CN111019232B - Thermoplastic composite material and preparation method and application thereof - Google Patents
Thermoplastic composite material and preparation method and application thereof Download PDFInfo
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
- B29C70/345—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation using matched moulds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B62—LAND VEHICLES FOR TRAVELLING OTHERWISE THAN ON RAILS
- B62D—MOTOR VEHICLES; TRAILERS
- B62D25/00—Superstructure or monocoque structure sub-units; Parts or details thereof not otherwise provided for
- B62D25/08—Front or rear portions
- B62D25/10—Bonnets or lids, e.g. for trucks, tractors, busses, work vehicles
- B62D25/105—Bonnets or lids, e.g. for trucks, tractors, busses, work vehicles for motor cars
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Health & Medical Sciences (AREA)
- Transportation (AREA)
- Combustion & Propulsion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
The invention discloses a thermoplastic composite material and a preparation method and application thereof, wherein the thermoplastic composite material comprises a surface layer material and a framework material; the surface layer material comprises the following components in parts by weight: 30-50 parts of high-fluidity polypropylene resin, 45-50 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 1-8 parts of highlight improver and 1-2 parts of carbon black; the framework material comprises the following components in parts by weight: 20-35 parts of medium-high fluidity polypropylene resin, 50-70 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 1-12 parts of low warpage improver and 1-2 parts of carbon black. The thermoplastic composite material provided by the invention has good mechanical properties, high surface gloss, high strength, low warpage and high temperature resistance, meets the requirements of automobile engine hood cover materials, and realizes the light weight of automobiles.
Description
Technical Field
The invention relates to the field of composite materials, in particular to a thermoplastic composite material and a preparation method and application thereof.
Background
The engine cover is an important part in the engine compartment of the automobile, and can guide the air flow around the engine to avoid the local overhigh temperature of the engine; the surface of the engine is prevented from falling ash, so that dust is sucked into the cylinder body to cause damage; isolating peripheral parts which are not high-temperature-resistant, and preventing the parts from being directly baked at high temperature; the sound insulation effect can be achieved to a certain extent, and the comfort of the vehicle is improved; after the engine compartment is opened, the engine is one of parts with larger areas, and the aesthetic degree of the vehicle can be greatly improved after the cover is arranged.
In light weight, safety and other aspects, various major automobile engine factories gradually adopt a scheme of replacing steel with plastic to manufacture automobile engine hoods, and establish corresponding standard requirements on the strength, heat resistance, long-term aging resistance, oil resistance and other aspects of plastic materials. In recent years, polypropylene resins have been used in large quantities for manufacturing automobile parts due to their characteristics of abundant sources, strong chemical corrosion resistance, low density, high cost performance, easy molding and processing, etc., but polypropylene materials have the problems of large shrinkage, easy generation of warp deformation, poor dimensional stability, poor toughness, easy brittle fracture at low temperature, poor aging resistance, etc. Before some researchers try to solve the problems through modification, the glass fiber reinforced polypropylene disclosed in CN104927193A has better mechanical properties and long-term heat aging resistance, but the warpage is difficult to control when large-scale parts are injection molded, the dimensional stability of the products is poor, and the surface fiber floating is serious, which affects the beauty. CN104231428A provides a preparation method of mineral filled polypropylene for an engine compartment, which has good appearance characteristics, but has low strength, large shrinkage rate, difficult size control and poor temperature resistance, and is only suitable for manufacturing engine covers with small heat productivity.
In addition, the traditional reinforced polypropylene material can crush the reinforcement in the double-screw extrusion production and injection molding processes, the mechanical property of the material is reduced, the use requirement can be met only by increasing the wall thickness of the product, and the phenomenon of fiber floating can occur when broken ends of glass fibers are irregularly exposed on the surface of a workpiece. Therefore, there is a need for a new material with high strength, good surface and easy processing for manufacturing high-grade automobile engine covers.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a thermoplastic composite material, a preparation method and application thereof.
