CN116655988B - Surface treatment method of vulcanized rubber, application of surface treatment method, rubber-polyurethane composite tire and preparation method of rubber-polyurethane composite tire - Google Patents

Surface treatment method of vulcanized rubber, application of surface treatment method, rubber-polyurethane composite tire and preparation method of rubber-polyurethane composite tire Download PDF

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CN116655988B
CN116655988B CN202310934867.3A CN202310934867A CN116655988B CN 116655988 B CN116655988 B CN 116655988B CN 202310934867 A CN202310934867 A CN 202310934867A CN 116655988 B CN116655988 B CN 116655988B
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rubber
polyurethane
adhesive layer
vulcanized rubber
plasma treatment
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CN116655988A (en
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杨文刚
徐婷
邓明虓
陈学思
陈通
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/123—Treatment by wave energy or particle radiation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0016—Compositions of the tread
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C1/0041—Compositions of the carcass layers
    • 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
    • C09J5/02—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers involving pretreatment of the surfaces to be joined
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
    • B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
    • B60C2001/0091—Compositions of non-inflatable or solid tyres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2307/00—Characterised by the use of natural rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2309/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08J2309/06—Copolymers with styrene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/80—Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86—Optimisation of rolling resistance, e.g. weight reduction 

Abstract

The invention provides a surface treatment method of vulcanized rubber, application of the surface treatment method, a rubber-polyurethane composite tire and a preparation method of the rubber-polyurethane composite tire, and belongs to the technical field of surface treatment of tire rubber. The surface treatment method comprises the following steps: the surface of vulcanized rubber is subjected to plasma treatment by taking the mixed gas of nitrogen and water vapor as a medium; the volume ratio of the nitrogen to the water vapor is 0.5-2:1; the temperature of the mixed gas is 120-150 ℃ and the pressure is 0.2-0.4 MPa; the plasma treatment speed is 0.1-1 m/min, and the power is 500-1000W. The surface treatment method provided by the invention has good timeliness, can obviously improve the bonding performance of vulcanized rubber and polyurethane, can be used for bonding the vulcanized rubber and polyurethane, and is particularly suitable for bonding the vulcanized rubber tread of the rubber-polyurethane composite tire and the polyurethane carcass.

Description

Surface treatment method of vulcanized rubber, application of surface treatment method, rubber-polyurethane composite tire and preparation method of rubber-polyurethane composite tire
Technical Field
The invention belongs to the technical field of surface treatment of tire rubber, and particularly relates to a surface treatment method of vulcanized rubber, application of the vulcanized rubber, a rubber-polyurethane composite tire and a preparation method of the rubber-polyurethane composite tire.
Background
The polyurethane elastomer has the advantages of strong bearing capacity, good wear resistance, strong tearing resistance, high chemical corrosion resistance and the like, and has wide application in the tire preparation industry. The rubber-polyurethane composite tire is a novel environment-friendly tire which mainly uses rubber as a tire tread (comprising a belt ply and a tread layer) and uses polyurethane elastomer as a tire body. According to the structural form of the main body part (polyurethane elastomer), there are classified into a rubber-polyurethane non-pneumatic tire and a rubber-polyurethane solid tire. The rubber-polyurethane non-pneumatic tire structurally mainly comprises an inner buffer layer, an elastic support body, an outer buffer layer, a belt layer, a tread layer and the like; the rubber-polyurethane solid tire mainly comprises a polyurethane solid main body, a belt layer, a tread layer and the like in structure. The two kinds of tires replace the tire pressure of the traditional pneumatic tire with an elastic supporting body or a polyurethane solid main body, play roles in supporting and damping the whole vehicle structure, and have the advantages of no maintenance, no tire burst and no leakage.
Most of the rubber used for the belt ply and the tread layer of the rubber-polyurethane composite tire is one or more of olefin rubber such as natural rubber, styrene-butadiene rubber, isoprene rubber and the like. In general, the polyurethane carcass and the rubber tread of the rubber-polyurethane composite tire are bonded by an adhesive to realize connection. At present, there are two manufacturing modes of the whole tire of the rubber-polyurethane composite tire: firstly, molding a carcass part in a polyurethane casting or polyurethane injection molding mode, then polishing and gluing the outer surface of the carcass, sequentially attaching a belt ply and raw rubber of a tread layer, and finally, conveying the tire into a vulcanizing tank, and vulcanizing to obtain a whole rubber-polyurethane composite tire; secondly, firstly, vulcanizing and molding the raw rubber of the belt ply and the tread layer to obtain an annular tread, then coating an adhesive on the inner surface of the annular tread, placing the annular tread into a tire processing mold, finally preparing a polyurethane carcass by adopting a pouring or injection molding mode, and obtaining the whole tire of the rubber-polyurethane composite tire through post curing. Among them, the second method can greatly improve the productivity of the tire, and is expected to be a main manufacturing method of the rubber-polyurethane composite tire.
