CN110819265A - Acrylate structural adhesive - Google Patents
Acrylate structural adhesive Download PDFInfo
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- CN110819265A CN110819265A CN201810905134.6A CN201810905134A CN110819265A CN 110819265 A CN110819265 A CN 110819265A CN 201810905134 A CN201810905134 A CN 201810905134A CN 110819265 A CN110819265 A CN 110819265A
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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
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- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention provides an acrylate structural adhesive. The structural adhesive comprises an acrylate monomer, an oxidant, a toughening agent, a reducing agent, a vanadium complex curing accelerator and an adhesion promoter, wherein the vanadium complex curing accelerator comprises a compound with a structure shown in a formula I and/or a formula II. The vanadium complex curing accelerator has good solubility and stability, effectively improves the stability of acrylate structural adhesive, and has good accelerating effect on the rapid curing of acrylate monomers. In addition, the vanadium complex curing accelerator is used, and the toughening agent and the adhesion promoter are matched, so that the acrylate structural adhesive provided by the invention has good bonding strength, and the structural adhesive has the characteristic of low odor because a low-boiling-point substance is not adopted.
Description
Technical Field
The invention relates to the field of acrylate adhesives, and particularly relates to an acrylate structural adhesive.
Background
The second-generation acrylate structural adhesive has the advantages of high adhesive force, wide adhesive base materials and the like, develops rapidly in more than 20 years, and is widely applied to the industries of rail transit, automobiles, buildings, wind power and the like. However, the structural adhesive still has some disadvantages, and one important disadvantage is that the structural adhesive has strong odor and severe irritation to human body, which seriously affects the large-scale application of the second generation acrylate structural adhesive. In recent years, with the promotion of environmental regulations and the improvement of safety and environmental awareness of operators, the development of low-odor environment-friendly acrylate structural adhesives mainly comprising high-boiling-point acrylate monomers gradually becomes the market development direction. However, the high boiling point acrylate monomer has the problems of low curing activity and the like, so that the peeling strength and the impact strength of the structural adhesive are affected.
In order to solve the problem of low curing activity of the high-boiling-point acrylate monomer, a curing accelerator needs to be added into the system, wherein the vanadium complex curing accelerator is used in the acrylate structural adhesive in a large amount. However, the vanadium ion accelerator on the market is generally solid and has a single structure, and the direct addition of the vanadium ion accelerator into an acrylic acid structural adhesive system has many problems, such as poor solubility; the storage stability is poor, and the acrylate monomer is easily oxidized or reduced by other substances in the system to initiate the polymerization of the acrylate monomer; low bonding strength after curing, and the like.
Disclosure of Invention
The invention mainly aims to provide an acrylate structural adhesive to solve the problems of poor structural adhesive stability and low bonding strength of the acrylate structural adhesive in the prior art due to the fact that a vanadium ion accelerator is solid.
In order to achieve the above object, according to one aspect of the present invention, there is provided an acrylate structural adhesive, which includes an acrylate monomer, an oxidant, a toughener, a reducing agent, a vanadium complex curing accelerator, and an adhesion promoter, wherein the vanadium complex curing accelerator includes a compound having a structure represented by formula I and/or formula II:
G∶V(R1)nformula I
G∶(VO)(R2)mFormula II
G is a ligand compound and represents a coordination bond, wherein in the formula I, n is an integer of 1-3, and V shows positive trivalent and is connected with n R through an ionic bond and/or a covalent bond1Connecting; in the formula II, m is 1 or 2, V shows positive quadrivalence and is connected with m R through ionic bond and/or covalent bond2Connecting; wherein n R1Each independently comprising reductionM R in the product formed by oxidizing the substance2The reducing substances respectively and independently comprise anions or electron-withdrawing groups in products formed after the reducing substances are oxidized, and the reducing substances can perform oxidation-reduction reaction with the vanadium with the positive pentavalent state.
Further, the reducing substance comprises one or more of inorganic salt reducing substances, aldehyde reducing substances, alcohol reducing substances, amine reducing substances, phenol reducing substances, imidazole reducing substances and thiourea reducing substances; preferably, the inorganic salt reducing substance comprises one or more of sulfite, hypochlorite and transition metal salt; preferably, the aldehyde reducing substance comprises one or more of substituted or unsubstituted alkyl aldehydes; preferably, the alcohol reducing substance comprises one or more of substituted or unsubstituted alkyl alcohols; preferably, the amine reducing substance comprises one or more of substituted or unsubstituted alkylamine, substituted or unsubstituted aromatic amine; preferably, the phenolic reducing substance comprises one or more of substituted or unsubstituted phenol; preferably, the imidazole reducing substance comprises 2-methylimidazole and/or 1-acetylimidazole; preferably, the thiourea-based reducing substance comprises thiourea and/or tetramethylthiourea.
Further, ligand compounds include compounds containing one or more of N, P, S and O; preferably, the ligand compound includes one or more of triphenylphosphine, tetramethylthiourea, N-acrylylthiourea, N-benzoylthiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, diphenylthiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetrakis [ (2-pyridyl) methyl ] ethylenediamine.
Further, the vanadium complex curing accelerator also comprises an organic solvent, preferably the organic solvent comprises one or more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, triisooctyl phosphate and diisooctyl phosphate; preferably, the vanadium complex curing accelerator further comprises a pH regulator, more preferably the pH regulator comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and further preferably the pH of the vanadium complex curing accelerator is 0-5.
Further, the acrylate monomers comprise a first acrylate monomer and a second acrylate monomer, the first acrylate monomer and the second acrylate monomer are the same or different, the toughening agent comprises a first toughening agent and a second toughening agent, and the first toughening agent and the second toughening agent are the same or different; the acrylate structural adhesive comprises a component A and a component B, wherein the component A comprises 0-75 parts by weight of a first acrylate monomer, 4-10 parts by weight of an oxidant and 13-35 parts by weight of a first toughening agent, the component B comprises 35-75 parts by weight of a second acrylate monomer, 1-6 parts by weight of a reducing agent, 1-6 parts by weight of a vanadium complex curing accelerator, 13-35 parts by weight of a second toughening agent and 2-7 parts by weight of an adhesion promoter, and the weight ratio of the component A to the component B is 1-10: 1.
Further, the first acrylate monomer and the second acrylate monomer each independently include hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkoxylated nonylphenol acrylate, 3,3, 3-trimethylcyclohexane acrylate, cyclotrimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, stearic acid acrylate, isodecyl acrylate, lauric acid methacrylate, isobornyl acrylate, methoxypolyethylene glycol methacrylate, cyclohexanedimethanol diacrylate, 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, tripropylene glycol diacrylate, triethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate, one or more of polyethylene glycol dimethacrylate and 1, 3 butanediol dimethacrylate;
preferably, the first toughening agent and the second toughening agent each independently comprise one or more of a block copolymer, core shell particles, neoprene, nitrile rubber, carboxylated nitrile rubber, chlorosulfonated polyethylene, C5 petroleum resin, C5 modified C9 petroleum resin, C9 petroleum resin; preferably, the block copolymer comprises one or more of polystyrene-b-butadiene-b- (methyl methacrylate) block copolymer, poly (methyl methacrylate) -b-poly (n-butyl acrylate) -b-poly (methyl methacrylate), MBS resin, ABS resin, SBS resin and SEBS resin; preferably, the core-shell particles are one or more of butyl acrylate/polymethyl methacrylate core-shell particles, styrene butadiene rubber/poly (methyl methacrylate-acrylonitrile) copolymer core-shell particles and butadiene rubber/poly (methyl methacrylate-glycidyl methacrylate) copolymer core-shell particles;
preferably, the oxidizing agent is a peroxide, and more preferably the peroxide may include benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di (t-butylperoxy) diisopropylbenzene, 1-di (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1-di (t-butylperoxy) cyclohexane, ethyl-3, 3-di (t-butylperoxy) butyrate, diisopropyl-peroxydicarbonate carbonate, tert-butyl-peroxyneodecanoate, tert-amyl-peroxyneodecanoate, tert-butyl-monoperoxy maleate, tert-butyl-peroxybenzoate, tert-butyl-peroxy2-ethylhexanoate, tert-amyl peroxy2-ethylhexanoate, or the like, Monoisopropyl-mono-tert-butyl-peroxycarbonate, dicyclohexyl-peroxycarbonate, dimyristyl-peroxycarbonate, dicetyl-peroxycarbonate, di (2-ethylhexyl) -peroxycarbonate, tert-butyl-peroxy- (2-ethylhexyl) carbonate or tert-butyl-peroxy3, 5, 5-trimethylhexanoate, one or more of benzoic acid-tert-amyl-peroxyester, acetic acid-tert-butyl-peroxyester, carbonic acid-di (4-tert-butyl-cyclohexyl) -peroxyester, neodecanoic acid-cumene-peroxyester, pivalic acid-tert-amyl-peroxyester and pivalic acid-tert-butyl-peroxyester;
preferably, the reducing agent comprises one or more of tetramethyl thiourea, N-acrylyl thiourea, N-benzoyl thiourea, 1-allyl-2 thiourea, 1-allyl-3- (2-hydroxyethyl) -2 thiourea, diphenyl thiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetra [ (2-pyridyl) methyl ] ethylenediamine;
preferably, the adhesion promoter is one or more of itaconic anhydride, 4' -oxydiphthalic anhydride and bisphenol-A-dititanic anhydride.
