CN110564341B - Adhesive for compounding thermoplastic elastomer and metal and preparation method thereof - Google Patents
Adhesive for compounding thermoplastic elastomer and metal and preparation method thereof Download PDFInfo
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- CN110564341B CN110564341B CN201910895843.5A CN201910895843A CN110564341B CN 110564341 B CN110564341 B CN 110564341B CN 201910895843 A CN201910895843 A CN 201910895843A CN 110564341 B CN110564341 B CN 110564341B
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- mixed solution
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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
- 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
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
- C09J123/28—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
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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
- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
- C09J5/06—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving heating of the applied adhesive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/04—Polymer mixtures characterised by other features containing interpenetrating networks
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/10—Presence of inorganic materials
- C09J2400/16—Metal
- C09J2400/163—Metal in the substrate
-
- 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
- C09J2400/00—Presence of inorganic and organic materials
- C09J2400/20—Presence of organic materials
- C09J2400/22—Presence of unspecified polymer
- C09J2400/226—Presence of unspecified polymer in the substrate
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
The invention belongs to the technical field of material bonding, and discloses an adhesive for thermoplastic elastomer and metal composite extrusion and a preparation method thereof, wherein the adhesive for thermoplastic elastomer and metal composite extrusion consists of a mixed solution 1, a mixed solution 2, a mixed solution 3 and a mixed solution 4; the mixed solution 1 consists of 10 to 20 mass percent of epoxy resin, 10 to 20 mass percent of acrylic resin and 70 to 80 mass percent of solvent; the mixed solution 2 consists of 5 to 15 mass percent of phenolic resin and 85 to 95 mass percent of solvent; the mixed solution 3 consists of 5 to 15 mass percent of polyurethane resin and 85 to 95 mass percent of solvent; the mixed solution 4 consists of 8 to 15 mass percent of chlorinated polypropylene, 5 mass percent of processing aid and 80 to 87 mass percent of solvent. The invention achieves better bonding strength to TPV and metal, can be quickly cured, and meets the requirements of TPV extrusion production lines.
Description
Technical Field
The invention belongs to the technical field of material bonding, and particularly relates to an adhesive for thermoplastic elastomer (TPV) and metal composite extrusion and a preparation method thereof.
Background
Currently, the closest prior art in the industry: thermoplastic elastomers (TPV) are excellent in flexibility, weather resistance, low temperature resistance and the like. The composite obtained by compounding TPV and metal is widely applied to the fields of automobile sealing strips, door and window sealing elements and the like. TPV has rubber-like elasticity and weather resistance, has good processability of plastics, and is widely applied to the fields of automobile sealing strips and door and window sealing elements. At present, the adhesive for compounding TPV and metal in China is mainly imported adhesives in Japan and Germany, and domestic reports are not yet available.
In summary, the adhesive between the thermoplastic polyurethane elastomer film and other materials has a single-component and a two-component composition, and the single-component has a high storage requirement and a short two-component processing window. In addition, the curing degree of the adhesive is controlled by the vehicle speed and the temperature during the use process, and the process is complicated.
In summary, the problems of the prior art are as follows: the adhesive between the existing thermoplastic polyurethane elastomer film and other materials is composed of a single component and a double component, the single component has high storage requirement, and the double component has short processing window. In addition, the curing degree of the adhesive is controlled by the vehicle speed and the temperature during the use process, and the process is complicated.
The difficulty of solving the technical problems is as follows:
TPVs are non-polar materials and are inherently difficult to bond to metals. As the automobile sealing strip, the adhesive still needs to be capable of enduring the temperature of about 80 ℃ for a long time, and is suitable for the continuous production of the sealing strip, thus increasing the difficulty of developing the adhesive.
The significance of solving the technical problems is as follows:
the adhesive is successfully developed, sealing strip production enterprises get rid of dependence on imported adhesives, production cost and purchase period are greatly reduced, and TPV can replace PVC and EPDM in large quantities.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an adhesive for the composite extrusion of a thermoplastic elastomer and metal and a preparation method thereof.
The invention is realized in such a way that the adhesive for compounding the thermoplastic elastomer and the metal consists of 5 to 15 parts of mixed solution 1, 5 to 15 parts of mixed solution 2, 3 to 10 parts of mixed solution 3 and 100 parts of mixed solution 4 according to the mass parts.