The second mode for preparing the rubber-polyurethane composite tire can involve the adhesion of polyurethane and vulcanized rubber, and the belt layer or tread layer is made of nonpolar materials after raw rubber vulcanization, and has low surface energy, large contact angle, no infiltration of adhesive and large polarity difference from polyurethane. Polyurethane adhesives commonly used in commerce at present are difficult to form effective chemical bonding with vulcanized rubber directly, so that the requirement of rubber-polyurethane composite tires on bonding strength is difficult to ensure. Therefore, the surface treatment is required to be carried out on the vulcanized rubber on the inner side of the annular tread so as to improve the chemical affinity between the vulcanized rubber and the polyurethane adhesive, thereby fully playing the bonding effect of the polyurethane adhesive and realizing the excellent bonding between the annular tread (vulcanized rubber) and the carcass (polyurethane).
Currently, the surface treatment method of vulcanized rubber includes a chemical method, a plasma treatment method, and the like. The chemical method is to change the properties of the rubber surface by forming chemical bonds on the rubber surface or changing chemical composition, and mainly comprises acid-base treatment, oxidation, reduction, vulcanization and the like. The chemical method has the advantages of large treatment depth, stable treatment effect, controllable effect, wide application range and the like; disadvantages include complex processing, the need for special equipment and toxic reagents, and the damage to the rubber to some extent, resulting in a decrease in its surface mechanical properties.
The plasma treatment is a surface modification method by spraying a gas containing positive ions and negative ions on the surface of vulcanized rubber to generate radicals or chemically react with the surface of the material. The plasma treatment can improve the adhesive property of the vulcanized rubber, and only modifies the surface of the material (usually from a few nanometers to hundreds of nanometers) without affecting the performance of the material matrix. However, the conventional plasma treatment has poor timeliness and limited improvement on the bonding effect, and the requirement of the rubber-polyurethane composite tire on the bonding strength under the condition of high-speed running or sudden stop and rapid acceleration is difficult to meet.
In order to solve the above problems, it is necessary to study a new vulcanized rubber surface treatment technique to promote the development of rubber-polyurethane composite tires.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a surface treatment method of vulcanized rubber, application thereof, a rubber-polyurethane composite tire and a preparation method thereof. Compared with the conventional plasma treatment, the surface treatment method has good timeliness, and can remarkably improve the bonding performance of vulcanized rubber and polyurethane. The rubber-polyurethane composite tire prepared by the surface treatment method has good high-low temperature static bonding performance and dynamic fatigue bonding performance.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a surface treatment method of vulcanized rubber, comprising the steps of:
the surface of vulcanized rubber is subjected to plasma treatment by taking the mixed gas of nitrogen and water vapor as a medium;
the volume ratio of nitrogen to water vapor is 0.5-2:1 (e.g., may be 0.5:1, 0.6:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.5:1, 1.6:1, 1.8:1, 2:1, etc.);
the temperature of the mixed gas is 120-150 ℃ (for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃ or 150 ℃ and the like) and the pressure is 0.2-0.4 MPa (for example, 0.2 MPa, 0.25 MPa, 0.3 MPa, 0.35 MPa or 0.4 MPa and the like);
the speed of the plasma treatment is 0.1-1 m/min;
the power of the plasma treatment (i.e., ionization power) is 500-1000W (e.g., 500W, 600W, 700W, 800W, 900W or 1000W, etc.).
In the actual plasma treatment, the plasma treatment may be repeated for the same region. The plasma processing rate in the present invention refers to the average processing rate of the region, that is, the relative movement speed between the plasma shower head and the processing surface/the number of times of processing.
