CN102250394B - Tire stock of IPN (Interpenetrating Polymer Network) crosslinked structure and mixing method as well as application thereof - Google Patents
Tire stock of IPN (Interpenetrating Polymer Network) crosslinked structure and mixing method as well as application thereof Download PDFInfo
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Abstract
The invention relates to the field of rubber tires, in particular to a tire stock and a mixing method as well as application thereof. The tire stock of an IPN (Interpenetrating Polymer Network) crosslinked structure is prepared by mixing the following raw material components in part by weight: 100 parts of first network material, 0.1-30 parts of second network material, 0.8-20 parts of co-melting assistant, 20-150 parts of carbon black, 1-30 parts of activating agent, 0-50 parts of softening agent, 0-20 parts of anti-aging agent, 0.1-10 parts of vulcanizing agent and 0.1-20 parts of vulcanization accelerator, wherein the first network material is one or the combination of more selected from diene rubbers; and the second network material is selected from natural resin or synthetic resin providing a crosslink bond and monomer of the synthetic resin. In the invention, the advantages of superior temperature resistance, high shear strength resistance and high torsion deformation resistance of an IPN vulcanization network bond are integrated while each item of physical performance and processing performance of the conventional single sulfur crosslink bond are kept; and the service performance of a tire formula is improved to the greatest extent.
Description
Technical field
The present invention relates to the rubber tyre field, relate in particular to a kind of tyre stock and compounding process thereof and application.
Background technology
Generally, the rubber compounding of each parts of rubber tyre, material of main part is take the synthetic rubber of the natural rubber of dienes or dienes as main, therefore, and when the design vulcanization system, mostly be the sulfur cross-linking system, when vulcanization crosslinking, its cross-link bond mostly is single cross-link bond, as use half the most general effective and effective sulfur cross-linking system in tire formulation, when vulcanization crosslinking, its cross-link bond namely is single "-S
X-" key, (" X " wherein can be according to performance need, is the different numeral such as 1～6); The peroxide vulcanizing system of and for example using occasionally in the Rubber Parts prescription, its cross-link bond then are single "-C-C-" keys etc.
The IPN technology is to utilize the method for chemistry or physics, two or more the macromolecular chain of different properties, the different molecular structures macromolecular chain that interts and obtain that crosses one another is curled up mixed system, in the film or coating that is applied to make with solution method or emulsion method more, and for the viscoelastic macromolecular material of the height IPN technology of elastomeric material particularly, because material itself is solid-state, therefore, can not finish the IPN technology with solution method, emulsion method or approximate method.
Disclosed IPN technology is at present except at macromolecule membrane, have on the high-molecular coating outside the report on probation, because the technical difficulty of its complete processing and the unstable of performance, there are no any report of in tire formulation, using, major cause is, the IPN processing technology of open report must be passed through the solution osmose process, emulsion dispersion or approximate method are mutually intersected the fractionated polymer subchain of several different structures to intert and are made, and this intersection is interted only be Wu Li Chan around, and this manufacture method is the technique that impossible realize in the tire manufacturing is produced, because tire material all is solid material, be impossible use the solution osmose process under present manufacturing condition, emulsion dispersion or approximate method are processed.
The patent of relevant IPN is a lot, typical IPN patent, patent such as the people such as J. Ka Tehaoze invention " is produced the method for interpenetrating polymer networks IPN, IPN and uses thereof ", the technology that relates to is to produce the silicone polymer of interpenetrating polymer networks with solvent method by monomer polymerization, and technology relates to is and the production method of tire without any related silicone polymer; The emerging patent that waits people's invention of Li Rong " interpenetrating(polymer)networks elastic composition and make the method for relevant elastomer product " and for example, the technology that relates to is that what technology related to also is without any related a kind of method of producing thermoplastic elastomer with tire with the thermoplastic elastomer polymer of emulsion method by monomer polymerization production interpenetrating polymer networks; Plum and for example. the patent " interpenetrating(polymer)networks and methods involving and composition " of the people such as Griffith, Li Fengfu invention, the technology that relates to is a kind of method for preparing hydrogel material, does not belong to the tire field; Thank for another example to the patent " multifunctional network interpenetrating composition " of people's inventions such as Hong Quan, the technology that relates to is a kind of tackiness agent with interpenetrating polymer networks, and is more irrelevant with tire technology.