The mixed solution 1 consists of 10 to 20 mass percent of epoxy resin, 10 to 20 mass percent of acrylic resin and 70 to 80 mass percent of solvent.
The mixed solution 2 consists of 5 to 15 mass percent of phenolic resin and 85 to 95 mass percent of solvent.
The mixed solution 3 consists of 5 to 15 mass percent of polyurethane resin and 85 to 95 mass percent of solvent.
The mixed solution 4 consists of 8 to 15 mass percent of chlorinated polypropylene, 5 mass percent of processing aid and 80 to 87 mass percent of solvent.
Further, the solvent is: one or more of toluene, xylene, methylcyclohexane, cyclohexanone, butanone, methyl isobutyl ketone, methanol, ethanol, isopropanol, ethyl acetate, isopropyl acetate and butyl acetate.
Further, the processing aid is one or more of a plasticizer, a leveling agent and a defoaming agent.
The invention also aims to provide a preparation method of the adhesive for compounding the thermoplastic elastomer and the metal, and the preparation method of the adhesive for compounding and extruding the thermoplastic elastomer and the metal comprises the following steps:
step one, stirring 20% of epoxy resin, 10% of acrylic resin and 70% of solvent for 60min, and dissolving uniformly to obtain a mixed solution 1; the self-made acrylic resin is carboxyl-containing acrylic resin and can be used for curing epoxy resin. The proportions are set according to the amount required for curing.
Secondly, stirring 10% of phenolic resin and 90% of solvent for 60min, and dissolving uniformly to obtain a mixed solution 2; the phenolic resin is used for reacting with the epoxy resin to generate the epoxy phenolic copolymer.
Step three, stirring 10% of polyurethane resin and 90% of solvent for 90min, and dissolving uniformly to obtain a mixed solution 3; the polyurethane resin is a hydroxyl-terminated polyurethane elastomer and is used as a toughening agent of epoxy resin and phenolic resin.
Fourthly, stirring 10% of chlorinated polypropylene, 5% of processing aid and 85% of solvent for 120min, and dissolving uniformly to obtain a mixed solution 4.
And fifthly, putting 10 parts of mixed solution 1, 10 parts of mixed solution 2, 5 parts of mixed solution 3 and 100 parts of mixed solution 4 into a dispersion tank, and stirring for 30min to obtain the product.
In summary, the advantages and positive effects of the invention are: the adhesive is an interpenetrating network copolymer formed by epoxy resin, acrylic resin, phenolic resin, polyurethane resin and chlorinated polypropylene. The adhesive is successfully developed, fills up the domestic blank, has only 1/2-1/3 of imported similar products, and greatly reduces the cost of production enterprises. The adhesive solves the bonding problem of TPV and metal composite extrusion, has the characteristics of high curing speed and high bonding strength, and can meet the production requirement of a production line under the curing condition of 200-220 ℃ for 60-15 seconds. The T-type peel strength is not less than 70N/25mm, and the requirement of imported similar adhesives is met. The TPV-metal continuous extrusion production line is suitable for TPV-metal continuous extrusion production lines, can replace imported like products, the price of the imported like adhesive exceeds 300 yuan/kg, the price of the product of the invention is only 100 yuan/kg and 150 yuan/kg, the price of the imported adhesive is generally high, and the main reason is that no domestic substitute exists. The price is only half of that of imported products.
Drawings
FIG. 1 is a flow chart of the preparation of an adhesive for coextrusion of thermoplastic elastomer and metal according to an embodiment of the present invention.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following embodiments are illustrated and described in detail with reference to the accompanying drawings.
Aiming at the problems in the prior art, the invention provides an adhesive for the composite extrusion of a thermoplastic elastomer and metal and a preparation method thereof, and the invention is described in detail below with reference to the accompanying drawings.
The adhesive for the composite extrusion of the thermoplastic elastomer and the metal provided by the embodiment of the invention comprises, by mass, 10 parts of mixed solution 1, 10 parts of mixed solution 2, 5 parts of mixed solution 3 and 100 parts of mixed solution 4.
The mixed solution 1 consists of 20 mass percent of epoxy resin, 10 mass percent of acrylic resin and 70 mass percent of solvent.
The mixed solution 2 consists of 10 percent of phenolic resin and 90 percent of solvent according to the mass portion.
