CN111978895A - Single-coating metal and rubber hot vulcanization adhesive and preparation method thereof - Google Patents
Single-coating metal and rubber hot vulcanization adhesive and preparation method thereof Download PDFInfo
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- CN111978895A CN111978895A CN202010762887.3A CN202010762887A CN111978895A CN 111978895 A CN111978895 A CN 111978895A CN 202010762887 A CN202010762887 A CN 202010762887A CN 111978895 A CN111978895 A CN 111978895A
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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
- C09J151/04—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 rubbers
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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
- C09J11/08—Macromolecular additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention relates to the technical field of metal and rubber bonding adhesives, and provides a single-coated metal and rubber hot vulcanization adhesive which at least comprises the following components in percentage by weight: 4-20% of liquid rubber, 5-20% of Diels-Alder graft polymer, 1-5% of hydroxy aromatic compound, 1-5% of formaldehyde source, 0.5-3% of cross-linking agent, 0.5-3% of vulcanizing agent, 0.5-5% of acid acceptor, 1-10% of inert pigment and filler, and the balance of solvent. The compounding use of the high vinyl liquid polybutadiene rubber in the adhesive is found to not only endow the adhesive layer with excellent peeling strength and crosslinking density, but also be beneficial to enhancing the bonding durability of the adhesive layer and still maintain excellent stability under harsh conditions.
Description
Technical Field
The invention relates to the technical field of metal and rubber bonding adhesives, in particular to a single-coating metal and rubber hot vulcanization adhesive and a preparation method thereof.
Background
In recent years, a wide variety of adhesive compositions have been developed for bonding various materials or objects, such as elastomeric substrates and metal surfaces. With the development of bonding technology, adhesive compositions are subject to increasingly demanding bonding conditions, and the range of ingredients employed in the compositions is subject to environmental regulations. In order to survive in this somewhat challenging atmospheric environment, future adhesive compositions will require the use of environmentally acceptable ingredients that will produce adhesive materials that can withstand the relatively stringent bonding conditions. Rubber and metal are bonded through an adhesive, and the method is the most effective method for linking metal and rubber. The rubber enables the metal to have the functions of wear resistance, vibration reduction, impact resistance, corrosion resistance, protection, sealing and the like. Rubber and metal components have found relatively wide application in automobiles, such as subframe bushings, hydraulic bushings, crankshaft torsional dampers, dynamic vibration absorbers. The materials of the elements are mainly characterized in that rubber is bonded on the surface of metal, so that the elements achieve good vibration damping effect. But more and more components are required to be exposed to high temperature, corrosive environments. For example, engine mounting locations containing fluids often have increasingly high temperatures that expose the adhesive between the rubber and metal in the elastomeric element to extremely high temperature fluid environments. Other resilient elements require contact with materials containing corrosive salts or other corrosive materials, which can degrade the bonding surface. Therefore, the adhesive composition has high temperature resistance, corrosion resistance and other performance requirements.
Among them, in the prior patent already published, CN92102610.2 discloses a one-coat type adhesive composition which employs environmentally acceptable ingredients and is capable of withstanding high temperature conditions as experienced in injection molding processes. The adhesive composition contains the following components: a) Diels-Alder adducts produced from perhalogenated cyclic co-dienes and ethylenically unsaturated dienophiles having a vinyl content of more than 50%; b) a phenolic resin; c) an aromatic hydroxy compound; d) a formaldehyde donor); e) a crosslinking agent for the heat-activated unsaturated rubber; f) a vulcanizing agent; and g) a metal oxide. CN200410090134.3 discloses a polymer grafted with at least halogenated cyclic co-diene, a polyhydroxy aromatic compound and a polyisocyanate composition.
