CN111732842A - Method for improving compatibility of carbon-based material in tire and flame-retardant tire tread using carbon-based material - Google Patents
Method for improving compatibility of carbon-based material in tire and flame-retardant tire tread using carbon-based material Download PDFInfo
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- CN111732842A CN111732842A CN202010631023.8A CN202010631023A CN111732842A CN 111732842 A CN111732842 A CN 111732842A CN 202010631023 A CN202010631023 A CN 202010631023A CN 111732842 A CN111732842 A CN 111732842A
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- Prior art keywords
- carbon
- montan wax
- based material
- expanded graphite
- tire
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Classifications
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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
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
- C09C1/48—Carbon black
- C09C1/56—Treatment of carbon black ; Purification
-
- 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
- B60C11/00—Tyre tread bands; Tread patterns; Anti-skid inserts
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
- C09C3/043—Drying, calcination
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
A method for improving the compatibility of carbon-based materials in tires and a flame-retardant tire tread using the carbon-based materials comprises the following steps: providing a carbon-based material; and (3) placing the carbon-based material in the montan wax solution, fully mixing, and removing the solvent in the montan wax solution to obtain residues, namely the modified carbon-based material. The carbon-based material is expanded graphite, and the montan wax solution is a toluene solution of montan wax. The expanded graphite has more pore structures and unsaturated groups, and is easy to generate excessive bonding reaction in the tire synthesis process, so that the wear resistance of the tire tread is lower than that of carbon black, and the trend is reduced after modification by the montan wax, and the wear resistance of the tire tread adopting the expanded graphite is improved.
Description
Technical Field
The application relates to a method for improving the compatibility of a carbon-based material in a tire and a flame-retardant tire tread using the carbon-based material.
Background
In the process of preparing the tire, carbon materials are generally required to be added to increase the wear resistance of the tire, and carbon black and the like are generally selected as the existing carbon materials. As a conventional component of a tire, carbon black is added to basically play a role of abrasion resistance, and for some special tires such as flame-retardant tires, phosphorus-containing flame retardants, inorganic flame retardants and the like are mostly adopted at present, so that some other functional substances need to be introduced, but the substances have certain adverse effects on the properties of the tires.
Disclosure of Invention
In order to solve the above problems, the present application proposes, in one aspect, a method of improving the compatibility of a carbon-based material in a tire, comprising the steps of: providing a carbon-based material;
and (3) placing the carbon-based material in the montan wax solution, fully mixing, and removing the solvent in the montan wax solution to obtain residues, namely the modified carbon-based material.
Preferably, the carbon-based material is expanded graphite, the montan wax solution is a toluene solution of montan wax, and the steps are as follows: extracting toluene from lignite by using toluene to obtain a toluene solution of montan wax or dissolving montan wax in toluene to obtain a toluene solution, then adding expanded graphite, fully stirring, and then carrying out micro-negative pressure constant pressure drying to obtain the montan wax modified expanded graphite. The expanded graphite has more pore structures and unsaturated groups, and is easy to generate excessive bonding reaction in the tire synthesis process, so that the wear resistance of the tire tread is lower than that of carbon black, and the trend is reduced after modification by the montan wax, and the wear resistance of the tire tread adopting the expanded graphite is improved.
Preferably, the expanded graphite is placed in an ultrasonic cleaning machine during the process of immersing the expanded graphite in the toluene solution, and the ultrasonic vibration time is not less than 30 min.
In another aspect, a flame retardant tire tread: the composite material comprises the following raw materials in parts by weight: rubber: 80-100 parts of a binder; carbon-based material: 24-38 parts; sulfur: 1-1.8 parts; zinc oxide: 0.5-3 parts; an anti-aging agent: 1-3 parts. This application has introduced two kinds of fire-retardant material, one is expanded graphite, one is silica gel, because expanded graphite still need play the function that improves the wearability, consequently under the condition of not modification treatment, can reduce the performance of tread, and then there is the problem with other material fusibility to silica gel, consequently on the basis of introducing expanded graphite and silica gel, modification treatment has still been carried out to this application, with under the prerequisite that improves tread fire resistance, can also guarantee other parameter requirements, if the requirement to the wearability.
