CN110655708A - Low-density polypropylene composite material with excellent comprehensive performance and preparation method thereof - Google Patents
Low-density polypropylene composite material with excellent comprehensive performance and preparation method thereof Download PDFInfo
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- CN110655708A CN110655708A CN201810696843.8A CN201810696843A CN110655708A CN 110655708 A CN110655708 A CN 110655708A CN 201810696843 A CN201810696843 A CN 201810696843A CN 110655708 A CN110655708 A CN 110655708A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
Hair brushThe low-density polypropylene composite material is prepared from 42-61 parts of polypropylene, 8-12 parts of whiskers, 14-18 parts of a toughening agent, 12-20 parts of hollow glass microspheres, 5-8 parts of a compatilizer, 0.2-0.5 part of an antioxidant and 0.2-0.5 part of other additives through mixing, extruding and granulating. The low-density polypropylene composite material with excellent comprehensive performance adopts the high-crystallization copolymerized polypropylene as the base material, and provides a basic guarantee for obtaining high rigidity of the prepared composite material; the silane coupling agent is used for surface treatment of the hollow glass beads and the whiskers, and the compatilizer with high maleic anhydride content is added, so that the bonding strength of the hollow glass beads, the whiskers and the polypropylene is enhanced, and the finally prepared composite material has higher strength; the polypropylene composite material prepared by the invention has tensile strength of more than 18MPa, flexural modulus of more than 1850MPa and notch impact strength of more than 20KJ/m2Has good sensitivity and toughness, and the density is only 0.88-0.92g/cm3And the requirement of light weight is met.
Description
Technical Field
The invention relates to the field of modification of high polymer materials, in particular to a low-density polypropylene composite material with excellent comprehensive performance and a preparation method thereof.
Background
The polypropylene has the advantages of good mechanical property, no toxicity, low relative density, heat resistance, chemical resistance, easy processing and forming and the like, and the price is low. The resin can be endowed with outstanding physical and mechanical properties through processing modification, and therefore, certain engineering plastics are replaced, great progress is made in the aspect of universal plastic engineering in recent years, and the resin is the most rapidly-growing variety and the most actively-developed new variety among five general synthetic resins.
With the rapid development of science and technology, the requirements of various large host computer factories in the automobile industry on materials are changed newly, and particularly with the implementation plan of issuing a new round of file for the comprehensive oil consumption requirements of automobiles at home and abroad in recent years, the light weight of automobiles becomes a research hotspot of various large host computer factories. Therefore, various plastic modification enterprises develop towards light weight of materials, resource saving, high performance and high function.
In the prior art, the traditional mineral filling modified polypropylene material is widely applied to the interior and exterior trimming parts of automobiles, such as traditional instrument boards, door panels,The column is made of PP + EPDM-T20 material with density of 1.04-1.07g/cm3The requirement of the automobile industry for light weight of materials is increasingly not met. The traditional method for reducing the density is to reduce the content of the filling minerals, so that although the density of the material can be reduced, the rigidity, the strength and the like of the material cannot meet the design requirements of actual properties of the material.
Therefore, a material with lower density than the traditional PP + EPDM-T20 material and other properties such as rigidity, toughness, fluidity, shrinkage rate and the like consistent with or even higher than those of the PP + EPDM-T20 material is urgently needed.
Disclosure of Invention
The invention aims to provide a low-density polypropylene composite material with excellent comprehensive performance and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
a low-density polypropylene composite material with excellent comprehensive performance is prepared from the following components in parts by weight:
in a further scheme, the polypropylene is high-crystalline co-polypropylene.
The diameter D of the whisker is 1.0-3.0 μm, and the average length L: 20-80 μm, length-diameter ratio L/D > 30; the whisker is preferably basic magnesium sulfate whisker surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing the basic magnesium sulfate whisker into a mixer to be stirred at a low speed of 40-60 r/min, adding the prepared silane coupling agent ethanol solution with the mass ratio of 1-2.5 percent of the basic magnesium sulfate whisker in a spraying mode, and processing for 5-15 min.
The toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer, the melt flow rate of the toughening agent is 0.5-20g/10min under the condition of 190 ℃/2.16kg, and the density of the toughening agent is 0.86-0.89g/cm3。
The particle size D50 of the hollow glass bead is 5-30Mu m, density 0.4-0.6g/cm3The compressive strength is more than or equal to 20MPa, and the hollow glass beads are surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing hollow glass beads into a mixer, stirring at a low speed of 40-60 r/min, adding a prepared silane coupling agent alcohol solution with the mass ratio of 1-2.5 percent of the glass beads in a spraying mode, and processing for 5-15 minutes.
The compatilizer is one or a mixture of more of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted polypropylene and maleic anhydride grafted polypropylene, wherein the content of maleic anhydride is 1.5-3.5%.
The antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl thiodipropionate.
The other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
Another object of the present invention is to provide a method for preparing a low density polypropylene composite material with excellent combination properties, comprising the following steps:
(1) 42-61 parts of polypropylene, 8-12 parts of whisker, 14-18 parts of toughening agent, 5-8 parts of compatilizer, 0.2-0.5 part of antioxidant and 0.2-0.5 part of other auxiliary agent are added into a high-speed mixer to be mixed for 5-15 min;
(2) adding the uniformly mixed materials obtained in the step (1) into a double-screw extruder, adding 12-20 parts of hollow glass beads into a side feeding port of the double-screw extruder, and melting, blending and extruding the materials together to obtain a low-density polypropylene composite material with excellent comprehensive performance;
wherein, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
The invention has the beneficial effects that:
(1) the high-crystallinity copolymerized polypropylene is adopted as a base material, so that a basic guarantee is provided for obtaining high rigidity of the prepared composite material;
(2) the hollow glass microspheres with the compressive strength of more than or equal to 20MPa are selected, and the crushing rate of the hollow glass microspheres is reduced in a side feeding processing mode, so that the density of the composite material is reduced fundamentally;
(3) the glass beads are treated by the surface of the silane coupling agent, the whiskers are treated by the silane coupling agent, and the compatilizer with high maleic anhydride content is added, so that the bonding strength of the glass beads, the whiskers and the polypropylene is enhanced, and the finally prepared composite material has higher strength;
(4) the invention discloses a polypropylene composite material which has tensile strength of more than 18MPa, flexural modulus of more than 1850MPa and notch impact strength of more than 20KJ/m2Has good sensitivity and toughness, and the density is only 0.88-0.92g/cm3And the requirement of light weight is met.
Detailed Description
The invention will now be further described with reference to the following examples, which are intended to illustrate, but not limit the invention.
The available types and manufacturer information of each component are as follows:
polypropylene: PP BX3800, PP BX3900, PP BX3920 produced by SK, PP-EA5074 produced by Basel
Whisker: WS-1S2 basic magnesium sulfate produced by Weiskk chemical process
Hollow glass beads: IM16K manufactured by 3M
A compatilizer: PP-G1001 produced by Polyram
A toughening agent: POE8200, POE8150 and POE8137 produced by Dow chemical production
The other auxiliary agents are typical products sold in the market.
The diameter D of the whiskers in the following examples is 1.0 to 3.0 μm and the average length L: 20-80 μm, length-diameter ratio L/D > 30; the whisker is preferably basic magnesium sulfate whisker surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing the basic magnesium sulfate whisker into a mixer to be stirred at a low speed of 40-60 r/min, adding the prepared silane coupling agent ethanol solution with the mass ratio of 1-2.5 percent of the basic magnesium sulfate whisker in a spraying mode, and processing for 5-15 min.
In the following examples, the hollow glass beads D50 have a particle size of 5 to 30 μm and a density of 0.4 to 0.6g/cm3The compressive strength is more than or equal to 20MPa, and the hollow glass beads are surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing hollow glass beads into a mixer, stirring at a low speed of 40-60 r/min, adding a prepared silane coupling agent alcohol solution with the mass ratio of 1-2.5 percent of the glass beads in a spraying mode, and processing for 5-15 minutes.
Example 1
Adding 61 parts of polypropylene, 8 parts of whisker, 14 parts of toughening agent, 5 parts of compatilizer, 0.2 part of antioxidant 1010 and 0.2 part of coupling agent into a high-speed mixer, and mixing for 5 min;
adding the mixed blend into a double-screw extruder for extrusion and granulation, simultaneously adding 12 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃ in sequence from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 350 r/min, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending, extrusion and granulation.
Example 2
Adding 57 parts of polypropylene, 9 parts of whisker, 15 parts of toughening agent, 5 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of coupling agent and 0.1 part of dispersing agent into a high-speed mixer, and mixing for 10 min;
adding the mixed blend into a double-screw extruder for extrusion and granulation, simultaneously adding 14 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 170 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃ in sequence from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 36, the rotating speed of the extrusion screw is 350 r/min, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending, extrusion and granulation.
Example 3
Adding 53 parts of polypropylene, 10 parts of whisker, 15 parts of toughening agent, 6 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of antioxidant DSTDP, 0.2 part of coupling agent and 0.1 part of lubricant into a high-speed mixer for mixing for 15 min;
adding the mixed blend into a double-screw extruder for extrusion granulation, simultaneously adding 16 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃ and 195 ℃ from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 350 r/min, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending extrusion granulation.
