CN112321904A - Triangular rubber taking synthetic natural rubber as base rubber and preparation method and application thereof - Google Patents
Triangular rubber taking synthetic natural rubber as base rubber and preparation method and application thereof Download PDFInfo
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- CN112321904A CN112321904A CN202011190664.0A CN202011190664A CN112321904A CN 112321904 A CN112321904 A CN 112321904A CN 202011190664 A CN202011190664 A CN 202011190664A CN 112321904 A CN112321904 A CN 112321904A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
Abstract
The invention relates to a triangular rubber taking synthetic natural rubber as a base rubber, a preparation method and application thereof, belonging to the technical field of triangular rubber. Solves the problems that the performance indexes of the triangular rubber taking natural rubber as the base rubber in the prior art are contradictory, the hardness of the rubber material is too high and the operation is difficult in the production process, and the like. The invention relates to a bead filler, which comprises the following components in parts by weight: 90-100 parts of polyisoprene rubber, 2-4 parts of an anti-aging agent, 85-105 parts of a reinforcing agent, 2-4 parts of a vulcanizing agent, 0.6-1.5 parts of an accelerator, 5-10 parts of an active agent, 0-5 parts of a plasticizer and 0.1-0.2 part of an anti-scorching agent. The apex has high hardness, high tensile strength and tear strength, low compression heat generation and heat conductivity, and good flexibility and ageing resistance.
Description
Technical Field
The invention belongs to the technical field of triangular glue, and particularly relates to triangular glue taking synthetic natural rubber as a base glue, and a preparation method and application thereof.
Background
Tires are ground-rolling annular elastic rubber articles fitted on various vehicles, airplanes, or machines. Generally, the wheel is mounted on a metal rim, and can support a vehicle body or a machine body, buffer external impact, realize contact with a road surface and ensure driving performance. In the case of vehicles, tires have a direct and important influence on vehicle handling performance, driving safety, fuel consumption, ride comfort, and the like. In the case of aircraft, tires play an important safety role, and the performance of the tires is directly related to the safety of the takeoff and landing stage.
The apex must be used as the transition between the rim and the rubber at other locations in an aircraft tire, and is an indispensable component of the tire bead structure. In the prior art, the aircraft tire apex mainly uses Natural Rubber (NR), reclaimed rubber, carbon black, argil, light calcium carbonate, sulfur, an accelerator and other components as raw materials, has the defects of low hardness, low tensile strength and tearing strength, contradiction between compression heat generation and flexing performance, over-quick reduction of comprehensive performance after thermal aging and the like, and easily causes the separation and the fracture damage of a bead part when the aircraft tire takes off and lands at high load and high speed, thereby seriously threatening the use safety of the aircraft tire and an aircraft. And the batch stability of the natural rubber quality changes with the production cycle.
Disclosure of Invention
In view of the above, the invention provides a bead filler using synthetic natural rubber as a base rubber, and a preparation method and an application thereof, aiming at solving the problems that the bead filler using natural rubber as a base rubber in the prior art is low in hardness, low in tensile strength and tear strength, contradictory between compressive heat generation and flexing performance, and poor in batch stability, and the comprehensive performance is reduced too fast after thermal aging.
The technical scheme adopted by the invention for solving the technical problems is as follows.
The invention relates to a triangular glue taking synthetic natural rubber as a base glue, which comprises the following components:
the active agent is a mixture of zinc oxide and stearic acid in a mass ratio of (2-3) to 1;
the accelerator is a mixture of N, N dicyclohexyl-2-benzothiazole sulfonamide (DZ) and tetramethyl thiuram disulfide (TMTD), or a mixture of cyclohexyl-benzothiazole sulfonamide (CZ) and tetramethyl thiuram disulfide (TMTD).
Preferably, the polyisoprene rubber is one or a mixture of SKI-5PM, SKI-3S, IR2200 and IR 80.
