CN114806190B - TPV material composition and preparation and application thereof - Google Patents
TPV material composition and preparation and application thereof Download PDFInfo
- Publication number
- CN114806190B CN114806190B CN202210238308.4A CN202210238308A CN114806190B CN 114806190 B CN114806190 B CN 114806190B CN 202210238308 A CN202210238308 A CN 202210238308A CN 114806190 B CN114806190 B CN 114806190B
- Authority
- CN
- China
- Prior art keywords
- low
- antioxidant
- melt index
- composition
- screw extruder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
-
- 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
-
- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (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 TPV material composition, and preparation and application thereof, and the composition comprises the following components: low melt index PP resin, high melt index PP resin, low mooney EPDM rubber, high mooney EPDM rubber, paraffin oil, vulcanizing agent, vulcanization accelerator, antioxidant, light stabilizer, lubricant. The components are synergistic, so that the TPV material with high fluidity and low glossiness is prepared.
Description
Technical Field
The invention belongs to the field of thermoplastic elastomers, and particularly relates to a TPV material composition, and preparation and application thereof.
Background
The state vulcanized thermoplastic vulcanizate (TPV) has the advantages of excellent low temperature resistance, good touch feeling, low high-temperature compression set, good heat resistance and weather resistance and the like, and is widely used for automobile interiors and exterior trim parts. However, for larger pieces of interior trim, a material with higher flow properties for better formability is required, while lower gloss gives a higher end of the interior trim feel.
TPV products are polymer elastomer materials prepared by using plastics as a continuous phase and rubber as a disperse phase and adopting a PP and EPDM dynamic vulcanization process, and have the difficulty of simultaneously having high flow and very low glossiness for low-hardness TPV products.
Disclosure of Invention
Based on the defects existing in the prior art, the technical problem to be solved by the invention is to provide a TPV material composition, and preparation and application thereof, which has high fluidity and low glossiness.
The invention provides a TPV material composition, which comprises the following components in parts by weight:
wherein the melt index of the low melt index PP resin is 230 ℃, and the melt index is less than or equal to 2g/10min under the condition of 2.16 kg;
the melt index of the high melt index PP resin is 230 ℃, and the melt index under the condition of 2.16kg is 30-50 g/10min;
the melt indexes of the low melt index PP resin and the high melt index PP resin are detected according to the ISO 1133-1-2011 standard method.
The Mooney viscosity of the low Mooney EPDM rubber is ML (1+4) 125 ℃ to 40-70;
the Mooney viscosity of the high Mooney EPDM rubber is ML (1+4) 125 ℃ to 75-120.
The Mooney viscosities of the low and high Mooney EPDM rubbers described above were measured according to ISO 289-1-2014 standard methods.
Preferably, the melt index of the low melt index PP resin is 230 ℃, and the melt index is less than or equal to 1g/10min under the condition of 2.16kg.
The inventor researches find that when the melt index of the low-melt-index PP resin is less than or equal to 1g/10min and the melt index of the high-melt-index PP resin is 30-50 g/10min, the flowability and the glossiness of the TPV material are lower.
Preferably, the ENB weight percent of the low-Mooney EPDM rubber is 3.5 to 6.5 weight percent; the ENB weight percentage content of the high-Mooney EPDM rubber is 3.5-6.5 wt%.
More preferably, the ENB weight percent of the low Mooney EPDM rubber is from 4 to 5.5 weight percent.
More preferably, the ENB weight percent of the high-Mooney EPDM rubber is from 4 to 5.5 weight percent.
The inventor researches that when the Mooney viscosity of the EPDM rubber is lower, the molecular weight of the EPDM rubber is lower, so that the EPDM rubber is favorable for blending with the PP material, and when the Mooney viscosity of the EPDM rubber is higher, the molecular weight of the EPDM rubber is higher, so that the glossiness of the material is reduced, and the low Mooney and high Mooney EPDM are used together, so that the good mixing performance of the PP and the EPDM is ensured, and the glossiness of the material is also effectively reduced. The low-melting-point PP resin is added in the content of 8-12 parts by weight, and the viscosity of the low-melting-point PP resin can be relatively close to that of the low-Mooney EPDM rubber, so that the low-melting-point PP resin is beneficial to mixing and dispersing of the PP resin and the EPDM rubber.