Further, the component A and the component B respectively comprise 8-25 parts by weight of solubilizing monomer, 5-15 parts by weight of oligomer and 0.5-5 parts by weight of stabilizer; preferably, the solubilizing monomer is acryloyl morpholine; preferably, the oligomer comprises one or more of aliphatic polyurethane acrylate oligomer, aromatic polyurethane acrylate oligomer, polyester acrylate oligomer and epoxy oligomer; preferably, the stabilizer comprises one or more of 2, 6-di-tert-butyl-p-cresol, 2,6, 6-tetramethylpiperidine oxide, an antioxidant TH-1790, 4-hydroxypiperidinol oxyl, hydroquinone and p-benzoquinone.
Further, the component A also comprises 4-10 parts of filler in parts by weight; the preferable filler is one or more of montmorillonite, ceramic microsphere, diatomite, attapulgite and white carbon black.
Further, the component B also comprises 2-7 parts by weight of a coupling agent.
Further, the coupling agent comprises one or more of bis- (3-triethoxysilylpropyl) amine, bis- (3-trimethoxysilylpropyl) amine, 3-aminopropylmethyldiethoxysilane, triamino-functional propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
The invention provides an acrylate structural adhesive which comprises an acrylate monomer, an oxidant, a toughening agent, a reducing agent, a vanadium complex curing accelerator and an adhesion promoter, wherein the vanadium complex curing accelerator comprises a compound with a structure shown in a formula I and/or a formula II. In the vanadium complex curing accelerator, vanadium element in the compound with the structure shown in the formula I and/or the formula II shows positive quadrivalence and positive tervalence, has better solubility compared with vanadium with positive pentavalence, and can be dissolved in an organic solvent to form a liquid vanadium complex curing accelerator. Meanwhile, the vanadium element is connected with the ligand compound in a coordination bond form, so that the stability of the compound can be effectively improved, and the redox reaction of the vanadium under the influence of an external environment can be effectively avoided. Based on the reasons, the vanadium complex curing accelerator has good solubility and stability, effectively improves the stability of the acrylate structural adhesive, and has good accelerating effect on the rapid curing of acrylate monomers. In addition, the vanadium complex curing accelerator is used, and the toughening agent and the adhesion promoter are matched, so that the acrylate structural adhesive provided by the invention has good bonding strength, and the structural adhesive has the characteristic of low odor because a low-boiling-point substance is not adopted.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
As described in the background section, the acrylate structural adhesive in the prior art has the problems of poor structural adhesive stability and low bonding strength because the vanadium ion promoter is in a solid state.
In order to solve the problems, the invention provides an acrylate structural adhesive, which is characterized by comprising an acrylate monomer, an oxidant, a toughening agent, a reducing agent, a vanadium complex curing accelerator and an adhesion promoter, wherein the vanadium complex curing accelerator comprises a compound with a structure shown in a formula I and/or a formula II:
G∶V(R1)nformula I
G∶(VO)(R2)mFormula II
G is a ligand compound and represents a coordination bond, wherein in the formula I, n is an integer of 1-3, and V shows positive trivalent and is connected with n R through an ionic bond and/or a covalent bond1Connecting; in the formula II, m is 1 or 2, V shows positive quadrivalence and is bonded through an ionic bondAnd/or covalent bonds to m R2Connecting; wherein n R1Each independently comprises an anion or electron-withdrawing group, m R in the product formed by oxidation of the reducing substance2The reducing substances respectively and independently comprise anions or electron-withdrawing groups in products formed after the reducing substances are oxidized, and the reducing substances can perform oxidation-reduction reaction with the vanadium with the positive pentavalent state.
In the vanadium complex curing accelerator, vanadium element in the compound with the structure shown in the formula I and/or the formula II shows positive quadrivalence and positive tervalence, has better solubility compared with vanadium with positive pentavalence, and can be dissolved in an organic solvent to form a liquid vanadium complex curing accelerator. Meanwhile, the vanadium element is connected with the ligand compound in a coordination bond form, so that the stability of the compound can be effectively improved, and the redox reaction of the vanadium under the influence of an external environment can be effectively avoided. Based on the reasons, the vanadium complex curing accelerator has good solubility and stability, effectively improves the stability of the acrylate structural adhesive, and has good accelerating effect on the rapid curing of acrylate monomers. In addition, the vanadium complex curing accelerator is used, and the toughening agent and the adhesion promoter are matched, so that the acrylate structural adhesive provided by the invention has good bonding strength, and the structural adhesive has the characteristic of low odor because a low-boiling-point substance is not adopted.
It should be noted here that, before the acrylate structural adhesive is used, the oxidizing agent and the reducing agent are separately placed, the oxidizing agent and the vanadium complex curing accelerator are also separately placed, and the other components are mixed and placed, for example, the oxidizing agent and the acrylate monomer may be mixed as one component, the remaining components may be mixed as one component, and all the components may be mixed and then coated and cured when in use.
In addition, when an electron-withdrawing group is bonded to V, V exhibits positive electrification due to the strong electron-withdrawing property of the electron-withdrawing group, and therefore R is not always present1Whether V is linked to V by an ionic or covalent bond is understood to mean that V exhibits a positive trivalent state. From this it can be understoodN of the formula I1The total valence of (a) is-3, n is an integer of 1-3, and n R1May be the same or different, and may be, for example, three of the same or different-1-valent anions or-1-valent electron-withdrawing groups, or a mixture thereof, and may be a-3-valent anion or-3-valent electron-withdrawing group, or may be a-1-valent anion (or-1-valent electron-withdrawing group) and 1-2-valent anion (or-2-valent electron-withdrawing group). When the group connected to VO is an electron-withdrawing group, the VO exhibits positive charge due to the strong electron-withdrawing property of the electron-withdrawing group, so that R is not only a positive charge but also a negative charge2Whether it is linked to VO by an ionic bond or a covalent bond is understood that VO exhibits a positive divalent state and V in VO exhibits a positive tetravalent state. It can be understood that in formula II, m R are2Has a total valence of-2, and m is 1 or 2 (in this case R2The valence Y of (a) varies) such as one-2-valent anion or-2-valent electron withdrawing group, or two identical or different-1-valent anions or-1-valent electron withdrawing groups, or a mixture thereof. As will be appreciated by those skilled in the art.
The reducing substance of the present invention may be any substance that can undergo an oxidation-reduction reaction with vanadium having a positive pentavalent state. In a preferred embodiment, the reducing substance includes, but is not limited to, one or more of inorganic salt reducing substances, aldehyde reducing substances, alcohol reducing substances, amine reducing substances, phenol reducing substances, imidazole reducing substances, and thiourea reducing substances.
Preferably, the inorganic salt reducing substance includes, but is not limited to, one or more of sulfite, hypochlorite and transition metal salt.
Preferably, the aldehyde reducing substance includes, but is not limited to, one or more of substituted or unsubstituted alkyl aldehydes. The substituent of the substituted alkyl aldehyde can be one or more of halogen, phenyl, sulfydryl, sulfonic group, carbonyl and hydroxyl.