The application of IPN technology on the high-polymer molecular film has more research and patent, and the application in tire formulation yet there are no any patent and report.Major cause is, the IPN processing technology of open report must get the mutual crossbar system of fractionated polymer subchain by solution osmose process, emulsion method or approximate method, and this method is the technique that impossible realize in the tire manufacturing is produced.
Summary of the invention
In order to realize the application of IPN technology in tire formulation, first purpose of the present invention provides a kind of tyre stock of IPN crosslinking structure, this sizing material has added high, the large advantage of anti-torsional deformation ability of good, the anti-shearing resistance of IPN vulcanized network key heatproof degree, improves to greatest extent the use properties of tire formulation; Second purpose of the present invention provides a kind of compounding process of tyre stock of IPN crosslinking structure; The 3rd purpose of the present invention is a kind of tire that adopts above-mentioned sizing material.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
The tyre stock of IPN crosslinking structure, this tyre stock are counted by weight by the raw material that comprises following component is mixing and are prepared:
The first network material, 100 parts, one or more in the first network material selection polydiene are also used;
The second network material is selected natural resin that cross-link bond is provided or the monomer of synthetic resins and synthetic resins: 0.1～30 part;
Help and melt altogether agent: 0.8～20 part; Carbon black: 20～150 parts;
Activator: 1～30 part; Tenderizer: 0～50 part;
Anti-aging agent: 0～20 part; Vulcanizing agent: 0.1～10 part;
Vulcanization accelerator: 0.1～20 part.
As preferably, above-mentioned tyre stock is counted by weight by the raw material that comprises following component is mixing and is prepared:
The first network material, 100 parts, one or more in the first network material selection polydiene are also used;
The second network material is selected natural resin that cross-link bond is provided or the monomer of synthetic resins and synthetic resins: 0.5～15 part;
Help and melt altogether agent: 0.8～10 part; Carbon black: 40～80 parts;
Activator: 2～20 parts; Tenderizer: 1～20 part;
Anti-aging agent: 1～10 part; Vulcanizing agent: 0.5～8 part;
Vulcanization accelerator: 0.5～5 part.
As preferably, above-mentioned tyre stock also comprises one or more mixing in scorch retarder, adhesion promotor, white carbon black, hardening filler, peptizer, Microcrystalline Wax, capric acid cobalt and the Resorcinol.
As preferred scheme again:
When using as the tyre pad glue sizing material, the raw material of described tyre stock comprises described white carbon black and described hardening filler, and white carbon black is 5～25 parts, and hardening filler is 0.5～2.5 part;
As wheel crown part glue sizing material the time, the raw material of described tyre stock comprises described Microcrystalline Wax and described scorch retarder, and Microcrystalline Wax is 0.5～1.5 part, and scorch retarder is 0.1～1 part;
As tire base glue sizing material the time, the raw material of described tyre stock comprises described peptizer and described scorch retarder, and peptizer is 0.5～3 part, and scorch retarder is 0.1～1 part;
As carcass glue sizing material the time, the raw material of described tyre stock comprises described scorch retarder, described adhesion promotor, described peptizer, described capric acid cobalt and described Resorcinol, scorch retarder is 0.1～1 part, adhesion promotor is 2～8 parts, 0.5～3 part of peptizer, the capric acid cobalt is 0.5～3 part, and Resorcinol is 0.5～3 part.
As preferably, one or more in above-mentioned first network material selection natural rubber, butadiene-styrene rubber and the cis-butadiene cement.
