CN116284948A - Preparation method of modified EVA elastomer - Google Patents
Preparation method of modified EVA elastomer Download PDFInfo
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- CN116284948A CN116284948A CN202310312004.2A CN202310312004A CN116284948A CN 116284948 A CN116284948 A CN 116284948A CN 202310312004 A CN202310312004 A CN 202310312004A CN 116284948 A CN116284948 A CN 116284948A
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- polyborosiloxane
- eva
- coupling agent
- blending
- foaming
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 17
- 239000000806 elastomer Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000005187 foaming Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007822 coupling agent Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 8
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 239000004088 foaming agent Substances 0.000 claims abstract description 6
- 238000003825 pressing Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims abstract description 3
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 235000021355 Stearic acid Nutrition 0.000 claims description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 7
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 7
- 239000008117 stearic acid Substances 0.000 claims description 7
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- GSFXLBMRGCVEMO-UHFFFAOYSA-N [SiH4].[S] Chemical compound [SiH4].[S] GSFXLBMRGCVEMO-UHFFFAOYSA-N 0.000 claims 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims 1
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical compound [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- 230000008569 process Effects 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 description 24
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 24
- 239000004156 Azodicarbonamide Substances 0.000 description 6
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 6
- 235000019399 azodicarbonamide Nutrition 0.000 description 6
- 238000000748 compression moulding Methods 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 230000000386 athletic effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- -1 polysiloxane Polymers 0.000 description 3
- 239000006260 foam Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920002725 thermoplastic elastomer Polymers 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000001282 organosilanes Chemical class 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000000446 sulfanediyl group Chemical group *S* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
- C08J9/102—Azo-compounds
- C08J9/103—Azodicarbonamide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0014—Use of organic additives
- C08J9/0042—Use of organic additives containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/04—N2 releasing, ex azodicarbonamide or nitroso compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
- C08J2323/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2483/04—Polysiloxanes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a preparation method of a modified EVA elastomer, which comprises the following steps: step one: weighing polyborosiloxane, a coupling agent, an accelerator and a foaming agent according to a certain mass ratio, and uniformly stirring and mixing at a certain temperature; step two: taking the mixture obtained in the step one, melting and blending the mixture with EVA according to a certain proportion, and granulating; step three: and (3) carrying out mould pressing foaming on the modified EVA master batch obtained in the step (II) to obtain the modified EVA blending elastomer. According to the invention, the polyborosiloxane and the EVA are blended and modified, and under the action of the coupling agent, the polyborosiloxane and the EVA can be uniformly mixed and dispersed, so that the interfacial binding force of the polyborosiloxane and the EVA in the blending material is improved, and the mechanical property of the blending material is improved. The use of the accelerator improves the fluidity of the polyborosiloxane in the processing process, thereby improving the plasticity of the blending material.
Description
Technical Field
The invention belongs to the field of rubber-plastic composite foaming materials, and relates to a modified EVA thermoplastic elastomer with stable dispersibility, excellent rebound rate and quick impact response time and a preparation method thereof.
Background
In recent years, various novel polymer materials have been developed as bamboo shoots after rain, and among them, foamed athletic shoe midsoles using EVA (ethylene-vinyl acetate copolymer) as a base material have been widely used in the industry because of their low density and good plasticity. However, as the market for athletic shoe materials expands year by year, consumers have increasingly demanded quality and performance from athletic shoes. The prior EVA foaming shoe material insole has hard texture and poor rebound and buffer performance, and after being worn for a period of time, the shoe can deform, has poor elasticity and other factors, and influences the experience of a wearer.
In order to solve the above problems, a blending process of EVA and a high polymer elastomer by melt-kneading is attracting attention in the field of composite foam materials. Among them, high polymer organosilane elastomers are considered as thermoplastic elastomer foaming materials with great application potential because of their excellent viscoelasticity, good self-adaptability, little pollution to production process and the like. In the Chinese patent of invention, "a P4U rubber-plastic composite foaming material and a preparation method thereof" (patent number 201910091927.3), it is proposed to blend and foam EVA with Polyborosiloxane (PBDMS) to improve the rebound resilience, in the patent, polyborosiloxane is used as an adaptive material, and has unique viscoelasticity, polyborosiloxane is used as an elastomer to blend and foam with EVA, so as to improve the rebound resilience and the impact response time of EVA foaming shoe materials. However, the technical route is only suitable for processing a small amount of EVA blending foaming material with the addition amount of polyborosiloxane (more than or equal to 5 percent), and the processing technology of the addition amount of polyborosiloxane (more than or equal to 5 percent) is difficult to realize. The main reason is that the compatibility of the polyborosiloxane and EVA is poor, the uniformly blended processing state is difficult to obtain, and when the polyborosiloxane is added into the blended elastomer with the addition amount of more than 5%, the defects of bubbles, holes and the like are easy to occur, so that the performance of the elastomer and the stability of a finished product are affected.
