, adding 10g of activated alumina, and standing for half an hour to obtain the methacrylic acid-tetrahydrofurfuryl alcohol monomer. The reaction mechanism is as follows:
Figure BDA0003779973490000092
EXAMPLE 2 preparation of methacrylic acid trimellitic anhydride triethylene glycol dimer monomer-Polymer mixture
The reactants were obtained based on the following formulation:
Figure BDA0003779973490000093
Figure BDA0003779973490000101
into a flask were charged 404g of toluene, and 38.76g of trimellitic anhydride, 100g of triethylene glycol, 0.046g of polymerization inhibitor and 86.4g of methacrylic acid were charged with stirring. When the internal temperature reaches 60 ℃, 3mL of concentrated sulfuric acid begins to be dripped, the temperature is about 110 ℃, and the theoretical water yield is 27.86g. After the reaction is finished, the internal temperature is not more than 112 ℃, and NH is used after the reaction liquid is cooled 4 SO 4 Washing with 10% water solution. The lower acid water was discharged, and the mixture was put into a distillation flask, and toluene was removed by low-pressure distillation, and 5g of alumina was added. After standing for half an hour, the alumina was removed and the composition stored in a polyethylene bucket for further use. The reaction mechanism is as follows:
Figure BDA0003779973490000102
EXAMPLE 3 preparation of organotitanium methacrylate epoxy monomer-Polymer mixture
The reactants were obtained based on the following formulation:
Figure BDA0003779973490000103
1 preparation of organic titanium epoxy resin
Adding epoxy resin Dow DER331 into a reaction kettle, heating and stirring to 110 ℃, carrying out vacuum dehydration for 2 hours, then cooling to 55-60 ℃, adding 12 parts of toluene into 100 parts of epoxy resin, and continuously cooling to 40-45 ℃. And (3) dropwise adding the n-butyl titanate solution, wherein the dropwise adding is finished within about 20min, and the original temperature is maintained for 15-20 min after the dropwise adding is finished. Gradually heating to 120-130 ℃, evaporating the by-product (butanol) together, then completely evaporating all low-boiling-point substances by using a vacuum pump, cooling and discharging to prepare the organic titanium epoxy resin.
2 preparation of methacrylic acid organic titanium epoxy resin monomer
Weighing organic titanium epoxy resin, pouring into a reaction kettle, adding the required amount of hydroquinone and the required amount of methacrylic acid when the internal temperature is 60 ℃. When the internal temperature reaches 70 ℃, triethylamine is added, the temperature is adjusted to 85-95 ℃, the reaction is carried out for 3 hours, and the mixture is poured into a polyethylene barrel when the reaction is finished.
The reaction mechanism is as follows:
Figure BDA0003779973490000111
EXAMPLE 4 preparation of anaerobic adhesive
Anaerobic adhesive S1: weighing 20 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 40 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 40 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid. Monomer B was added to the flask at room temperature, monomer C was added with stirring, and after completion monomer A was added with stirring. Adding oxalic acid and stirring at room temperature for 45min, adding dimethylaniline and SQ salt, stirring for 30min, adding cumene hydroperoxide, and stirring for 10min. And finally, adding methacrylic acid, and uniformly stirring to obtain a final product.
Anaerobic adhesive S2: 33.33 parts of monomer A (methacrylic acid-organic titanium epoxy resin monomer), 33.33 parts of monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 33.33 parts of monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 1.8 parts of dimethylaniline, 0.45 part of saccharin-tertiary amine salt (SQ salt), 0.005 part of oxalic acid, 0.45 part of cumene hydroperoxide and 8.5 parts of methacrylic acid are weighed. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S3: weighing 40 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 30 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 30 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S4: weighing 45 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 27.5 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 27.5 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol dimer monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S5: weighing 50 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 25 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 25 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S6: 55 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 20 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 25 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid are weighed. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S7: 60 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 20 parts of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 20 parts of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 2 parts of dimethylaniline, 0.5 part of saccharin-tertiary amine salt (SQ salt), 0.006 part of oxalic acid, 0.5 part of cumene hydroperoxide and 10 parts of methacrylic acid are weighed. The preparation process is the same as that of the anaerobic adhesive S1.
