CN117362767A - Rubber material and preparation method thereof - Google Patents
Rubber material and preparation method thereof Download PDFInfo
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- CN117362767A CN117362767A CN202311210111.0A CN202311210111A CN117362767A CN 117362767 A CN117362767 A CN 117362767A CN 202311210111 A CN202311210111 A CN 202311210111A CN 117362767 A CN117362767 A CN 117362767A
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 99
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000006229 carbon black Substances 0.000 claims abstract description 24
- 239000012744 reinforcing agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 37
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 34
- 244000043261 Hevea brasiliensis Species 0.000 claims description 25
- 229920003052 natural elastomer Polymers 0.000 claims description 25
- 229920001194 natural rubber Polymers 0.000 claims description 25
- 235000021355 Stearic acid Nutrition 0.000 claims description 17
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 17
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 17
- 239000008117 stearic acid Substances 0.000 claims description 17
- 239000011787 zinc oxide Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 230000003213 activating effect Effects 0.000 claims description 7
- 239000012190 activator Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 230000020169 heat generation Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000002035 prolonged effect Effects 0.000 description 4
- 238000010074 rubber mixing Methods 0.000 description 4
- 230000006835 compression Effects 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000003712 anti-aging effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 scorch retarders Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a rubber material, which reduces the small rubber particle ratio, further enhances the dispersibility of a reinforcing agent (such as carbon black), reduces the heat generation loss of the rubber material, improves the fatigue resistance and prolongs the service life of rubber products under the condition of dynamic load by optimizing the weight average molecular weight and the Mooney viscosity of rubber. In addition, the invention also relates to a preparation method of the rubber material.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to a rubber material and a preparation method thereof.
Background
Rubber, which is an organic high-elasticity material and has excellent heat resistance and oil resistance, has been applied to the aviation industry for a long time, and is widely applied to products in dynamic working conditions such as elastic elements, vibration reduction supports and the like as a strategic material and important engineering material.
The viscoelastic characteristic of the rubber material enables the rubber material to have two large responses of elastic energy storage and hysteresis loss under the action of dynamic working conditions. The elastic energy storage response may promote the continued propagation of the original microcracks (or crack precursors) within the rubber until the material breaks, i.e., the material experiences fatigue failure problems. The hysteresis loss response can cause the rubber to dissipate part of external acting power into heat energy, namely the problem of hysteresis temperature rise of the material occurs, and the rising temperature in turn accelerates the fatigue aging of the rubber material, and finally leads to the damage and failure of the rubber material.
In recent years, with the rapid development of aviation industry in China, the use level of natural rubber materials in the aviation field is greatly increased, and with the improvement of the technical requirements on the performance and the service life of products, the requirements on the dynamic loss and the fatigue resistance of the rubber materials are higher.
In view of the current situation, the invention provides a rubber material with low hysteresis loss and high fatigue resistance, which has great application value.
Disclosure of Invention
In view of the problems in the background art, the invention provides the rubber material, which can generate smaller dynamic hysteresis loss in the periodic motion process, improve fatigue resistance and prolong the service life of the rubber material on the basis of meeting the functional requirements.
In a first aspect, the invention provides a rubber material, which comprises the following components in parts by weight:
90-120 parts of rubber, 1.5-3 parts of vulcanizing agent, 1-1.5 parts of accelerator, 35-50 parts of reinforcing agent and 6-9 parts of activating agent;
wherein the weight average molecular weight of the rubber is 160×10 4 g/mol or more, and Mooney viscosity ML (1+4) is 55 or more.
According to the invention, the weight average molecular weight and the Mooney viscosity of the rubber are optimized, so that the small rubber particle ratio is reduced, the dispersibility of the reinforcing agent (such as carbon black) is further enhanced, the heat generation loss of the rubber material is reduced, the fatigue resistance is improved, and the service life of the rubber product under the dynamic load condition is prolonged. When the weight average molecular weight and the mooney viscosity of the rubber are both in the above ranges, dynamic hysteresis loss can be reduced and fatigue resistance can be improved. On the other hand, when either one or both of the above ranges are not included, the dynamic hysteresis loss is high, and the fatigue resistance is deviated.
In some embodiments, the rubber may have a weight average molecular weight of 16×10 5 g/mol-30×10 5 The Mooney viscosity ML (1+4) may be 55-65 g/mol. The weight average molecular weight and the Mooney viscosity of the rubber are optimized, so that the dynamic hysteresis loss is further reduced, and the fatigue resistance is improved.
In some embodiments, the weight average molecular weight of the rubber may be 16X 10 5 g/mol、17×10 5 g/mol、18×10 5 g/mol、19×10 5 g/mol、20×10 5 g/mol、21×10 5 g/mol、22×10 5 g/mol、23×10 5 g/mol、24×10 5 g/mol、25×10 5 g/mol、26×10 5 g/mol、27×10 5 g/mol、28×10 5 g/mol、29×10 5 g/mol or 30X 10 5 g/mol。
In some embodiments, the mooney viscosity ML (1+4) may be 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, or 65.