In order to achieve the above object, the present invention provides a thermoplastic composite material comprising a skin material and a skeleton material; the surface layer material comprises the following components in parts by weight: 30-50 parts of high-fluidity polypropylene resin, 45-50 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 1-8 parts of highlight improver and 1-2 parts of carbon black;
the framework material comprises the following components in parts by weight: 20-35 parts of medium-high fluidity polypropylene resin, 50-70 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 1-12 parts of low warpage improver and 1-2 parts of carbon black.
As a preferred embodiment, the melt index of the high-fluidity polypropylene resin is 60-300g/10 min; the melt index of the medium-high fluidity polypropylene resin is 25-110g/10 min.
Preferably, the untwisted continuous glass fiber has a linear density of 900-2400 Tex.
As a preferred embodiment, the compatibilizer is maleic anhydride grafted polypropylene; the lubricant is selected from one or more of silicone and polytetrafluoroethylene.
As a preferred embodiment, the high light modifier is selected from one or more of ultrafine barium sulfate and calcium carbonate.
As a preferred embodiment, the low warpage improving agent is selected from one or more of a fiber, a whisker or a carbon nanotube. Preferably, the fibers are selected from chopped glass fibers, carbon fibers, silicon carbide fibers; the whisker is selected from wollastonite whisker, calcium sulfate whisker and hydroxyapatite whisker.
The invention also provides a preparation method of the thermoplastic composite material, which comprises the steps of overlapping the surface layer material and the framework material in a layering mode to form the surface layer and the framework layer respectively, and then carrying out compression molding.
In a preferred embodiment, the ply angle of the skin material is one of 0 °, 0 °/90 ° or 0 °/0 °;
the layering angle of the framework material is one or a combination of more than one of 0 degree/90 degree, 0 degree/90 degree/0 degree, 0 degree/90 degree/0 degree, 45 degree/0 degree/90 degree/0 degree/45 degree.
As a preferred embodiment, the process conditions of the die pressing are as follows: preheating for 5-10s under the conditions of the temperature of 200-230 ℃, and then maintaining the pressure for 28-30s under the condition of the pressure of 50-55 MPa.
The invention also provides an application of the thermoplastic composite material, and the thermoplastic composite material is used for preparing the automobile engine hood.
Compared with the prior art, the invention has the following advantages:
first, the thermoplastic composite of the present invention comprises a surface material and a matrix material. The framework material is symmetrically layered to reduce the warping amount after layering, so that the flatness of the workpiece is improved. In addition, the low warpage improver in the framework material can weaken the orientation effect, has a certain effect on improvement of warpage, and can generate a synergistic effect when the low warpage improver simultaneously adopts fibers, whiskers and carbon nanotubes, so that the warpage amount is obviously reduced.
Secondly, the thermoplastic composite material of the invention comprises a surface material and a framework material. The surface material is in a thermoplastic material mould pressing mode, and resin melt of the surface layer is enriched to the surface and gradually filled among fibers through the pressure of a mould to form a high-gloss workpiece surface, so that the problem of material surface gloss is solved.
Thirdly, in the process of die pressing of the thermoplastic composite material, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be combined through the fusion connection of the resin, and the low-warpage improver in the framework layer can be inserted into other layers to achieve the riveting effect, so that the interlayer bonding strength is further improved.
Fourthly, the thermoplastic composite material disclosed by the invention has better mechanical property, can meet the requirement of the mechanical property by designing smaller thickness, has high surface gloss, high strength, small warpage and high temperature resistance, meets the requirement of an automobile engine hood cover material, realizes the lightweight of an automobile, and the preparation method of the material disclosed by the invention is simple in process operation, high in production efficiency and easy to industrialize.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
The formulations of examples 1 to 13 of the thermoplastic composite material of the present invention are shown in tables 1 and 2.