Preferably, the alcohol reducing substance includes, but is not limited to, one or more of substituted or unsubstituted alkyl alcohols. The substituent of the substituted alkyl alcohol can be one or more of halogen, phenyl, sulfydryl, sulfonic group, amino, isocyanate and carbonyl.
Preferably, the amine-type reducing substance includes, but is not limited to, one or more of substituted or unsubstituted aromatic amine, substituted or unsubstituted alkylamine. The substituent of the substituted alkylamine or substituted aromatic amine can be one or more of halogen, phenyl, sulfydryl, sulfonic group and carbonyl.
Preferably, the phenolic reducing species include, but are not limited to, one or more of substituted or unsubstituted phenols. The substituent of the substituted phenol can be one or more of halogen, alkyl, keto and amino.
The alkyl group in the above alkyl aldehyde, alkyl alcohol or alkyl amine may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group.
In a preferred embodiment, the sulfite includes, but is not limited to, one or more of sodium sulfite, potassium sulfite, ammonium sulfite, hypochlorite includes, but is not limited to, one or more of sodium hypochlorite, potassium hypochlorite, ammonium hypochlorite, transition metal salts include, but is not limited to, one or more of cuprous chloride, cuprous sulfate, cuprous nitrate, ferrous sulfate, ferrous chloride; the substituted or non-substituted alkyl aldehyde reducing substance at least contains 1 aldehyde group, preferably an alkyl aldehyde reducing substance with the carbon atom number less than or equal to 12, and further preferably one or more of acetaldehyde, propionaldehyde, malonaldehyde, butyraldehyde, succinaldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, glucose, benzaldehyde, phenylacetaldehyde, tolualdehyde and methylacetaldehyde; preferably, the alkyl alcohol reducing substance contains at least one hydroxyl group, preferably an alkyl alcohol reducing substance with less than or equal to 12 carbon atoms, preferably one or more of butanol, isobutanol, butanediol, pentanol, isopentyl glycol, isoamyl alcohol, octanol, isooctanol, benzyl alcohol and dichlorobutanol; preferably, the amine reducing substance contains at least one amine group, preferably aniline and/or butylamine; preferably, the phenolic reducing substance comprises phenol and/or p-tert-butylphenol; preferably, the imidazole reducing substance comprises 2-methylimidazole and/or 1-acetylimidazole; preferably, the thiourea-based reducing substance comprises thiourea and/or tetramethylthiourea.
By the action of the reducing substance, the vanadium with the valence of five in the solid vanadium source can be more easily reduced into the vanadium with the valence of four or three, so that the vanadium can be dissolved in the organic solvent. The corresponding anion after the reduction substance is oxidized can be acid radical ion, alkoxy, imidazole, urea and piperidine electron-withdrawing groups generated after oxidation.
Illustratively, different types of reducing species may undergo one of the following reactions:
the oxidation of the valence-variable metal is from a low valence state to a high valence state, such as cuprous ion to cupric ion, ferrous ion to ferric ion, active metal to high valence metal ion, and the reducing agent corresponds to the above-mentioned R1And R2Anions which are oxidation products thereof, such as: after cuprous chloride is oxidized to cupric chloride, R1And R2Is chloride ion; the anion containing the valency-changing element is oxidized to a higher anion, e.g. sulfurous acid to sulfuric acid, hypochlorous acid to chloric acid, when R is as defined above1And R2Is sulfate or chloride; oxidation of aldehydes to form acids, e.g. acetaldehyde to form acetic acid, in which case R is as defined above1And R2Are the corresponding electron withdrawing groups; oxidation of the alcohol to form a ketone or aldehyde or acid, in which case R is as defined above1And R2Are the corresponding electron withdrawing groups; the phenols are oxidized to form quinones.
In particular, R in the case where the aldehyde reducing substance, the alcohol reducing substance, the amine reducing substance, the phenol reducing substance, the imidazole reducing substance, and the thiourea reducing substance are oxidized and contain a lone pair of N or O1And R2Can also be used as a ligand compound, which is beneficial to further improving the stability of the vanadium complex curing accelerator.
The ligand compound may carry a lone pair of electrons and may be bonded to a V coordinate bond. In a preferred embodiment, the ligand compound comprises a compound comprising one or more of N, P, S and O; preferably one or more of triphenylphosphine, tetramethylthiourea, N-acrylylthiourea, N-benzoylthiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, diphenylthiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetrakis [ (2-pyridyl) methyl ] ethylenediamine. Compared with other ligand compounds, the ligand compound is more favorable for improving the stability and the solubility of the vanadium complex curing accelerator, and the ligand compound and the acrylate monomer have better compatibility, so that the use performance of the acrylate structural adhesive is more favorable for improving.
It should be noted that some compounds such as tetramethylthiourea can be used as both the complex and the reducing substance to perform the oxidation-reduction reaction with the pentavalent vanadium, and both do not conflict with each other.
In a preferred embodiment, the vanadium complex cure accelerator further comprises an organic solvent, preferably the organic solvent comprises one or more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, triisooctyl phosphate, and diisooctyl phosphate. The compound with the structure shown in the formula I and/or the formula II is dissolved in an organic solvent to form a liquid vanadium complex curing accelerator, and then the liquid vanadium complex curing accelerator is mixed with other components, so that the formed acrylate structural adhesive has better stability.
Preferably, the vanadium complex curing accelerator further comprises a pH regulator, more preferably the pH regulator comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and further preferably the pH of the vanadium complex curing accelerator is 0-5. In the above pH regulator, P, N, O in phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, for example, will also carry lone pair electrons, and can also play a role as a ligand compound in the actual accelerator, thereby being more beneficial to improving the stability of the accelerator and further improving the stability of the structural adhesive.
In a preferred embodiment, the raw materials for preparing the vanadium complex curing accelerator comprise, by weight, 2 to 8 parts of a vanadium source, 35 to 65 parts of an organic solvent, 3 to 10 parts of a reducing substance, and 2 to 10 parts of a ligand compound. The pentavalent vanadium in the vanadium source can be reduced into trivalent positive or tetravalent positive by utilizing the reducing substance, so that the pentavalent vanadium can be dissolved in the organic solvent. The reduced vanadium can be connected with anions in a product obtained by oxidation reaction of a reducing agent through an ionic bond, and can also be connected with electron-withdrawing groups in a product obtained by oxidation reaction of a reducing substance through a covalent bond. The ligand compound can form a coordinate bond with the vanadium element to form the vanadium complex represented by the above formula I and/or II. Based on the reasons, the vanadium complex curing accelerator provided by the invention has good solubility and stability when being applied to an acrylic adhesive, and can effectively improve the curing effect of a structural adhesive and improve the curing speed and the comprehensive performance of a cured coating.
The vanadium source may be any vanadium compound containing vanadium pentavalent. In a preferred embodiment, the vanadium source comprises one or more of sodium metavanadate, vanadium pentoxide, potassium metavanadate, sodium orthovanadate, potassium orthovanadate, sodium pyrovanadate and potassium pyrovanadate.
Preferably, the reducing substance includes one or more of an inorganic salt reducing agent, an aldehyde reducing agent, an alcohol reducing agent, an amine reducing agent, a phenol reducing agent, an imidazole reducing agent, and a thiourea reducing agent. Compared with other reducing substances, the reducing effects of the reducing substances are better. In particular, R in the case where the aldehyde reducing agent, the alcohol reducing agent, the amine reducing agent, the phenol reducing agent, the imidazole reducing agent and the thiourea reducing agent are oxidized and contain a lone pair of N or O1And R2And the vanadium complex curing accelerator can also be used as a ligand compound, so that the stability of the vanadium complex curing accelerator is further improved, and the stability of the structural adhesive is further improved.