Preferably, the emulsion also comprises tert-butyl peroxybenzoate, and the mass part is 0.1-0.3 part.
Preferably, the rubber comprises the following raw materials in percentage by mass: butadiene rubber: 60-90 parts; silica gel: 10-20 parts.
Preferably, the montan wax is a residue obtained by repeatedly washing montan with toluene as a solvent to obtain a solution containing an extract, and then distilling off the solvent from the toluene under mild conditions.
Preferably, the preparation process is as follows: modifying silica gel by tert-butyl oxybenzoate to obtain methyl sulfide silica gel, and modifying expanded graphite by montan wax to obtain montan wax modified expanded graphite; and then putting the vulcanized methyl silica gel, the lignite wax modified expanded graphite, the butadiene rubber, the zinc oxide and the anti-aging agent into an internal mixer for primary internal mixing, cooling, and then adding sulfur for secondary internal mixing to obtain the tread. This application vulcanizes silica gel earlier, namely pass through oxidation component network structure with linear methyl silica gel, this at first is in order to make methyl silica gel exist with the mode of a cluster in the tire in later stage, combines the expanded graphite of equipartition, has formed the network of an isolated oxygen and burning to fire-retardant effect has been played.
Preferably, after once banburying, once cooling and then once standing treatment are carried out, wherein the time of once standing is not less than 3 hours.
Preferably, after the secondary banburying, the secondary cooling is performed, and then the secondary standing treatment is performed, wherein the time of the secondary standing is not less than 5 hours.
This application can bring following beneficial effect:
1. the expanded graphite has more pore structures and unsaturated groups, and is easy to generate excessive bonding reaction in the tire synthesis process, so that the wear resistance of the tire tread is lower than that of carbon black, and the trend is reduced after modification by the montan wax, and the wear resistance of the tire tread adopting the expanded graphite is improved;
2. the tire tread is characterized in that two flame-retardant substances are introduced, one is expanded graphite and the other is silica gel, and the expanded graphite also needs to have the function of improving the wear resistance, so that the performance of the tire tread can be reduced under the condition of not modifying, and the silica gel has the problem of fusibility with other materials, so that on the basis of introducing the expanded graphite and the silica gel, the tire tread is modified, and on the premise of improving the flame retardance of the tire tread, other parameter requirements can be ensured;
3. this application vulcanizes silica gel earlier, namely pass through oxidation component network structure with linear methyl silica gel, this at first is in order to make methyl silica gel exist with the mode of a cluster in the tire in later stage, combines the expanded graphite of equipartition, has formed the network of an isolated oxygen and burning to fire-retardant effect has been played.
Detailed Description
In order to clearly illustrate the technical features of the present solution, the present application will be explained in detail through the following embodiments.
In a first embodiment, a method of preparing a flame-retardant tire tread is performed as follows:
s1, preparing raw materials:
and (3) vulcanizing methyl silica gel: vulcanizing methyl silica gel by using tert-butyl peroxybenzoate, wherein the specific mass is shown in table 1;
modified expanded graphite: repeatedly washing lignite by using methylbenzene as a solvent to obtain a solution containing an extract, wherein the mass ratio of the methylbenzene to the dried lignite is 1:1, adding expanded graphite after the extract is colorless and transparent, fully stirring, and then drying under a micro-negative pressure and a constant pressure to obtain expanded graphite attached with montan wax, and measuring the relative amount of residual montan wax methylbenzene before and after the expanded graphite is attached to obtain the mass ratio of the expanded graphite to the montan wax;
s2, tire tread banburying:
placing the expanded graphite attached with the montan wax, the zinc oxide and the anti-aging agent into an internal mixer for primary internal mixing, carrying out primary standing treatment after primary cooling, wherein the primary standing time is 3 hours, then adding the sulfur for secondary internal mixing, carrying out secondary standing treatment after secondary cooling, and the secondary standing time is 5 hours; the contents of the components are shown in Table 1;
table 1:
s3, taking S2 to obtain a tread material, and measuring the tensile strength and the limiting oxygen index as shown in Table 2.