Disclosure of Invention
In order to solve the technical problems, the invention provides a single-coating type metal and rubber hot vulcanization adhesive which is characterized by comprising the following components in percentage by weight: 4-20% of liquid rubber, 5-20% of Diels-Alder graft polymer, 1-5% of hydroxy aromatic compound, 1-5% of formaldehyde source, 0.5-3% of cross-linking agent, 0.5-3% of vulcanizing agent, 0.5-5% of acid acceptor, 1-10% of inert pigment and filler, and the balance of solvent.
As a preferable technical solution, the liquid rubber in the present invention is liquid polybutadiene rubber.
As a preferable technical scheme, the content of side chain vinyl in the liquid polybutadiene rubber is more than or equal to 80mol percent.
As a preferred technical scheme, the liquid rubber in the invention is selected from one or more of 1, 2-polybutadiene homopolymer, hydroxyl-terminated 1, 2-polybutadiene, epoxy-terminated 1, 2-polybutadiene, acrylate-terminated 1, 2-polybutadiene, cis-anhydrized 1, 2-polybutadiene and isocyanate-terminated 1, 2-polybutadiene.
As a preferred technical scheme, the grafting monomer of the Diels-Alder graft polymer is halogenated cyclic co-diene, and the grafting rate is 60-75 mol%.
In a preferred embodiment, the halogenated cyclic co-diene in the present invention is selected from one or more of hexafluorocyclopentadiene, hexabromocyclopentadiene, 5-difluorotetrachlorocyclopentadiene, 5-dibromotetrachlorocyclopentadiene, and hexachlorocyclopentadiene.
In a preferred embodiment, the hydroxyaromatic compound in the present invention is selected from the group consisting of phenol, p-tert-butylphenol, o-cresol, m-cresol, hydroquinone, resorcinol, catechol, and trihydroxyphenol.
In a preferred embodiment, the formaldehyde source in the present invention is selected from one or more of paraformaldehyde, acetal homopolymer, hexamethylenetetramine, hexamethoxymethylmelamine, trioxymethyleneaniline, and ethylenediamine formaldehyde.
In a preferred embodiment, the formaldehyde source in the present invention is selected from one or more of paraformaldehyde, acetal homopolymer, hexamethylenetetramine, hexamethoxymethylmelamine, trioxymethyleneaniline, and ethylenediamine formaldehyde.
In a preferred embodiment, the formaldehyde source in the present invention is selected from one or more of paraformaldehyde, acetal homopolymer, hexamethylenetetramine, hexamethoxymethylmelamine, trioxymethyleneaniline, and ethylenediamine formaldehyde.
The second aspect of the invention provides a preparation method of the single-coated metal and rubber hot vulcanization adhesive, which at least comprises the following steps: mixing the liquid rubber and the Diels-Alder graft polymer, then adding the inert pigment filler, the acid absorbent, the vulcanizing agent and the crosslinking agent, and mixing and stirring to obtain the rubber.
Compared with the prior art, the invention has the following excellent beneficial effects:
the invention provides a single-coating metal and rubber heat vulcanization adhesive, and the inventor finds that the Diels-Alder graft polymer at a specific grafting ratio provides combined corrosion resistance, and the compounding of high-vinyl liquid polybutadiene rubber is used, so that the adhesive layer not only can be endowed with excellent peeling strength and crosslinking density, but also can be beneficial to enhancing the bonding durability of the adhesive layer and can still maintain excellent stability under harsher conditions.
Detailed Description
The technical features of the technical solutions provided by the present invention will be further clearly and completely described below with reference to the specific embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
In order to solve the technical problems, the invention provides a single-coating metal and rubber hot vulcanization adhesive which at least comprises the following components in percentage by weight: 4-20% of liquid rubber, 5-20% of Diels-Alder graft polymer, 1-5% of hydroxy aromatic compound, 1-5% of formaldehyde source, 0.5-3% of cross-linking agent, 0.5-3% of vulcanizing agent, 0.5-5% of acid acceptor, 1-10% of inert pigment and filler, and the balance of solvent.