Example 4
Adding 51 parts of polypropylene, 10 parts of whisker, 16 parts of toughening agent, 5 parts of compatilizer, 0.1 part of antioxidant 168, 0.1 part of antioxidant 1010, 0.1 part of antioxidant DSTDP, 0.2 part of coupling agent, 0.1 part of lubricant and 0.1 part of dispersant into a high-speed mixer for mixing for 5 min;
adding the mixed blend into a double-screw extruder for extrusion and granulation, simultaneously adding 18 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ and 195 ℃ from the feeding section to the head, the length-diameter ratio of an extrusion screw is 44, the rotating speed of the extrusion screw is 300 revolutions per minute, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending, extrusion and granulation.
Example 5
Adding 45 parts of polypropylene, 11 parts of whisker, 17 parts of toughening agent, 7 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.1 part of coupling agent, 0.1 part of lubricant and 0.1 part of dispersant into a high-speed mixer for mixing for 15 min;
adding the mixed blend into a double-screw extruder for extrusion and granulation, simultaneously adding 20 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 160 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃ from a feeding section to a machine head, the length-diameter ratio of an extrusion screw is 36, the rotating speed of the extrusion screw is 400 r/min, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending, extrusion and granulation.
Example 6
Adding 42 parts of polypropylene, 12 parts of whisker, 18 parts of toughening agent, 8 parts of compatilizer, 0.1 part of antioxidant 168, 0.2 part of antioxidant 1010, 0.2 part of coupling agent, 0.2 part of lubricant and 0.1 part of dispersing agent into a high-speed mixer for mixing for 15 min;
adding the mixed blend into a double-screw extruder for extrusion and granulation, simultaneously adding 20 parts of hollow glass microspheres into the extruder from a side feed, wherein the temperature of each zone of the extruder is 160 ℃, 170 ℃, 175 ℃, 185 ℃, 190 ℃ from the feeding section to the head, the length-diameter ratio of an extrusion screw is 40, the rotating speed of the extrusion screw is 400 r/min, and the low-density polypropylene composite material with excellent comprehensive performance is obtained through melt blending, extrusion and granulation.
The low density polypropylene composites with excellent overall properties prepared in examples 1-6 were tested for properties and the results are shown in Table 1.
TABLE 1
Comparative example 1
Mixing 61 parts of polypropylene copolymer, 14 parts of toughening agent, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent in a high-speed mixer for 5min, extruding and granulating the mixed blend by a double-screw extruder, simultaneously adding 8 parts of whisker and 12 parts of talcum powder into the side feed of the extruder, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃ and 185 ℃ in sequence from the feeding section to the head, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 revolutions per minute.
Comparative example 2
Mixing 61 parts of polypropylene copolymer, 14 parts of toughening agent, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent in a high-speed mixer for 5min, extruding and granulating the mixed blend by a double-screw extruder, simultaneously adding 12 parts of hollow glass microspheres and 8 parts of talcum powder into the side feed of the extruder, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 revolutions per minute.
Comparative example 3
Mixing 61 parts of polypropylene copolymer, 8 parts of whisker, 14 parts of toughening agent, 12 parts of hollow glass microsphere, 5 parts of compatilizer, 0.2 part of antioxidant and 0.2 part of coupling agent in a high-speed mixer for 5min, extruding and granulating the mixed blend by a double-screw extruder, wherein the temperature of each zone of the extruder is 150 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, the length-diameter ratio of an extrusion screw is 40, and the rotating speed of the extrusion screw is 350 revolutions per minute.
The materials prepared in comparative examples 1 to 3 were subjected to performance tests, and the test results are shown in Table 2.
TABLE 2
| Test item/Unit | Test standard | Example 1 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Finger melt/g/10 min | ISO 1133 | 22.5 | 24.2 | 25.8 | 24.5 |
| Tensile strength/MPa | ISO 527 | 18.5 | 18.8 | 17.5 | 19.1 |
| Flexural strength/MPa | ISO 178 | 29.5 | 28.5 | 25.2 | 28.5 |
| Flexural modulus/MPa | ISO 178 | 1850 | 1550 | 1220 | 1480 |
| Izod notched impact Strength/KJ/m2 | ISO 180 | 20.1 | N | 24.1 | 26.8 |
| Density/g/cm3 | ISO 1183 | 0.922 | 1.054 | 1.056 | 1.014 |
As can be seen from the data in tables 1 and 2, the composite material prepared by the invention has higher tensile strength, flexural modulus and notched impact strength, and has lower density compared with the conventional PP + EPDM-T20 material, and the composite material disclosed by the invention has excellent comprehensive performance and can meet the requirement of the performance of weight reduction of the material.
The embodiments described above are intended to facilitate one of ordinary skill in the art in understanding and using the present invention. It will be readily apparent to those skilled in the art that various modifications can be made to the embodiments and the generic principles defined herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the embodiments described herein, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (9)
1. A low-density polypropylene composite material with excellent comprehensive performance is characterized in that: the composition is prepared from the following components in parts by weight:
42-61 parts of polypropylene, namely polypropylene,
8-12 parts of whisker, wherein,
14-18 parts of a toughening agent,
12-20 parts of hollow glass micro-beads,
5-8 parts of a compatilizer,
0.2 to 0.5 portion of antioxidant,
0.2 to 0.5 portion of other auxiliary agents.
2. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the polypropylene is high-crystalline co-polypropylene.
3. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the diameter D of the whisker is 1.0-3.0 μm, and the average length L: 20-80 μm, length-diameter ratio L/D > 30; the whisker is preferably basic magnesium sulfate whisker surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing the basic magnesium sulfate whisker into a mixer to be stirred at a low speed of 40-60 r/min, adding the prepared silane coupling agent ethanol solution with the mass ratio of 1-2.5 percent of the basic magnesium sulfate whisker in a spraying mode, and processing for 5-15 min.
4. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the toughening agent is at least one of ethylene-octene copolymer and ethylene-propylene copolymer, the melt flow rate of the toughening agent is 0.5-20g/10min under the condition of 190 ℃/2.16kg, and the density of the toughening agent is 0.86-0.89g/cm3。
5. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the particle size D50 of the hollow glass bead is 5-30 mu m, and the density is 0.4-0.6g/cm3The compressive strength is more than or equal to 20MPa, and the hollow glass beads are surface-treated by a silane coupling agent; the processing method comprises the steps of preparing a silane coupling agent into an ethanol solution with the mass ratio of 25 percent, adding acetic acid to adjust the pH value of the solution to 4.5-5.5, placing hollow glass beads into a mixer, stirring at a low speed of 40-60 r/min, adding a prepared silane coupling agent alcohol solution with the mass ratio of 1-2.5 percent of the glass beads in a spraying mode, and processing for 5-15 minutes.
6. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the compatilizer is one or a mixture of more of maleic anhydride grafted polyolefin elastomer, maleic anhydride grafted polypropylene and maleic anhydride grafted polypropylene, wherein the content of maleic anhydride is 1.5-3.5%.
7. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the antioxidant is at least one of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris- (2, 4-di-tert-butylphenyl) phosphite and dioctadecyl thiodipropionate.
8. The low density polypropylene composite of claim 1, wherein the polypropylene composite has excellent balance of properties: the other auxiliary agents comprise a coupling agent, a lubricating agent and a dispersing agent.
9. A method for preparing a low density polypropylene composite material with excellent combination property as claimed in claim 1, wherein: the method comprises the following steps:
(1) 42-61 parts of polypropylene, 8-12 parts of whisker, 14-18 parts of toughening agent, 5-8 parts of compatilizer, 0.2-0.5 part of antioxidant and 0.2-0.5 part of other auxiliary agent are added into a high-speed mixer to be mixed for 5-15 min;
(2) adding the uniformly mixed materials obtained in the step (1) into a double-screw extruder, adding 12-20 parts of hollow glass beads into a side feeding port of the double-screw extruder, and melting, blending and extruding the materials together to obtain a low-density polypropylene composite material with excellent comprehensive performance;
wherein, the extrusion temperature of each extrusion zone in the twin-screw extruder is 150-.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499968A (en) * | 2020-04-14 | 2020-08-07 | 江阴市鑫宝铁塑制品有限公司 | Antistatic polypropylene composite material, and preparation method and application method thereof |
| CN112708201A (en) * | 2021-01-11 | 2021-04-27 | 郑州圣莱特空心微珠新材料有限公司 | Preparation method of door panel material and automobile door panel |
| CN113637261A (en) * | 2021-09-23 | 2021-11-12 | 广东腾熙科技咨询有限公司 | Scratch-resistant reinforced PP plastic and preparation method thereof |
| CN115594923A (en) * | 2022-10-17 | 2023-01-13 | 上海奉坤新材料有限公司（Cn） | Weather-resistant enhanced polypropylene material and preparation method and application thereof |
-
2018
- 2018-06-29 CN CN201810696843.8A patent/CN110655708A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111499968A (en) * | 2020-04-14 | 2020-08-07 | 江阴市鑫宝铁塑制品有限公司 | Antistatic polypropylene composite material, and preparation method and application method thereof |
| CN112708201A (en) * | 2021-01-11 | 2021-04-27 | 郑州圣莱特空心微珠新材料有限公司 | Preparation method of door panel material and automobile door panel |
| CN113637261A (en) * | 2021-09-23 | 2021-11-12 | 广东腾熙科技咨询有限公司 | Scratch-resistant reinforced PP plastic and preparation method thereof |
| CN115594923A (en) * | 2022-10-17 | 2023-01-13 | 上海奉坤新材料有限公司（Cn） | Weather-resistant enhanced polypropylene material and preparation method and application thereof |
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Application publication date: 20200107 |