Disclosure of Invention
In view of the problems in the prior art, it is an object of the present invention to provide a modified EVA elastomer that has better rebound and impact response time properties than EVA elastomers prior to modification.
The second object of the present invention is to provide a preparation method of the modified EVA elastomer, which can meet the blending process requirement of the polyborosiloxane elastomer and EVA.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the polyborosiloxane is a novel high molecular material of element modified polysiloxane, and is a polymer obtained by introducing boron atoms into a polysiloxane siloxane skeleton. The boron atom in the Si-O-B structure in the polyborosiloxane molecular chain can form a B-O electronic bridge pair with the oxygen atom in the adjacent chain, and the electronic bridge pair is a dynamically variable physical crosslinking and is in a dynamic process of continuous dissociation and reformation. It therefore has a particular rheology and good viscoelasticity. According to the invention, a melt blending method is adopted to modify EVA by polyborosiloxane, a coupling agent is added to improve compatibility of polyborosiloxane and EVA, a blending dispersion state is improved, and then melt banburying blending is carried out to obtain a modified blending elastomer, and the method comprises the following steps of:
step one: weighing polyborosiloxane, a coupling agent, an accelerator and a foaming agent according to a certain mass ratio, and uniformly stirring and mixing at a certain temperature;
step two: taking the mixture obtained in the step one, melting and blending the mixture with EVA according to a certain proportion, and granulating;
step three: and (3) carrying out mould pressing foaming on the modified EVA master batch obtained in the step (II) to obtain the modified EVA blending elastomer.
Preferably, the molar ratio of silicon atoms to boron atoms in the polyborosiloxane described in step one is 15.1:1 to 5.3:1.
Preferably, the coupling agent in step one includes, but is not limited to, vinyl-based silane coupling agents (e.g., WD-20, WD-26), amino-based silane coupling agents (e.g., KH550, KH 570), thio-based silane coupling agents (e.g., si-69, si-75), polyol-based silane coupling agents (BH-076), and the like.
Preferably, the mass ratio of the coupling agent to the polyborosiloxane in the first step is 1:60-1:7.5.
Preferably, the accelerator described in step one includes, but is not limited to, stearic acid, zinc stearate, dicumyl peroxide, and the like.
Preferably, the mass ratio of the accelerator to the polyborosiloxane in the first step is 1:14-1:7.9.
Preferably, the foaming agent in the first step includes, but is not limited to, azodicarbonamide and the like.
Preferably, the mass ratio of the foaming agent to the polyborosiloxane in the step one is 1:2.
Preferably, the ratio of the polyborosiloxane to EVA in the second step is 1:10.7.
Preferably, in the third step, the molding foaming pressure is 20MPa, the temperature is 185 ℃ and the time is 11 minutes.
The invention has the beneficial effects that:
according to the invention, the polyborosiloxane and the EVA are blended and modified, and under the action of the coupling agent, the polyborosiloxane and the EVA can be uniformly mixed and dispersed, so that the interfacial binding force of the polyborosiloxane and the EVA in the blending material is improved, and the mechanical property of the blending material is improved. The use of the accelerator improves the fluidity of the polyborosiloxane in the processing process, thereby improving the plasticity of the blending material.
Detailed Description
The invention is described in further detail below with reference to specific embodiments using EVA6110M of yankee basf as the elastomeric substrate.