In some preferred embodiments, the single-coated metal and rubber heat-curable adhesive comprises, in weight percent, at least the following components: 4-10% of liquid rubber, 5-15% of Diels-Alder graft polymer, 2-4% of hydroxy aromatic compound, 2-4% of formaldehyde source, 1-2% of cross-linking agent, 0.5-2% of vulcanizing agent, 1-3% of acid acceptor, 1-5% of inert pigment and filler and solvent for balancing.
In some more preferred embodiments, the one-coat metal and rubber heat-curable adhesive comprises, in weight percent, at least the following components: 6.8% of liquid rubber, 8.9% of Diels-Alder graft polymer, 2% of hydroxyaromatic compound, 2% of formaldehyde source, 1.4% of crosslinking agent, 0.7% of vulcanizing agent, 1.4% of acid acceptor, 1.7% of inert pigment and filler, and the balance solvent.
In some embodiments, the liquid rubber is a liquid polybutadiene rubber.
In some embodiments, the liquid polybutadiene rubber has a side chain vinyl content of 80 mol% or more.
In some preferred embodiments, the liquid polybutadiene rubber has a side chain vinyl content of 90 mol% or more.
In some embodiments, the liquid rubber is selected from the group consisting of 1, 2-polybutadiene homopolymer, hydroxyl-terminated 1, 2-polybutadiene, epoxy-terminated 1, 2-polybutadiene, acrylate-terminated 1, 2-polybutadiene, maleated 1, 2-polybutadiene, isocyanate-terminated 1, 2-polybutadiene, and combinations of one or more thereof.
In some preferred embodiments, the liquid rubber is a 1, 2-polybutadiene homopolymer.
In some embodiments, the grafting monomer of the Diels-Alder graft polymer is a halogenated cyclic co-diene, and the grafting ratio is 60 to 75 mol%; preferably, the graft ratio is 66 mol%.
The method for testing the grafting rate of the Diels-Alder graft polymer comprises the following steps: a sample of the grafted Diels-Alder graft polymer was extracted repeatedly with cyclohexane in a Soxhlet extractor for 10h and the graft ratio was calculated using the IC anion determination of the chlorine content of the polymer.
In some embodiments, the halogenated cyclic co-diene is selected from the group consisting of one or more combinations of hexafluorocyclopentadiene, hexabromocyclopentadiene, 5-difluorotetrachlorocyclopentadiene, 5-dibromotetrachlorocyclopentadiene, hexachlorocyclopentadiene; preferably, the halogenated cyclic co-diene is selected from hexachlorocyclopentadiene.
The kind of the Diels-Alder graft polymer in the present invention is not particularly limited, and is preferably prepared by the following preparation method.
The preparation method is as follows: adding pseudocumene and polybutadiene rubber into a four-neck flask, dissolving for 2 hours at 100 ℃, heating to 165 ℃, adding halogenated cyclic co-diene, and preserving heat for 17 hours at 165 ℃. And precipitating the solution after the reaction in methanol, washing, adding xylene to dissolve, adding the solution into the methanol to precipitate, repeatedly washing for three times to remove unreacted halogenated cyclic co-diene, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the Diels-Alder graft polymer.
In some preferred embodiments, the process for preparing the Diels-Alder graft polymer is as follows:
540g of pseudocumene and 54g of polybutadiene rubber are added into a four-neck flask and dissolved for 2 hours at the temperature of 100 ℃, 327g of hexachlorocyclopentadiene is added after the temperature is raised to 165 ℃, and the temperature is kept for 17 hours at 165 ℃. And precipitating the solution after the reaction in methanol, washing, adding xylene to dissolve, adding the solution into the methanol to precipitate, repeatedly washing for three times to remove unreacted hexachlorocyclopentadiene, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the graft polymer.
The inventors have found that excellent synergy can be achieved between the Diels-Alder graft polymer and the high vinyl liquid polybutadiene rubber at a particular grafting ratio, presumably because the graft polymer, although maintaining good stability against the environment, has a reduced bonding effect with the rubber, but when compounded with liquid polybutadiene rubber, not only is the bonding strength relieved, but the bonding strength is significantly synergistically enhanced, and because the liquid polybutadiene rubber with a high side chain vinyl content has a suitable molecular weight, the crosslinking density can be more uniform when the two are mixed, the inventors have found that the effect of selecting 1, 2-polybutadiene homopolymer is most excellent.
In some embodiments, the hydroxyaromatic compound is selected from the group consisting of phenol, p-tert-butylphenol, o-cresol, m-cresol, hydroquinone, resorcinol, catechol, trihydroxyphenol, and combinations of one or more thereof; preferably, the hydroxyaromatic compound is resorcinol.
In some embodiments, the formaldehyde source is selected from the group consisting of one or more of paraformaldehyde, acetal homopolymer, hexamethylenetetramine, hexamethoxymethylmelamine, trioxymethyleneaniline, ethylenediamine formaldehyde; preferably, the formaldehyde source is hexamethylenetetramine.
In some embodiments, the crosslinking agent is selected from the group consisting of one or more of p-benzoquinone dioxime, diphenoquinone dioxime, 1,2,4, 5-tetrachlorobenzoquinone, dibenzoyl p-benzoquinone dioxime; preferably, the cross-linking agent is selected from parabenzoquinone dioxime.
In some embodiments, the sulfiding agent is selected from at least one of sulfur, selenium, tellurium; preferably, the vulcanizing agent is selenium.
In some embodiments, the acid scavenger is magnesium oxide and/or zinc oxide; preferably, the acid scavenger is zinc oxide.
In some embodiments, the inert pigment filler is carbon black and/or fumed silica; preferably, the inert pigment filler is a combination of carbon black and fumed silica.
In some embodiments, the weight ratio of carbon black to fumed silica is (1-2): 1; further preferably, the weight ratio of carbon black to fumed silica is 1.5: 1.
in some embodiments, the solvent is an aromatic hydrocarbon solvent and/or a ketone solvent; preferably, the solvent is a combination of an aromatic hydrocarbon solvent and a ketone solvent; preferably, the volume ratio of the aromatic hydrocarbon solvent to the ketone solvent is 1 (0.5-1.5); more preferably, the volume ratio of the aromatic hydrocarbon solvent to the ketone solvent is 1: 1.
In some embodiments, the aromatic hydrocarbon solvent is selected from at least one of xylene, toluene, aromatic hydrocarbon solvent oils; preferably, the aromatic hydrocarbon solvent is xylene.
In some embodiments, the ketone solvent is selected from at least one of methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; preferably, the ketone solvent is methyl isobutyl ketone.
The second aspect of the invention provides a preparation method of the single-coating metal and rubber hot vulcanization adhesive, which at least comprises the following steps: mixing the liquid rubber and the Diels-Alder graft polymer, then adding the inert pigment filler, the acid absorbent, the vulcanizing agent and the crosslinking agent, and mixing and stirring to obtain the rubber.
The present invention is described in detail below by way of examples, and it should be noted that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention.
The preparation method of the single-coated metal and rubber hot vulcanization adhesive comprises the following steps: mixing the liquid rubber and the Diels-Alder graft polymer, then adding the inert pigment filler, the acid absorbent, the vulcanizing agent and the crosslinking agent, and mixing and stirring to obtain the rubber.
Examples 1-3 the components provided were prepared in different weight ratios to provide one-coat metal and rubber heat-cure adhesives as shown in table 1.
Wherein the liquid polybutadiene rubber is 1, 2-polybutadiene homopolymer with the trademark of NISPPON-PB B-2000; the solvent is a mixture of xylene and methyl isobutyl ketone, and the volume ratio is 1: 1.
The grafting rate of the Diels-Alder graft polymer is 66.4 percent, and the specific preparation method comprises the following steps: 540g of pseudocumene and 54g of polybutadiene rubber are added into a four-neck flask and dissolved for 2 hours at the temperature of 100 ℃, 327g of hexachlorocyclopentadiene is added after the temperature is raised to 165 ℃, and the temperature is kept for 17 hours at 165 ℃. And precipitating the solution after the reaction in methanol, washing, adding xylene to dissolve, adding the solution into the methanol to precipitate, repeatedly washing for three times to remove unreacted hexachlorocyclopentadiene, and drying in a vacuum oven at 60 ℃ for 4 hours to obtain the graft polymer.
Table 1 examples 1 to 3
| Example 1 | Example 2 | Example 3 | |
| Diels-Alder graft Polymer (%) | 10.3 | 9.4 | 8.90 |
| Liquid polybutadiene rubber (%) | 4.0 | 5.8 | 6.85 |
| Resorcinol (%) | 2.4 | 2.2 | 2.05 |
| Hexamethylenetetramine (%) | 2.4 | 2.2 | 2.05 |
| P-benzoquinone dioxime (%) | 1.6 | 1.4 | 1.37 |
| Selenium (%) | 0.8 | 0.7 | 0.68 |
| Zinc oxide (%) | 1.6 | 1.4 | 1.37 |
| Gas phase silica (%) | 0.8 | 0.7 | 0.68 |
| Carbon Black (%) | 1.2 | 1.1 | 1.03 |
| Organic solvent (%) | 75.0 | 75.0 | 75.0 |
| In total (%) | 100 | 100 | 100 |
Performance testing
After the series of examples 1 to 3 above were prepared, the metal base material to be bonded was subjected to sand blasting and cleaning as a single coat, the present single-coated metal and rubber hot-vulcanization adhesive was coated on the surface of the metal base material with a dry film thickness of 25. + -.2 μm, and then rubber ( A, 55 ℃ hardness natural rubber) and the coated metal base material (iron plate and 304 stainless steel) were vulcanized with a plate vulcanizing agent at 165 ℃ and 8 to 10MPa for 10 minutes. Standing at room temperature for 24 hours after cooling, and measuring peak peel strength and rubber retention percentage according to a method for measuring the bonding strength of GB/T7760-2003 vulcanized rubber or thermoplastic elastomer and a hard plate by a 90-degree peel method; percentage rubber retention was observed after 72 hours of salt spray testing at temperature (35 ℃) in 5% saline, according to ASTM B177; test observation of the percentage rubber retention after 2 hours of experiment in boiling water at 2kg with pre-load; the results of the performance tests are shown in tables 2-4.
TABLE 2 examples with common iron and stainless steels Peak Peel Strength at Room temperature and percent rubber
Table 3 percent rubber retention after salt spray test 72H of examples and plain iron, 304 stainless steel
TABLE 4 percent rubber retention after boiling water 2H for the examples and plain iron sheet, 304 stainless steel
| Boiling Water experiments | Adhesive 1 | Adhesive 2 | Adhesive 3 |
| Iron sheet | 100R | 100R | 100R |
| Stainless steel | 91R 9RC | 95R 1M | 97R 3M |
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in other forms, and any person skilled in the art may modify or change the technical content disclosed above into an equivalent embodiment with equivalent changes, but all those simple modifications, equivalent changes and modifications made on the above embodiment according to the technical spirit of the present invention still belong to the protection scope of the present invention.
Claims (10)
1. The single-coated metal and rubber hot vulcanization adhesive is characterized by comprising the following components in percentage by weight: 4-20% of liquid rubber, 5-20% of Diels-Alder graft polymer, 1-5% of hydroxy aromatic compound, 1-5% of formaldehyde source, 0.5-3% of cross-linking agent, 0.5-3% of vulcanizing agent, 0.5-5% of acid acceptor, 1-10% of inert pigment and filler, and the balance of solvent.
2. The single-coated metal and rubber heat-vulcanizable adhesive as in claim 1 wherein the liquid rubber is a liquid polybutadiene rubber.
3. The single-coated metal and rubber heat-vulcanizable adhesive as claimed in claim 2, wherein the content of side chain vinyl groups in the liquid polybutadiene rubber is 80 mol% or more.
4. The single-coated metal and rubber heat-vulcanizable adhesive of claim 2 wherein the liquid rubber is selected from the group consisting of 1, 2-polybutadiene homopolymer, hydroxyl-terminated 1, 2-polybutadiene, epoxy-terminated 1, 2-polybutadiene, acrylate-terminated 1, 2-polybutadiene, anhydrized 1, 2-polybutadiene, isocyanate-terminated 1, 2-polybutadiene, and combinations thereof.
5. The single-coated metal and rubber heat-vulcanizable adhesive as claimed in claim 1, wherein the grafting monomer of the Diels-Alder graft polymer is a halogenated cyclic co-diene, and the grafting ratio is 60 to 75 mol%.
6. A single-coated metal and rubber heat-vulcanizable binder as in claim 5 wherein the halogenated cyclic co-diene is selected from the group consisting of one or more of hexafluorocyclopentadiene, hexabromocyclopentadiene, 5-difluorotetrachlorocyclopentadiene, 5-dibromotetrachlorocyclopentadiene, hexachlorocyclopentadiene.
7. The single-coated metal and rubber heat-cure adhesive as in claim 1, wherein the hydroxyaromatic compound is selected from the group consisting of one or more of phenol, p-tert-butylphenol, o-cresol, m-cresol, hydroquinone, resorcinol, catechol, and trihydroxyphenol.
8. A single-coated metal and rubber heat-cure adhesive as in claim 1, wherein the formaldehyde source is selected from the group consisting of paraformaldehyde, acetal homopolymers, hexamethylenetetramine, hexamethoxymethylmelamine, trioxymethyleneaniline, and ethylenediamine formaldehyde in combination with one or more of these.
9. The single-coated metal and rubber heat-cure adhesive as in claim 1, wherein the cross-linking agent is selected from the group consisting of one or more of p-benzoquinone dioxime, diphenoquinone dioxime, 1,2,4, 5-tetrachlorobenzoquinone, dibenzoyl-p-benzoquinone dioxime.
10. A method for preparing a single-coated metal and rubber heat-vulcanising adhesive as claimed in any one of claims 1 to 9, characterized in that it comprises at least the following steps: mixing the liquid rubber and the Diels-Alder graft polymer, then adding the inert pigment filler, the acid absorbent, the vulcanizing agent and the crosslinking agent, and mixing and stirring to obtain the rubber.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778865A (en) * | 2020-12-31 | 2021-05-11 | 宁波普力通化学有限公司 | Perhalodiolefine modified polymer anticorrosive paint |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065672A (en) * | 1991-04-10 | 1992-10-28 | 洛德公司 | The high-temperature adhesives composition |
| US20060105178A1 (en) * | 2004-11-12 | 2006-05-18 | Roitman Lipa L | Materials for bonding elastomer |
| CN103881615A (en) * | 2014-04-17 | 2014-06-25 | 上海依多科化工有限公司 | Rubber adhesive and preparation method thereof |
-
2020
- 2020-07-31 CN CN202010762887.3A patent/CN111978895A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1065672A (en) * | 1991-04-10 | 1992-10-28 | 洛德公司 | The high-temperature adhesives composition |
| US20060105178A1 (en) * | 2004-11-12 | 2006-05-18 | Roitman Lipa L | Materials for bonding elastomer |
| CN103881615A (en) * | 2014-04-17 | 2014-06-25 | 上海依多科化工有限公司 | Rubber adhesive and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778865A (en) * | 2020-12-31 | 2021-05-11 | 宁波普力通化学有限公司 | Perhalodiolefine modified polymer anticorrosive paint |
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