As preferably, above-mentioned second network material selection provides one or more in the monomer of the natural resin of ehter bond, acyl key, amido linkage or C-C cross-link bond and synthetic resins and synthetic resins; As preferred version again, one or more in described second network material selection alkene ether, cross-linking type resol, the inferior acid amides of two toxilic acid.
As preferably, above-mentioned helping melted altogether agent and selected in terpine resin and the modified rosin resin one or more.
As preferably, above-mentioned activator is selected one or both mixing in zinc oxide and the stearic acid, and zinc oxide is 1～10 part, and stearic acid is 0.5～5 part; Described anti-aging agent is selected one or both mixing in anti-aging agent RD and the antioxidant 4020, and anti-aging agent RD is 0.5～10 part, and antioxidant 4020 is 1～10 part.
As preferably, above-mentioned vulcanization accelerator is selected one or more in vulkacit D TDM, accelerator NS, vulkacit D CP, vulkacit D and the vulkacit H, vulkacit D TDM is 0.5～2.0 part, accelerator NS is 1.0～2.5 parts, vulkacit D CP is 0.08～0.8 part, vulkacit D is 0.1～0.5 part, and vulkacit H is 0～0.5 part.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of compounding process of tyre stock of above-mentioned IPN crosslinking structure, the method comprises the steps:
Step 1: by the prescription requirement, first network material, second network material are provided during weighing is filled a prescription well and impel helping that the two accelerates to melt mutually to melt altogether agent;
Step 2: at 10 ℃～60 ℃, in the Ben Baili Banbury mixer that load weighted different materials is mixing in advance, and the internal friction between macromolecular material is elevated to 60 ℃～165 ℃ with the outlet temperature of premix when utilizing premix, make the viscosity of each the macromolecular material mixture in the prescription reach mooney viscosity below 80, system viscosity is reduced to and makes macromolecule mixture be approximated to newton's rheid;
Step 3: satisfying under the condition of step 2, adds again carbon black in filling a prescription and other solid ingredient except vulcanizing agent and vulcanization accelerator by prescription requirements, carry out mixing, temperature when temperature reaches 125～145 ℃, adds the liquid ingredient in the prescription below 120 ℃ when flex point appears in mixing load power curve at this moment, continue mixing, binder removal when reaching 145 ℃～170 ℃ to temperature, slice makes without sulphur blend glue;
Step 4: after obtaining without sulphur blend glue, again according to concrete prescription, in the Ben Baili Banbury mixer or rubber mixing mill add various vulcanizing agents, vulcanization accelerator and carry out mixingly, slice namely gets the rubber unvulcanizate of making each parts of tire.
In order to realize the 3rd above-mentioned purpose, the present invention has adopted following technical scheme:
A kind of tire has at least a kind of sizing material to adopt the tyre stock of an above-mentioned arbitrary described IPN crosslinking structure of technical scheme in the bizet glue of this tire, pad glue, base portion glue and the carcass glue.
The present invention is owing to adopted above-mentioned technical scheme, changed the unicity of sulfide cross-linked bond in the conventional tire rubber compounding, can adopt two or more the cross-linking vulcanized network of intersection, so that behind the tyre element rubber vulcanization, in maintenance traditional single sulfur cross-linking key physical properties and processing technology, incorporate high, the large advantage of anti-torsional deformation ability of good, the anti-shearing resistance of IPN vulcanized network key heatproof degree, improved to greatest extent the use properties of tire formulation.
Present technique has not only been invented the patent formulation at each position of tire with IPN structure of tire special use, simultaneously, the art of this patent has also solved and has not adopted solution method or emulsion method, and with special processing method, namely use special, the melt blending refining, reach mixing stage by stage method, the temperature that internal friction when utilizing the macromolecular material blend and internal friction produce, make the snappiness solid rubber viscous state occur, and carry out at this moment multi-component blend, effectively solved several different structures, the full-bodied tire of different performance carries out the difficult problem of active block IPN with the macromolecular material molecular chain, make the molecular chain of each macromolecular material in the tire formulation not only have the physical intersection network, having again chemistry intersects crosslinked, so that the stable performance of goods is controlled, component capabilities has larger lifting, has realized the breakthrough of zero that the IPN technology is used in tire formulation.