According to the invention, nitrogen and water vapor with the volume ratio of 0.5-2:1 are used as the medium, and the surface of vulcanized rubber is subjected to plasma treatment under specific conditions, so that the amino and hydroxyl contents on the surface of vulcanized rubber can be obviously improved and stably exist, and the specific surface area is increased. The free energy of the surface of the vulcanized rubber treated by the method is improved, the contact angle of the surface is obviously reduced, the wettability is improved, and the subsequent coating of the adhesive is facilitated; the improvement of the amino and hydroxyl contents ensures that the surface of vulcanized rubber can generate chemical bonding with the isocyanate groups of polyurethane through addition reaction, so that the bonding strength of the vulcanized rubber and the polyurethane is obviously improved, and finally the bonding effect between the vulcanized rubber and the polyurethane is improved.
In some embodiments of the invention, the step of plasma treating comprises: and introducing nitrogen and steam into a gas mixing chamber by using plasma equipment to mix, introducing the mixed gas of the nitrogen and the steam into a plasma generating device to ionize, and spraying the mixed gas on the surface of the vulcanized rubber.
In some embodiments of the invention, the surface treatment method further comprises: the surface of the vulcanized rubber was sanded with sandpaper prior to the plasma treatment.
Polishing the surface of vulcanized rubber can remove the compact vulcanized layer on the surface of vulcanized rubber, increase the specific surface area of vulcanized rubber, increase the total bonding area and facilitate final bonding.
In some embodiments of the invention, the sandpaper has a mesh size of 100-300 mesh; for example, the mesh size may be 100 mesh, 120 mesh, 150 mesh, 180 mesh, 200 mesh, 220 mesh, 250 mesh, 280 mesh, 300 mesh, or the like.
In some embodiments of the invention, the sanding depth is 20-40 μm; for example, it may be 20 μm, 22 μm, 25 μm, 28 μm, 30 μm, 32 μm, 35 μm, 38 μm or 40 μm, etc.
In some embodiments of the invention, the rubber is a polyolefin-based rubber.
In some embodiments of the invention, the polyolefin-based rubber is selected from one or more of natural rubber, styrene-butadiene rubber, and isoprene rubber.
In a second aspect, the present invention provides the use of a surface treatment method as described in the first aspect for the adhesion of vulcanized rubber to polyurethane.
In a third aspect, the present invention provides a method for producing a rubber-polyurethane composite tire, the method comprising the steps of:
(1) Treating the inner surface of the vulcanized rubber tread with the surface treatment method as described in the first aspect;
(2) Coating a polyurethane adhesive layer on the inner surface of the vulcanized rubber tread treated in the step (1);
(3) And (3) placing the vulcanized rubber tread treated in the step (2) in a mould, forming a polyurethane carcass at the inner side of the vulcanized rubber tread, and curing to obtain the rubber-polyurethane composite tire.
In the present invention, specific process conditions (e.g., coating manner, composition of the polyurethane adhesive layer, shape of the mold, method of forming the polyurethane carcass, material of the polyurethane carcass, curing method, etc.) of the step (2) and the step (3) are not particularly limited, and those skilled in the art may select according to conventional processes for preparing rubber-polyurethane composite tires in the art.
In some embodiments of the present invention, the polyurethane adhesive layer in step (2) comprises a primer polyurethane adhesive layer and a topcoat polyurethane adhesive layer, the primer polyurethane adhesive layer being interposed between the vulcanized rubber tread and the topcoat polyurethane adhesive layer.
Exemplary types of the primer polyurethane adhesives include, but are not limited to, TEROSON PU 8511, THINKBOND-12, THINKBOND-11H; the types of the top-coat polyurethane adhesive include, but are not limited to, THINKBOND-26M, THINKBOND-80.
In some embodiments of the invention, the primer polyurethane adhesive layer has a thickness of 15 to 25 μm; for example, 15 μm, 16 μm, 17 μm, 18 μm, 19 μm, 20 μm, 21 μm, 22 μm, 23 μm, 24 μm, 25 μm, or the like can be used.
In some embodiments of the invention, the topcoat polyurethane adhesive layer has a thickness of 25-35 μm; for example, 25 μm, 26 μm, 27 μm, 28 μm, 29 μm, 30 μm, 31 μm, 32 μm, 33 μm, 34 μm, 35 μm, or the like can be used.
In the invention, the thickness of the primer polyurethane adhesive layer and the surface coating polyurethane adhesive layer refers to the thickness of the adhesive layer after drying.
In some embodiments of the invention, the polyurethane carcass in step (3) is formed by a method of casting a CPU (cast polyurethane elastomer) or injection molding a TPU (thermoplastic polyurethane elastomer).