Table 2:
| serial number | Tensile strength (Mpa) | Limiting oxygen index (%) |
| 1 | 12.5 | 35.3 |
| 2 | 13.2 | 36.2 |
| 3 | 11.8 | 34.8 |
| 4 | 7.3 | 27.4 |
| 5 | 8.1 | 28.5 |
| 6 | 8.4 | 27.8 |
| 7 | 7.8 | 26.5 |
| 8 | 8.2 | 25.4 |
| 9 | 8.3 | 29.2 |
Therefore, the expanded graphite is modified, and the silica gel is arranged, so that the tread material obtained by the method has very good flame retardant performance on the premise of better tensile strength.
In a second example, the carbon-based material obtained in the present application can also be used for steel wire encapsulation to improve the combination of strength and toughness, and the synthesis method of the steel wire encapsulation is as follows.
S1, preparing raw materials:
tire pyrolysis oil: placing the tire in a pyrolysis furnace, wherein the pyrolysis temperature is 420-500 ℃, the absolute pressure of operation is 0.07-0.09MPa, condensing the obtained gas to obtain tire pyrolysis oil, and distilling the primary oil obtained after condensation to obtain 300-400 ℃ fraction which is the tire pyrolysis oil;
modified carbon black: repeatedly washing lignite by using toluene as a solvent to obtain a solution containing an extract, wherein the mass ratio of the toluene to the dried lignite is 1:1, adding carbon black after the extract is colorless and transparent, fully stirring, and then drying under a micro-negative pressure and a constant pressure to obtain carbon black attached with montan wax, and measuring the relative amount of residual montan wax toluene before and after the carbon black is attached to obtain the mass ratio of the carbon black to the montan wax;
s2, tire tread banburying:
putting the carbon black, the rubber, the carbon black, the montan wax, the silane coupling agent, the stearic acid and the paraffin wax attached with the montan wax into an internal mixer for primary internal mixing, carrying out primary standing treatment after primary cooling, wherein the primary standing time is 3 hours, then adding the sulfur, the phenolic resin and the tire pyrolysis oil for secondary internal mixing, carrying out secondary standing treatment after secondary cooling, and the secondary standing time is 5 hours; the contents of the respective components are shown in Table 3;
table 3:
s3, preparing a tire bead:
and S2, obtaining a rubber coating material, placing the rubber coating material in a four-roll calender, introducing the steel cord into the calender at equal intervals, and coating rubber on the surface of the steel cord at the temperature of 100 ℃ to obtain the tire bead.
S4, measuring the tensile strength and the steel wire bonding strength of the tire bead, wherein the specific data are shown in Table 4.
Table 4:
| serial number | Tensile strength (Mpa) | Adhesion strength to Steel wire (N/50mm) |
| 1 | 23 | 2500 |
| 2 | 25 | 2450 |
| 3 | 22 | 2600 |
| 4 | 18 | 1800 |
| 5 | 19 | 1850 |
| 6 | 19 | 1700 |
| 7 | 17 | 1650 |
| 8 | 18 | 1600 |
| 9 | 18 | 1750 |
Therefore, the carbon black, the phenolic resin and the tire pyrolysis oil which are modified by the montan wax can greatly improve the tensile strength and the bonding strength with steel wires, and have more optimized properties compared with paraffin modified carbon black or unmodified carbon black and no phenolic resin or tire pyrolysis oil, so that the mechanical property of the tire bead is greatly improved.
The embodiments in the present specification are described in a progressive manner, and the same and similar parts among the embodiments are referred to each other, and each embodiment focuses on the differences from the other embodiments. In particular, for the system embodiment, since it is substantially similar to the method embodiment, the description is simple, and for the relevant points, reference may be made to the partial description of the method embodiment.
The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. A method of improving the compatibility of carbon-based materials in a tire, characterized by: the method comprises the following steps: providing a carbon-based material;
and (3) placing the carbon-based material in the montan wax solution, fully mixing, and removing the solvent in the montan wax solution to obtain residues, namely the modified carbon-based material.