Anaerobic adhesive S8: weighing 100 parts of a monomer A (methacrylic acid-organic titanium epoxy resin monomer), 0 part of a monomer B (methacrylic acid-tetrahydrofurfuryl alcohol monomer), 0 part of a monomer C (methacrylic acid-trimellitic anhydride-triethylene glycol monomer), 1.8 parts of dimethylaniline, 0.4 part of saccharin-tertiary amine salt (SQ salt), 0.005 part of oxalic acid, 0.5 part of cumene hydroperoxide and 5 parts of methacrylic acid. The preparation process is the same as that of the anaerobic adhesive S1.
EXAMPLE 5 anaerobic adhesive Performance test
1> tensile shear strength; testing the tensile shear strength of the anaerobic adhesive by referring to GB/T7124-2008;
2> viscosity test: performing viscosity test on the anaerobic adhesive according to GB/T2794-2013;
3> strength retention test: and (3) performing a strength retention test on the anaerobic adhesive by referring to GB/T7124-2008.
The results are shown in Table 1.
TABLE 1 anaerobic adhesive Performance test results
Figure BDA0003779973490000131
As shown in Table 2, the test results show that the tensile shear strength of the anaerobic adhesives S2-S7 can reach more than 30MPa, and the tensile shear strength of the anaerobic adhesives S1 and S8 is close to 30MPa. And each anaerobic adhesive is high temperature resistant, and the strength retention rate is at least over 90 percent and can reach as high as 98 percent after the anaerobic adhesive is placed at 250 ℃ for 30 min.
The anaerobic adhesive disclosed by the application has good thermal stability and high bonding strength.
Having thus described the basic concept, it will be apparent to those skilled in the art that the foregoing detailed disclosure is to be considered merely illustrative and not restrictive of the broad application. Various modifications, improvements and adaptations to the present application may occur to those skilled in the art, although not explicitly described herein. Such modifications, improvements and adaptations are proposed in some embodiments of the present application and are therefore within the spirit and scope of the exemplary embodiments of the present application.
Also, this application uses specific language to describe embodiments of the application. Reference throughout this specification to "one embodiment," "an embodiment," and/or "some embodiments" means that a particular feature, structure, or characteristic described in connection with at least one embodiment of the present application is included in at least one embodiment of the present application. Therefore, it is emphasized and should be appreciated that two or more references to "one embodiment," "an embodiment," or "an alternative embodiment" in various places throughout this specification are not necessarily all referring to the same embodiment. Furthermore, some features, structures, or characteristics of one or more embodiments of the present application may be combined as appropriate.
Similarly, it should be noted that in the preceding description of embodiments of the application, various features are sometimes grouped together in a single embodiment or description thereof for the purpose of streamlining the disclosure aiding in the understanding of one or more of the embodiments. This method of disclosure, however, is not intended to imply that more features are required than are expressly recited in the claims. Indeed, the embodiments may be characterized as having less than all of the features of a single disclosed embodiment.
Numerals describing the number of components, attributes, etc. are used in some embodiments, it being understood that such numerals used in the description of the embodiments are modified in some instances by the use of the modifier "about", "approximately" or "substantially". Unless otherwise indicated, "about", "approximately" or "substantially" indicates that the number allows a variation of ± 20%. Accordingly, in some embodiments, the numerical parameters used in the specification and claims are approximations that may vary depending upon the desired properties of the individual embodiments. In some embodiments, the numerical parameter should take into account the specified significant digits and employ a general digit preserving approach. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the range are approximations, in the specific examples, such numerical values are set forth as precisely as possible within the scope of the application.
The entire contents of each patent, patent application publication, and other material cited in this application, such as articles, books, specifications, publications, documents, and the like, are hereby incorporated by reference into this application. Except where the application history document is inconsistent or conflicting with the present application as to the extent of the present claims, which are now or later appended to this application. It is noted that the descriptions, definitions and/or use of terms in this application shall control if they are inconsistent or contrary to the statements and/or uses of the present application in the material attached to this application.
Finally, it should be understood that the embodiments described herein are merely illustrative of the principles of embodiments of the present application. Other variations are also possible within the scope of the present application. Thus, by way of example, and not limitation, alternative configurations of the embodiments of the present application may be viewed as being consistent with the teachings of the present application. Accordingly, the embodiments of the present application are not limited to only those embodiments explicitly described and depicted herein.