The mixed solution 3 is composed of 10% of polyurethane resin and 90% of solvent according to the mass portion.
The mixed solution 4 consists of 10 mass percent of chlorinated polypropylene, 5 mass percent of processing aid and 85 mass percent of solvent.
The adhesive for the composite extrusion of the thermoplastic elastomer and the metal, provided by the embodiment of the invention, is used for an adhesive for the composite extrusion of the thermoplastic elastomer (TPV) and the metal, and is mainly used for bonding steel, stainless steel, aluminum alloy and the like when the TPV is compositely extruded in the production of automobile sealing profiles. A pale yellow translucent liquid, with possibly a small amount of precipitate. Is a solvent adhesive, is inflammable and explosive, has no corrosiveness and is insoluble in water. The solvent has low toxicity and needs to ensure good ventilation of the production field. Flash point 27 ℃. The fire extinguishing agent is carbon dioxide or dry powder fire extinguishing agent, and foam or water mist can also be used.
The acrylic resin, the phenolic resin and the polyurethane resin used in the invention are self-made; the solvent is as follows: toluene, xylene, methylcyclohexane, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, isopropanol, ethyl acetate, isopropyl acetate, butyl acetate, and the like. The processing aids comprise a plasticizer, a flatting agent and a defoaming agent.
As shown in fig. 1, a method for preparing an adhesive for coextrusion of a thermoplastic elastomer and a metal according to an embodiment of the present invention includes the following steps:
s101: 20% of epoxy resin, 10% of acrylic resin (self-made) and 70% of solvent, stirring for 60min, and dissolving uniformly to obtain a mixed solution 1.
S102: 10% of phenolic resin (self-made) and 90% of solvent are stirred for 60min and dissolved uniformly to obtain a mixed solution 2.
S103: 10% of polyurethane resin (self-made) and 90% of solvent, stirring for 90min, and dissolving uniformly to obtain a mixed solution 3.
S104; 10% of chlorinated polypropylene, 5% of processing aid and 85% of solvent, stirring for 120min, and dissolving uniformly to obtain a mixed solution 4.
S105: and putting 10 parts of mixed solution 1, 10 parts of mixed solution 2, 5 parts of mixed solution 3 and 100 parts of mixed solution 4 into a dispersion tank, and stirring for 30min to obtain the water-based paint.
The adhesive solves the bonding problem of composite extrusion of TPV and metal, has the characteristics of high curing speed and high bonding strength, is suitable for a TPV-metal continuous extrusion production line, can replace imported like products, and has the price of about half of that of the imported products.
The invention is further described with reference to specific examples.
Examples 1
Two pieces of 25 x 100mm aluminum strips are cleaned, coated with the adhesive respectively, and dried in an oven at 200 ℃ for 60 seconds. After taking out and cooling, 25 x 80mm TPV slices (thickness 1mm) are clamped between two aluminum strips, clamped by a clamp and placed in an oven at 200 ℃ for drying for 10 minutes. And (5) taking out, cooling, and testing the T-type peeling strength not less than 100N, wherein the TPV material is damaged.
EXAMPLES example 2
Moh manufacturer automobile sealing strip production line. Cleaning a steel belt, coating the adhesive, passing through a drying tunnel with the length of 1 meter, setting the temperature of the drying tunnel at 220 ℃, and extruding at the linear speed of 8 meters per minute. Directly enters the machine head for secondary pressing after coming out of the drying channel. And (4) after cooling, sampling and testing T-type peel strength ≧ 50N/10mm, and TPV material destruction.
EXAMPLE 3
In the production line of the automobile sealing strip, the steel strip is cleaned, coated with the adhesive, dried by a high-frequency heating coil (the length of the high-frequency heating coil is 100mm, the temperature is set at 400 ℃, and the extrusion linear velocity is 10 m/min), and then enters a machine head for secondary extrusion. And testing the T-type peel strength of not less than 50N/10mm after cooling, and damaging the TPV material.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (4)
1. The adhesive for compounding the thermoplastic elastomer and the metal is characterized by comprising, by mass, 5-15 parts of mixed solution 1, 5-15 parts of mixed solution 2, 3-10 parts of mixed solution 3 and 100 parts of mixed solution 4; the adhesive is an interpenetrating network copolymer formed by epoxy resin, acrylic resin, phenolic resin, polyurethane resin and chlorinated polypropylene;
the mixed solution 1 consists of 10 to 20 mass percent of epoxy resin, 10 to 20 mass percent of acrylic resin and 70 to 80 mass percent of solvent; the acrylic resin is self-made acrylic resin, and the self-made acrylic resin is carboxyl-containing acrylic resin and is used for curing epoxy resin;
the mixed solution 2 consists of 5 to 15 mass percent of phenolic resin and 85 to 95 mass percent of solvent;
the mixed solution 3 consists of 5 to 15 mass percent of polyurethane resin and 85 to 95 mass percent of solvent; the polyurethane resin is a hydroxyl-terminated polyurethane elastomer and is used as a toughening agent of epoxy resin and phenolic resin;
the mixed solution 4 consists of 8 to 15 mass percent of chlorinated polypropylene, 5 mass percent of processing aid and 80 to 87 mass percent of solvent.
