CN111484680A - High-gloss and high-temperature-resistant polypropylene composite material and preparation method thereof - Google Patents
High-gloss and high-temperature-resistant polypropylene composite material and preparation method thereof Download PDFInfo
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- CN111484680A CN111484680A CN201911322069.5A CN201911322069A CN111484680A CN 111484680 A CN111484680 A CN 111484680A CN 201911322069 A CN201911322069 A CN 201911322069A CN 111484680 A CN111484680 A CN 111484680A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 43
- -1 polypropylene Polymers 0.000 title claims abstract description 43
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 23
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 19
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 19
- 239000002667 nucleating agent Substances 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 13
- 239000012745 toughening agent Substances 0.000 claims abstract description 13
- 239000011256 inorganic filler Substances 0.000 claims abstract description 10
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000004594 Masterbatch (MB) Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920005606 polypropylene copolymer Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 4
- 239000008116 calcium stearate Substances 0.000 claims description 4
- 235000013539 calcium stearate Nutrition 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 3
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 239000010445 mica Substances 0.000 claims description 3
- 229910052618 mica group Inorganic materials 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000600 sorbitol Substances 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 239000010456 wollastonite Substances 0.000 claims description 3
- 229910052882 wollastonite Inorganic materials 0.000 claims description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 239000013022 formulation composition Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- HHKVOYUYPYZFHJ-SOFGYWHQSA-N (e)-3-(3,4-dihydroxyphenyl)-1-phenylprop-2-en-1-one Chemical compound C1=C(O)C(O)=CC=C1\C=C\C(=O)C1=CC=CC=C1 HHKVOYUYPYZFHJ-SOFGYWHQSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005429 filling process Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 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
- 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
- C08L23/14—Copolymers of propene
-
- 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
-
- 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
-
- 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
- C08L2205/24—Crystallisation aids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-gloss and high-temperature-resistant polypropylene composite material and a preparation method thereof; the polypropylene composite material is composed of the following raw materials in percentage by mass: 52-71.2% of polypropylene; 20-30% of an inorganic filler; 8-15% of a toughening agent; 0.2-1% of a lubricant; 0.4-1% of antioxidant; 0.2 to 1 percent of nucleating agent; the invention has the advantages that the prepared polypropylene composite material has the characteristics of high modulus, high impact resistance and high fluidity, meets the requirements of thin-walled materials for vehicles, can reduce the mass of the whole vehicle and achieve the effect of light weight, can achieve more ideal rigidity-toughness balance compared with the traditional polypropylene, and has simple preparation process, lower cost and easy large-scale industrial production.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a high-gloss and high-temperature-resistant polypropylene composite material and a preparation method thereof.
Background
The polypropylene has the outstanding advantages of excellent mechanics, heat resistance, light weight, chemical solvent resistance, low water absorption, low price and the like, and is widely used in a plurality of fields of automobiles, household appliances, foods, medical treatment, building pipes and the like; with the further improvement of the national requirements on energy conservation and emission reduction and the high-speed development of the Chinese automobile industry, the light weight of the automobile becomes an important way for energy conservation and emission reduction of the automobile and becomes a main trend for the development of the automobile; the thin-walled material is one of the important directions for the development of light weight of automobiles; as a part having the largest surface area of an automobile exterior, thinning of a bumper has become a preferred weight reduction scheme for various automobile manufacturers.
The problems faced by thinning are mainly: the mechanical property, particularly the rigidity, of the thin-walled material cannot be reduced, and the material is required to have higher toughness so as to achieve good rigidity-toughness balance; secondly, the flowing space of the material after thinning is reduced, and the flowing resistance is increased, so that the material is required to have higher fluidity; on the other hand, in addition to mechanical properties and fluidity, the thin-walled bumper requires that the used raw material PP has three high properties, namely high fluidity, high modulus and high toughness; the thin-walled material is subjected to a rapid mold filling process during injection molding, the cooling time is short, and the crystallization speed and the crystallinity of the material at different positions are difficult to reach the same value, so that the part after injection molding is easy to generate the buckling deformation phenomenon.