The ENB content of the EPDM rubber influences the vulcanization speed and the performance of the vulcanized rubber, the ENB content is high in rubber vulcanization speed, scorching is easy to generate, the rubber is not easy to shear and crush into fine size, the rubber phase size is too large, the comprehensive mechanical property of the material is poor, the ENB content is too low, the rubber vulcanization speed is too low, the rubber cannot be vulcanized completely within the screw residence time, the comprehensive mechanical property of the material is also poor, and when the ENB content in the EPDM is 3.5-6.5%, the rubber vulcanization speed is proper, the crushing size of the vulcanized rubber is smaller, and the comprehensive performance of the material is better.
Preferably, the paraffin oil is high-flash-point paraffin oil without polycyclic aromatic hydrocarbon, and the open flash point is more than or equal to 260 ℃.
The flash point of the opening is tested according to the GB/T267-1988 standard method, and the temperature rising speed is 1 ℃/min.
The paraffin oil does not contain polycyclic aromatic hydrocarbon, and is more environment-friendly. The open flash point is higher, and the TPV product prepared by the method has better heat resistance and lower haze.
More preferably, the paraffinic oil has an open flash point of 265 to 300 ℃.
Preferably, the vulcanizing agent is a peroxide-based vulcanizing agent.
Preferably, the peroxide vulcanizing agent is one or more of isopropyl tert-butyl peroxycarbonate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and bis-tert-butyl cumyl peroxide.
Preferably, the vulcanization accelerator is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate and diphenylmethane maleimide.
Preferably, the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168, antioxidant DLTP and antioxidant 626.
Preferably, the light stabilizer is one or more of hindered amine light stabilizer and triazine light stabilizer.
Further preferably, the light stabilizer is a mixture of hindered amine light stabilizer and triazine light stabilizer compounded in a weight ratio of 3:2.
Preferably, the hindered amine light stabilizer may be one or more of light stabilizer 622, light stabilizer 944, light stabilizer 783, light stabilizer 3853, light stabilizer 292, or light stabilizer 123; preferably, the triazine light stabilizer is one or more of UV-234, UV-236 or UV-237.
Preferably, the lubricant is one or more of fatty amide, stearate and polyethylene wax.
Preferably, the components comprise, by weight:
the invention provides a preparation method of the TPV material composition, which comprises the following steps:
(1) Weighing all the components according to the parts by weight, mixing low-melt-index PP resin, high-melt-index PP resin, low-Mooney EPDM rubber, a vulcanization accelerator, an antioxidant, a lubricant and a light stabilizer, adding the mixture into a main feeding port of a double-screw extruder, adding paraffin oil into a section 3 screw barrel of the double-screw extruder, melting, mixing, extruding and granulating to obtain a TPV one-step material;
(2) Mixing the TPV one-step material prepared in the step (1) and the high-Mooney EPDM, adding the mixture into a double-screw extruder, adding a vulcanizing agent into a section 6 screw cylinder of the double-screw extruder, and performing melt extrusion granulation to obtain the TPV material.
Preferably, the screw speed of the twin-screw extruder in the step (1) is 350-450 r/min, and the melt mixing temperature is 120-180 ℃;
preferably, the screw speed of the twin-screw extruder in the step (2) is 400-500 r/min, and the melt mixing temperature is 120-200 ℃;
preferably, in the step (2), water is injected into a section 10 screw barrel of the double-screw extruder, the injection weight of the water is 5-10% of the one-step material weight of the TPV, and vacuum is pumped into a section 13 screw barrel of the double-screw extruder, wherein the vacuum degree is less than or equal to 0.09MPa.
The invention provides an application of the TPV material composition in automotive interiors.