In some embodiments, the mass fraction of rubber may be, for example, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, or 120 parts.
In some embodiments, the vulcanizing agent may be, for example, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts, 2.0 parts, 2.1 parts, 2.2 parts, 2.3 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.7 parts, 2.8 parts, 2.9 parts, or 3 parts by mass.
In some embodiments, the accelerator may be, for example, 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, or 1.5 parts by mass.
In some embodiments, the mass fraction of the reinforcing agent may be, for example, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50 parts.
In some embodiments, the activator may be, for example, 6 parts, 6.5 parts, 7 parts, 7.5 parts, 8 parts, 8.5 parts, or 9 parts by mass.
In some specific embodiments, the rubber material comprises the following components in parts by mass: 95-105 parts of rubber, 1.5-2.0 parts of vulcanizing agent, 1.1-1.3 parts of accelerator, 38-42 parts of reinforcing agent and 6.5-7.5 parts of activating agent.
The use amount of each component in the rubber material is optimized, so that the dynamic hysteresis loss is further reduced, and the fatigue resistance is improved.
In some specific embodiments, the rubber material comprises the following components in parts by mass: 100 parts of rubber, 1.7 parts of vulcanizing agent, 1.2 parts of accelerator, 40 parts of reinforcing agent and 7 parts of activating agent.
In some embodiments, the rubber comprises natural rubber.
In some embodiments, the vulcanizing agent comprises vulcanizing agent S-80. The variety of the vulcanizing agent is optimized, so that the dynamic hysteresis loss is reduced, and the fatigue resistance is improved.
In some embodiments, the reinforcing agent comprises carbon black. Preferably, the carbon black is carbon black N550. By optimizing the type of the carbon black, the dynamic hysteresis loss is reduced, and the fatigue resistance is improved.
In some embodiments, the activator comprises 4-6 parts zinc oxide and 2-3 parts stearic acid. By optimizing the type of the activator, the dynamic hysteresis loss is reduced, and the fatigue resistance is improved. The zinc oxide may be 4 parts, 4.5 parts, 5 parts, 5.5 parts, or 6 parts by mass. The mass fraction of stearic acid may be 2 parts, 2.5 parts or 3 parts.
In some specific embodiments, the rubber material comprises the following components in parts by mass: 100 parts of natural rubber, 1.7 parts of vulcanizing agent, 1.2 parts of accelerator, 40 parts of carbon black, 5 parts of zinc oxide and 2 parts of stearic acid. The rubber material of the formula has remarkably reduced dynamic hysteresis loss and remarkably improved fatigue resistance.
In some embodiments, the accelerator is a mixture of accelerator DPG and accelerator NS. By optimizing the types of the accelerators, the dynamic hysteresis loss is reduced, and the fatigue resistance is improved.
In some embodiments, the ratio of parts by weight of the accelerator DPG and the accelerator NS may be (4.5-5.5): 6.5-7.5. The consumption relation of DPG and NS is optimized, so that the dynamic hysteresis loss is reduced, and the fatigue resistance is improved.
In some embodiments, the weight fraction ratio of the accelerator DPG to the accelerator NS may be 4.5:6.5, 4.5:7, 4.5:7.5, 5:6.5, 5:7, 5:7.5, 5.5:6.5, 5.5:7 or 5.5:7.5, preferably 5:7.
In a second aspect, the present invention provides a method for preparing the rubber material, comprising the steps of:
mixing rubber, a reinforcing agent and an activating agent to obtain a mixed material;
mixing the mixed materials with a vulcanizing agent and an accelerator to obtain a mixed rubber;
and vulcanizing the rubber compound to obtain the rubber material.
The method can be used for preparing the low-hysteresis-loss and fatigue-resistant rubber material.
In some embodiments, the banburying is performed at 60-110℃for 20-25min. By optimizing the temperature and time of banburying, the natural rubber matrix and the filler can be fully blended. The banburying temperature may be, for example, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or 110 ℃. The banburying time may be, for example, 20min, 21min, 22min, 23min, 24min, or 25min.
In some embodiments, the curing is performed at 130-160℃for 15-20 minutes to ensure adequate curing of the mix. The vulcanization temperature may be 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, or 160 ℃, for example. The vulcanization time may be 15min, 16min, 17min, 18min, 19min or 20min.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the weight average molecular weight and the Mooney viscosity of the rubber are optimized, so that the small rubber particle ratio is reduced, the dispersibility of the reinforcing agent (such as carbon black) is further enhanced, the heat generation loss of the rubber material is reduced, the fatigue resistance is improved, and the service life of the rubber product under the dynamic load condition is prolonged. In addition, the rubber material disclosed by the invention has good mechanical property and processability, and the service life of the rubber material under the dynamic complex load condition is further prolonged. Compared with the prior art that the heat generation of rubber is reduced and the fatigue life is prolonged by blending other kinds of rubber, reinforcing agents, anti-aging agents, scorch retarders, softening agents and other compounding agents, the invention simplifies the production flow, reduces the environmental pollution and simultaneously reduces the production cost.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the invention is further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. In the examples, the starting materials used were all commercially available, and the methods used in the examples described below were conventional in the art unless otherwise specified.
In the present invention, the Mooney viscosity ML (1+4) was measured in accordance with the specifications of GB/T1232.1-2016.
Example 1
The rubber material comprises the following components in parts by mass: 100 parts of natural rubber, 40 parts of carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of accelerator DPG, 0.7 part of accelerator NS and 1.7 parts of vulcanizing agent S-80. Wherein the weight average molecular weight of the natural rubber is 21×10 5 g/mol, mooney viscosity ML (1+4) is 59.
The preparation method comprises the following steps:
(1) Adding natural rubber, carbon black, zinc oxide and stearic acid into an internal mixer, and carrying out internal mixing for 20min at the temperature of 60-110 ℃ to obtain a mixed material;
(2) Mixing the mixed material obtained in the step (1), a vulcanizing agent and an accelerator uniformly on a two-roll rubber mixing machine to obtain a mixed rubber;
(3) Vulcanizing the mixed rubber at 145 ℃ for 15min to obtain the low hysteresis loss and fatigue resistant rubber material.
The rubber material is subjected to various performance tests according to corresponding national standards.
The Shore A hardness test was carried out in accordance with GB/T531.1-2008.
The tensile strength and elongation at break were measured in accordance with GB/T528-2009.
The tear strength test was carried out as specified in GB/T529-2008.
Tandelta (60 ℃) was tested according to Q/6S 2645-2012.
The test of the temperature rise by heat generation by compression was carried out in accordance with the specifications of GB/T1687.3-2016.
Compression fatigue times were tested according to the Q/6S2646-2012 standard.
Example 2
The rubber material comprises the following components in parts by mass: 110 parts of natural rubber, 45 parts of carbon black, 6 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of accelerator DPG, 0.7 part of accelerator NS and 2 parts of vulcanizing agent S-80.
The preparation method comprises the following steps:
(1) Adding natural rubber, carbon black, zinc oxide and stearic acid into an internal mixer for banburying for 25min; adding a vulcanizing agent and an accelerator on a two-roller rubber mixing mill, and uniformly mixing;
(2) Vulcanizing the mixed rubber at 145 ℃ for 20min to obtain the low hysteresis loss and fatigue resistant rubber material. The rubber material is subjected to various performance tests according to corresponding national standards, and the test method is the same as the above.
Example 3
The rubber material comprises the following components in parts by mass: 110 parts of natural rubber, 50 parts of carbon black, 6 parts of zinc oxide, 3 parts of stearic acid, 0.5 part of accelerator DPG, 0.7 part of accelerator NS and 3 parts of vulcanizing agent S-80.
The preparation method comprises the following steps:
(1) Adding natural rubber, carbon black, zinc oxide and stearic acid into an internal mixer for banburying for 20-25min; adding a vulcanizing agent and an accelerator on a two-roller rubber mixing mill, and uniformly mixing;
(2) Vulcanizing the mixed rubber at 145 ℃ for 15min to obtain the low hysteresis loss and fatigue resistant rubber material. The rubber material is subjected to various performance tests according to corresponding national standards, and the test method is the same as the above.
Example 4
The rubber material comprises the following components in parts by mass: 100 parts of natural rubber, 45 parts of carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of accelerator DPG, 0.7 part of accelerator NS and 2 parts of vulcanizing agent S-80.
The preparation method comprises the following steps:
(1) Adding natural rubber, carbon black, zinc oxide and stearic acid into an internal mixer for banburying for 20-25min; adding a vulcanizing agent and an accelerator on a two-roller rubber mixing mill, and uniformly mixing;
(2) Vulcanizing the mixed rubber at 145 ℃ for 20min to obtain the low hysteresis loss and fatigue resistant rubber material. The rubber material is subjected to various performance tests according to corresponding national standards, and the test method is the same as the above.
Example 5
A rubber material was prepared in accordance with the method of example 1, except that the weight average molecular weight of the natural rubber was 16X 10 5 g/mol, mooney viscosity ML (1+4) is 56.
Example 6
A rubber material was prepared in accordance with the method of example 1, except that the weight average molecular weight of the natural rubber was 29X 10 5 g/mol, mooney viscosity ML (1+4) is 65.
Example 7
A rubber material was prepared in accordance with the method of example 1, except that the weight average molecular weight of the natural rubber was 32X 10 5 g/mol, mooney viscosity ML (1+4) is 99.
Example 8
A rubber material was prepared in the same manner as in example 1 except that 90 parts of natural rubber, 35 parts of carbon black, 4 parts of zinc oxide, 2 parts of stearic acid, 0.5 part of accelerator DPG, 0.7 part of accelerator NS and 1.5 parts of vulcanizing agent S-80.
Example 9
A rubber material was prepared in the same manner as in example 1 except that 100 parts of natural rubber, 40 parts of carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 0.45 part of accelerator DPG, 0.75 part of accelerator NS and 1.7 parts of vulcanizing agent S-80.
Example 10
A rubber material was prepared in the same manner as in example 1 except that 100 parts of natural rubber, 40 parts of carbon black, 5 parts of zinc oxide, 2 parts of stearic acid, 0.55 part of accelerator DPG, 0.65 part of accelerator NS and 1.7 parts of vulcanizing agent S-80.
Comparative example 1
The natural rubber used was commercially available (weight average molecular weight 13X 10 5 The weight portions of the composition are 100 portions of natural rubber, 50 portions of carbon black, 5 portions of zinc oxide, 3 portions of stearic acid, 2 portions of accelerator NS, 803 portions of vulcanizing agent S and 1 portion of anti-aging agent.
Comparative example 2
A rubber material was prepared in accordance with the method of example 1, except that the weight average molecular weight of the natural rubber was 2X 10 5 g/mol。
Comparative example 3
A rubber material was prepared as in example 1, except that the Mooney viscosity ML (1+4) of the natural rubber was 45.
Table 1 shows the physical and mechanical properties of the rubber materials of examples and comparative examples, and it can be seen from Table 1 that the rubber materials prepared according to the invention have lower hysteresis loss and compression heat generation temperature rise, and have better mechanical properties.
TABLE 1
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. The rubber material is characterized by comprising the following components in parts by weight:
90-120 parts of rubber, 1.5-3 parts of vulcanizing agent, 1-1.5 parts of accelerator, 35-50 parts of reinforcing agent and 6-9 parts of activating agent;
wherein the weight average molecular weight of the rubber is 16×10 5 g/mol or more, and Mooney viscosity ML (1+4) is 55 or more.
2. The rubber material according to claim 1, wherein the weight average molecular weight of the rubber is 16 x 10 5 g/mol-30×10 5 g/mol, mooney viscosity ML (1+4) is from 55 to 65.
3. Rubber material according to claim 1 or 2, characterized in that it comprises the following components in parts by mass:
95-105 parts of rubber, 1.5-2.0 parts of vulcanizing agent, 1.1-1.3 parts of accelerator, 38-42 parts of reinforcing agent and 6.5-7.5 parts of activating agent.
4. A rubber material according to claim 1 or 2, wherein,
the rubber comprises natural rubber;
the vulcanizing agent comprises a vulcanizing agent S-80;
the reinforcing agent comprises carbon black; preferably, the carbon black is carbon black N550;
the activator comprises 4-6 parts of zinc oxide and 2-3 parts of stearic acid.
5. The rubber material according to claim 4, which comprises the following components in parts by mass:
100 parts of natural rubber, 1.7 parts of vulcanizing agent, 1.2 parts of accelerator, 40 parts of carbon black, 5 parts of zinc oxide and 2 parts of stearic acid.
6. Rubber material according to claim 1 or 2, wherein the accelerator is a mixture of accelerator DPG and accelerator NS.
7. The rubber material according to claim 6, wherein the weight ratio of the accelerator DPG to the accelerator NS is (4.5-5.5) (6.5-7.5).
8. A method for producing a rubber material according to any one of claims 1 to 7, comprising the steps of:
mixing rubber, a reinforcing agent and an activating agent to obtain a mixed material;
mixing the mixed materials with a vulcanizing agent and an accelerator to obtain a mixed rubber;
and vulcanizing the rubber compound to obtain the rubber material.
9. The method according to claim 8, wherein the banburying is performed at 60 to 110 ℃ for 20 to 25min.
10. The preparation method according to claim 8 or 9, wherein the vulcanization is carried out at 130-160 ℃ for 15-20min.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202311210111.0A CN117362767A (en) | 2023-09-19 | 2023-09-19 | Rubber material and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311210111.0A CN117362767A (en) | 2023-09-19 | 2023-09-19 | Rubber material and preparation method thereof |
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| CN202311210111.0A Pending CN117362767A (en) | 2023-09-19 | 2023-09-19 | Rubber material and preparation method thereof |
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- 2023-09-19 CN CN202311210111.0A patent/CN117362767A/en active Pending
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