In a fourth aspect, the invention provides a rubber-polyurethane composite tire prepared by any one of the preparation methods.
Compared with the prior art, the invention has the following beneficial effects:
according to the surface treatment method for the vulcanized rubber, provided by the invention, nitrogen and water vapor are combined to be used as a medium, and plasma treatment is carried out on the surface of the vulcanized rubber, so that the specific surface area of the vulcanized rubber can be further increased, the amino and hydroxyl content of the surface is increased, the polarity is increased, chemical bonding with polyurethane can be formed, and the bonding strength of the vulcanized rubber and the polyurethane is improved.
The amino and hydroxyl groups on the surface of the vulcanized rubber treated by the method can exist stably, and the polarity of the rubber surface can be maintained stably after the primer adhesive is coated.
The medium used for plasma treatment in the surface treatment method provided by the invention is nitrogen and water vapor, the purity requirement is low, the air source is simple and easy to obtain, and the cost investment of the step is reduced.
The surface treatment method provided by the invention can obviously improve the high-low temperature static state bonding performance and dynamic fatigue bonding performance of the vulcanized rubber and polyurethane composite material, and is particularly suitable for bonding the vulcanized rubber tread of the rubber-polyurethane composite tire and the polyurethane carcass.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It should be apparent to those skilled in the art that the detailed description is merely provided to aid in understanding the invention and should not be taken as limiting the invention in any way.
Example 1
The embodiment provides a rubber-polyurethane composite tire, the preparation method of which comprises the following steps:
(1) Polishing the inner surface of the vulcanized annular tread by using an industrial polishing machine, (the inner surface is belt rubber, the belt rubber is mixed rubber taking natural rubber as a main body, the main components are 100 parts of natural rubber, 48 parts of carbon black, 3 parts of cobalt salt, 8 parts of wet zinc oxide, 1 part of age resistor 4020, 2 parts of age resistor RD, 4 parts of sulfur and 1 part of accelerator NOBS, the belt rubber is obtained by vulcanizing at 150 ℃ under the pressure condition of 0.7 MPa for 20 min), the mesh number of sand paper used is 300 meshes, and the polishing depth is 25 mu m; sucking rubber particles peeled off from the surface of the annular tread by using an industrial dust collector after polishing;
(2) Carrying out plasma treatment on the inner surface of the annular tread treated in the step (1), respectively providing two gas sources by using a high-pressure nitrogen cylinder and a water vapor generator, mixing nitrogen and water vapor in a volume ratio of 1:1 in a gas mixing chamber under the conditions of the temperature of 140 ℃ and the pressure of 0.4 MPa, introducing the mixed gas into a plasma generating device through a gas connecting pipe for ionization, spraying the mixed gas on the inner surface of the annular tread for plasma treatment, wherein the plasma treatment power is 1000W, and the plasma treatment speed is 0.4 m/min;
(3) Spraying a primer adhesive (THINKBOND-11H) on the inner surface of the annular tread treated in the step (2), and drying, wherein the thickness of the dried adhesive layer is 25 mu m; then spraying a surface gluing adhesive (THINKBOND-80), and drying, wherein the thickness of the dried adhesive layer is 30 mu m;
(4) Placing the annular tread treated in the step (3) into a prefabricated mold, and forming a polyurethane tire body through a TPU injection molding process, wherein the TPU is WANTHANE ® WHT-1695AB, TPU particles are injected into a die in a melt form at the processing temperature of 192-215 ℃ in an injection molding machine, the pressure is maintained for 5 min under the pressure condition of 65 bar, and the rubber-polyurethane composite tire is obtained after cooling molding.
Example 2
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 220, the polishing depth is 28 mu M, the volume ratio of hot nitrogen to hot water vapor is 0.5:1, the air pressure of mixed gas is 0.3M Pa, the temperature of the mixed gas is 120 ℃, the plasma treatment power is 1000W, and the plasma treatment speed is 1M/min;
gluing: the thickness of the adhesive layer after the primer adhesive and the surface adhesive are dried is 25 μm and 35 μm respectively.