Embodiment
Embodiment 1
The tyre pad glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Alkene ether | 1 |
| Terpine resin | 2 | Carbon black | 35.0 |
| White carbon black | 15 | Zinc oxide | 7.5 |
| 9010 | 1.2 | Anti-aging agent RD | 1 |
| Stearic acid | 1.0 | Tenderizer | 2 |
| Antioxidant 4020 | 3 | Vulkacit D TDM | 0.8 |
| Sulphur | 3.8 | Accelerator NS | 1.2 |
| DCP | 0.1 | Vulkacit D | 0.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, alkene ether, terpine resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drop into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, white carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit D CP, vulkacit D, vulkacit D TDM, 9010,30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 2
The tyre pad glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Cross-linking type resol | 1 |
| Modified rosin resin | 2 | Carbon black | 35.0 |
| White carbon black | 15 | Zinc oxide | 7.5 |
| 9010 | 1.2 | Anti-aging agent RD | 1 |
| Stearic acid | 1.0 | Tenderizer | 2 |
| Antioxidant 4020 | 3 | Vulkacit D TDM | 0.8 |
| Sulphur | 3.8 | Accelerator NS | 1.2 |
| Vulkacit H | 0.1 | Vulkacit D | 0.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, cross-linking type resol, modified rosin resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, white carbon black, and pressurization is carried stone roller when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit H, vulkacit D, vulkacit D TDM, 9010,30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 3
The tire tyre cushion glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | The inferior acid amides of two toxilic acids | 1 |
| Terpine resin | 2 | Carbon black | 35.0 |
| White carbon black | 15 | Zinc oxide | 7.5 |
| 9010 | 1.2 | Anti-aging agent RD | 1 |
| Stearic acid | 1.0 | Tenderizer | 2 |
| Antioxidant 4020 | 3 | Vulkacit D TDM | 0.8 |
| Sulphur | 3.8 | Accelerator NS | 1.2 |
| DCP | 0.1 | Vulkacit D | 0.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add the inferior acid amides of natural rubber, terpine resin, two toxilic acid after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, white carbon black, and pressurization is carried stone roller, binder removal when causing 155 ℃ when temperature reaches 125 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit D CP, vulkacit D, vulkacit D TDM, 9010,30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
The above embodiments 1, embodiment 2, embodiment 3 test-results data and the conventional data that require are as shown in the table:
The prescription of embodiment 1, embodiment 2, embodiment 3 as can be seen from the above table, 300% stress at definite elongation before and after the patent formulation sizing material is aging, the sizing material that the tensile strength at yield performance all is higher than conventional formulation, the physical property of sizing material reaches the pad glue glue requirement of branded tire.