Preferably, the antioxidant is one or more of trimethyldihydroquinoline (RD), cyclohexylphenyl-p-phenylenediamine (4010NA), and N-1, 3-dimethyl-N' -phenyl-p-phenylenediamine (4020, DMPPD).
Preferably, the reinforcing agent is carbon black, the CTAB adsorption specific surface area is more than 83, and the compressed DBP oil absorption value is more than 70; more preferred are mixtures of one or more of N220, N330, N660.
Preferably, the vulcanizing agent IS insoluble sulfur IS-80 or IS-90.
Preferably, the plasticizer is one or more of aromatic oil and unsaturated fatty acid zinc soap.
Preferably, the scorch retarder is N-Cyclohexylthiophthalimide (CTP).
The invention also provides a preparation method of the triangular glue taking the synthetic natural rubber as the base glue, which comprises the following steps:
step one, weighing raw materials of each component according to a formula;
preheating an internal mixer to 80 ℃, adding polyisoprene rubber into the internal mixer, mixing for 1-3min, adding an activating agent and an anti-aging agent, mixing for 1-3min, adding a reinforcing agent and a plasticizer, mixing for 3-5min, discharging rubber, discharging sheets, and standing for more than 24h to obtain internally mixed raw rubber;
and step three, adding the internally mixed raw rubber into an open mill for open milling, adding a vulcanizing agent, an accelerant and an anti-scorching agent in the open milling process, uniformly opening, then taking out the pieces, and standing for more than 24 hours to obtain the triangular rubber taking the synthetic natural rubber as the base rubber.
Preferably, the speed of the internal mixer is 30-60 rpm.
Preferably, the banburying temperature is less than or equal to 110 ℃.
The invention also provides application of the apex taking the synthetic natural rubber as the base rubber as the apex of the aircraft tire.
Compared with the prior art, the invention has the beneficial effects that:
the triangular rubber based on the synthetic natural rubber has higher hardness, high tensile strength and tearing strength, lower compression heat generation and heat conduction performance, better flexibility and ageing resistance, and better solves the problems of contradiction among various performance indexes of the triangular rubber, difficult operation of too high hardness of the rubber material in the production process and the like. Tests prove that the tensile strength of the triangular rubber can reach more than 16MPa, the tear strength reaches more than 40KN/m, the elongation at break change rate is lower than-30% after the triangular rubber is aged in hot air at 100 ℃ for 24h, the number of times of deflection reaching 6 grades exceeds 10 ten thousand, and the resilience value is more than 35%. The aviation tire with the triangular rubber can adapt to high-speed take-off and landing under high load, bear severe use conditions such as large deformation, large bearing capacity and high temperature, ensure the reliability of the tire bead part in the use process of the aviation tire, improve the safety of the aviation tire and prolong the service life of the aviation tire.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the detailed description, but it is to be understood that the description is intended to further illustrate the features and advantages of the invention and not to limit the claims to the invention.
The invention relates to a triangular rubber taking synthetic natural rubber as a base rubber, which comprises the following components: 90-100 parts of polyisoprene rubber, 2-4 parts of an anti-aging agent, 85-105 parts of a reinforcing agent, 2-4 parts of a vulcanizing agent, 0.6-1.5 parts of an accelerator, 5-10 parts of an activator, 0-5 parts of a plasticizer and 0.1-0.2 part of an anti-scorching agent. It may consist of only the above-mentioned components.
In the above technical solution, the polyisoprene rubber is a high-elasticity polymer synthesized from isoprene monomers and containing cis-1, 4-polyisoprene as a main component, wherein the content of the cis-1, 4-polyisoprene is more than 95%. In the present embodiment, the polyisoprene rubber used is SKI-5PM imported from Russia, SKI-3S imported from Russia, IR2200 imported from Japan, or Dushan isoprene rubber IR80 imported from Japan. The invention adopts polyisoprene rubber as a raw material, avoids the problems of mixing and dispersion uniformity caused by the need of using multiple rubbers such as natural rubber, butadiene rubber and the like in a triangle rubber formula in the prior art, directly realizes higher tensile strength and tear strength, better flex resistance and other properties, and has high batch stability and good comprehensive performance.