In view of the foregoing, there is a need for a low shrinkage, high modulus, high impact, high flow polypropylene composite.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides the high-modulus, high-impact-resistance and high-flow polypropylene composite material; the material has the characteristics of high modulus, high impact resistance and high fluidity, meets the requirements of thin-walled materials for vehicles, can achieve more ideal rigidity and toughness balance compared with the traditional polypropylene, has simple preparation process and lower cost, and is easy to carry out large-scale industrial production; the technical scheme adopted by the invention is as follows:
the detailed formula of the raw materials comprises the following components in percentage by mass:
52-71.2 percent of polypropylene copolymer
20 to 30 percent of inorganic filler
8-15% of toughening agent
0.2 to 1 percent of lubricant
0.4 to 1 percent of antioxidant
0.2 to 1 percent of nucleating agent.
1. Copolymerized polypropylene consists of at least one copolymerized polypropylene; the melt index of the copolymerized polypropylene is 30-100g/10min (230 ℃, 2.16 Kg).
2. The filler is at least one of talcum powder master batch, wollastonite master batch, mica powder and crystal whisker.
3. The toughening agent is composed of at least one of ethylene-octene copolymer (POE), SEBS and EPDM.
4. The lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, EBS, and TAF.
5. The antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.
6. The nucleating agent is composed of at least one of organic phosphate nucleating agent NA-11 and sorbitol NX 8000.
7. The preparation process comprises the following steps: adding the co-polypropylene, the toughening agent, the lubricant, the antioxidant and the nucleating agent into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the inorganic filler into the mixture from a side feed, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-modulus, high-impact-resistance and high-flow polypropylene composite material, wherein the processing temperature is 180-200 ℃.
8. The invention has the beneficial effects that:
(1) the polypropylene material for thinning has the advantages of high rigidity, good flowing property, excellent shock resistance, good buckling deformation resistance and lower shrinkage rate, and compared with the traditional material, the polypropylene material for thinning has better performance and more balanced rigidity and toughness, and solves the problem of buckling deformation easily caused by thinning materials
(2) The preparation process is simple, the cost is low, and the large-scale industrial production is easy to carry out.
Detailed Description
The high-modulus, high-impact-resistance and high-flow polypropylene composite material comprises the following components in percentage by mass:
52-71.2 percent of polypropylene copolymer
20 to 30 percent of inorganic filler
8-15% of toughening agent
0.2 to 1 percent of lubricant
0.4 to 1 percent of antioxidant
0.2 to 1 percent of nucleating agent.
1. Preferably, the polypropylene copolymer consists of at least one polypropylene copolymer; the melt index of the copolymerized polypropylene is 30-100g/10min (230 ℃, 2.16 Kg).
2. Preferably, the filler is at least one of talcum powder master batch, wollastonite master batch, mica powder and crystal whisker, and more preferably, the filler is the talcum powder master batch of Jishan Jiaquan GmbH, the particle diameter is 1-15 mu m, and the proportion of the talcum powder is 72-75%.
3. Preferably, the toughening agent is composed of at least one of ethylene-octene copolymer (POE), SEBS and EPDM; further preferred is a toughener POE8411 from Dow.
4. Preferably, the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, EBS and TAF.
5. Preferably, the antioxidant is prepared by compounding a hindered phenol antioxidant and a phosphite antioxidant according to the proportion of 1:1, and further preferably, the hindered phenol antioxidant and the phosphite antioxidant are 1010 and 168 of Rianlong respectively.
6. Preferably, the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, EBS and TAF.
7. Preferably, the nucleating agent is composed of at least one of an organic phosphate nucleating agent NA-11 and sorbitol NX 8000. Further preferably, the nucleating agent NA-11 is an organophosphate salt of Asahi Kasei (Asahi Kasei) compound.