Preferably, the ligand compound includes one or more of triphenylphosphine, tetramethylthiourea, N-acrylylthiourea, N-benzoylthiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, diphenylthiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetrakis [ (2-pyridyl) methyl ] ethylenediamine; preferably, the organic solvent comprises one or more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, triisooctyl phosphate and diisooctyl phosphate. Preferably, the inorganic salt type reducing agent includes, but is not limited to, one or more of sulfite, hypochlorite and transition metal salt. Preferably, the aldehyde reducing agent includes, but is not limited to, one or more of substituted or unsubstituted alkyl aldehydes. The substituent of the substituted alkyl aldehyde can be one or more of halogen, phenyl, sulfydryl, sulfonic group, carbonyl and hydroxyl. Preferably, the alcoholic reducing agent includes, but is not limited to, one or more of a substituted or unsubstituted alkyl alcohol. The substituent of the substituted alkyl alcohol can be one or more of halogen, phenyl, sulfydryl, sulfonic group, amino, isocyanate and carbonyl. Preferably, the amine-based reducing agent includes, but is not limited to, one or more of substituted or unsubstituted aromatic amine, substituted or unsubstituted alkylamine. The substituent of the substituted alkylamine or substituted aromatic amine can be one or more of halogen, phenyl, sulfydryl, sulfonic group and carbonyl. Preferably, the phenolic reducing agent includes, but is not limited to, one or more of substituted or unsubstituted phenols. The substituent of the substituted phenol can be one or more of halogen, alkyl, keto and amino.
The alkyl group in the above alkyl aldehyde, alkyl alcohol or alkyl amine may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group.
In a preferred embodiment, the sulfite includes, but is not limited to, one or more of sodium sulfite, potassium sulfite, ammonium sulfite, hypochlorite includes, but is not limited to, one or more of sodium hypochlorite, potassium hypochlorite, ammonium hypochlorite, transition metal salts include, but is not limited to, one or more of cuprous chloride, cuprous sulfate, cuprous nitrate, ferrous sulfate, ferrous chloride; the substituted or unsubstituted alkyl aldehyde reducing agent at least contains 1 aldehyde group, preferably an alkyl aldehyde reducing agent with the carbon atom number less than or equal to 12, and further preferably one or more of acetaldehyde, propionaldehyde, malonaldehyde, butyraldehyde, succinaldehyde, isobutyraldehyde, valeraldehyde, isovaleraldehyde, glucose, benzaldehyde, phenylacetaldehyde, tolualdehyde and methylphenaldehyde; preferably, the alkyl alcohol reducing agent contains at least one hydroxyl group, preferably an alkyl alcohol reducing agent with the carbon number less than or equal to 12, preferably one or more of butanol, isobutanol, butanediol, pentanol, isopentyl glycol, isoamyl alcohol, octanol, isooctanol, benzyl alcohol and dichlorobutanol; preferably, the amine-based reducing agent contains at least one amine group, preferably aniline and/or butylamine; preferably, the phenolic reducing agent comprises phenol and/or p-tert-butylphenol; preferably, the imidazole-based reducing agent comprises 2-methylimidazole and/or 1-acetylimidazole; preferably, the thiourea-based reducing agent comprises thiourea and/or tetramethylthiourea.
In order to further improve the stability of the vanadium complex accelerator and improve the reaction effect of the reducing agent and the vanadium source, in a preferred embodiment, the raw material of the vanadium complex curing accelerator further comprises 3-10 parts by weight of a pH regulator; preferably, the pH regulator comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid; more preferably, the raw material of the vanadium complex curing accelerator further comprises 30-60 parts of a cosolvent, and the cosolvent is water. The cosolvent is favorable for dissolving in the solid vanadium source organic solvent, and the reaction is promoted.
The preparation method of the vanadium complex accelerator can be as follows: reacting a vanadium source and a reducing substance in an organic solvent to form an intermediate product; and adding a ligand compound into the intermediate product for reaction to obtain the vanadium complex curing accelerator.
The reaction process of each step can be adjusted, and in a preferred embodiment, the step of reacting the vanadium source and the reducing substance in the organic solvent comprises the following steps: mixing a vanadium source, a reducing substance and an organic solvent, and simultaneously adding a pH regulator into the mixture to form a mixture; and reacting the mixture at the temperature of 90-110 ℃ for 1-3h to obtain an intermediate product. This is advantageous in that the reaction between vanadium and the reduced matter proceeds more sufficiently to dissolve it in the organic solvent more sufficiently.
Preferably, after the step of reacting the mixture at the temperature of 90-110 ℃ for 1-3h, the preparation method further comprises the step of adding a cosolvent into a reaction system of the mixture for further reaction for 0.5-1.5h to obtain an intermediate product, wherein the cosolvent is water.
In a preferred embodiment, after the step of adding the ligand compound to the intermediate product to carry out the reaction, the production method further comprises a step of purifying the reaction system, the purification step comprising: carrying out water-oil separation on a reaction system after adding a ligand compound for reaction to obtain an organic phase; and (4) carrying out water removal treatment on the organic phase to obtain the vanadium complex curing accelerator. The water in the vanadium complex curing accelerator can be removed through purification treatment, and a more stable accelerator system is obtained.
As described above, the above acrylate structural adhesive is used before the oxidizing agent and the reducing agent are separately placed, the oxidizing agent and the vanadium complex curing accelerator are also separately placed, and the other components are mixed and placed, for example, the oxidizing agent and the acrylate monomer can be mixed as one component, the remaining components can be mixed as one component, and all the components can be mixed and then coated and cured when in use. In a preferred embodiment, the acrylate monomers include a first acrylate monomer and a second acrylate monomer, the first acrylate monomer and the second acrylate monomer are the same or different, the toughening agent includes a first toughening agent and a second toughening agent, the first toughening agent and the second toughening agent are the same or different; the acrylate structural adhesive comprises a component A and a component B, wherein the component A comprises 35-75 parts by weight of a first acrylate monomer, 4-10 parts by weight of an oxidant and 13-35 parts by weight of a first toughening agent, the component B comprises 0-75 parts by weight of a second acrylate monomer, 1-6 parts by weight of a reducing agent, 1-6 parts by weight of a vanadium complex curing accelerator, 2-7 parts by weight of an adhesion promoter and 13-35 parts by weight of a second toughening agent, and the weight ratio of the component A to the component B is 1: 1-10: 1.
The structural adhesive component is divided into a component A and a component B so as to separate an oxidizing agent, a reducing agent and a curing accelerator. The acrylic monomer and the toughening agent are divided into two parts and placed in the component A and the component B, so that the components can be better mixed to form two components with more suitable viscosity, fluidity and stability, the mixed liquid of the two components is easier and the mixing and dispersing effects of different components are better when the structural adhesive is used, and the use performance of the structural adhesive can be improved. And the dosage relation of each component is controlled in the range, so that the physical and chemical properties of the structural adhesive can be further improved, such as the viscosity, the fluidity and the curing speed are more matched, the dispersibility of each component is better through a coupling agent and the like, the adhesive strength of the adhesive layer after the structural adhesive is cured is higher, and the like.
In the above acrylate structural adhesive, the acrylate monomer may be of a type commonly used in the art. To further improve the overall performance of the structural adhesive, in a preferred embodiment, the first acrylate monomer and the second acrylate monomer each independently comprise hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkoxylated nonylphenol acrylate, 3,3, 3-trimethylcyclohexane acrylate, cyclotrimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, stearic acid acrylate, isodecyl acrylate, lauric acid methacrylate, isobornyl acrylate, methoxypolyethylene glycol methacrylate, cyclohexanedimethanol diacrylate, 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, poly (ethylene glycol) acrylate, One or more of tripropylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and 1 and 3-butanediol dimethacrylate. The acrylate monomers have the advantages of high boiling point and good adhesive property, and the structural adhesive formed by matching the vanadium complex curing accelerator has the advantages of lower odor, higher curing speed and better adhesive property.
In a preferred embodiment, the first toughening agent and the second toughening agent each independently comprise one or more of a block copolymer, core shell particles, neoprene, nitrile rubber, carboxylated nitrile rubber, chlorosulfonated polyethylene, C5 petroleum resin, C5 modified C9 petroleum resin, C9 petroleum resin; preferably, the block copolymer comprises one or more of polystyrene-b-butadiene-b- (methyl methacrylate) block copolymer, poly (methyl methacrylate) -b-poly (n-butyl acrylate) -b-poly (methyl methacrylate), MBS resin, ABS resin, SBS resin and SEBS resin; preferably, the core-shell particles are one or more of butyl acrylate/polymethyl methacrylate core-shell particles, styrene butadiene rubber/poly (methyl methacrylate-acrylonitrile) copolymer core-shell particles, and butadiene rubber/poly (methyl methacrylate-glycidyl methacrylate) copolymer core-shell particles. The toughening agents and other components in the structural adhesive have better mixing performance, and the toughening effect is better, so that the bonding performance of the structural adhesive is further improved.