Claims (12)

1. An anaerobic adhesive, comprising:
a monomer-inhibitor mixture;
an initiator selected from one or more of organic peroxides;
the first accelerator and the second accelerator are respectively selected from one or more of first amine, hydrazine and derivatives thereof or first organic dibasic acid; and
the auxiliary accelerator is selected from one or more of saccharine salt or second organic dibasic acid;
wherein the mass ratio of the monomer-polymerization inhibitor mixture, the initiator, the first accelerator, the second accelerator and the auxiliary accelerator is 100:0.4-0.5:1.8-2.0:0.005-0.006:0.4-0.5.
2. The anaerobic adhesive according to claim 1, wherein the monomer in the monomer-polymerization inhibitor mixture comprises methacrylic acid monomers, including one or more of methacrylic acid, bis-methacrylic acid polyethylene glycol ester monomers, bisphenol A dimethacrylate epoxy resin monomers, tetrahydrofurfuryl methacrylate alcohol monomers, methacrylic acid aliphatic epoxy compound monomers, hydantoin methacrylate epoxy resin monomers, methacrylic acid silicone epoxy resin monomers, organotitanium methacrylate epoxy resin monomers, methacrylic acid trimellitic anhydride-triethylene glycol monomers.
3. The anaerobic adhesive as claimed in claim 2, wherein the methacrylic acid monomer at least comprises a methacrylic acid organic titanium epoxy resin monomer, and the mass percentage of the methacrylic acid organic titanium epoxy resin monomer is 20-100%.
4. An anaerobic glue according to any of the claims 1-3, characterized in that the organic peroxide comprises one or more of di-tert-butyl peroxide, benzoyl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate.
5. The anaerobic adhesive according to claim 4, wherein the organic peroxide is cumene hydroperoxide.
6. An anaerobic adhesive as claimed in any one of claims 1 to 3 or claim 5, wherein the first amine comprises one or more of triethylamine, N-dimethylaniline, N-diethyl-p-toluidine, 1, 2-propanediamine, triethanolamine, dimethylamide.
7. The composition of claim 6, wherein the first amine is triethylamine or N, N-dimethylaniline, the hydrazine and its derivatives are phenylhydrazine, and the first organic diacid is oxalic acid.
8. An anaerobic glue according to any of claims 1-3 or claim 7, characterized in that the saccharinate salt comprises one or more of SQ, STQ, SMQ, SQA salts.
9. The anaerobic adhesive according to claim 8, wherein the saccharinate is SQ salt and the second organic diacid is maleic acid.
10. An anaerobic glue according to any of claims 1-3 or claim 9, characterized in that the anaerobic glue further comprises a polymerization inhibitor selected from phenols, quinones or second amines; the phenol is hydroquinone or p-tert-butyl catechol, the quinone is p-benzoquinone, and the second amine is N-nitrosodiphenylamine or vulcanized diphenylamine.
11. The anaerobic adhesive of claim 10, further comprising a solvent, wherein the solvent is methacrylic acid or acrylic acid.
12. A method of preparing the anaerobic glue of any of claims 1-11, comprising:
obtaining one or more monomer-polymerization inhibitor mixtures based on the preparation process of one or more monomers, respectively;
mixing the one or more monomer-inhibitor mixtures with stirring in a reaction vessel;
adding an initiator, a first promoter, a second promoter and an auxiliary promoter into the reaction container at the reaction temperature, and uniformly stirring;
and adding a solvent into the reaction container, and uniformly stirring to obtain the anaerobic adhesive.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004010740A (en) * 2002-06-06 2004-01-15 Denki Kagaku Kogyo Kk Acrylic adhesive composition
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
CN111925756A (en) * 2019-05-13 2020-11-13 湖州欧美化学有限公司 Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004010740A (en) * 2002-06-06 2004-01-15 Denki Kagaku Kogyo Kk Acrylic adhesive composition
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
CN111925756A (en) * 2019-05-13 2020-11-13 湖州欧美化学有限公司 Initiator composition for anaerobic adhesive, anaerobic adhesive and preparation method thereof

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