The low melt index PP resin, the high melt index PP resin, the low viscosity EPDM, the high viscosity EPDM rubber and other components are matched with each other to synergistically prepare the TPV material with high fluidity and low glossiness;
the high melt index PP resin and the low melt index PP resin form a bimodal system, the viscosity difference between the PP resin and the EPDM is reduced, and a small amount of high-content EPDM is added in the dynamic vulcanization process to participate in the dynamic vulcanization, so that a small amount of large EPDM phase structure is formed, and the lower glossiness is realized.
Advantageous effects
The TPV material composition of the invention has high fluidity, low glossiness and aging resistance.
Detailed Description
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
1. Table 1 raw materials involved in examples and comparative examples
The lubricant, vulcanizing agent, vulcanization accelerator, antioxidant and light stabilizer adopted in the parallel experiment are all the same commercial products.
2. The TPV materials prepared in the examples and comparative examples were tested for performance by the following method:
the material flow properties are described as the ability of the melt to fill the mold cavity, and the method of measurement is melt index measurement.
Melt index:
the test conditions were 230℃and 2.16kg according to ISO 1133-1-2011 standard.
Gloss level:
the test conditions were 60℃angular gloss as measured according to ISO 2813-2014 standard.
Gloss after aging:
firstly, carrying out heat aging according to an ISO 188-2011 standard method, wherein the aging condition is 125 ℃ for 24 hours, taking out, cooling to room temperature, and then detecting glossiness according to an ISO 2813-2014 standard method, wherein the test condition is 60 degrees.
Examples 1 to 11
The components are weighed according to parts by weight and are specifically shown in table 2.
(1) Mixing low-melt-index PP resin, high-melt-index PP resin, low-Mooney EPDM rubber, a vulcanization accelerator, an antioxidant, a lubricant and a light stabilizer, adding the mixture to a main feeding port of a double-screw extruder, adding paraffin oil into a section 3 screw cylinder of the double-screw extruder, and carrying out melt mixing and extrusion granulation to obtain a TPV one-step material, wherein the screw speed of the double-screw extruder is 350-450 r/min, and the melt mixing temperature is 120-180 ℃;
(2) Mixing the one-step TPV rubber and the high-Mooney EPDM rubber, adding the mixture into a double-screw extruder, adding a vulcanizing agent into a section 6 screw cylinder of the double-screw extruder, injecting water into a section 10 screw cylinder of the double-screw extruder, wherein the injection weight of the water is 5-10% of the one-step TPV rubber, vacuumizing a section 13 screw cylinder of the double-screw extruder, and the vacuum degree is less than or equal to 0.09MPa; granulating through melt extrusion to obtain the TPV material; wherein the screw rotating speed of the double screw extruder is 400-550 r/min, and the melting mixing temperature is 120-200 ℃.
TABLE 2 component content (parts by weight) of TPV materials of examples 1 to 11
Comparative examples 1 to 8
The components are weighed according to parts by weight, and the preparation method is the same as in the example, and the specific parts are shown in table 3.
TABLE 3 component content (parts by weight) of TPV materials of comparative examples 1 to 8
The performance test tables of the TPVs obtained in examples 1-11 are shown in Table 4.
Table 4 test results for examples 1 to 11
Performance test tables for the TPVs obtained in comparative examples 1-8 are shown in table 5.
Table 5 test results for comparative examples 1 to 8
Compared with the comparative examples 1-4 and the example 1, the invention ensures that the TPV material composition has high fluidity, low glossiness and ageing resistance simultaneously by the synergistic compounding of the low melt index PP resin, the high melt index PP resin, the low viscosity EPDM and the high viscosity EPDM rubber.
Claims (10)
1. A TPV material composition, comprising, in parts by weight:
wherein the melt index of the low melt index PP resin is 230 ℃, and the melt index is less than or equal to 2g/10min under the condition of 2.16 kg;
the melt index of the high melt index PP resin is 230 ℃, and the melt index under the condition of 2.16kg is more than or equal to 30g/10min and less than 50g/10min;
the Mooney viscosity of the low Mooney EPDM rubber is ML (1+4) 125 ℃ to 55-70;
the Mooney viscosity of the high Mooney EPDM rubber is ML (1+4) 125 ℃ to 75-90 or 120.