The oxidizing agent and the reducing agent may be those conventionally used in the art. To further enhance the curing and bonding effects of the structural adhesive, in a preferred embodiment, the oxidizing agent is a peroxide, more preferably a peroxide including, but not limited to, benzoyl peroxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, di (t-butylperoxy) diisopropylbenzene, 1-di (t-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1-di (t-butylperoxy) cyclohexane, ethyl-3, 3-di (t-butylperoxy) butyrate, diisopropyl-peroxydiester carbonate, neodecanoic acid-t-butyl-peroxyester, neodecanoic acid-t-amyl-peroxyester, maleic acid-t-butyl-monoperoxyester, benzoic acid-t-butyl-peroxyester, and mixtures thereof, 2-ethylhexanoic acid-tert-butyl-peroxyester, 2-ethylhexanoic acid-tert-amyl-peroxyester, monoisopropyl-mono-tert-butyl-peroxyester carbonate, dicyclohexyl-peroxyester carbonate, dimyristyl-peroxyester carbonate, dicetyl-peroxyester carbonate, di (2-ethylhexyl) -peroxyester carbonate, tert-butyl-peroxy- (2-ethylhexyl) carbonate or 3,5, 5-trimethylhexanoic acid-tert-butyl-peroxyester, benzoic acid-tert-amyl-peroxyester, acetic acid-tert-butyl-peroxyester, di (4-tert-butyl-cyclohexyl) -peroxyester carbonate, neodecanoic acid-cumene-peroxyester, 2-ethylhexanoic acid-tert-amyl-peroxyester, di (2-ethylhexyl) -peroxyester carbonate, di (4-tert-butyl-cyclohexyl, One or more of pivalic acid-tert-amyl-peroxyester and pivalic acid-tert-butyl-peroxyester. Preferably, the reducing agent comprises one or more of tetramethyl thiourea, N-acrylyl thiourea, N-benzoyl thiourea, 1-allyl-2 thiourea, 1-allyl-3- (2-hydroxyethyl) -2 thiourea, diphenyl thiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetra [ (2-pyridyl) methyl ] ethylenediamine.
Preferably, the adhesion promoter is one or more of itaconic anhydride, 4' -oxydiphthalic anhydride and bisphenol-A-dititanic anhydride, and the addition of the adhesion promoter is beneficial to further improving the bonding strength of the adhesive to various base materials.
In order to further improve the bonding property, the stability and the coating property of the structural adhesive, in a preferred embodiment, the component A and the component B respectively comprise 8-25 parts by weight of solubilizing monomer, 5-15 parts by weight of oligomer and 0.5-5 parts by weight of stabilizer. Preferably, the solubilizing monomer is acryloyl morpholine; preferably, the oligomer comprises one or more of aliphatic polyurethane acrylate oligomer, aromatic polyurethane acrylate oligomer, polyester acrylate oligomer and epoxy oligomer; preferably, the stabilizer comprises one or more of 2, 6-di-tert-butyl-p-cresol, 2,6, 6-tetramethylpiperidine oxide, an antioxidant TH-1790, 4-hydroxypiperidinol oxyl, hydroquinone and p-benzoquinone.
In a preferred embodiment, the component A further comprises 4-10 parts by weight of filler; the preferable filler is one or more of montmorillonite, ceramic microsphere, diatomite, attapulgite and fumed silica. The addition of the filler is also beneficial to improving the mechanical property of the adhesive layer after the structural adhesive is cured.
In order to further improve the bonding strength of the structural adhesive, in a preferred embodiment, the component B also comprises 1-5 parts of a coupling agent, and the preferred coupling agent comprises one or more of bis- (3-triethoxysilylpropyl) amine, bis- (3-trimethoxysilylpropyl) amine, 3-aminopropylmethyldiethoxysilane, triamino-functionalized propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane. By using the coupling agent, the compatibility among the components is better, and the stability of the structural adhesive is better.
The invention also provides a method for preparing the acrylate structural adhesive, which is specifically to mix the components according to the formula of the component A and the formula of the component B to prepare the component A and the component B, and then mix the component A and the component B during sizing. The method specifically comprises the following steps:
preparation of component A: putting a first acrylate monomer, an optional solubilizing monomer, an optional oligomer and a first toughening agent into a reaction kettle, and stirring until the first toughening agent is completely dissolved; adding an oxidant, an optional stabilizer and an optional filler into the reaction kettle, stirring for 1-3 hours until the components are uniformly mixed, and removing bubbles in vacuum to obtain a component A;
preparation of the component B: putting a second acrylate monomer, an optional solubilizing monomer, an optional oligomer and a second toughening agent into a reaction kettle, and stirring until the second toughening agent is completely dissolved; then adding a reducing agent and an optional stabilizing agent into the reaction kettle, and stirring for 1-2 hours until the mixture is uniformly mixed; sequentially adding an adhesion promoter, an optional coupling agent and a vanadium complex curing promoter, stirring for 1-3h until the mixture is uniformly mixed, and removing bubbles in vacuum to obtain a component B;
mixing the component A and the component B according to a volume ratio of 1:1, proportioning and sizing.
The beneficial effects of the present invention are further illustrated by the following examples:
< preparation of curing Accelerator for vanadium Complex >
Example 1
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Pentaoxide(s)Vanadium di (II) | 2 |
| Phosphoric acid tributyl ester | 35 |
| Isooctyl alcohol | 6 |
| Tetramethyl thiourea | 8 |
| Water (W) | 40 |
| Hydrochloric acid | 9 |
The preparation process comprises the following steps:
adding vanadium pentoxide, tributyl phosphate, isooctyl alcohol and hydrochloric acid into a four-neck flask, stirring and heating to 90 ℃ for reaction for 1h, adding water for continuous reaction for 1.5h until solid substances in the system are completely dissolved, adding tetramethyl thiourea, and continuously reacting for 1 h. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 2
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
the preparation process comprises the following steps:
adding sodium metavanadate, diisooctyl phosphate, sodium sulfite and phosphoric acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 3 hours, adding water for continuous reaction for 1.5 hours until solid substances in the system are completely dissolved, adding N, N-dimethylbenzylamine, and continuously reacting for 2 hours. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 3
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Vanadium pentoxide | 4 |
| Dibutyl phthalate | 40 |
| Cuprous chloride | 8 |
| 2-methylimidazole | 10 |
| Water (W) | 33 |
| Acetic acid | 5 |
The preparation process comprises the following steps:
adding vanadium pentoxide, dibutyl phthalate, cuprous chloride and acetic acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 3h, adding water for continuous reaction for 0.5h until solid substances in the system are completely dissolved, adding 2-methylimidazole, and continuously reacting for 2 h. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 4
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
the preparation process comprises the following steps:
adding sodium n-vanadate, dioctyl phthalate, butyraldehyde and oxalic acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 2 hours, adding water for continuous reaction for 1.5 hours until solid matters in the system are completely dissolved, adding 1-acetylpiperidine, and continuously reacting for 2 hours. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 5
The liquid vanadium accelerant comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Sodium pyrovanadate | 6 |
| Phosphoric acid trioctyl ester | 50 |
| Tetramethyl thiourea | 6 |
| N, N, N ', N' -tetramethyl-1, 6-hexanediamine | 5 |
| Water (W) | 30 |
| Citric acid | 3 |
The preparation process comprises the following steps:
adding sodium pyrovanadate, trioctyl phosphate, tetramethylthiourea and citric acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 1h, adding water for continuous reaction for 1.5h until solid substances in the system are completely dissolved, adding N, N, N ', N' -tetramethyl-1, 6-hexanediamine, and continuously reacting for 2 h. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 6
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Potassium orthovanadate | 4 |
| Phosphoric acid diisooctyl ester | 40 |
| 2-methylimidazole | 8 |
| Triphenylphosphine | 10 |
| Water (W) | 33 |
| Formic acid | 5 |
The preparation process comprises the following steps:
adding potassium orthovanadate, diisooctyl phosphate, 2-methylimidazole and formic acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 3 hours, adding water for continuous reaction for 0.5 hour until solid substances in the system are completely dissolved, adding triphenylphosphine, and continuously reacting for 2 hours. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 7
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Potassium metavanadate | 4 |
| Phosphoric acid trioctyl ester | 40 |
| 1, 6-hexanediamine | 8 |
| 1-benzoyl-4-piperidones | 10 |
| Water (W) | 33 |
| Nitric acid | 5 |
The preparation process comprises the following steps:
adding potassium metavanadate, trioctyl phosphate, 1, 6-hexanediamine and nitric acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 1-3h, adding water for continuous reaction for 0.5-1.5h until solid substances in the system are completely dissolved, adding 1-benzoyl-4-piperidone, and continuously reacting for 1-2 h. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 8
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Potassium metavanadate | 6 |
| Phosphoric acid dioctyl ester | 50 |
| P-tert-butylphenol | 6 |
| Tetramethyl thiourea | 5 |
| Water (W) | 30 |
| Sulfuric acid | 3 |
The preparation process comprises the following steps:
adding potassium metavanadate, dioctyl phosphate, p-tert-butylphenol and sulfuric acid into a four-neck flask, stirring and heating to 90-110 ℃ for reaction for 1-3h, adding water for continuous reaction for 0.5-1.5h until solid substances in the system are completely dissolved, adding tetramethyl thiourea, and continuously reacting for 1-2 h. And cooling to room temperature, and layering the system, wherein the upper layer is an organic solvent layer, and the lower layer is a cosolvent layer. And (3) taking the upper organic solvent, adding anhydrous sodium sulfate to remove water, and filtering to obtain the vanadium complex curing accelerator.
