CN115386166B - Polypropylene composite material, and preparation method and application thereof - Google Patents
Polypropylene composite material, and preparation method and application thereof Download PDFInfo
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- CN115386166B CN115386166B CN202211137843.7A CN202211137843A CN115386166B CN 115386166 B CN115386166 B CN 115386166B CN 202211137843 A CN202211137843 A CN 202211137843A CN 115386166 B CN115386166 B CN 115386166B
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- 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
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Abstract
The invention provides a polypropylene composite material, a preparation method and application thereof, and belongs to the technical field of high polymer materials. The polypropylene composite material provided by the invention comprises the following components in parts by weight: 40-95 parts of polypropylene, 0-40 parts of filler and 5-20 parts of linear low density polyethylene; wherein the melt mass flow rate of the polypropylene is 30-100 g/10min, the test standard ISO1133-1-2011, 230 ℃,2.16Kg load, and the two-phase glass transition temperature difference of the PP phase in the polypropylene resin and the EPR phase in the linear low density polyethylene is less than or equal to 50 ℃. The invention takes the high-flow polypropylene material as the main resin, and the linear low-density polyethylene is added to obviously reduce the effect of two-phase separation, so that the problems that microscopic voids appear in the plastic melt and air and micromolecular organic gas mixed with the plastic melt are difficult to thoroughly remove are solved, and the injection molded interior trim part has particularly good appearance quality and outstanding low-odor quality.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene composite material, a preparation method and application thereof.
Background
In recent years, along with the development of the automobile industry, more and more plastics are applied to automobile interior trim parts, wherein polypropylene materials occupy a larger proportion of the plastic consumption for automobiles due to the advantages of excellent comprehensive performance, wide sources, excellent quality, low price and the like. With the increasing standard of living of people, the requirements of consumers on automotive interior parts are also increasing, such as the appearance, the emission performance and the like of the interior parts are of great concern. At present, the size of a molding die for a large-sized automotive interior part is larger, the injection molding period is required to be shorter, if the structure of a finished product is complex, the structural design of the die cannot be matched with each other with high precision, or the number and the position of exhaust grooves or exhaust holes are unreasonable, the molded finished product is easy to have the appearance defect of bulge, the qualification rate of the finished product is seriously influenced, the common solution is to continuously optimize the structure of the die, design and processing the die and put forward very high precision requirements, a great amount of practical experience is required to be accumulated, in addition, the molding period is required to be prolonged in the aspect of molding technology, the method for optimizing and improving in the aspect of materials is not more in the past, and the effect is not obvious. In addition, the odor quality of the automotive interior parts is always a great difficulty in the industry, reports on the odor reduction method of the polypropylene composite material are quite large, and the reports comprise adding an adsorbent, adding an extracting agent, baking and devolatilizing, and the like, but even if the odor effect of the prepared polypropylene composite material is quite good, in an injection molding process, the material is subjected to melt shearing again to continuously generate small molecular organic substances, so that the odor of the injection molded automotive interior parts is quite large and can not meet the requirements expected by a host factory and end consumers, the efficiency of the batch baking treatment of the parts with unqualified odor is quite low, and the continuous production operability is not achieved, so that the development of the low-odor polypropylene composite material suitable for the injection molding requirements is also an urgent task.
The prior art discloses a polypropylene composition for automotive upholstery, which is mainly prepared by adding reactive polyamide, bonding and coating the reactive polyamide on the surface of talcum powder to form a protective film, and inhibiting the degradation of an antioxidant caused by metal ions in the talcum powder, so that the generation of organic volatile compounds is inhibited, and the reactive polyamide is alkaline, so that the acidic organic volatile compounds can be neutralized to play a role in removing, and the odor of the polypropylene composition is reduced. The polypropylene composition for solving the odor problem needs to be additionally added with other auxiliary agents, and cannot solve the appearance problem of the polypropylene composite material at the same time.
Disclosure of Invention
The invention aims to overcome the defects and defects of appearance and odor problems of the existing polypropylene composite material injection molding parts, and provides the polypropylene composite material, wherein the high-flow polypropylene material main body resin is cooperated with the linear low-density polyethylene resin with a specific glass transition temperature difference, so that the appearance defect of bulge of the injection molding parts is eliminated, the odor quality of the directly injection molded automobile interior parts is excellent, and the standard requirements of large host factories are met.