2. The composition of claim 1, wherein the low melt index PP resin has a melt index of less than or equal to 1g/10min at 230 ℃ and 2.16kg.
3. The composition of claim 1, wherein the low mooney EPDM rubber has an ENB weight percent content of 3.5 to 6.5wt%; the ENB weight percentage content of the high-Mooney EPDM rubber is 3.5-6.5 wt%.
4. The composition of claim 1, wherein the paraffinic oil has an open flash point of greater than or equal to 260 ℃.
5. The composition of claim 1, wherein the vulcanizing agent is a peroxide-based vulcanizing agent; the peroxide vulcanizing agent is one or more of isopropyl tert-butyl peroxycarbonate, 2, 5-dimethyl-2, 5-di (tert-butylperoxy) hexane and di-tert-butyl cumyl peroxide; the vulcanization accelerator is one or more of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, triallyl isocyanurate and diphenylmethane maleimide.
6. The composition of claim 1, wherein the antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1790, antioxidant 168, antioxidant DLTP, antioxidant 626; the light stabilizer is one or more of hindered amine light stabilizer and triazine light stabilizer; the lubricant is one or more of fatty amide, stearate and polyethylene wax.
7. The composition of claim 1, wherein the composition comprises, in parts by weight:
8. a process for preparing the TPV material composition of any of claims 1-7, comprising:
(1) Weighing all the components according to the parts by weight, mixing low-melt-index PP resin, high-melt-index PP resin, low-Mooney EPDM rubber, a vulcanization accelerator, an antioxidant, a lubricant and a light stabilizer, adding the mixture into a main feeding port of a double-screw extruder, adding paraffin oil into a section 3 screw barrel of the double-screw extruder, melting, mixing, extruding and granulating to obtain a TPV one-step material;
(2) Mixing the TPV one-step material prepared in the step (1) and the high-Mooney EPDM, adding the mixture into a double-screw extruder, adding a vulcanizing agent into a section 6 screw cylinder of the double-screw extruder, and performing melt extrusion granulation to obtain the TPV material.
9. The method according to claim 8, wherein the twin-screw extruder in the step (1) has a screw speed of 350 to 450r/min and a melt mixing temperature of 120 to 180 ℃; the screw speed of the twin-screw extruder in the step (2) is 400-500 r/min, and the melting mixing temperature is 120-200 ℃; in the step (2), water is injected into a section 10 screw cylinder of the double-screw extruder, the injection weight of the water is 5-10% of the weight of one-step TPV material, and the section 13 screw cylinder of the double-screw extruder is vacuumized, so that the vacuum degree is less than or equal to 0.09MPa.
10. Use of the TPV material composition of claim 1 in automotive interiors.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210238308.4A CN114806190B (en) | 2022-03-11 | 2022-03-11 | TPV material composition and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210238308.4A CN114806190B (en) | 2022-03-11 | 2022-03-11 | TPV material composition and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114806190A CN114806190A (en) | 2022-07-29 |
| CN114806190B true CN114806190B (en) | 2023-06-27 |
Family
ID=82528090
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210238308.4A Active CN114806190B (en) | 2022-03-11 | 2022-03-11 | TPV material composition and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114806190B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116003919B (en) * | 2022-12-29 | 2024-08-09 | 金发科技股份有限公司 | TPV material fast bonded with alpha-ethyl cyanoacrylate adhesive |
| CN116063798B (en) * | 2022-12-29 | 2024-07-23 | 金发科技股份有限公司 | High-temperature-resistant open mill TPV material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007009129A (en) * | 2005-07-04 | 2007-01-18 | Sumitomo Chemical Co Ltd | Rubber composition for extrusion material and extrusion material |
| CN112745681A (en) * | 2020-12-30 | 2021-05-04 | 金发科技股份有限公司 | TPV material capable of being foamed by injection molding and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7615589B2 (en) * | 2007-02-02 | 2009-11-10 | Exxonmobil Chemical Patents Inc. | Properties of peroxide-cured elastomer compositions |