TABLE 1
TABLE 2
Examples 1 to 9
The thermoplastic composites of examples 1-9 were prepared as follows:
the surface layer materials of the formula are overlapped according to the layer laying angle of 0 degree/90 degrees, the framework materials are overlapped according to the layer laying angle of 0 degree/90 degrees/0 degrees, the specific shape is cut out through machining after the overlapping, the screw to be installed and the rear end of the insert are clamped in the middle of the layer laying, the head is exposed, the screw and the layer laying are placed into a mold together, and the mold is well positioned. Preheating materials before mould pressing, wherein the process is that polypropylene resin on the surface layer of a strip material is melted without dripping of melt, the preheating temperature is 200 ℃, the preheating time is 10s, the mould pressing pressure is 50MPa in the mould pressing process, the pressure is maintained for 30s, and the resin melt on the surface layer is enriched on the surface and gradually filled between fibers through the pressure of a mould to form the surface of a high-gloss workpiece; on the other hand, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be connected and combined through melting of resin, the low-warpage improver in the framework layer can be inserted into other layers to achieve a riveting effect, the interlayer bonding strength is further improved, and after cooling and solidification, the finished product is trimmed to obtain a finished product.
Example 10
The thermoplastic composite of this example was prepared as follows:
the surface layer materials of the formula are overlapped according to the layer spreading angle of 0 degree/0 degree, the framework materials are overlapped according to the layer spreading angle of 0 degree/90 degree/0 degree, the specific shape is cut out through machining after the overlapping, the screw to be installed and the rear end of the insert are clamped in the middle of the layer spreading, the head is exposed, the screw and the layer spreading are placed into a mold together, and the positioning is carried out. Preheating materials before mould pressing, wherein the process is that polypropylene resin on the surface layer of a strip material is melted without dripping of melt, the preheating temperature is 210 ℃, the preheating time is 8s, the mould pressing pressure is 52MPa in the mould pressing process, the pressure is maintained for 30s, and the resin melt on the surface layer is enriched on the surface and gradually filled between fibers through the pressure of a mould to form the surface of a high-gloss workpiece; on the other hand, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be connected and combined through melting of resin, the low-warpage improver in the framework layer can be inserted into other layers to achieve a riveting effect, the interlayer bonding strength is further improved, and after cooling and solidification, the finished product is trimmed to obtain a finished product.
Example 11
The thermoplastic composite of this example was prepared as follows:
the surface layer materials of the formula are overlapped according to the layer spreading angle of 0 degree/0 degree, the framework materials are overlapped according to the layer spreading angle of 0 degree/90 degree/0 degree, the specific shape is cut out through machining after the overlapping, the screw to be installed and the rear end of the insert are clamped in the middle of the layer spreading, the head is exposed, the screw and the layer spreading are placed into a mold together, and the positioning is carried out. Preheating materials before mould pressing, wherein the process is that polypropylene resin on the surface layer of a strip material is melted without melt dripping, the preheating temperature is 220 ℃, the preheating time is 7s, the mould pressing pressure is 52MPa in the mould pressing process, the pressure is maintained for 29s, and the resin melt on the surface layer is enriched on the surface and gradually filled between fibers through the pressure of a mould to form the surface of a high-gloss workpiece; on the other hand, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be connected and combined through melting of resin, the low-warpage improver in the framework layer can be inserted into other layers to achieve a riveting effect, the interlayer bonding strength is further improved, and after cooling and solidification, the finished product is trimmed to obtain a finished product.
Example 12
The thermoplastic composite of this example was prepared as follows:
the surface layer materials of the formula are overlapped according to the layer spreading angle of 0 degree/90 degrees, the framework materials are overlapped according to the layer spreading angle of 0 degree/90 degrees/0 degrees, the specific shape is cut out through machining after the overlapping, the screw to be installed and the rear end of the insert are clamped in the middle of the layer spreading, the head is exposed, the screw and the layer spreading are placed into a mold together, and the positioning is carried out. Preheating materials before mould pressing, wherein the process is that polypropylene resin on the surface layer of a strip material is melted without dripping of melt, the preheating temperature is 230 ℃, the preheating time is 5s, the mould pressing pressure is 55MPa in the mould pressing process, the pressure is maintained for 28s, and the resin melt on the surface layer is enriched on the surface and gradually filled between fibers through the pressure of a mould to form the surface of a high-gloss workpiece; on the other hand, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be connected and combined through melting of resin, the low-warpage improver in the framework layer can be inserted into other layers to achieve a riveting effect, the interlayer bonding strength is further improved, and after cooling and solidification, the finished product is trimmed to obtain a finished product.