The above object of the present invention is achieved by the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight:
40-95 parts of polypropylene, 0-40 parts of filler and 5-20 parts of linear low density polyethylene;
wherein the melt mass flow rate of the polypropylene is 30-100 g/10min, and the test standard ISO1133-1-2011 is 230 ℃ and the load of 2.16 Kg;
the difference Tg (PP phase) -Tg (EPR phase) of the glass transition temperature of the two phases of the PP phase and the EPR phase in the linear low-density polyethylene in the polypropylene resin is less than or equal to 50 ℃.
The following description is needed:
the method for testing the glass transition temperature adopts a DSC method, the DSC is used for characterizing the glass transition temperature of the material, the change of the specific heat capacity of the material along with the temperature is measured, the specific heat capacity can be greatly changed before and after the glass transition temperature Tg, and the glass transition temperature can be determined according to the curve. The glass transition temperature is usually a step in the direction of heat absorption, the glass transition is a region, the intersection point of a line and a curve, which is equal to the distance between two extrapolated base lines, is usually used as the glass transition temperature, the test temperature range is-60 ℃ to 100 ℃, the temperature rising and falling rate is 20 ℃/min, the temperature is firstly increased from 23 ℃ to 100 ℃, then the temperature is reduced from 100 ℃ to-60 ℃, and then the temperature is increased from-60 ℃ to 100 ℃.
The polypropylene composite material of the invention can be added with filler components, and the filler can be one or more of talcum powder, calcium carbonate, wollastonite and whisker.
In the polypropylene composite material, the melt mass flow rate of the polypropylene serving as the main resin is 30-100 g/10min, and the polypropylene composite material is a high-flow polypropylene material, has good flow property, can quickly fill all large mold cavities at a lower injection molding temperature, reduces the degree of heating and shearing of the material, can be subjected to injection molding processing at a lower injection molding temperature, can effectively avoid overheat decomposition of the material at a lower processing temperature, reduces volatilization of odor micromolecules, and is beneficial to guaranteeing the odor quality.
The two-phase glass transition temperature difference between the added polypropylene matrix resin and the linear low-density polyethylene is less than or equal to 50 ℃, the difference is smaller, the linear low-density polyethylene is easy to form a continuous distribution phase in the polypropylene matrix resin, the compatibility between the EPR phase of the linear low-density polyethylene resin and the PP phase of the polypropylene resin is better, too many microscopic gaps are not formed between the two phases in the processing process, thus the problem that small molecular substances mixed in a plastic melt are difficult to thoroughly discharge is solved, the small molecular substances in the plastic melt can be smoothly discharged, the phenomenon of bulge of an injection molded product is avoided, the appearance quality of the injection molded product is improved, meanwhile, the odor of the injection molded product is reduced because the small molecular substances are smoothly discharged in the preparation process, the problem of exceeding standard odor is solved, and the injection molded product has good appearance effect and low odor quality level, and is particularly suitable for high-efficiency production of large-scale interior low-odor products.
The polypropylene composite material has good injection molding appearance performance, particularly can have good appearance performance when being molded by a large-size mold, can be widely applied to various mold structures, and reduces the high requirements on the structural design of the mold.
The content of the linear low-density polyethylene in the polypropylene composite material is also critical, and if the synergistic amount of the linear low-density polyethylene is too small, the toughness of the composite material is poor (less than or equal to 10 KJ/m) 2 ) And the linear low-density polyethylene can not form a continuous phase in the polypropylene material, microscopic separation is easy to form between the two phases, and bubbling and odor small molecule residues are easy to generate. If the synergistic amount of the linear low-density polyethylene is too large, the rigidity of the polypropylene composite material is poor, the whole product is softer, and the use requirements of most working conditions cannot be met.
Preferably, the composition comprises the following components in parts by weight:
65-80 parts of polypropylene and 10-20 parts of filler; 10-15 parts of linear low density polyethylene.