In the technical scheme, the anti-aging agent is one or a mixture of more of trimethyldihydroquinoline (RD), cyclo-ethyl phenyl p-phenylenediamine (4010NA) and N-1, 3-dimethyl-N' -phenyl p-phenylenediamine (4020, DMPPD). The addition of the anti-aging agent into the triangular glue increases the thermal-oxidative aging resistance and the deflection performance of the triangular glue, so that the elongation at break change rate of the triangular glue is lower than-30% after the triangular glue is aged in hot air at 100 ℃ for 24h, and the number of times of deflection reaching 6 grades exceeds 10 ten thousand.
In the technical scheme, the reinforcing agent is carbon black, the CTAB adsorption specific surface area is more than 83, and the compressed DBP oil absorption value is more than 70; preferably a mixture of one or more of N220, N330, N660. The apex disclosed by the invention can solve the problems of poor tear resistance, low elasticity, low tensile strength, poor processability and the like generated after argil and light calcium carbonate are added into the apex formula in the prior art, and can improve the hardness of the apex under the condition of not reducing other properties, so that the apex is more suitable for the requirements of an actual formula.
In the technical scheme, the vulcanizing agent is insoluble sulfur which is one or a mixture of two of oil-filled sulfur powder and rubber particles containing sulfur. The rubber particles containing insoluble sulfur are preferably those having 10 to 20 wt% EPDM as a carrier and 80 to 90 wt% sulfur, such as IS-80 or IS-90. The insoluble sulfur is selected from the apex of the invention, so that the blooming phenomenon in the standing process of the rubber compound can be prevented, the surface state, the viscosity and the physical property of the apex can be maintained, and the adhesion of the apex and the adjacent formula rubber can be facilitated.
In the technical scheme, the accelerator is a mixture of N, N dicyclohexyl-2-benzothiazole sulfonamide (DZ) and tetramethyl thiuram disulfide (TMTD), or a mixture of cyclohexyl-benzothiazole sulfonamide (CZ) and tetramethyl thiuram disulfide (TMTD). 0.55-1.3 parts by weight of N, N-dicyclohexyl-2-benzothiazolesulfenamide (DZ) or cyclohexyl-benzothiazolesulfenamide (CZ) and 0.05-0.3 parts by weight of tetramethylthiuram disulfide (TMTD).
The invention relates to a V-shaped rubber which is prepared by compounding sulfenamide accelerator and thiuram super accelerator, and has the advantages that the V-shaped rubber has relatively long scorching time and high vulcanization speed, the flatness of a vulcanization curve can be kept, the over-vulcanization phenomenon can be prevented, the vulcanization condition can be better matched with formula rubber at other parts of a tire for use, and the best effect that rubber at different parts can be closer to synchronous vulcanization in the actual production process of an aircraft tire can be achieved.
In the technical scheme, the activating agent is a mixture of zinc oxide and stearic acid in a mass ratio of (2-3) to 1. According to the triangular glue, the zinc oxide and the stearic acid active agent are used together, so that the thermal conductivity and the mechanical strength of the triangular glue can be further improved, and the addition of the zinc oxide can effectively reduce the addition of the filler and improve the comprehensive performance of a rubber product under the condition of ensuring that the active agent is uniformly dispersed in a system.
In the technical scheme, the plasticizer is one or a mixture of more of aromatic oil and unsaturated fatty acid zinc soap.
In the technical scheme, the scorch retarder is N-Cyclohexyl Thiophthalimide (CTP).