2. An adhesive for thermoplastic elastomer and metal compounding as claimed in claim 1, wherein said solvent is: one or more of toluene, xylene, methylcyclohexane, cyclohexanone, butanone, methyl isobutyl ketone, methanol, ethanol, isopropanol, ethyl acetate, isopropyl acetate and butyl acetate.
3. The adhesive for compounding the thermoplastic elastomer and the metal according to claim 1, wherein the processing aid is one or more of a plasticizer, a leveling agent and an antifoaming agent.
4. The method for preparing the adhesive for compounding the thermoplastic elastomer and the metal as claimed in claim 1, wherein the method for preparing the adhesive for compounding and extruding the thermoplastic elastomer and the metal comprises the following steps:
step one, stirring 20% of epoxy resin, 10% of acrylic resin and 70% of solvent for 60min, and dissolving uniformly to obtain a mixed solution 1;
secondly, stirring 10% of phenolic resin and 90% of solvent for 60min, and dissolving uniformly to obtain a mixed solution 2;
step three, stirring 10% of polyurethane resin and 90% of solvent for 90min, and dissolving uniformly to obtain a mixed solution 3;
fourthly, stirring 10% of chlorinated polypropylene, 5% of processing aid and 85% of solvent for 120min, and dissolving uniformly to obtain a mixed solution 4;
and fifthly, putting 10 parts of mixed solution 1, 10 parts of mixed solution 2, 5 parts of mixed solution 3 and 100 parts of mixed solution 4 into a dispersion tank, and stirring for 30min to obtain the product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910895843.5A CN110564341B (en) | 2019-09-21 | 2019-09-21 | Adhesive for compounding thermoplastic elastomer and metal and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910895843.5A CN110564341B (en) | 2019-09-21 | 2019-09-21 | Adhesive for compounding thermoplastic elastomer and metal and preparation method thereof |
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| CN110564341A CN110564341A (en) | 2019-12-13 |
| CN110564341B true CN110564341B (en) | 2021-07-20 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112059935B (en) * | 2020-09-02 | 2021-11-26 | 东莞金太阳研磨股份有限公司 | Environment-friendly waterproof abrasive paper and preparation method thereof |
| CN113913143A (en) * | 2021-07-06 | 2022-01-11 | 深圳博林新材料科技有限公司 | Hot-bonding adhesive suitable for polypropylene and blend thereof |
| CN116589974B (en) * | 2023-06-30 | 2024-09-03 | 山东北方现代化学工业有限公司 | Single-component high-temperature-resistant and fast-curing adhesive for silicon steel sheet rotor and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57126644A (en) * | 1981-01-28 | 1982-08-06 | Mitui Toatsu Chem Inc | Adhesion of polyurethane elastomer with metal |
| CN101421370A (en) * | 2006-04-13 | 2009-04-29 | Nok株式会社 | Vulcanizing adhesive composition |
| CN101512199A (en) * | 2006-08-22 | 2009-08-19 | Nok株式会社 | Bonded piston seal |
-
2019
- 2019-09-21 CN CN201910895843.5A patent/CN110564341B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57126644A (en) * | 1981-01-28 | 1982-08-06 | Mitui Toatsu Chem Inc | Adhesion of polyurethane elastomer with metal |
| CN101421370A (en) * | 2006-04-13 | 2009-04-29 | Nok株式会社 | Vulcanizing adhesive composition |
| CN101512199A (en) * | 2006-08-22 | 2009-08-19 | Nok株式会社 | Bonded piston seal |
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