Preferably, the linear low density polyethylene has a Tg (EPR phase) and a two-phase glass transition temperature of 45 to 48 ℃ different from the Tg (PP phase) of the polypropylene resin.
It should be noted here that the two-phase glass transition temperature difference needs to be controlled within a reasonable range, and that too small a temperature difference indicates that the Tg (EPR phase) of LLDPE is too high, and that the composite material is too hard and not tough enough under low temperature (less than-20 ℃).
Preferably, the melt mass flow rate of the polypropylene is 50-90 g/10min, and the test standard ISO1133-1-2011, 230 ℃, and 2.16Kg load.
Preferably, the linear low density polyethylene has a melt mass flow rate of 15-25 g/10min, test standard ISO1133-1-2011, 190 ℃,2.16Kg load,
on the basis of taking the polypropylene as matrix resin, the invention is also added with the linear low-density polyethylene, and the low melt index of the linear low-density polyethylene is not beneficial to forming stable continuous dispersion phase in the polypropylene matrix resin, and simultaneously the fluidity of the whole composite material is reduced; the high melt index of the linear low density polyethylene is disadvantageous for improving the appearance performance after injection molding into interior articles.
Further, in order to further improve the odor quality of the polypropylene composite, it is preferable that the odor of the polypropylene is of the order of 3.5 to 4.0 as tested according to the popular PV3900 standard.
Preferably, the linear low density polyethylene odor is of grade 3.5 to 4.0 as tested according to the popular PV3900 standard.
The control of the odor class of the raw materials is the basis for obtaining a low odor composite material, but the low odor of the raw materials is not enough to meet the strict odor quality requirements of the host factory, and the polypropylene and the linear low density polyethylene are preferably combined with the specific formulation of the invention to achieve higher quality requirements.
Preferably, the filler is one or more of talcum powder, calcium carbonate, wollastonite and whisker.
In a specific embodiment, in order to meet other application requirements of the polypropylene composite material, 0.05-5 parts of processing aid by weight parts can be added into the polypropylene composite material, wherein the processing aid can be one or more of pigment, antioxidant, weather-proof agent and lubricant.
Among these, the pigment of the present invention may be an organic or inorganic pigment.
The inorganic pigment may be titanium white, chrome yellow, cadmium yellow, molybdenum chrome red, iron red (yellow), cadmium red, ultramarine, cobalt blue, iron blue, chrome green, cobalt green, metal powder, mica pearlescent, carbon black, etc.
The organic pigment may be azo, color pyridine, phthalocyanine, dye, etc.
The antioxidant of the invention may be: hindered phenol antioxidants, phosphite antioxidants, and the like.
The weathering agent of the invention may be: hindered amine weather-proofing agents.
The lubricant of the present invention may be: calcium stearate, zinc stearate, and the like.
The invention also specifically protects a preparation method of the polypropylene composite material, which comprises the following steps:
the components are evenly mixed, added into an extruder, melted and mixed at 170-240 ℃, and then granulated, cooled and dried to obtain the polypropylene composite material.
The extruder of the invention can be a double-screw extruder or a reciprocating single-screw extruder, and the length-diameter ratio of the screw is not less than 32.
The application of the polypropylene composite material in preparing the automotive trim is also within the protection scope of the invention.
The polypropylene composite material has good injection molding appearance quality, can well eliminate bulge appearance defects on the surface of a finished piece, has good odor quality, can be widely applied to injection molding production of automobile interior trim parts with different structures and sizes, such as automobile door panels, instrument panels, upright posts and the like, and can meet the requirements of high appearance and low odor quality.
Compared with the prior art, the invention has the beneficial effects that:
the polypropylene composite material takes the high-flow polypropylene material as the main resin, can quickly fill cavities with different wall thicknesses, can realize low-temperature injection molding, reduces the degree of heating and shearing decomposition of the material, and ensures the odor quality. And the linear low-density polyethylene with the difference value of the glass transition temperature difference between the polypropylene and the polypropylene being less than or equal to 50 ℃ is also added, so that the effect of obviously reducing the phase separation of the two phases can be achieved, the problems that microscopic gaps appear in the plastic melt and the air and small molecular organic gas mixed with the plastic melt are difficult to thoroughly remove are avoided, and the injection molded interior decoration part has particularly good appearance quality and outstanding low-odor quality advantage.