8. Preferably, the preparation process comprises the following steps: adding the co-polypropylene, the toughening agent, the lubricant, the antioxidant and the nucleating agent into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the inorganic filler into the mixture from a side feed, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-modulus, high-impact-resistance and high-flow polypropylene composite material, wherein the processing temperature is 180-200 ℃.
The present invention will be further described with reference to specific examples.
The formulation compositions of the examples and comparative examples are shown in Table 1
TABLE 1 formulation composition (in mass%) of examples and comparative examples
| Raw materials | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Polypropylene copolymer | 52 | 71.2 | 61.8 | 57.1 | 64 | 71.4 |
| Toughening agent | 15 | 8 | 12 | 12 | 15 | 8 |
| Inorganic filler | 30 | 20 | 25 | 30 | 20 | 20 |
| Nucleating agent | 1 | 0.2 | 0.4 | 0.2 | 0.3 | |
| Lubricant agent | 1 | 0.2 | 0.3 | 0.3 | 0.2 | 0.2 |
| Antioxidant agent | 1 | 0.4 | 0.5 | 0.4 | 0.5 | 0.4 |
The lubricant used in table 1 is polypropylene wax, the talc powder masterbatch extender with 5 μm inorganic filler is POE8411 copolymer of ethylene and octene, and the antioxidant used is 1010 and 168 in a ratio of 1: 2.
The raw materials are weighed according to the proportion, added into a high-speed stirrer and uniformly mixed, then added into a double-screw extruder from a main feed, added with inorganic fillers from a side material, subjected to melt mixing extrusion and bracing water-cooling granulation to obtain the high-modulus, high-impact-resistance and high-flow polypropylene composite material, and the processing temperature is 180-200 ℃.
The composite materials obtained after processing were tested by the test standards shown in table two, and table 3 shows the test results of the corresponding examples and comparative examples.
| Detecting items | Unit of | Test standard |
| Tensile strength | Mpa | ISO527-2 |
| Bending strength | Mpa | ISO 178 |
| Flexural modulus | Mpa | ISO 178 |
| Fuse finger | g/10min | ISO 1133 |
| Shrinkage rate | % | ISO 2577 |
| Notched impact strength of cantilever beam | Kj/m2 | ISO 180 |
| Detecting items | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Comparative example 1 |
| Tensile strength | 25.3 | 26 | 23.3 | 26.2 | 22.8 | 24.8 |
| Bending strength | 38.5 | 35.6 | 32.8 | 38.7 | 31.5 | 33.6 |
| Flexural modulus | 2200 | 2486 | 2256 | 2568 | 2056 | 2288 |
| Fuse finger | 26 | 43 | 36.8 | 28 | 31 | 39.5 |
| Shrinkage rate | 0.46 | 0.67 | 0.49 | 0.45 | 0.59 | 0.74 |
| Notched impact strength of cantilever beam | 30.6 | 23.6 | 32.5 | 27.8 | 42 | 21.8 |
| Whether or not warping or deformation | Whether or not | Whether or not | Whether or not | Whether or not | Whether or not | Is that |
As can be seen from Table 3, comparative example 1 shows that the shrinkage of the material is higher than that of examples 1-5 due to the absence of the nucleating agent, and the material is warped, but the shrinkage of the material after the nucleating agent is added is obviously reduced, the warping phenomenon is improved, and the overall mechanical property is improved to a certain extent, mainly because the nucleating agent accelerates the crystallization of the material, refines the grains of the material, reduces the post-shrinkage of the material, and improves the dimensional stability and the mechanical property of the material; by reasonably matching the proportion of the toughening agent to the filler, better rigidity and toughness balance is achieved.
It should be understood by those skilled in the art that various changes and modifications can be made to the above embodiments without departing from the scope of the present invention, and any simple modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention are within the scope of the present invention.