Example 3
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 120 meshes, the polishing depth is 35 mu m, the volume ratio of hot nitrogen to hot water vapor is 0.5:1, the mixed gas pressure is 0.2 MPa, the mixed gas temperature is 125 ℃, the plasma treatment power is 500W, and the plasma treatment speed is 0.3 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Example 4
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 120 meshes, the polishing depth is 38 mu m, the volume ratio of hot nitrogen to hot water vapor is 1:1, the mixed gas pressure is 0.2 MPa, the mixed gas temperature is 130 ℃, the plasma treatment power is 1000W, and the plasma treatment speed is 0.3 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Example 5
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 300 meshes, the polishing depth is 40 mu m, the volume ratio of hot nitrogen to hot water vapor is 1.5:1, the mixed gas pressure is 0.3 MPa, the mixed gas temperature is 150 ℃, the plasma treatment power is 900W, and the plasma treatment speed is 0.5 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Example 6
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 100 meshes, the polishing depth is 40 mu m, the volume ratio of hot nitrogen to hot water vapor is 1:1, the air pressure of mixed gas is 0.4 MPa, and the plasma treatment power is 1000W;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 25 mu m.
Example 7
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 220, the polishing depth is 28 mu m, the volume ratio of hot nitrogen to hot water vapor is 2:1, the mixed gas pressure is 0.3 MPa, the plasma treatment power is 1000W, and the plasma treatment speed is 1m/min;
gluing: the thickness of the adhesive layer after the primer adhesive and the surface adhesive are dried is 25 μm and 35 μm respectively.
Example 8
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 120 meshes, the polishing depth is 35 mu m, the volume ratio of hot nitrogen to hot water vapor is 0.5:1, the air pressure of mixed gas is 0.2 MPa, the plasma treatment power is 500W, and the plasma treatment speed is 0.1 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Example 9
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 300 meshes, the polishing depth is 38 mu m, the volume ratio of hot nitrogen to hot water vapor is 1.7:1, the air pressure of mixed gas is 0.4 MPa, the plasma treatment power is 1000W, and the plasma treatment speed is 0.3 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Example 10
This example provides a rubber-polyurethane composite tire, which differs from example 1 in that:
surface treatment: the number of sand paper for polishing is 150 meshes, the polishing depth is 30 mu m, the volume ratio of hot nitrogen to hot water vapor is 1:1, the mixed gas pressure is 0.4 MPa, the plasma treatment power is 1000W, and the plasma treatment speed is 0.5 m/min;
gluing: the thickness of the adhesive layer after the bottom adhesive layer and the surface adhesive layer are dried is 15 μm and 35 μm respectively.
Comparative example 1
This comparative example provides a rubber-polyurethane composite tire differing from example 6 in that step (3) is performed directly with the annular tread treated in step (1) without performing step (2).
Comparative example 2
This comparative example provides a rubber-polyurethane composite tire differing from example 7 in that step (3) is performed directly with the annular tread treated in step (1) without performing step (2).
Comparative example 3
This comparative example provides a rubber-polyurethane composite tire differing from example 8 in that step (3) is performed directly with the annular tread treated in step (1) without performing step (2).
Comparative example 4
This comparative example provides a rubber-polyurethane composite tire differing from example 9 in that step (3) is performed directly with the annular tread treated in step (1) without performing step (2).
Comparative example 5
This comparative example provides a rubber-polyurethane composite tire differing from example 10 in that step (3) is performed directly with the annular tread treated in step (1) without performing step (2).
Comparative example 6
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in the volume ratio of nitrogen to water vapor being 1:4.
Comparative example 7
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in the volume ratio of nitrogen to water vapor being 4:1.
Comparative example 8
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the temperature of the mixed gas is 80 ℃.
Comparative example 9
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the temperature of the mixed gas is 170 ℃.
Comparative example 10
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the pressure of the mixed gas is 0.15 MPa.
Comparative example 11
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the pressure of the mixed gas is 0.5 MPa.
Comparative example 12
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the power of the plasma treatment is 400W.
Comparative example 13
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in that the power of the plasma treatment is 1200W.
Comparative example 14
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in the rate of plasma treatment of 2 m/min.
Comparative example 15
This comparative example provides a rubber-polyurethane composite tire differing from example 1 only in the rate of plasma treatment of 0.02 m/min.
Performance test:
1. contact angle test: the contact angle reflects the liquid wettability of vulcanized rubber after surface treatment, and has strong relevance with the subsequent gluing effect. The smaller the contact angle is, the better the surface wettability is, and the better the gluing effect is. The present invention uses the contact angle measuring instrument (DSA 25E) of KRUSS company in germany under normal temperature and pressure (temperature and humidity are 25 ℃ and 55% rh, respectively) to perform contact angle test on the vulcanized rubber surface at the time of finishing the surface treatment (0 h) and at the time of placing 48h after finishing the surface treatment in the above examples and comparative examples, so as to verify the timeliness thereof. The test results are shown in table 1 below.