The polypropylene composite material of the invention has the appearance bulge grade reaching 2 grade or below, the odor grade reaching 3.5 grade or below, outstanding bulge-resistant appearance effect and good odor quality, the bending performance reaching above 1600MPa, and the notch impact performance of the toughness test cantilever beam reaching 15kJ/m 2 The above meets the comprehensive mechanical property requirement of rigidity and toughness balance.
Detailed Description
The invention will be further described with reference to the following specific embodiments, but the examples are not intended to limit the invention in any way. Raw materials reagents used in the examples of the present invention are conventionally purchased raw materials reagents unless otherwise specified.
The raw material information of the examples and comparative examples of the present invention are as follows:
polypropylene:
PP-1: PP-BX3900, melt mass flow rate of 60g/10min, test standard ISO1133-1-2011, test conditions of 230 ℃,2.16Kg, odor grade 3.5 (PV 3900 standard), manufacturer: SK;
PP-2: PP BX3920, melt mass flow rate of 100g/10min, test standard ISO1133-1-2011, test conditions 230 ℃,2.16Kg, odor grade 3.5 (PV 3900 standard), manufacturer: SK;
PP-3: PP BX3800, melt mass flow rate of 30g/10min, test standard ISO1133-1-2011, test conditions 230 ℃,2.16Kg, odor grade 4.0 (PV 3900 standard), manufacturer: SK;
PP-4: PP EP640V, melt mass flow rate 90g/10min, test Standard ISO1133-1-2011, test conditions 230 ℃,2.16Kg, odor grade 3.5 (PV 3900 Standard), manufacturer: middle sea shell;
PP-5: PP SP179 (blue), melt mass flow rate 10g/10min, test Standard ISO1133-1-2011, test conditions 230 ℃,2.16Kg, odor grade 3.5 (PV 3900 Standard), manufacturer: lanzhou petrochemical;
linear low density polyethylene 1: LLDPE M2320, melt mass flow rate 20g/10min, test standard ISO1133-1-2011, test condition 190 ℃,2.16Kg, odor grade 3.5 (PV 3900 standard), manufacturer: the name is luxuriant and petrochemical;
linear low density polyethylene 2: LLDPE M2320 (DNDA-7144), melt mass flow rate 20g/10min, test standard ISO1133-1-2011, test conditions 190 ℃,2.16Kg, odor grade 3.5 (PV 3900 standard), manufacturer: the name is luxuriant and petrochemical;
linear low density polyethylene 3: LLDPE-L M2320 (ZHONGYUAN) with a melt mass flow rate of 17g/10min, test standard ISO1133-1-2011, 190 ℃,2.16Kg, odor grade 3.5 (PV 3900 standard), manufacturer: the name is luxuriant and petrochemical;
linear low density polyethylene 4: SABIC 6201RQ powder, melt mass flow rate of 50g/10min, test standard ISO1133-1-2011, test condition 190 ℃,2.16Kg, odor grade 4.0 (PV 3900 standard), manufacturer: SABIC;
linear low density polyethylene 5: LLDPE EXCEED 3518PA, melt mass flow rate 1g/10min, test Standard ISO1133-1-2011, test conditions 190 ℃,2.16Kg, odor grade 4.0 (PV 3900 Standard), manufacturer: exxon Mobil;
talcum powder is commercially available, and the parallel examples and comparative examples of the invention are all of the same kind;
an antioxidant: the mass ratio of the hindered phenol main antioxidant to the phosphite ester auxiliary antioxidant is 1:1, and the hindered phenol main antioxidant and the phosphite ester auxiliary antioxidant are commercially available, and the parallel examples and the comparative examples of the invention are the same commercial products.
Examples 1 to 15
A polypropylene composite material comprises the components shown in the following table 1 in parts by weight.
TABLE 1 composition of Polypropylene composite materials of examples 1-15
The preparation method of the polypropylene composite materials of the above examples 1 to 15 comprises the following steps:
the components were uniformly mixed in a mixing apparatus according to the parts by weight of the components shown in Table 1, and then added into a twin-screw extruder having an aspect ratio of 40:1, melt-kneaded at a temperature of 200℃and then pelletized, cooled and baked at 120℃for 6 hours to obtain a polypropylene composition.
And respectively obtaining the plastic light plate with the size of 100mm x 3mm and ISO standard bending and notch impact splines through injection molding under the conditions of the injection temperature of 200 ℃, the injection pressure of 45MPa, the injection speed of 45m/s, the pressure maintaining pressure of 30MPa and the pressure maintaining time of 5 s.
Comparative examples 1 to 3
A polypropylene composite material comprises the components shown in the following table 2 in parts by weight.
TABLE 2 composition of Polypropylene composite materials of comparative examples 1-3
| Comparative example | 1 | 2 | 3 |
| PP-2 | 40 | 95 | |
| PP-5 | 70 | ||
| Talc powder | 40 | 0 | 15 |
| Linear low density polyethylene 3 | 25 | 3 | 10 |
| Antioxidant | 0 | 1 | 1 |
The preparation method of the polypropylene composite materials of the comparative examples 1 to 3 comprises the following steps:
the components were uniformly mixed in a mixing apparatus according to the parts by weight of the components shown in Table 2, and then added into a twin-screw extruder having an aspect ratio of 40:1, melt-kneaded at a temperature of 200℃and then pelletized, cooled and baked at 120℃for 6 hours to obtain a polypropylene composition.
And respectively obtaining the plastic light plate with the size of 100mm x 3mm and ISO standard bending and notch impact splines through injection molding under the conditions of the injection temperature of 200 ℃, the injection pressure of 45MPa, the injection speed of 45m/s, the pressure maintaining pressure of 30MPa and the pressure maintaining time of 5 s.
Result detection
The appearance quality, odor quality and related mechanical properties of the polypropylene composites of examples 1 to 15 and comparative examples 1 to 3 were examined as follows:
(1) Odor and appearance test
The plastic light panels (100 mm length, 100mm thickness, 3 mm) were evaluated for odor (VDA 270 standard, 1L test flask, experimental conditions 80 ℃/2 h) and swell effects (visual evaluation), preferably 1 grade, and worst 6 grades, respectively, and scored and averaged (rounded) by 5 panelists.
Specific rating criteria are shown in table 3 below:
TABLE 3 odor and appearance evaluation criteria
| Level of | Odor standard | Bulge standard |
| Level 1 | Is not perceived | Without macroscopic bulges |
| Level 2 | Can check and have no interference | Bulges visible to naked eyes, and the number is less than 3 |
| 3 grade | Clearly can be checked but has no interference | Bulges visible to naked eyes, and the number of the bulges is 3 to 5 |
| Grade 4 | Interference (I) | Bulges visible to naked eyes and the number of the bulges is 6 to 10 |
| Grade 5 | Intense interference | Bulges visible to naked eyes, and the number of bulges is 11-20 |
| Grade 6 | Cannot tolerate | The number of bulges visible to naked eyes is more than 20 |
(2) Mechanical property test
The detection bending performance represents the rigidity of the polypropylene composite material, and the detection standard is ISO 178-2010 MPa.
Detecting toughness of the polypropylene composite material represented by notch impact performance of cantilever beam, detecting standard ISO180-2019, A-type notch and kJ/m 2 。
The specific evaluation results are shown in Table 4 below.
TABLE 4 detection results of Polypropylene composite materials of examples 1-15 and comparative examples 1-3
As can be seen from the data of Table 4 above, the polypropylene composite material having the bump defect eliminated (2.0 grade or less) and the odor quality (3.5 grade or less) can be produced by adding LLDPE resin having a small difference in two-phase glass transition temperature Tg (PP phase) -Tg (EPR phase) as a main resin and controlling the addition amount thereof within a proper range, and the polypropylene composite material of the present invention has an outstanding appearance effect against the bump and a good odor quality by injection molding of automotive upholstery.
The polypropylene composite material also has good mechanical property, the rigidity test bending property can reach more than 1600MPa, and the toughness test cantilever notch impact property can reach 15kJ/m 2 The above meets the comprehensive mechanical property requirement of rigidity and toughness balance.
The material is particularly suitable for the injection molding requirement of the large-sized interior low-odor and good-appearance parts of the automobile, and effectively solves the problems of over-standard odor and easy swelling of the parts facing the injection molding industry of the automobile.
The amount of the linear low-density polyethylene in the comparative example 1 is too high, so that the appearance and the smell of the polypropylene composite material cannot meet the related requirements, the rigidity of the polypropylene composite material is poor, and the comprehensive mechanical property requirement of rigidity and toughness balance cannot be met.
The linear low-density polyethylene in comparative example 2 is too low in dosage, so that the appearance and the smell of the polypropylene composite material cannot meet the related requirements, and the polypropylene composite material is poor in toughness and cannot meet the comprehensive mechanical property requirements of rigidity and toughness balance.
In the comparative example 3, the polypropylene PP-5 is not in the protection scope of the invention, the appearance and the smell of the polypropylene composite material are obviously deteriorated, the rigidity of the polypropylene composite material is also seriously deteriorated, and the comprehensive mechanical property requirement of rigidity and toughness balance cannot be met.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
40-95 parts of polypropylene, 0-40 parts of filler and 5-20 parts of linear low density polyethylene;
wherein the melt mass flow rate of the polypropylene is 30-100 g/10min, and the test standard ISO1133-1-2011 is 230 ℃ and the load of 2.16 Kg;
the two-phase glass transition temperature difference Tg (PP phase) -Tg (EPR phase) of the PP phase and the EPR phase in the linear low density polyethylene in the polypropylene resin is 45-50 ℃.
2. The polypropylene composite material according to claim 1, comprising the following components in parts by weight:
65-80 parts of polypropylene and 10-20 parts of filler; 10-15 parts of linear low density polyethylene.
3. The polypropylene composite material according to claim 1, wherein the two-phase glass transition temperature difference Tg (PP phase) -Tg (EPR phase) of the PP phase and the EPR phase in the linear low density polyethylene in the polypropylene resin is 45 to 48 ℃.
4. The polypropylene composite material according to claim 1, wherein the polypropylene has a melt mass flow rate of 50-90 g/10min, test standard ISO1133-1-2011, 230 ℃,2.16Kg load.
5. The polypropylene composite according to claim 1, wherein the linear low density polyethylene has a melt mass flow rate of 15 to 25g/10min, test standard ISO1133-1-2011, 190 ℃,2.16Kg load.
6. The polypropylene composite material according to claim 1, wherein the odor of the polypropylene is in accordance with mass PV3900: the 2019-04 standard test is grade 3.5-4.0.
7. The polypropylene composite of claim 1, wherein the linear low density polyethylene odor is in accordance with mass PV3900:2019-04, standard test grade 3.5-4.0.
8. The polypropylene composite material of claim 1, wherein the filler is one or more of talc, calcium carbonate, wollastonite, and whisker.
9. A method for preparing the polypropylene composite material according to any one of claims 1 to 8, comprising the steps of:
the components are evenly mixed, added into an extruder, melted and mixed at 170-240 ℃, and then granulated, cooled and dried to obtain the polypropylene composite material.
10. Use of the polypropylene composite material according to any one of claims 1 to 8 for the preparation of automotive interior articles.
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| PCT/CN2023/118864 WO2024061104A1 (en) | 2022-09-19 | 2023-09-14 | Polypropylene composite material, preparation method, and use |
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| CN116462915A (en) * | 2023-04-26 | 2023-07-21 | 成都金发科技新材料有限公司 | Polypropylene composition and preparation method and application thereof |
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2022
- 2022-09-19 CN CN202211137843.7A patent/CN115386166B/en active Active
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- 2023-09-14 WO PCT/CN2023/118864 patent/WO2024061104A1/en unknown
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| CN114672092A (en) * | 2022-03-28 | 2022-06-28 | 成都金发科技新材料有限公司 | Polypropylene composite material, preparation method and application |
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| CN115386166A (en) | 2022-11-25 |
| WO2024061104A1 (en) | 2024-03-28 |
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