Example 9
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
| raw materials | Mass fraction |
| Vanadium pentoxide | 8 |
| Phosphoric acid tributyl ester | 47 |
| Isooctyl alcohol | 10 |
| Tetramethyl thiourea | 2 |
| Water (W) | 30 |
| Hydrochloric acid | 3 |
The preparation process is the same as in example 1.
Example 10
The curing accelerator for the vanadium complex comprises the following components in parts by weight:
the preparation process is the same as in example 1.
Comparative example 1
Commercial vanadium acetylacetonate solid vanadium promoters were used for comparison.
Comparative example 2
Comparison with No vanadium Accelerator
< preparation of acrylate structural adhesive >
Examples 20 to 30, comparative example 1, comparative example 2
Acrylate structural adhesives were prepared according to the same formulation and process in examples 20 to 30, comparative example 1 and comparative example 2, except that the curing accelerator was the vanadium complex curing accelerator prepared in examples 1 to 10 and the vanadium acetylacetonate solid vanadium accelerator in comparative example 1, respectively.
The acrylic structural adhesive has the following formula:
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
A. b, mixing the two components according to a volume ratio of 1:1 mixing evenly, adopting vanadium complex of different embodiments as vanadium accelerator in component B
A cure accelerator or the solid vanadium accelerator of the comparative example.
The preparation method of the structural adhesive comprises the following steps:
preparation of component A: putting a first acrylate monomer, an oligomer and a first toughening agent into a reaction kettle, and stirring until the first toughening agent is completely dissolved; adding an oxidant, a stabilizer and a filler into the reaction kettle, stirring for 3 hours until the components are uniformly mixed, and removing bubbles in vacuum to obtain a component A;
preparation of the component B: putting a second acrylate monomer, an oligomer and a second toughening agent into a reaction kettle, and stirring until the second toughening agent is completely dissolved; then adding a reducing agent and a stabilizing agent into the reaction kettle, and stirring for 2 hours until the reducing agent and the stabilizing agent are uniformly mixed; then adding a coupling agent and a vanadium complex curing accelerator in sequence, stirring for 1-3h until the materials are uniformly mixed, and removing bubbles in vacuum to obtain a component B;
mixing the component A and the component B according to a volume ratio of 1:1, mixing in proportion to obtain the structural adhesive.
The peel strength of the adhesive was tested according to GB/T2791-. The shear strength of the adhesive after curing at 30 ℃ for 10min and the storage stability of the adhesive at 80 ℃ were tested. Specific performance results are shown in table 1:
TABLE 1
The vanadium complex curing accelerator prepared in example 2 was used in each of examples 31 to 42, except that: the types or the use amounts of the components are different, and the specific formula is as follows:
example 31
The structural adhesive has the following formula:
the preparation process comprises the following steps:
preparation of component A: putting alkoxylated nonylphenol acrylate, hydroxyethyl methacrylate, cyclohexane dimethanol diacrylate, acryloyl morpholine, aliphatic polyurethane acrylate oligomer, nitrile rubber and C5 petroleum resin into a reaction kettle, and stirring until the functional resin is completely dissolved; adding cumene hydroperoxide, di (tert-butyl peroxide) diisopropylbenzene, 2, 6-di-tert-butyl-p-cresol, 4-hydroxypiperidinol oxygen free radical and montmorillonite into the reaction kettle, stirring for 1-3h until the mixture is uniformly mixed, and removing bubbles in vacuum to obtain a component A;
preparation of the component B: putting alkoxylated nonylphenol acrylate, hydroxyethyl methacrylate, cyclohexane dimethanol diacrylate, acryloyl morpholine, aliphatic polyurethane acrylate oligomer, nitrile rubber and C5 petroleum resin into a reaction kettle, and stirring until the functional resin is completely dissolved; adding N-benzoylthiourea, N-dimethylbenzylamine, 2, 6-di-tert-butyl-p-cresol and 4-hydroxypiperidinol oxyradical into the reaction kettle, and stirring for 1-2h until the materials are uniformly mixed; then sequentially adding itaconic anhydride, bis- (3-triethoxysilylpropyl) amine and the vanadium complex curing accelerator, stirring for 1-3h until the mixture is uniformly mixed, and removing bubbles in vacuum to obtain the component B.
Mixing the component A and the component B according to a volume ratio of 1:1, proportioning and sizing.
Example 32
The structural adhesive has the following formula:
the preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 33
The structural adhesive has the following formula:
the preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 34
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 35
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 36
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 37
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 38
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 39
The preparation process is the same as example 31, and the component A and the component B are mixed according to the volume ratio of 1:1, proportioning and sizing.
Example 40
The preparation process comprises the following steps:
preparation of component A: putting diisodecyl adipate, epoxy resin E51 and nitrile rubber into a reaction kettle, and stirring until the rubber is completely dissolved; adding cumene hydroperoxide, 2, 6-di-tert-butyl-p-cresol, 4-hydroxypiperidinol oxyradical and fumed silica into the reaction kettle, stirring for 1-3h until the mixture is uniformly mixed, and removing bubbles in vacuum to obtain a component A;
preparation of the component B: putting alkoxylated nonylphenol acrylate, hydroxyethyl methacrylate, cyclohexane dimethanol diacrylate, acryloyl morpholine, aliphatic polyurethane acrylate oligomer, nitrile rubber and C5 petroleum resin into a reaction kettle, and stirring until the functional resin is completely dissolved; adding N-benzoylthiourea, N-dimethylbenzylamine, 2, 6-di-tert-butyl-p-cresol and 4-hydroxypiperidinol oxyradical into the reaction kettle, and stirring for 1-2h until the materials are uniformly mixed; then sequentially adding itaconic anhydride, bis- (3-triethoxysilylpropyl) amine and the vanadium complex curing accelerator, stirring for 1-3h until the mixture is uniformly mixed, and removing bubbles in vacuum to obtain the component B.
Mixing the component A and the component B according to a volume ratio of 1: 10, proportioning and sizing.
EXAMPLE 41
The preparation process is the same as in example 38, and the component A and the component B are mixed according to the volume ratio of 1: 10, proportioning and sizing.
Example 42
The preparation process is the same as in example 38, and the component A and the component B are mixed according to the volume ratio of 1: 10, proportioning and sizing.