TABLE 1
As shown by the test results in Table 1, the contact angle of the vulcanized rubber treated by the surface treatment method is obviously reduced, and the smaller contact angle can be still maintained after the vulcanized rubber is placed by 48 and h, so that the surface treatment method can effectively improve the wettability of the surface of the vulcanized rubber, and is beneficial to the subsequent gluing work.
Compared with the embodiment 1, the volume ratio of nitrogen to water vapor in the comparative example 6 is smaller, so that the quantity of amino groups on the surface of the rubber after treatment is far smaller than that of hydroxyl groups, the contact angle is greatly improved after the rubber is placed for 48 hours, the timeliness of infiltration is poor, and the gluing effect is affected; the volume ratio of nitrogen to water vapor in comparative example 7 is larger, so that the quantity of amino groups on the surface of the treated rubber is far greater than that of hydroxyl groups, the contact angle is greatly improved after the treated rubber is placed for 48 hours, the timeliness of infiltration is poor, and the gluing effect is affected.
Compared with the embodiment 1, the temperature of the mixed gas in the comparative example 8 is lower, so that the water vapor in the mixed gas is condensed, the hydroxyl number on the surface of the rubber after treatment is small, the wettability on the surface of the rubber is greatly reduced, and the gluing effect is greatly influenced; in comparative example 9, the temperature of the mixed gas is higher, so that a compact oxide layer appears on the surface of the treated rubber, and the wettability of the surface of the rubber is greatly reduced, thereby greatly influencing the gluing effect.
Compared with the embodiment 1, the pressure of the mixed gas in the comparative example 10 is smaller, so that the quantity of amino groups and hydroxyl groups on the surface of the rubber after treatment is smaller, the surface wettability is poor, and the gluing effect is affected; the pressure of the mixed gas in comparative example 11 is too high, so that the quantity of amino groups and hydroxyl groups on the surface of the rubber after treatment is too high, side reactions occur, the wettability of the surface of the rubber is greatly reduced, and the gluing effect is greatly affected.
Compared with the example 1, the plasma treatment in the comparative example 12 has lower power, so that the ionization effect of the plasma is reduced, the quantity of amino groups and hydroxyl groups on the surface of the rubber after the treatment is less, the surface wettability is poor, and the gluing effect is influenced; the plasma treatment power in comparative example 13 is higher, so that a compact oxide layer appears on the surface of the treated rubber, and the wettability of the surface of the rubber is greatly reduced, thereby greatly influencing the rubber coating effect.
Compared with the example 1, the plasma treatment speed in the comparative example 14 is larger, so that the residence time of ionized gas on the rubber surface is shorter, the effect on rubber surface modification is greatly reduced, the number of amino groups and hydroxyl groups on the treated rubber surface is smaller, the surface wettability is poor, and the gluing effect is influenced; the plasma treatment rate in comparative example 15 is smaller, so that the residence time of ionized gas on the rubber surface is longer, the number of amino groups and hydroxyl groups on the rubber surface after treatment is too high, side reactions are caused, the wettability of the rubber surface is greatly reduced, and the rubber coating effect is greatly affected.
2. And (3) adhesive property test: adhesive test pieces were prepared according to the methods of examples and comparative examples of the present invention, and adhesive property test was performed. The bonding performance of the invention comprises static bonding performance and dynamic fatigue bonding performance. The method for evaluating the static bonding performance refers to the method for testing the T peeling strength of a flexible material by using a national standard GBT2791-1995 adhesive, wherein related tests are carried out on the flexible material by using a universal tensile testing machine, the normal temperature test is carried out at 25 ℃, the test at 100 ℃ is carried out in an environment box, and the T-type peeling strength is obtained according to a standard calculation method; (2) The dynamic fatigue bonding performance test is carried out on a fatigue testing machine, a bonding sample block is clamped on the fatigue testing machine (one end is made of rubber, the other end is made of polyurethane, a bonding surface is positioned on a middle line of an upper clamp and a lower clamp), a pull-press test is carried out at a frequency of 30 Hz, a strain of 20% and a duration of 100 h, and if the test is finished and a degumming phenomenon does not occur, the dynamic fatigue bonding test is considered to be passed, otherwise, the dynamic fatigue bonding test is not passed. The test results are shown in table 2 below.