Claims (8)
1. A high modulus, high impact, high flow polypropylene composite characterized by: the material is composed of the following raw materials by mass percent:
52-71.2 percent of polypropylene copolymer
20 to 30 percent of inorganic filler
8-15% of toughening agent
0.2 to 1 percent of lubricant
0.4 to 1 percent of antioxidant
0.2 to 1 percent of nucleating agent.
2. The high modulus, high impact, high flow polypropylene composite of claim 1, wherein: the polypropylene is composed of at least one copolymerized polypropylene; the melt index of polypropylene is 30-100g/10min (230 ℃, 2.16 Kg).
3. A high modulus, high impact, high flow polypropylene composite according to claim 1 wherein: the filler is at least one of talcum powder master batch, wollastonite master batch, mica powder and crystal whisker.
4. A high modulus, high impact, high flow polypropylene composite according to claim 1 wherein: the toughening agent is composed of at least one of ethylene-octene copolymer (POE), SEBS and EPDM.
5. A high modulus, high impact, high flow polypropylene composite according to claim 1 wherein: the lubricant is one or more of polyethylene wax, polypropylene wax, calcium stearate, EBS and TAF.
6. A high modulus, high impact, high flow polypropylene composite according to claim 1 wherein: the antioxidant is prepared by compounding hindered phenol antioxidant and phosphite antioxidant according to the proportion of 1: 1.
7. A high modulus, high impact, high flow polypropylene composite according to claim 1 wherein: the nucleating agent is composed of at least one of an organic phosphate nucleating agent NA-11 and sorbitol NX 8000.
8. The high modulus, high impact, high flow polypropylene composite of any one of claims 1 to 7, wherein: the preparation method comprises the following preparation processes: adding the co-polypropylene, the toughening agent, the lubricant, the antioxidant and the nucleating agent into a high-speed stirrer in proportion, uniformly mixing, adding the mixture into a double-screw extruder from a main feed, adding the inorganic filler into the mixture from a side feed, performing melt mixing extrusion, bracing, water cooling and granulating to obtain the high-modulus, high-impact-resistance and high-flow polypropylene composite material, wherein the processing temperature is 180-200 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911322069.5A CN111484680A (en) | 2019-12-20 | 2019-12-20 | High-gloss and high-temperature-resistant polypropylene composite material and preparation method thereof |
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| CN201911322069.5A CN111484680A (en) | 2019-12-20 | 2019-12-20 | High-gloss and high-temperature-resistant polypropylene composite material and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961288A (en) * | 2020-08-26 | 2020-11-20 | 东莞市鑫塑源塑胶科技有限公司 | High-gloss high-temperature-resistant heat-resistant oxidation polypropylene composite material and preparation method thereof |
| CN115232403A (en) * | 2022-08-31 | 2022-10-25 | 宁波恒拓高分子材料有限公司 | Tear-resistant film material capable of resisting temperature of above 100 ℃ and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912885A (en) * | 2019-03-08 | 2019-06-21 | 广东聚益新材有限公司 | PP composite material and its preparation method and application, automobile component, automobile |
| CN111484679A (en) * | 2019-09-27 | 2020-08-04 | 四川鑫达企业集团有限公司 | High-rigidity, high-toughness and high-fluidity polypropylene composite material and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109912885A (en) * | 2019-03-08 | 2019-06-21 | 广东聚益新材有限公司 | PP composite material and its preparation method and application, automobile component, automobile |
| CN111484679A (en) * | 2019-09-27 | 2020-08-04 | 四川鑫达企业集团有限公司 | High-rigidity, high-toughness and high-fluidity polypropylene composite material and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111961288A (en) * | 2020-08-26 | 2020-11-20 | 东莞市鑫塑源塑胶科技有限公司 | High-gloss high-temperature-resistant heat-resistant oxidation polypropylene composite material and preparation method thereof |
| CN115232403A (en) * | 2022-08-31 | 2022-10-25 | 宁波恒拓高分子材料有限公司 | Tear-resistant film material capable of resisting temperature of above 100 ℃ and preparation method thereof |
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