Embodiment one:
firstly, mixing polyborosiloxane with EVA6110M, WD-20, stearic acid and zinc stearate at normal temperature by a kneader for 0.5 hour; the mixture was then blended in an internal mixer at 135℃for 15 minutes, and dicumyl peroxide and azodicarbonamide were added at 12 minutes. Extruding and granulating after banburying is finished, and then weighing a certain mass of blending master batch, and performing compression molding foaming by using a flat vulcanizing machine, wherein the mold temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
Embodiment two:
the material for improving the invention is prepared from the following raw materials in percentage by mass:
firstly, mixing polyborosiloxane with EVA6110M, si-69, stearic acid and zinc stearate by a kneader at normal temperature for 0.5 hour; the mixture was then blended in an internal mixer at 135℃for 15 minutes, and dicumyl peroxide and azodicarbonamide were added at 12 minutes. Extruding and granulating after banburying is finished, and then weighing a certain mass of blending master batch, and performing compression molding foaming by using a flat vulcanizing machine, wherein the mold temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
Example III
The material for improving the invention is prepared from the following raw materials in percentage by mass:
firstly, mixing polyborosiloxane with EVA6110M, si-75, stearic acid and zinc stearate at normal temperature by a kneader for 0.5 hour; the mixture was then blended in an internal mixer at 135℃for 15 minutes, and dicumyl peroxide and azodicarbonamide were added at 12 minutes. Extruding and granulating after banburying is finished, and then weighing a certain mass of blending master batch, and performing compression molding foaming by using a flat vulcanizing machine, wherein the mold temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
Example IV
The material for improving the invention is prepared from the following raw materials in percentage by mass:
firstly, mixing polyborosiloxane with EVA6110M, KH550, KH570, stearic acid and zinc stearate by a kneader at normal temperature for 0.5 hour; the mixture was then blended in an internal mixer at 135℃for 15 minutes, and dicumyl peroxide and azodicarbonamide were added at 12 minutes. Extruding and granulating after banburying is finished, and then weighing a certain mass of blending master batch, and performing compression molding foaming by using a flat vulcanizing machine, wherein the mold temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
Example five
The material for improving the invention is prepared from the following raw materials in percentage by mass:
firstly, mixing polyborosiloxane with EVA6110M, BH-076, stearic acid and zinc stearate by a kneader at normal temperature for 0.5 hour; the mixture was then blended in an internal mixer at 135℃for 15 minutes, and dicumyl peroxide and azodicarbonamide were added at 12 minutes. Extruding and granulating after banburying is finished, and then weighing a certain mass of blending master batch, and performing compression molding foaming by using a flat vulcanizing machine, wherein the mold temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
Comparative example 1
Mixing polyborosiloxane with EVA6110M, extruding and granulating by a granulator, and then performing mould pressing foaming, wherein the mould temperature is 185 ℃, the pressure is 20MPa, and the time is 11 minutes.
The above examples and comparative examples were each tested for the resilience performance of the material and for the impact response time using an Exeter impact tester.
Table 1 comparison of rebound Rate of examples and comparative examples
Table 2 comparison of impact response times for examples and comparative examples
The above description of the present invention is only a part of the embodiments, but the present invention is not limited to the above embodiments. The above embodiments are illustrative and not limiting. All specific extensions fall within the scope of the present invention when materials and methods of the present invention are employed without departing from the spirit of the invention and the scope of the claims.
Claims (9)
1. The preparation method of the modified EVA elastomer is characterized by comprising the following steps:
step one: weighing polyborosiloxane, a coupling agent, an accelerator and a foaming agent according to a certain mass ratio, and uniformly stirring and mixing at a certain temperature;
step two: taking the mixture obtained in the step one, melting and blending the mixture with EVA according to a certain proportion, and granulating;
step three: and (3) carrying out mould pressing foaming on the modified EVA master batch obtained in the step (II) to obtain the modified EVA blending elastomer.
2. The method of claim 1, wherein the molar ratio of silicon atoms to boron atoms in the polyborosiloxane in step one is 15.1:1 to 5.3:1.
3. The method according to claim 1, wherein the coupling agent in the first step is a vinyl silane coupling agent, an aminosilane coupling agent, a sulfur silane coupling agent or a polyhydric alcohol silane coupling agent.
4. The method according to claim 1, wherein the mass ratio of the coupling agent to the polyborosiloxane in the first step is 1:60 to 1:7.5.
5. The method of claim 1, wherein the accelerator in step one is one of stearic acid, zinc stearate, and dicumyl peroxide.
6. The method of claim 1, wherein the mass ratio of the accelerator to the polyborosiloxane in the first step is 1:14 to 1:7.9.
7. The method of claim 1, wherein the mass ratio of the foaming agent to the polyborosiloxane in the first step is 1:2.
8. The method of claim 1, wherein the ratio of polyborosiloxane to EVA in step two is 1:10.7.
9. The method according to claim 1, wherein the molding foaming pressure in the third step is 20MPa, the temperature is 185 ℃ and the time is 11 minutes.
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| CN202310312004.2A CN116284948A (en) | 2023-03-28 | 2023-03-28 | Preparation method of modified EVA elastomer |
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2023
- 2023-03-28 CN CN202310312004.2A patent/CN116284948A/en active Pending
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