TABLE 2
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Cohesive failure of the rubber means that the adhesive strength of the gelatin adhesive to the rubber is sufficiently high; the adhesive and the rubber are separated, so that the adhesive property of the gelatin adhesive and the rubber is poor.
As can be seen from the test results in Table 2, compared with comparative examples 1 to 5 (without plasma treatment), the rubber-polyurethane composite tires provided in examples 6 to 10 have higher normal temperature T-type peel strength at 100 ℃ and better fatigue resistance, indicating that the surface treatment method provided by the invention can remarkably improve the adhesion performance of vulcanized rubber and polyurethane.
Compared with the embodiment 1, the volume ratio of nitrogen to water vapor in the comparative example 6 is smaller, so that the timeliness of the surface infiltration of the rubber is poorer, the gluing effect is affected, and the adhesive property is reduced; in the comparative example 7, the volume ratio of nitrogen to water vapor is larger, so that the timeliness of the surface infiltration of the rubber is poor, the gluing effect is affected, and the adhesive property is reduced.
Compared with the embodiment 1, the temperature of the mixed gas in the comparative example 8 is lower, so that the water vapor in the mixed gas is condensed, the hydroxyl number on the surface of the rubber after treatment is small, the wettability on the surface of the rubber is greatly reduced, the gluing effect is greatly influenced, and the adhesive property is greatly reduced; in comparative example 9, the temperature of the mixed gas is higher, so that a compact oxide layer appears on the surface of the treated rubber, the wettability of the surface of the rubber is greatly reduced, the gluing effect is greatly affected, and the adhesive property is greatly reduced.
Compared with the embodiment 1, the pressure of the mixed gas in the comparative example 10 is smaller, so that the quantity of amino groups and hydroxyl groups on the surface of the rubber after treatment is smaller, the surface wettability is poor, the gluing effect is affected, and the adhesive property is poor; the pressure of the mixed gas in comparative example 11 is too high, so that the quantity of amino groups and hydroxyl groups on the surface of the treated rubber is too high, side reactions occur, the wettability of the surface of the rubber is greatly reduced, the gluing effect is greatly affected, and the adhesive property is deteriorated.
Compared with the example 1, the plasma treatment in the comparative example 12 has lower power, so that the ionization effect of the plasma is reduced, the number of amino groups and hydroxyl groups on the surface of the treated rubber is smaller, the surface wettability is poor, the gluing effect is affected, and the adhesive property is poor; the plasma treatment in comparative example 13 has higher power, which results in the appearance of a dense oxide layer on the surface of the treated rubber, but greatly reduces the wettability of the surface of the rubber, greatly influences the gluing effect and deteriorates the adhesive property.
Compared with the example 1, the plasma treatment speed in the comparative example 14 is larger, so that the residence time of ionized gas on the rubber surface is shorter, the effect on the rubber surface modification is greatly reduced, the number of amino groups and hydroxyl groups on the treated rubber surface is smaller, the surface wettability is poor, the gluing effect is affected, and the adhesive property is poor; the plasma treatment rate in comparative example 15 was low, resulting in a long residence time of ionized gas on the rubber surface, and the number of amino groups and hydroxyl groups on the rubber surface after the treatment was too high, resulting in side reactions, which in turn greatly reduced the wettability of the rubber surface, greatly affected the rubber coating effect, and deteriorated the adhesive property.
The foregoing is merely a specific embodiment of the disclosure to enable one skilled in the art to understand or practice the disclosure. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown and described herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (8)

1. A method for preparing a rubber-polyurethane composite tire, comprising the steps of:
(1) Adopting a surface treatment method to treat the inner surface of the vulcanized rubber tread;
the surface treatment method comprises the following steps:
the surface of vulcanized rubber is subjected to plasma treatment by taking the mixed gas of nitrogen and water vapor as a medium;
the volume ratio of the nitrogen to the water vapor is 0.5-2:1;
the temperature of the mixed gas is 120-150 ℃ and the pressure is 0.2-0.4 MPa;
the speed of the plasma treatment is 0.1-1 m/min;
the power of the plasma treatment is 500-1000W;
wherein the rubber is polyolefin rubber, and the polyolefin rubber is one or more selected from natural rubber, styrene-butadiene rubber, butadiene rubber and isoprene rubber;
(2) Coating a polyurethane adhesive layer on the inner surface of the vulcanized rubber tread treated in the step (1);
(3) And (3) placing the vulcanized rubber tread treated in the step (2) in a mould, forming a polyurethane carcass at the inner side of the vulcanized rubber tread, and curing to obtain the rubber-polyurethane composite tire.