Embodiment 3
The wheel crown part glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 50 | Butadiene-styrene rubber | 30 |
| Cis-butadiene cement | 20 | Carbon black | 50.0 |
| Terpine resin | 2 | Cross-linking type resol | 3.0 |
| Stearic acid | 2.0 | Zinc oxide | 4 |
| Antioxidant 4020 | 2.0 | Tenderizer | 5 |
| Microcrystalline Wax 517P | 1.0 | Anti-aging agent RD | 1.0 |
| Common S | 1.1 | Anti-scorching agent CTP | 0.15 |
| Vulkacit H | 0.3 | Accelerator NS | 1.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), cross-linking type resol, terpine resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, then, drop into wet oxidation zinc, stearic acid, antioxidant 4020, anti-aging agent RD, Microcrystalline Wax 517P, dispersion agent and carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 160 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit H, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 5
The wheel crown part glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 50 | Butadiene-styrene rubber | 30 |
| Cis-butadiene cement | 20 | Carbon black | 50.0 |
| Modified rosin resin | 2 | Alkene ether | 1.0 |
| Stearic acid | 2.0 | Zinc oxide | 4 |
| Antioxidant 4020 | 2.0 | Tenderizer | 5 |
| Microcrystalline Wax 517P | 1.0 | Anti-aging agent RD | 1.0 |
| Common S | 1.1 | Anti-scorching agent CTP | 0.15 |
| Vulkacit D CP | 0.1 | Accelerator NS | 1.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), alkene ether, modified rosin resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, Microcrystalline Wax 517P, dispersion agent and carbon black, and pressurization is carried stone roller when temperature reaches 125 ℃, add tenderizer, binder removal when causing 160 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit D CP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 6
The wheel crown part glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 50 | Butadiene-styrene rubber | 30 |
| Cis-butadiene cement | 20 | Carbon black | 50.0 |
| Terpine resin | 2 | The inferior acid amides of two toxilic acids | 1.0 |
| Stearic acid | 2.0 | Zinc oxide | 4 |
| Antioxidant 4020 | 2.0 | Tenderizer | 5 |
| Microcrystalline Wax 517P | 1.0 | Anti-aging agent RD | 1.0 |
| Common S | 1.1 | Anti-scorching agent CTP | 0.15 |
| Vulkacit D CP | 0.2 | Accelerator NS | 1.2 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add the inferior acid amides of natural rubber, cis-1,4-polybutadiene rubber, styrene-butadiene rubber(SBR), two toxilic acid, terpine resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, Microcrystalline Wax 517P and carbon black, and pressurization is carried stone roller, binder removal when causing 160 ℃ when temperature reaches 125 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit D CP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
The above embodiments 4, embodiment 5, embodiment 6 test-results data and the conventional data that require are as shown in the table:
The prescription of embodiment 4, embodiment 5, embodiment 6 as can be seen from the above table, 300% stress at definite elongation of this patent formulated rubber material of same body rubber, tensile strength at yield, pull apart elongation, wear resisting property apparently higher than the sizing material of conventional formulation, particularly the aging rear down ratio of the wear resisting property of patent formulation sizing material is very little, even also slightly be improved, as seen, with respect to conventional formulation, the physical property of patent formulation sizing material has clear superiority.
Embodiment 7
The tire base glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Alkene ether | 1 |
| Terpine resin | 2 | Carbon black | 45.0 |
| The WP peptizer | 1 | Zinc oxide | 4 |
| Stearic acid | 2.0 | Anti-aging agent RD | 1.5 |
| Antioxidant 4020 | 1.5 | Tenderizer | 4 |
| Sulphur | 1.7 | Anti-scorching agent CTP | 0.15 |
| DCP | 0.2 | Accelerator NS | 0.9 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, alkene ether, terpine resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drop into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, DCP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 8
The tire base glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Cross-linking type resol | 2 |
| Modified rosin resin | 2 | Carbon black | 45.0 |
| The WP peptizer | 1 | Zinc oxide | 4 |
| Stearic acid | 2.0 | Anti-aging agent RD | 1.5 |
| Antioxidant 4020 | 1.5 | Tenderizer | 4 |
| Sulphur | 1.7 | Anti-scorching agent CTP | 0.15 |
| Vulkacit H | 0.2 | Accelerator NS | 1.1 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, cross-linking type resol, modified rosin resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, and pressurization is carried stone roller when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit H, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 9
The tire base glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | The inferior acid amides of two toxilic acids | 1 |
| Terpine resin | 2 | Carbon black | 45.0 |
| The WP peptizer | 1 | Zinc oxide | 4 |
| Stearic acid | 2.0 | Anti-aging agent RD | 1.5 |
| Antioxidant 4020 | 1.5 | Tenderizer | 4 |
| Sulphur | 1.7 | Anti-scorching agent CTP | 0.15 |
| Vulkacit D CP | 0.1 | Accelerator NS | 1.0 |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add the inferior acid amides of natural rubber, terpine resin, two toxilic acid after plasticating, 50 rev/mins of Banbury mixer rotating speeds; Pressurization 60s carries stone roller, and at this moment, each component high polymer material all has been viscous state, then, drops into zinc oxide, stearic acid, antioxidant 4020, anti-aging agent RD, carbon black, and pressurization is carried stone roller, binder removal when causing 155 ℃ when temperature reaches 125 ℃;
C) two-stage mixing: add one section rubber unvulcanizate in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator NS, vulkacit D CP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
The above embodiments 7, embodiment 8, embodiment 9 test-results data and the conventional data that require are as shown in the table:
The prescription of embodiment 7, embodiment 8, embodiment 9 as can be seen from the above table, 300% stress at definite elongation, tensile strength at yield before and after the patent formulation sizing material is aging, pull apart the sizing material that the elongation performance is higher than conventional formulation, the physical property of sizing material reaches the base portion glue requirement of branded tire.
Embodiment 10
The carcass sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Alkene ether | 1 |
| Terpine resin | 2 | Carbon black | 58.0 |
| The WP peptizer | 1 | Zinc oxide | 8 |
| The capric acid cobalt | 0.75 | RD | 1 |
| Antioxidant 4020 | 2 | Resorcinol | 0.8 |
| Sulphur | 5 | Anti-scorching agent CTP | 0.1 |
| DCP | 0.2 | Accelerator DZ | 1 |
| FA608 | 4 | ? | ? |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, alkene ether, terpine resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, then, drop into zinc oxide, antioxidant 4020, anti-aging agent RD, carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate and capric acid cobalt in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator DZ, Resorcinol, FA608, DCP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 11
The carcass sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | The inferior acid amides of span acid | 1 |
| Modified rosin resin | 2 | Carbon black | 58.0 |
| The WP peptizer | 1 | Zinc oxide | 8 |
| The capric acid cobalt | 0.75 | RD | 1 |
| Antioxidant 4020 | 2 | Resorcinol | 0.8 |
| Sulphur | 5 | Anti-scorching agent CTP | 0.1 |
| DCP | 0.1 | Accelerator DZ | 1 |
| FA608 | 4 | ? | ? |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, the inferior acid amides of span acid, modified rosin resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, then, drop into zinc oxide, antioxidant 4020, anti-aging agent RD, carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate and capric acid cobalt in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator DZ, Resorcinol, FA608, DCP, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Embodiment 12
The carcass glue sizing material of IPN crosslinking structure, this sizing material is comprised of following composition by weight:
| Natural rubber | 100 | Cross-linking type resol | 2 |
| Modified rosin resin | 2 | Carbon black | 58.0 |
| The WP peptizer | 1 | Zinc oxide | 8 |
| The capric acid cobalt | 0.75 | RD | 1 |
| Antioxidant 4020 | 2 | Resorcinol | 0.8 |
| Sulphur | 5 | Anti-scorching agent CTP | 0.1 |
| Vulkacit H | 0.2 | Accelerator DZ | 1 |
| FA608 | 4 | ? | ? |
The compounding process of above-mentioned sizing material, the method comprises the steps:
A) plasticate: add natural rubber in Banbury mixer, 50 rev/mins of rotating speeds pressurize and carried stone roller in 40 seconds, pressurize and carry stone roller, binder removal in 35 seconds;
B) one section mixing: in Banbury mixer, add natural rubber, cross-linking type resol, modified rosin resin after plasticating, 50 rev/mins of Banbury mixer rotating speeds, pressurization 60s carries stone roller, then, drop into zinc oxide, antioxidant 4020, anti-aging agent RD, carbon black, stone roller is carried in pressurization when temperature reaches 125 ℃, add tenderizer, binder removal when causing 155 ℃;
C) two-stage mixing: add one section rubber unvulcanizate and capric acid cobalt in Banbury mixer, press floating weight to carry stone roller in 35 seconds, pressurization 35s carries stone roller, 40 rev/mins of binder removals;
D) add sulphur technique: drop into two-stage mixing glue in Banbury mixer, add common S, accelerator DZ, Resorcinol, FA608, vulkacit H, anti-scorching agent CTP, 30 rev/mins of rotating speeds pressurize and carried stone roller, binder removal in 30 seconds.