2. A method of improving the compatibility of carbon-based materials in a tire as in claim 1, wherein: the carbon-based material is expanded graphite, the montan wax solution is a toluene solution of montan wax, and the steps are as follows: extracting toluene from lignite by using toluene to obtain a toluene solution of montan wax or dissolving montan wax in toluene to obtain a toluene solution, then adding expanded graphite, fully stirring, and then carrying out micro-negative pressure constant pressure drying to obtain the montan wax modified expanded graphite.
3. The method of claim 2, wherein the carbon-based material is selected from the group consisting of: and (3) placing the expanded graphite in an ultrasonic cleaning machine in the process of immersing the expanded graphite in the toluene solution, wherein the ultrasonic vibration time is not less than 30 min.
4. A flame retardant tire tread with the carbon-based material of any one of claims 1 to 3: the composite material comprises the following raw materials in parts by weight: rubber: 80-100 parts of a binder; carbon-based material: 24-38 parts; sulfur: 1-1.8 parts; zinc oxide: 0.5-3 parts; an anti-aging agent: 1-3 parts.
5. A flame retarded tire tread according to claim 4, wherein: and tert-butyl peroxybenzoate in 0.1-0.3 weight portions.
6. A flame retarded tire tread according to claim 4, wherein: the rubber comprises the following raw materials in percentage by mass: butadiene rubber: 60-90 parts; silica gel: 10-20 parts.
7. A flame retarded tire tread as in claim 1, wherein: the montan wax is residue obtained by repeatedly washing lignite with toluene as a solvent to obtain a solution containing an extract, and then distilling off the solvent from the toluene under mild conditions.
8. A flame retarded tire tread as in claim 1, wherein: the preparation process comprises the following steps: modifying silica gel by tert-butyl oxybenzoate to obtain methyl sulfide silica gel, and modifying expanded graphite by montan wax to obtain montan wax modified expanded graphite; and then putting the vulcanized methyl silica gel, the lignite wax modified expanded graphite, the butadiene rubber, the zinc oxide and the anti-aging agent into an internal mixer for primary internal mixing, cooling, and then adding sulfur for secondary internal mixing to obtain the tread.
9. A flame retarded tire tread according to claim 8, wherein: and carrying out primary banburying, primary cooling and primary standing treatment, wherein the primary standing time is not less than 3 h.
10. A flame retarded tire tread according to claim 8, wherein: and after secondary banburying, carrying out secondary standing treatment after secondary cooling, wherein the time of secondary standing is not less than 5 h.
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| CN202010631023.8A CN111732842B (en) | 2020-07-03 | 2020-07-03 | Method for improving compatibility of carbon-based material in tire and flame-retardant tire tread using carbon-based material |
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| CN202010631023.8A CN111732842B (en) | 2020-07-03 | 2020-07-03 | Method for improving compatibility of carbon-based material in tire and flame-retardant tire tread using carbon-based material |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2336741A2 (en) * | 2008-02-05 | 2010-04-15 | David Cano Anton | Manufactured pneumatic, among other materials, with pcm materials (Machine-translation by Google Translate, not legally binding) |
| US20170342240A1 (en) * | 2016-05-25 | 2017-11-30 | Leibniz-Institut Fuer Polymerforschung Dresden E.V. | Rubber or elastomer compositions and processes for their manufacturing |
| CN109912986A (en) * | 2019-03-05 | 2019-06-21 | 中国工程物理研究院化工材料研究所 | A kind of wax class aggregation and preparation method thereof of carbons powder thickening |
-
2020
- 2020-07-03 CN CN202010631023.8A patent/CN111732842B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2336741A2 (en) * | 2008-02-05 | 2010-04-15 | David Cano Anton | Manufactured pneumatic, among other materials, with pcm materials (Machine-translation by Google Translate, not legally binding) |
| US20170342240A1 (en) * | 2016-05-25 | 2017-11-30 | Leibniz-Institut Fuer Polymerforschung Dresden E.V. | Rubber or elastomer compositions and processes for their manufacturing |
| CN109912986A (en) * | 2019-03-05 | 2019-06-21 | 中国工程物理研究院化工材料研究所 | A kind of wax class aggregation and preparation method thereof of carbons powder thickening |
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