| CN104861314B (en) * | 2015-06-12 | 2017-05-24 | 衡水中铁建工程橡胶有限责任公司 | Microporous rubber base plate and preparation process thereof |
| US10508179B2 (en) * | 2017-02-28 | 2019-12-17 | Exxonmobil Chemical Patents Inc. | Thermoplastic vulcanizate prepared with oil-extended, bimodal metallocene-synthesized EPDM |
| CN112795105B (en) * | 2020-12-30 | 2022-04-19 | 金发科技股份有限公司 | High-fluidity scratch-resistant TPV material and preparation method and application thereof |
-
2022
- 2022-03-11 CN CN202210238308.4A patent/CN114806190B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007009129A (en) * | 2005-07-04 | 2007-01-18 | Sumitomo Chemical Co Ltd | Rubber composition for extrusion material and extrusion material |
| CN112745681A (en) * | 2020-12-30 | 2021-05-04 | 金发科技股份有限公司 | TPV material capable of being foamed by injection molding and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| Ultra high molecular weight nordel epdm for tpv and low hardness molded goods enabled by advanced molecular catalyst;Wu s et al;IOP conference series:materials science and engineering;第548卷(第2期);1-12 * |
| 低硬度动态硫化热塑性弹性体的制备及性能;郑略;杨晋涛;钟明强;;材料科学与工程学报(第02期);277-281，267 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114806190A (en) | 2022-07-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112795105B (en) | High-fluidity scratch-resistant TPV material and preparation method and application thereof | |
| CN114806190B (en) | TPV material composition and preparation and application thereof | |
| CN103980621A (en) | High-performance dynamic vulcanization thermoplastic elastomer and preparation method thereof | |
| CN112745681B (en) | TPV material capable of being foamed by injection molding and preparation method and application thereof | |
| CN111607236B (en) | High-fluidity low-gloss styrene-based thermoplastic elastomer material and preparation method thereof | |
| CN102260392A (en) | Low-precipitation thermoplastic elastomer and preparation method thereof | |
| CN112375324B (en) | HIPS (high impact polystyrene) composite material as well as preparation method and application thereof | |
| CN111849069A (en) | Composite rubber thermoplastic elastomer and preparation method thereof | |
| CN111269581A (en) | Thermoplastic elastomer material and preparation method thereof | |
| CN110791031A (en) | Low-hardness brominated butyl rubber polypropylene thermoplastic elastomer | |
| CN102093708B (en) | Blend of beta nucleated thermoplastic vulcanizate plasticizer and modified polyamid 6 and preparation method thereof | |
| CN116496580A (en) | Oil-resistant TPV material and preparation method thereof | |
| CN116003919B (en) | TPV material fast bonded with alpha-ethyl cyanoacrylate adhesive | |
| CN115058086B (en) | Extrusion-grade thermoplastic vulcanized rubber and preparation method thereof | |
| CN115490950B (en) | Solvent-resistant modified polyethylene and preparation method thereof | |
| CN113930013B (en) | Vulcanized enhanced scratch-resistant silicone master batch and preparation method thereof | |
| CN110791030A (en) | Zinc-free halogenated butyl rubber/polypropylene thermoplastic elastomer and preparation method thereof | |
| CN112778676B (en) | TPV material formed by secondary coating with PA substrate and preparation method and application thereof | |
| CN116063798B (en) | High-temperature-resistant open mill TPV material and preparation method and application thereof | |
| CN105820440A (en) | High-performance PP/EPDM thermoplastic elastomer and preparing method thereof | |
| CN114410053B (en) | Thermoplastic elastomer material and preparation method and application thereof | |
| CN116120672B (en) | Ultrahigh-fluidity thermoplastic elastomer for automobile parts and preparation method thereof | |
| CN115418055B (en) | High-fluidity polypropylene plastic and preparation method thereof | |
| US20030092839A1 (en) | Melt processible thermoplastic polyolefin blends for car bumpers and other articles and a process for the preparation thereof | |
| CN107501716B (en) | Polypropylene filling master batch prepared from polypropylene reclaimed material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |