CN112250916A - Hard rubber and preparation method thereof - Google Patents
Hard rubber and preparation method thereof Download PDFInfo
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- CN112250916A CN112250916A CN202011139510.9A CN202011139510A CN112250916A CN 112250916 A CN112250916 A CN 112250916A CN 202011139510 A CN202011139510 A CN 202011139510A CN 112250916 A CN112250916 A CN 112250916A
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- rubber
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- mixture
- hard rubber
- banburying
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- 229920001875 Ebonite Polymers 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 36
- 229920001971 elastomer Polymers 0.000 claims abstract description 34
- 239000005060 rubber Substances 0.000 claims abstract description 34
- 244000043261 Hevea brasiliensis Species 0.000 claims abstract description 32
- 238000002156 mixing Methods 0.000 claims abstract description 32
- 229920003052 natural elastomer Polymers 0.000 claims abstract description 31
- 229920001194 natural rubber Polymers 0.000 claims abstract description 31
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 28
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 14
- 238000001914 filtration Methods 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 9
- 239000010439 graphite Substances 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 9
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000008117 stearic acid Substances 0.000 claims abstract description 9
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- BUZICZZQJDLXJN-UHFFFAOYSA-N 3-azaniumyl-4-hydroxybutanoate Chemical compound OCC(N)CC(O)=O BUZICZZQJDLXJN-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003490 calendering Methods 0.000 claims description 7
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 abstract description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 1
- 238000004073 vulcanization Methods 0.000 description 22
- 238000005303 weighing Methods 0.000 description 15
- 238000007599 discharging Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 229920003023 plastic Polymers 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010276 construction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920003051 synthetic elastomer Polymers 0.000 description 2
- 239000005061 synthetic rubber Substances 0.000 description 2
- 241000209504 Poaceae Species 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
-
- 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
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Extrusion Moulding Of Plastics Or The Like (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a hard rubber and a preparation method thereof, the hard rubber comprises 80-120 parts of natural rubber, 10-50 parts of butadiene styrene rubber, 5-15 parts of zinc oxide, 1-3 parts of stearic acid, 10-30 parts of graphite, 40-60 parts of sulfur, 5-15 parts of rubber accelerator and 4-12 parts of high styrene by weight, the preparation method comprises the following steps, the method comprises the following steps of banburying natural rubber, then banburying the natural rubber, styrene butadiene rubber and high styrene, banburying the banburied mixture, mixing and banburying zinc oxide, stearic acid, graphite, sulfur and a rubber accelerator, and carrying out thin-pass treatment, filtering to obtain sheets and extrusion molding on the obtained mixture to obtain the hard rubber.
Description
Technical Field
The invention relates to the technical field of rubber materials, in particular to hard rubber and a preparation method thereof.
Background
The rubber is divided into two types, namely natural rubber and synthetic rubber, wherein the natural rubber is latex taken from rubber trees, rubber grasses and other duties, and the synthetic rubber is obtained by polymerizing various monomers. The rubber product is widely applied to various industrial or living aspects, and has the characteristics of high elasticity, insulativity, sealability, easiness in processing and forming and the like. However, common rubber products become soft when heated, become hard and brittle after precooling, are not easy to form and wear, are easy to dissolve in organic solvents such as gasoline and the like, have double bonds in molecules, are easy to generate addition reaction and age. Therefore, in order to improve the performance of rubber products, rubber needs to be vulcanized, that is, under certain conditions, raw rubber in the rubber material and a vulcanizing machine are subjected to chemical reaction, and macromolecules with linear structures are crosslinked into macromolecules with three-dimensional network structures, so that the rubber material has excellent performances of high strength, high elasticity, high wear resistance, corrosion resistance and the like.
Generally, the vulcanization process is divided into four stages, namely induction, prevulcanization, normal vulcanization and overcuring, in order to realize the reaction, energy must be added to enable the reaction to reach a certain vulcanization condition, then the rubber is kept warm within the vulcanization temperature range to complete all vulcanization reactions, and main factors influencing the vulcanization effect comprise vulcanization pressure, vulcanization temperature and vulcanization time.
At present, industrial hard rubber is mainly vulcanized by using a steam vulcanizing tank, the method has the advantages of stable performance, high hardness and firm bonding, but the method needs to use special equipment for corresponding vulcanization operation and use steam, and for project site construction, the method cannot directly adopt the steam vulcanizing tank for vulcanization treatment and only can transport the rubber to the place of the project after factory production, so that the transportation cost and the construction period of the project are greatly increased.
Disclosure of Invention
In view of the above, the present invention provides a hard rubber that can be vulcanized with hot water and a method for preparing the same.
The technical scheme of the invention is realized as follows: the invention provides hard rubber which comprises the following components in parts by weight:
on the basis of the technical scheme, preferably, the components comprise the following components in parts by weight:
on the basis of the technical scheme, preferably, the components comprise the following components in parts by weight:
based on the above technical solution, preferably, the rubber accelerator includes tetramethylthiuram monosulfide.
In addition to the above technical solutions, preferably, the rubber accelerator further includes 2, 2' -dithiodibenzothiazole.
On the basis of the above technical solution, preferably, the tetramethylthiuram monosulfide: 2. the mass ratio of the 2' -dithiodibenzothiazole is 7: 3.
The invention also provides a preparation method of the hard rubber, which comprises the following steps:
plasticating natural rubber on an internal mixer at the plasticating temperature of 40-60 ℃ for 1-3min to obtain plasticated natural rubber after the plastication is finished;
step two, adding the plasticated natural rubber, styrene-butadiene rubber and high styrene into an internal mixer, wherein the internal mixing temperature is 40-60 ℃, the internal mixing time is 2-6min, and a first mixture is obtained after internal mixing is finished;
and step three, mixing the first mixture with zinc oxide, stearic acid, graphite, sulfur and a rubber accelerator, and then continuously banburying in a banbury mixer at the banburying temperature of 40-60 ℃ for 1-3min to obtain a second mixture after banburying is finished.
And step four, performing thin passing on the second mixture obtained in the step three for three times through an open mill, filtering to obtain sheets, and then cooling, extruding, calendering and molding to obtain the hard rubber plate.
Compared with the prior art, the hard rubber and the preparation method thereof have the following beneficial effects:
(1) the invention provides a hard rubber with lower vulcanization temperature and a preparation method thereof, the hard rubber can be vulcanized by hot water, and the performances of the vulcanized hard rubber can meet the requirements, so that the problem of inconvenient vulcanization of the hard rubber is effectively solved, and the hard rubber can be vulcanized on a construction site;
(2) the main components of the hard rubber are conventional rubber raw materials, the raw materials are easy to obtain, the processing treatment can be carried out by conventional equipment, the vulcanization speed and the bonding property of a rubber product can be improved by adding the styrene-butadiene rubber, the corrosion resistance and the insulativity of the rubber can be improved, the sulfur is used as a vulcanizing agent to be matched with a rubber accelerator, the temperature requirement of the integral vulcanization of the rubber is reduced, and therefore the hard rubber can be vulcanized by using hot water.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1
Weighing 80 parts of natural rubber, adding the natural rubber into an internal mixer for plastication, wherein the temperature of plastics is 40 ℃, the plastication is 1min, obtaining plasticated natural rubber, weighing 10 parts of styrene-butadiene rubber and 4 parts of high styrene, adding the styrene-butadiene rubber and the 4 parts of high styrene into the internal mixer, mixing and banburying with the plasticated natural rubber at 40 ℃, the banburying temperature is 2min, obtaining a first mixture, weighing 5 parts of zinc oxide, 1 part of stearic acid, 10 parts of graphite, 40 parts of sulfur and 5 parts of tetramethylthiuram monosulfide, mixing the mixture with the first mixture, banburying in the internal mixer at 40 ℃, banburying for 1min, obtaining a second mixture, performing thin-pass treatment on the second mixture through an open mixer, processing the third time, filtering the mixture through a filter to obtain sheets, and performing cooling extrusion calendering molding to obtain the hard rubber plate.
Example 2
Weighing 90 parts of natural rubber, adding the natural rubber into an internal mixer for plastication, wherein the temperature of plastics is 45 ℃, the plastication is 2min, obtaining plasticated natural rubber, weighing 20 parts of styrene-butadiene rubber and 6 parts of high styrene, adding the styrene-butadiene rubber and the 6 parts of high styrene into the internal mixer for mixing and internal mixing with the plasticated natural rubber, wherein the internal mixing temperature is 45 ℃, the internal mixing is 3min, obtaining a first mixture, weighing 8 parts of zinc oxide, 2 parts of stearic acid, 15 parts of graphite, 45 parts of sulfur, 4 parts of tetramethylthiuram monosulfide and 4 parts of 2, 2' -dithiodibenzothiazole, mixing the first mixture with the first mixture, banburying in a banbury mixer at 45 deg.C for 2min to obtain a second mixture, subjecting the second mixture to thin pass treatment in an open mill for three times, and then filtering and sheet discharging are carried out by a filtering sheet discharging machine, and then cooling, extruding, calendaring and forming are carried out to obtain the hard rubber plate.
Example 3
Weighing 100 parts of natural rubber, adding the natural rubber into an internal mixer for plastication, wherein the temperature of plastics is 50 ℃, the plastication is 3min to obtain plasticated natural rubber, weighing 30 parts of styrene-butadiene rubber and 8 parts of high styrene, adding the styrene-butadiene rubber and the 8 parts of high styrene into the internal mixer for mixing and internal mixing with the plasticated natural rubber, wherein the mixing temperature is 50 ℃, the internal mixing is 4min to obtain a first mixture, weighing 10 parts of zinc oxide, 2 parts of stearic acid, 20 parts of graphite, 50 parts of sulfur, 7 parts of tetramethylthiuram monosulfide and 3 parts of 2, 2' -dithiodibenzothiazole, mixing the first mixture with the first mixture, banburying in a banbury mixer at 50 deg.C for 2min to obtain a second mixture, subjecting the second mixture to thin pass treatment in an open mill for three times, and then filtering and sheet discharging are carried out by a filtering sheet discharging machine, and then cooling, extruding, calendaring and forming are carried out to obtain the hard rubber plate.
Example 4
Weighing 110 parts of natural rubber, adding the natural rubber into an internal mixer for plastication, wherein the temperature of plastics is 55 ℃, the plastication is 2min, obtaining plasticated natural rubber, weighing 40 parts of styrene-butadiene rubber and 10 parts of high styrene, adding the styrene-butadiene rubber and the high styrene into the internal mixer for mixing and internal mixing with the plasticated natural rubber, wherein the internal mixing temperature is 55 ℃, the internal mixing is 5min, obtaining a first mixture, weighing 12 parts of zinc oxide, 3 parts of stearic acid, 25 parts of graphite, 55 parts of sulfur, 8.5 parts of tetramethylthiuram monosulfide and 3.5 parts of 2, 2' -dithiodibenzothiazole, mixing the first mixture with the first mixture, banburying in a banbury mixer at 55 deg.C for 3min to obtain a second mixture, subjecting the second mixture to thin pass treatment in an open mill for three times, and then filtering and sheet discharging are carried out by a filtering sheet discharging machine, and then cooling, extruding, calendaring and forming are carried out to obtain the hard rubber plate.
Example 5
Weighing 120 parts of natural rubber, adding the natural rubber into an internal mixer for plastication, wherein the temperature of plastics is 60 ℃, the plastication is 3min to obtain plasticated natural rubber, weighing 50 parts of styrene-butadiene rubber and 12 parts of high styrene, adding the styrene-butadiene rubber and the 12 parts of high styrene into the internal mixer for mixing and internal mixing with the plasticated natural rubber, wherein the mixing temperature is 60 ℃, the mixing and internal mixing are 6min to obtain a first mixture, weighing 15 parts of zinc oxide, 3 parts of stearic acid, 30 parts of graphite, 60 parts of sulfur, 10.5 parts of tetramethylthiuram monosulfide and 4.5 parts of 2, 2' -dithiodibenzothiazole, mixing the first mixture with the first mixture, banburying in a banbury mixer at 60 deg.C for 2min to obtain a second mixture, subjecting the second mixture to thin pass treatment in an open mill for three times, and then filtering and sheet discharging are carried out by a filtering sheet discharging machine, and then cooling, extruding, calendaring and forming are carried out to obtain the hard rubber plate.
Comparative example
A commercially available unvulcanized rubber sheet was used as a comparative example.
The rubber sheets of examples 1 to 5 and comparative example were subjected to hot water vulcanization and steam vulcanization, respectively, and the properties of the rubber sheets before treatment were measured, and the results were as follows:
the hot water vulcanization method comprises the steps of immersing the rubber plates of examples 1-5 and comparative examples in water, heating for 6 hours to reach 95-98 ℃, keeping the temperature for vulcanization for 70-80 hours, and detecting the hardness value, the sealing property and the physical property of the rubber plates after vulcanization, wherein the detection results are as follows:
the steam vulcanization method comprises the steps of respectively placing the rubber plates of the embodiments 1-5 and the comparative example on a flat car, then stably feeding the rubber plates into a steam tank, vulcanizing the rubber plates in the steam tank, raising the pressure in the tank to 3bar, raising the temperature to 120 ℃ within 2 hours, preserving the heat for 4-5 hours, slowly cooling the temperature to 60 ℃, and detecting the hardness value of the rubber plates after vulcanization, wherein the detection result is as follows:
the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The hard rubber is characterized by comprising the following components in parts by weight:
2. the hard rubber according to claim 1, comprising the following components:
3. the hard rubber according to claim 1, comprising the following components:
4. the hard rubber of claim 1, wherein the rubber accelerator comprises tetramethylthiuram monosulfide.
5. The hard rubber of claim 4, wherein the rubber accelerator further comprises 2, 2' -dithiodibenzothiazole.
6. The hard rubber of claim 5, wherein the tetramethylthiuram monosulfide: 2. the mass ratio of the 2' -dithiodibenzothiazole is 7: 3.
7. The process for producing the hard rubber according to any one of claims 1 to 6, characterized by comprising the steps of:
plasticating natural rubber on an internal mixer at the plasticating temperature of 40-60 ℃ for 1-3min to obtain plasticated natural rubber after the plastication is finished;
step two, adding the plasticated natural rubber, styrene-butadiene rubber and high styrene into an internal mixer, wherein the internal mixing temperature is 40-60 ℃, the internal mixing time is 2-6min, and a first mixture is obtained after internal mixing is finished;
and step three, mixing the first mixture with zinc oxide, stearic acid, graphite, sulfur and a rubber accelerator, and then continuously banburying in a banbury mixer at the banburying temperature of 40-60 ℃ for 1-3min to obtain a second mixture after banburying is finished.
And step four, performing thin passing on the second mixture obtained in the step three for three times through an open mill, filtering to obtain sheets, and then cooling, extruding, calendering and molding to obtain the hard rubber plate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011139510.9A CN112250916A (en) | 2020-10-22 | 2020-10-22 | Hard rubber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011139510.9A CN112250916A (en) | 2020-10-22 | 2020-10-22 | Hard rubber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112250916A true CN112250916A (en) | 2021-01-22 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011139510.9A Pending CN112250916A (en) | 2020-10-22 | 2020-10-22 | Hard rubber and preparation method thereof |
Country Status (1)
| Country | Link |
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| CN (1) | CN112250916A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965524A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Low-temperature-resistant sole material and preparation method thereof |
| CN109517229A (en) * | 2018-11-30 | 2019-03-26 | 上海双浦橡胶防腐衬里有限公司 | A kind of low-temp low-pressure vulcanized rubber liner compositions and its application method |
| CN109721772A (en) * | 2018-12-30 | 2019-05-07 | 际华三五一五皮革皮鞋有限公司 | Vibration-damping foamed rubber soles of a kind of hard height and preparation method thereof |
-
2020
- 2020-10-22 CN CN202011139510.9A patent/CN112250916A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103965524A (en) * | 2014-05-20 | 2014-08-06 | 南京东亚橡塑制品有限公司 | Low-temperature-resistant sole material and preparation method thereof |
| CN109517229A (en) * | 2018-11-30 | 2019-03-26 | 上海双浦橡胶防腐衬里有限公司 | A kind of low-temp low-pressure vulcanized rubber liner compositions and its application method |
| CN109721772A (en) * | 2018-12-30 | 2019-05-07 | 际华三五一五皮革皮鞋有限公司 | Vibration-damping foamed rubber soles of a kind of hard height and preparation method thereof |
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Application publication date: 20210122 |
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