Above-mentioned example 10, example 11, example 12 test-results data and the conventional data that require are as shown in the table:
The prescription of embodiment 10, embodiment 11, embodiment 12 as can be seen from the above table, 300% stress at definite elongation, tensile strength at yield before and after the patent formulation sizing material is aging, pull apart the elongation performance and be higher than normal sizing material, particularly the bond strength of aging front and back sizing material and steel wire cord is apparently higher than normal carcass glue, meaningfully, steel wire bounding force after example two prescriptions are aging does not only descend, but also be improved to some extent, as seen, the prescription of IPN technology is conducive to produce high-quality tyre.
Claims (11)
1.IPN the tyre stock of crosslinking structure is characterized in that this tyre stock counts by weight by mixing the preparing of raw material that comprises that following component consists of:
The first network material, 100 parts, one or more in the first network material selection polydiene are also used;
The second network material is selected natural resin that cross-link bond is provided or the monomer of synthetic resins and synthetic resins: 0.1～30 part;
Help and melt altogether agent: 0.8～20 part; Carbon black: 20～150 parts;
Activator: 1～30 part; Tenderizer: 0～50 part;
Anti-aging agent: 0～20 part; Vulcanizing agent: 0.1～10 part;
Vulcanization accelerator: 0.1～20 part.
2. the tyre stock of IPN crosslinking structure according to claim 1 is characterized in that this tyre stock counts by weight by mixing the preparing of raw material that comprises that following component consists of:
The first network material, 100 parts, one or more in the first network material selection polydiene are also used;
The second network material is selected natural resin that cross-link bond is provided or the monomer of synthetic resins and synthetic resins: 0.5～15 part;
Help and melt altogether agent: 0.8～10 part; Carbon black: 40～80 parts;
Activator: 2～20 parts; Tenderizer: 1～20 part;
Anti-aging agent: 1～10 part; Vulcanizing agent: 0.5～8 part;
Vulcanization accelerator: 0.5～5 part.
3. the tyre stock of IPN crosslinking structure according to claim 1 and 2 is characterized in that this tyre stock also comprises one or more mixing in scorch retarder, adhesion promotor, white carbon black, hardening filler, peptizer, Microcrystalline Wax, capric acid cobalt and the Resorcinol.
4. the tyre stock of IPN crosslinking structure according to claim 3, it is characterized in that when using as the tyre pad glue sizing material, the raw material of described tyre stock comprises described white carbon black and described hardening filler, and white carbon black is 5～25 parts, and hardening filler is 0.5～2.5 part;
As wheel crown part glue sizing material the time, the raw material of described tyre stock comprises described Microcrystalline Wax and described scorch retarder, and Microcrystalline Wax is 0.5～1.5 part, and scorch retarder is 0.1～1 part;
As tire base glue sizing material the time, the raw material of described tyre stock comprises described peptizer and described scorch retarder, and peptizer is 0.5～3 part, and scorch retarder is 0.1～1 part;
As carcass glue sizing material the time, the raw material of described tyre stock comprises described scorch retarder, described adhesion promotor, described peptizer, described capric acid cobalt and described Resorcinol, scorch retarder is 0.1～1 part, adhesion promotor is 2～8 parts, 0.5～3 part of peptizer, the capric acid cobalt is 0.5～3 part, and Resorcinol is 0.5～3 part.
5. the tyre stock of IPN crosslinking structure according to claim 1 and 2 is characterized in that: one or more in first network material selection natural rubber, butadiene-styrene rubber and the cis-butadiene cement.
6. the tyre stock of IPN crosslinking structure according to claim 1 and 2 is characterized in that: one or more in described second network material selection alkene ether, cross-linking type resol, the inferior acid amides of two toxilic acid.
7. the tyre stock of IPN crosslinking structure according to claim 1 and 2 is characterized in that: help and melt altogether agent and select in terpine resin and the modified rosin resin one or more.