And (3) performance testing:
the peel strength of the adhesive was tested according to GB/T2791-. The shear strength of the adhesive after curing at 30 ℃ for 10min and the storage stability of the adhesive at 80 ℃ were tested. Specific performance results are shown in table 2:
TABLE 2
The data show that the vanadium complex curing accelerator in the structural adhesive provided by the invention has good solubility and stability, effectively improves the stability of the acrylate structural adhesive, and has good accelerating effect on the rapid curing of acrylate monomers. In addition, the vanadium complex curing accelerator is used, and the toughening agent and the coupling agent are matched, so that the acrylate structural adhesive provided by the invention also has good bonding strength, and the structural adhesive has the characteristic of low odor because a low-boiling-point substance is not adopted.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The acrylate structural adhesive is characterized by comprising an acrylate monomer, an oxidant, a flexibilizer, a reducing agent, a vanadium complex curing accelerator and an adhesion promoter, wherein the vanadium complex curing accelerator comprises a compound with a structure shown in a formula I and/or a formula II:
G∶V(R1)nformula I
G∶(VO)(R2)mFormula II
G is a ligand compound and represents a coordination bond, wherein in the formula I, n is an integer of 1-3, and V shows positive trivalent and is connected with n R through an ionic bond and/or a covalent bond1Connecting; in the formula II, m is 1 or 2, V shows positive quadrivalence and is connected with m R through ionic bond and/or covalent bond2Connecting; wherein n of said R1Each independently comprises an anion or electron-withdrawing group in the product formed by oxidizing the reducing substance, m of the R2The reducing substances are respectively and independently included in anions or electron-withdrawing groups in products formed after the reducing substances are oxidized, and the reducing substances can perform oxidation-reduction reaction with the vanadium with the positive pentavalent state.
2. The acrylate structural adhesive according to claim 1, wherein the reducing substance comprises one or more of an inorganic salt reducing substance, an aldehyde reducing substance, an alcohol reducing substance, an amine reducing substance, a phenol reducing substance, an imidazole reducing substance, and a thiourea reducing substance; preferably, the inorganic salt reducing substance comprises one or more of sulfite, hypochlorite and transition metal salt; preferably, the aldehyde reducing substance comprises one or more of substituted or unsubstituted alkyl aldehydes; preferably, the alcohol reducing substance comprises one or more of substituted or unsubstituted alkyl alcohols; preferably, the amine reducing substance comprises one or more of substituted or unsubstituted alkylamine, substituted or unsubstituted aromatic amine; preferably, the phenolic reducing substance comprises one or more of substituted or unsubstituted phenol; preferably, the imidazole reducing substance comprises 2-methylimidazole and/or 1-acetylimidazole; preferably, the thiourea-based reducing substance includes thiourea and/or tetramethylthiourea.
3. The acrylate structural adhesive of claim 1, wherein the ligand compound comprises a compound comprising one or more of N, P, S and O; preferably, the ligand compound includes one or more of triphenylphosphine, tetramethylthiourea, N-acrylylthiourea, N-benzoylthiourea, 1-allyl-2-thiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, diphenylthiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N' -tetramethyl-1, 6-hexanediamine, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetrakis [ (2-pyridyl) methyl ] ethylenediamine.
4. The acrylate structural adhesive according to any one of claims 1 to 3, wherein the vanadium complex cure accelerator further comprises an organic solvent, preferably the organic solvent comprises one or more of dibutyl phthalate, dioctyl phthalate, tributyl phosphate, trioctyl phosphate, triisooctyl phosphate and diisooctyl phosphate;
preferably, the vanadium complex curing accelerator further comprises a pH regulator, more preferably the pH regulator comprises one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, formic acid, acetic acid, oxalic acid and citric acid, and further preferably the pH of the vanadium complex curing accelerator is 0-5.
5. The acrylate structural adhesive according to any one of claims 1 to 4, wherein the acrylate monomer comprises a first acrylate monomer and a second acrylate monomer, the first acrylate monomer and the second acrylate monomer are the same or different, the toughening agent comprises a first toughening agent and a second toughening agent, the first toughening agent and the second toughening agent are the same or different;
the acrylate structural adhesive comprises a component A and a component B, wherein the component A comprises 35-75 parts by weight of a first acrylate monomer, 4-10 parts by weight of an oxidant and 13-35 parts by weight of a first toughening agent, the component B comprises 0-75 parts by weight of a second acrylate monomer, 1-6 parts by weight of a reducing agent, 1-6 parts by weight of a vanadium complex curing accelerator, 13-35 parts by weight of a second toughening agent and 2-7 parts by weight of an adhesion promoter, and the weight ratio of the component A to the component B is 1-10: 1.
6. The acrylate structural adhesive of claim 5, wherein said first acrylate monomer and said second acrylate monomer each independently comprise hydroxyethyl methacrylate, hydroxypropyl methacrylate, alkoxylated nonylphenol acrylate, 3,3, 3-trimethylcyclohexane acrylate, cyclic trimethylolpropane formal acrylate, tetrahydrofurfuryl acrylate, stearic acid acrylate, isodecyl acrylate, lauric acid methacrylate, isobornyl acrylate, methoxypolyethylene glycol methacrylate, cyclohexane dimethanol diacrylate, 3-hydroxy-2, 2-dimethylpropyl-3-hydroxy-2, 2-dimethylpropyl diacrylate, propoxylated neopentyl glycol diacrylate, tricyclodecane dimethanol diacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, One or more of tripropylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate and 1 and 3-butanediol dimethacrylate;
preferably, the first toughening agent and the second toughening agent each independently comprise one or more of a block copolymer, core shell particles, neoprene, nitrile rubber, carboxylated nitrile rubber, chlorosulfonated polyethylene, C5 petroleum resin, C5 modified C9 petroleum resin, C9 petroleum resin; preferably, the block copolymer comprises one or more of a polystyrene-b-butadiene-b- (methyl methacrylate) block copolymer, poly (methyl methacrylate) -b-poly (n-butyl acrylate) -b-poly (methyl methacrylate), an MBS resin, an ABS resin, an SBS resin, and an SEBS resin; preferably, the core-shell particles are one or more of butyl acrylate/polymethyl methacrylate core-shell particles, styrene butadiene rubber/poly (methyl methacrylate-acrylonitrile) copolymer core-shell particles and butadiene rubber/poly (methyl methacrylate-glycidyl methacrylate) copolymer core-shell particles;
preferably, the oxidizing agent is a peroxide, more preferably the peroxide comprises benzoyl peroxide, cumene hydroperoxide, di-tert-butyl peroxide, dicumyl peroxide, di (tert-butylperoxy) diisopropylbenzene, 1-di (tert-butylperoxy) -3, 3, 5-trimethylcyclohexane, 1-di (tert-butylperoxy) cyclohexane, ethyl-3, 3-di (tert-butylperoxy) butyrate, diisopropyl-peroxydicarbonate carbonate, tert-butyl-peroxyneodecanoate, tert-amyl-peroxyneodecanoate, tert-butyl-monoperoxy maleate, tert-butyl-peroxybenzoate, tert-butyl-peroxy2-ethylhexanoate, tert-amyl-peroxy1-peroxydicarbonate, or a mixture thereof, Monoisopropyl-mono-tert-butyl-peroxycarbonate, dicyclohexyl-peroxycarbonate, dimyristyl-peroxycarbonate, dicetyl-peroxycarbonate, di (2-ethylhexyl) -peroxycarbonate, tert-butyl-peroxy- (2-ethylhexyl) carbonate or tert-butyl-peroxy3, 5, 5-trimethylhexanoate, one or more of benzoic acid-tert-amyl-peroxyester, acetic acid-tert-butyl-peroxyester, carbonic acid-di (4-tert-butyl-cyclohexyl) -peroxyester, neodecanoic acid-cumene-peroxyester, pivalic acid-tert-amyl-peroxyester and pivalic acid-tert-butyl-peroxyester;
preferably, the reducing agent comprises one or more of tetramethyl thiourea, N-acrylyl thiourea, N-benzoyl thiourea, 1-allyl-2 thiourea, 1-allyl-3- (2-hydroxyethyl) -2 thiourea, diphenyl thiocarbazone, 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-vinylimidazole, diethylenetriamine, N, N, N ', N' -tetramethyl-1, 6-hexanediamine, N, N-dimethylbenzylamine, 1-acetylpiperidine, 1-benzoyl-4-piperidone, pentamethyldiethylenetriamine and tetra [ (2-pyridyl) methyl ] ethylenediamine;
preferably, the adhesion promoter is one or more of itaconic anhydride, 4' -oxydiphthalic anhydride and bisphenol-A-dititanic anhydride.
7. The acrylate structural adhesive according to claim 5, wherein the component A and the component B respectively comprise 8-25 parts by weight of solubilizing monomer, 5-15 parts by weight of oligomer and 0.5-5 parts by weight of stabilizer;
preferably, the solubilizing monomer is acryloyl morpholine;
preferably, the oligomer comprises one or more of aliphatic polyurethane acrylate oligomer, aromatic polyurethane acrylate oligomer, polyester acrylate oligomer and epoxy oligomer;
preferably, the stabilizer comprises one or more of 2, 6-di-tert-butyl-p-cresol, 2,6, 6-tetramethylpiperidine oxide, an antioxidant TH-1790, 4-hydroxypiperidinol oxyl, hydroquinone and p-benzoquinone.
8. The acrylate structural adhesive according to claim 7, wherein the component A further comprises 4-10 parts by weight of a filler; preferably, the filler is one or more of montmorillonite, ceramic microspheres, diatomite, attapulgite and white carbon black.
9. The acrylate structural adhesive according to claim 7 or 8, wherein the component B further comprises 1-5 parts by weight of a coupling agent.
10. The acrylate structural adhesive according to claim 9, wherein the coupling agent comprises one or more of bis- (3-triethoxysilylpropyl) amine, bis- (3-trimethoxysilylpropyl) amine, 3-aminopropylmethyldiethoxysilane, triamino-functionalized propyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane.
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| CN201810905134.6A CN110819265A (en) | 2018-08-09 | 2018-08-09 | Acrylate structural adhesive |
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| CN201810905134.6A CN110819265A (en) | 2018-08-09 | 2018-08-09 | Acrylate structural adhesive |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240613A (en) * | 2018-03-09 | 2019-09-17 | 北京天山新材料技术有限公司 | Vanudium complex, including its liquid vanudium complex promotor and the promotor preparation method |
| CN111662654A (en) * | 2020-07-23 | 2020-09-15 | 北京高盟新材料股份有限公司 | Long-operation-time two-component acrylate structural adhesive and preparation method thereof |
| CN112778942A (en) * | 2021-01-29 | 2021-05-11 | 厦门韦尔通科技有限公司 | Bi-component acrylate structural adhesive capable of being rapidly cured by hot pressing and long in operable time after being mixed at normal temperature and preparation method thereof |
| WO2024108715A1 (en) * | 2022-11-26 | 2024-05-30 | 夜视丽新材料(仙居)有限公司 | Improved high-strength polyester thin film and acrylic resin joint adhesive |
| CN118516071A (en) * | 2024-07-23 | 2024-08-20 | 浙江中科立德新材料有限公司 | Water-based carboxyl-terminated nitrile rubber binder for lithium iron phosphate anode, and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB840021A (en) * | 1957-11-13 | 1960-07-06 | Allied Chem | Improvements in or relating to curing polyester resins |
| GB907363A (en) * | 1960-02-23 | 1962-10-03 | Distillers Co Yeast Ltd | Improvements in or relating to the cure of unsaturated polyester compositions |
| US3480561A (en) * | 1965-06-24 | 1969-11-25 | Makhteshim Chem Works Ltd | Curing of polyester compositions |
| EP0232226A2 (en) * | 1986-02-07 | 1987-08-12 | Ciba-Geigy Ag | Two-component adhesives based on acrylate containing vanadium-phosphites |
| AU2010200120A1 (en) * | 2009-01-13 | 2010-07-29 | Hilti Aktiengesellschaft | Chemical two-component mortar composition with improved adhesion to the surface of moist boreholes in a mineral substrate and their use |
| CN101805564A (en) * | 2010-03-22 | 2010-08-18 | 北京天山新材料技术有限责任公司 | Novel low-odor acrylate structural adhesive and preparation method thereof |
| CN102816534A (en) * | 2012-08-14 | 2012-12-12 | 北京海斯迪克新材料有限公司 | Structure adhesive for metal adhesion, and preparation method thereof |
| CN104302725A (en) * | 2012-04-17 | 2015-01-21 | 德莎欧洲公司 | Cross-linkable adhesive compound with hard and soft blocks as a permeant barrier |
| FR3030547A1 (en) * | 2014-12-22 | 2016-06-24 | Arkema France | LIQUID (METH) ACRYLIC SYRUP, PROCESS FOR THE IMPREGNATION OF A FIBROUS SUBSTRATE BY THE SAME, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE IMPREGNATION SYRUP |
| CN110240613A (en) * | 2018-03-09 | 2019-09-17 | 北京天山新材料技术有限公司 | Vanudium complex, including its liquid vanudium complex promotor and the promotor preparation method |
-
2018
- 2018-08-09 CN CN201810905134.6A patent/CN110819265A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB840021A (en) * | 1957-11-13 | 1960-07-06 | Allied Chem | Improvements in or relating to curing polyester resins |
| GB907363A (en) * | 1960-02-23 | 1962-10-03 | Distillers Co Yeast Ltd | Improvements in or relating to the cure of unsaturated polyester compositions |
| US3480561A (en) * | 1965-06-24 | 1969-11-25 | Makhteshim Chem Works Ltd | Curing of polyester compositions |
| EP0232226A2 (en) * | 1986-02-07 | 1987-08-12 | Ciba-Geigy Ag | Two-component adhesives based on acrylate containing vanadium-phosphites |
| AU2010200120A1 (en) * | 2009-01-13 | 2010-07-29 | Hilti Aktiengesellschaft | Chemical two-component mortar composition with improved adhesion to the surface of moist boreholes in a mineral substrate and their use |
| CN101805564A (en) * | 2010-03-22 | 2010-08-18 | 北京天山新材料技术有限责任公司 | Novel low-odor acrylate structural adhesive and preparation method thereof |
| CN104302725A (en) * | 2012-04-17 | 2015-01-21 | 德莎欧洲公司 | Cross-linkable adhesive compound with hard and soft blocks as a permeant barrier |
| CN102816534A (en) * | 2012-08-14 | 2012-12-12 | 北京海斯迪克新材料有限公司 | Structure adhesive for metal adhesion, and preparation method thereof |
| FR3030547A1 (en) * | 2014-12-22 | 2016-06-24 | Arkema France | LIQUID (METH) ACRYLIC SYRUP, PROCESS FOR THE IMPREGNATION OF A FIBROUS SUBSTRATE BY THE SAME, AND COMPOSITE MATERIAL OBTAINED AFTER POLYMERIZATION OF THE IMPREGNATION SYRUP |
| CN110240613A (en) * | 2018-03-09 | 2019-09-17 | 北京天山新材料技术有限公司 | Vanudium complex, including its liquid vanudium complex promotor and the promotor preparation method |
Non-Patent Citations (2)
| Title |
|---|
| MAX HERBERHOLD，ET.AL: ""Neue vanadium-komplexe mit substituentenfreien phosphorliganden"", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| 曾小君等: ""高效异辛酸钒促进剂的研究"", 《玻璃钢/复合材料》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110240613A (en) * | 2018-03-09 | 2019-09-17 | 北京天山新材料技术有限公司 | Vanudium complex, including its liquid vanudium complex promotor and the promotor preparation method |
| CN111662654A (en) * | 2020-07-23 | 2020-09-15 | 北京高盟新材料股份有限公司 | Long-operation-time two-component acrylate structural adhesive and preparation method thereof |
| CN112778942A (en) * | 2021-01-29 | 2021-05-11 | 厦门韦尔通科技有限公司 | Bi-component acrylate structural adhesive capable of being rapidly cured by hot pressing and long in operable time after being mixed at normal temperature and preparation method thereof |
| WO2024108715A1 (en) * | 2022-11-26 | 2024-05-30 | 夜视丽新材料(仙居)有限公司 | Improved high-strength polyester thin film and acrylic resin joint adhesive |
| CN118516071A (en) * | 2024-07-23 | 2024-08-20 | 浙江中科立德新材料有限公司 | Water-based carboxyl-terminated nitrile rubber binder for lithium iron phosphate anode, and preparation method and application thereof |
| CN118516071B (en) * | 2024-07-23 | 2024-10-29 | 浙江中科立德新材料有限公司 | Water-based carboxyl-terminated nitrile rubber binder for lithium iron phosphate anode, and preparation method and application thereof |
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