2. The method of manufacturing according to claim 1, wherein the step of plasma treatment comprises: and introducing nitrogen and steam into a gas mixing chamber by using plasma equipment to mix, introducing the mixed gas of the nitrogen and the steam into a plasma generating device to ionize, and spraying the mixed gas on the surface of the vulcanized rubber.
3. The production method according to claim 1 or 2, characterized in that the surface treatment method further comprises: the surface of the vulcanized rubber was sanded with sandpaper prior to the plasma treatment.
4. A method of making according to claim 3 wherein the sandpaper has a mesh size of 100-300 mesh;
and/or the polishing depth is 20-40 μm.
5. The method of claim 1, wherein the polyurethane adhesive layer in step (2) comprises a primer polyurethane adhesive layer and a topcoat polyurethane adhesive layer, the primer polyurethane adhesive layer being interposed between the vulcanized rubber tread and the topcoat polyurethane adhesive layer.
6. The method of claim 5, wherein the primer polyurethane adhesive layer has a thickness of 15 to 25 μm;
and/or the thickness of the surface-coated polyurethane adhesive layer is 25-35 mu m.
7. The method of claim 1, wherein the polyurethane carcass in step (3) is formed by casting CPU or injection molding TPU.
8. A rubber-polyurethane composite tire prepared by the preparation method of any one of claims 1 to 7.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057414A (en) * 1999-02-24 2000-05-02 Micron Coating, Inc. Process of plasma treating polymer materials
CN1788970A (en) * 2005-12-05 2006-06-21 广州华工百川自控科技有限公司 Polyester-rubber composite tyre and its production method
CN1915648A (en) * 2006-08-18 2007-02-21 广州华工百川自控科技有限公司 Method for preparing composite procuring tread of polyurethane - common rubber in use for recap
DE102012220286A1 (en) * 2012-11-07 2014-05-08 Tesa Se Increasing adhesion between pressure-sensitive adhesive layer comprising surface facing opposite to substrate and surface facing substrate, and surface of substrate, comprises treating substrate facing surface of adhesive layer with plasma
CN108410372A (en) * 2018-04-03 2018-08-17 苏州睿研纳米医学科技有限公司 The adhering method and silicon rubber bond of silicon rubber
CN114161739A (en) * 2021-12-07 2022-03-11 广州悍马轮胎科技有限公司 Composite tyre and manufacturing method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6057414A (en) * 1999-02-24 2000-05-02 Micron Coating, Inc. Process of plasma treating polymer materials
CN1788970A (en) * 2005-12-05 2006-06-21 广州华工百川自控科技有限公司 Polyester-rubber composite tyre and its production method
AU2006203253A1 (en) * 2005-12-05 2007-06-21 Bestire (Xin Xing) New Material Technology Co., Ltd. Method for manufacturing a composite tire of polyurethane tread and radial carcase
CN1915648A (en) * 2006-08-18 2007-02-21 广州华工百川自控科技有限公司 Method for preparing composite procuring tread of polyurethane - common rubber in use for recap
DE102012220286A1 (en) * 2012-11-07 2014-05-08 Tesa Se Increasing adhesion between pressure-sensitive adhesive layer comprising surface facing opposite to substrate and surface facing substrate, and surface of substrate, comprises treating substrate facing surface of adhesive layer with plasma
CN108410372A (en) * 2018-04-03 2018-08-17 苏州睿研纳米医学科技有限公司 The adhering method and silicon rubber bond of silicon rubber
CN114161739A (en) * 2021-12-07 2022-03-11 广州悍马轮胎科技有限公司 Composite tyre and manufacturing method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
全氟橡胶:应对新挑战;陆明;苏正涛;;橡胶参考资料(第06期);4-12 *
增强硫化橡胶与金属粘接的表面处理技术;石磊;;材料开发与应用(第03期);37-42 *
复合材料胶接表面的等离子处理技术;袁协尧;杨洋;陈萍;刘卫平;;玻璃钢/复合材料(第05期);95-101 *

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