The invention relates to a method for preparing a triangular glue by using synthetic natural rubber as a base glue, which comprises the following steps:
step one, weighing raw materials of each component according to a formula;
preheating an internal mixer to 80 ℃, adding polyisoprene rubber into the internal mixer, mixing for 1-3min, adding an activating agent and an anti-aging agent, mixing for 1-3min, adding a reinforcing agent and a plasticizer, mixing for 3-5min, discharging rubber, discharging sheets, and standing for more than 24h to obtain internally mixed raw rubber;
and step three, adding the internally mixed raw rubber into an open mill for open milling, adding a vulcanizing agent, an accelerant and an anti-scorching agent in the open milling process, uniformly opening, then taking out the pieces, and standing for more than 24 hours to obtain the triangular rubber taking the synthetic natural rubber as the base rubber.
In the technical scheme, the rotating speed of the internal mixer is preferably 30-60 rpm; the banburying temperature is preferably less than or equal to 110 ℃;
the vulcanization molding conditions of the triangular rubber taking the synthetic natural rubber as the base rubber are as follows: the vulcanization temperature is 130-155 ℃, the pressure is 0.2-20MPa, the preferred vulcanization temperature is 145 ℃, and the pressure is 20 MPa; the vulcanization time is tc90+1-2 min.
The invention relates to an application of a triangular rubber taking synthetic natural rubber as a base rubber as an aviation tire triangular rubber.
The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art, unless otherwise specified.
In order to make those skilled in the art better understand the technical solution of the present invention, the present invention will be further described in detail with reference to the following embodiments.
In the following examples, various procedures and methods not described in detail are conventional methods well known in the art. Materials, reagents, devices, instruments, apparatuses and the like used in the following examples are commercially available unless otherwise specified.
Examples 1 to 3 and comparative examples 1 to 2
The formulations of the apex of examples 1-3 and comparative examples 1-2 are shown in Table 1. The preparation method comprises the following steps:
step one, weighing raw materials of each component according to a formula;
preheating an internal mixer to 80 ℃, adding polyisoprene rubber into the internal mixer, mixing for 1-3min, adding an activating agent, an anti-aging agent and phenolic resin SL2005, mixing for 1-3min, adding a reinforcing agent, a coupling agent SI69 and a plasticizer, mixing for 3-5min, discharging rubber, discharging sheets, and standing for more than 24h to obtain internally mixed raw rubber; the rotating speed of the internal mixer is 30-60rpm, and the internal mixing temperature is less than or equal to 110 ℃;
and step three, adding the internally mixed raw rubber into an open mill for open milling, adding a vulcanizing agent, an accelerant and an anti-scorching agent in the open milling process, uniformly opening, then taking out the pieces, and standing for more than 24 hours to obtain the triangular rubber taking the synthetic natural rubber as the base rubber.
TABLE 1 formulation of apex for examples 1-3 and comparative examples 1-2
The performance of the apex formulations of examples 1-3 and comparative examples 1-2 were tested and the results are shown in Table 2.
TABLE 2 Properties of apex of examples 1-3 and comparative examples 1-2
It should be understood that the above embodiments are only examples for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither necessary nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the spirit or scope of the invention.
Claims (10)
1. The apex with synthetic natural rubber as basic rubber is characterized by comprising the following components:
the active agent is a mixture of zinc oxide and stearic acid in a mass ratio of (2-3) to 1;
the accelerator is a mixture of N, N dicyclohexyl-2-benzothiazole sulfonamide and tetramethyl thiuram disulfide, or a mixture of cyclohexyl-benzothiazole sulfonamide and tetramethyl thiuram disulfide.
2. The apex rubber based on synthetic natural rubber of claim 1, wherein the polyisoprene rubber is a mixture of one or more of SKI-5PM, SKI-3S, IR2200, IR 80.
3. A apex for a synthetic natural rubber based gum according to claim 1 wherein the antioxidant is a mixture of one or more of trimethyldihydroquinoline, cyclohexylphenyl-p-phenylenediamine, N-1, 3-dimethyl-N' -phenyl-p-phenylenediamine.
4. The apex based on synthetic natural rubber of claim 1 wherein the reinforcing agent is carbon black, CTAB adsorption specific surface area > 83, compressed DBP oil absorption > 70.
5. An apex rubber based on synthetic natural rubber according to claim 1, characterized in that the vulcanizing agent IS insoluble sulfur IS-80 or IS-90.
6. The apex gum based on synthetic natural rubber of claim 1, wherein the plasticizer is a mixture of one or more of aromatic oil, unsaturated fatty acid zinc soap.
7. The apex based on synthetic natural rubber of claim 1 wherein said scorch retarder is N-cyclohexylthiophthalimide.
8. A process for the preparation of an apex based on synthetic natural rubber according to any one of claims 1 to 7, comprising the steps of:
step one, weighing raw materials of each component according to a formula;
preheating an internal mixer to 80 ℃, adding polyisoprene rubber into the internal mixer, mixing for 1-3min, adding an activating agent and an anti-aging agent, mixing for 1-3min, adding a reinforcing agent and a plasticizer, mixing for 3-5min, discharging rubber, discharging sheets, and standing for more than 24h to obtain internally mixed raw rubber;
and step three, adding the internally mixed raw rubber into an open mill for open milling, adding a vulcanizing agent, an accelerant and an anti-scorching agent in the open milling process, uniformly opening, then taking out the pieces, and standing for more than 24 hours to obtain the triangular rubber taking the synthetic natural rubber as the base rubber.
9. The method for preparing a apex rubber based on synthetic natural rubber according to claim 8, wherein the rotation speed of the internal mixer is 30-60 rpm; the banburying temperature is less than or equal to 110 ℃.
10. Use of the apex based on synthetic natural rubber according to any of claims 1 to 7 as an aircraft tire apex.
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| CN202011190664.0A CN112321904A (en) | 2020-10-30 | 2020-10-30 | Triangular rubber taking synthetic natural rubber as base rubber and preparation method and application thereof |
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| CN202011190664.0A CN112321904A (en) | 2020-10-30 | 2020-10-30 | Triangular rubber taking synthetic natural rubber as base rubber and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131063A (en) * | 2011-11-25 | 2013-06-05 | 固特异轮胎和橡胶公司 | Tire containing internal cord reinforced rubber layer |
| CN103923356A (en) * | 2013-01-15 | 2014-07-16 | 住友橡胶工业株式会社 | Rubber Composition For Canvas Chafer, And Pneumatic Tire |
| CN107090101A (en) * | 2017-05-03 | 2017-08-25 | 沈阳化工大学 | A kind of tire gutta-percha triangle rubber and preparation method thereof |
| CN107163315A (en) * | 2017-05-23 | 2017-09-15 | 山东玲珑轮胎股份有限公司 | Tread rubber composition for all-steel radial tire and preparation method thereof |
| JP2019203070A (en) * | 2018-05-23 | 2019-11-28 | 住友ゴム工業株式会社 | Rubber composition for tire, and pneumatic tire |
-
2020
- 2020-10-30 CN CN202011190664.0A patent/CN112321904A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103131063A (en) * | 2011-11-25 | 2013-06-05 | 固特异轮胎和橡胶公司 | Tire containing internal cord reinforced rubber layer |
| CN103923356A (en) * | 2013-01-15 | 2014-07-16 | 住友橡胶工业株式会社 | Rubber Composition For Canvas Chafer, And Pneumatic Tire |
| CN107090101A (en) * | 2017-05-03 | 2017-08-25 | 沈阳化工大学 | A kind of tire gutta-percha triangle rubber and preparation method thereof |
| CN107163315A (en) * | 2017-05-23 | 2017-09-15 | 山东玲珑轮胎股份有限公司 | Tread rubber composition for all-steel radial tire and preparation method thereof |
| JP2019203070A (en) * | 2018-05-23 | 2019-11-28 | 住友ゴム工業株式会社 | Rubber composition for tire, and pneumatic tire |
Non-Patent Citations (1)
| Title |
|---|
| 橡胶工业原材料与装备简明手册编审委员会 编著: "《橡胶工业原材料与装备简明手册 2016年版》", 31 December 2016, 北京理工大学出版社 * |
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Application publication date: 20210205 |