8. the tyre stock of IPN crosslinking structure according to claim 1, it is characterized in that: described activator is selected zinc oxide and stearic acid, and zinc oxide is 1～10 part, and stearic acid is 0.5～5 part; Described anti-aging agent is selected one or both mixing in anti-aging agent RD and the antioxidant 4020, and anti-aging agent RD is 0.5～10 part, and antioxidant 4020 is 1～10 part.
9. the tyre stock of IPN crosslinking structure according to claim 1 and 2, it is characterized in that: vulcanization accelerator is selected vulkacit D TDM, accelerator NS, vulkacit D CP, vulkacit D and vulkacit H, vulkacit D TDM is 0.5～2.0 part, accelerator NS is 1.0～2.5 parts, vulkacit D CP is 0.08～0.8 part, vulkacit D is 0.1～0.5 part, and vulkacit H is 0～0.5 part.
10. the compounding process of the tyre stock of a claim 1 or 2 described IPN crosslinking structures is characterized in that the method comprises the steps:
Step 1: by the prescription requirement, first network material, second network material are provided during weighing is filled a prescription well and impel helping that the two accelerates to melt mutually to melt altogether agent;
Step 2: at 10 ℃～60 ℃, in the Ben Baili Banbury mixer that load weighted different materials is mixing in advance, and the internal friction between macromolecular material is elevated to 60 ℃～165 ℃ with the outlet temperature of premix when utilizing premix, make the viscosity of each the macromolecular material mixture in the prescription reach mooney viscosity below 80, system viscosity is reduced to and makes macromolecule mixture be approximated to newton's rheid;
Step 3: satisfying under the condition of step 2, adds again carbon black in filling a prescription and other solid ingredient except vulcanizing agent and vulcanization accelerator by prescription requirements, carry out mixing, temperature when temperature reaches 125～145 ℃, adds the liquid ingredient in the prescription below 120 ℃ when flex point appears in mixing load power curve at this moment, continue mixing, binder removal when reaching 145 ℃～170 ℃ to temperature, slice makes without sulphur blend glue;
Step 4: after obtaining without sulphur blend glue, again according to concrete prescription, in the Ben Baili Banbury mixer or rubber mixing mill add various vulcanizing agents, vulcanization accelerator and carry out mixingly, slice namely gets the rubber unvulcanizate of making each parts of tire.
11. a tire is characterized in that: have at least a kind of sizing material to adopt the tyre stock of claim 1 or 2 described IPN crosslinking structures in the bizet glue of this tire, pad glue, base portion glue and the carcass glue.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110155167 CN102250394B (en) | 2011-06-10 | 2011-06-10 | Tire stock of IPN (Interpenetrating Polymer Network) crosslinked structure and mixing method as well as application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110155167 CN102250394B (en) | 2011-06-10 | 2011-06-10 | Tire stock of IPN (Interpenetrating Polymer Network) crosslinked structure and mixing method as well as application thereof |
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| CN103819695B (en) * | 2014-02-27 | 2017-03-22 | 单东成 | Preparation and performance of tri-polymer interpenetrating network elastomer |
| CN105461955B (en) * | 2016-01-08 | 2018-02-27 | 山东金山橡塑装备科技有限公司 | A kind of special plasticizing synthetics of waste and old reclaimed rubber |
| CN108300089A (en) * | 2017-12-25 | 2018-07-20 | 陈维红 | A kind of spraying glue of anti-tie flat |
| CN109233007A (en) * | 2018-09-11 | 2019-01-18 | 万力轮胎股份有限公司 | A kind of rubber composition and the preparation method and application thereof |
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| CN101481473A (en) * | 2008-01-07 | 2009-07-15 | 严晓敏 | Rubber composition and product thereof |
| CN101812191A (en) * | 2010-04-16 | 2010-08-25 | 青岛科技大学 | Method for preparing polyurethane/rubber interpenetrating network type water-swellable rubber |
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