Example 13
The thermoplastic composite of this example was prepared as follows:
the surface layer materials of the formula are layered according to the layering angle of 0 degree, the framework materials are overlapped according to the layering angle of 45 degrees/0 degrees/90 degrees/0 degrees/45 degrees, the specific shape is cut out through machining after the overlapping, the screw to be installed and the rear end of the insert are clamped in the middle of the layering, the head is exposed, the screw and the layering are placed into a mold together, and the positioning is carried out. Preheating materials before mould pressing, wherein the process is that polypropylene resin on the surface layer of a strip material is melted without dripping of melt, the preheating temperature is 200 ℃, the preheating time is 10s, the mould pressing pressure is 50MPa in the mould pressing process, the pressure is maintained for 30s, and the resin melt on the surface layer is enriched on the surface and gradually filled between fibers through the pressure of a mould to form the surface of a high-gloss workpiece; on the other hand, the surface layer and the framework layer and the paving layers of the surface layer and the framework layer can be connected and combined through melting of resin, the low-warpage improver in the framework layer can be inserted into other layers to achieve a riveting effect, the interlayer bonding strength is further improved, and after cooling and solidification, the finished product is trimmed to obtain a finished product.
Comparative example
A workpiece produced by injection molding of long glass fiber reinforced polypropylene particles is used as a comparative example, and the injection molding process comprises the following steps: the temperature is 250 ℃, and the pressure is 70 MPa.
Examples of effects
The mechanical properties, warpage and surface of the products prepared in examples 1-13 were evaluated and compared with the glass fiber reinforced injection molded parts, and the test results are shown in tables 3 and 4 below.
TABLE 3
TABLE 4
According to the test results in tables 3 and 4, it can be seen that, compared with the injection molding production process, the weight of the parts produced in examples 1-13 is reduced by about 20%, and the strength, the warping amount and the surface effect are improved to a certain extent.
The above description is only an embodiment of the present invention, and it should be noted that the details which are not described in the present specification are the prior art which is known to those skilled in the art, and any changes or substitutions which can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.
Claims (8)
1. A thermoplastic composite characterized by: comprises a surface layer material and a framework material; the surface layer material comprises the following components in parts by weight: 30-50 parts of high-fluidity polypropylene resin, 45-50 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 1-8 parts of highlight improver and 1-2 parts of carbon black;
the framework material comprises the following components in parts by weight: 20-35 parts of medium-high fluidity polypropylene resin, 50-70 parts of untwisted continuous glass fiber, 1-8 parts of compatilizer, 0.5-1 part of lubricant, 1-2 parts of antioxidant, 8 parts of low warpage improver and 1-2 parts of carbon black;
the low warpage improver is formed by mixing fibers, whiskers and carbon nanotubes according to a mass ratio of 1:5: 2;
the melt index of the high-fluidity polypropylene resin is 60-300g/10 min; the melt index of the medium-high fluidity polypropylene resin is 25-110g/10 min.
2. The thermoplastic composite of claim 1, wherein: the linear density of the untwisted continuous glass fiber is 900-2400 Tex.
3. The thermoplastic composite of claim 1, wherein: the compatilizer is maleic anhydride grafted polypropylene; the lubricant is selected from one or more of silicone and polytetrafluoroethylene.
4. The thermoplastic composite of claim 1, wherein: the high light improver is one or more of superfine barium sulfate and calcium carbonate.
5. A method of making the thermoplastic composite of any of claims 1-4, wherein: firstly, the surface layer material and the framework material are respectively overlapped in a layering mode to form the surface layer and the framework layer, and then compression molding is carried out.
6. The method of preparing a thermoplastic composite according to claim 5, characterized in that: the layering angle of the surface layer material is one of 0 degree, 0 degree/90 degree or 0 degree/0 degree; the ply angle of the framework material is one or more of 0 °/90 °, 0 °/90 °/0 °, 45 °/0 °/90 °/0 °/45 °.
7. The method of preparing a thermoplastic composite according to claim 5, characterized in that: the process conditions of the die pressing are as follows: preheating for 5-10s under the conditions of the temperature of 200-230 ℃, and then maintaining the pressure for 28-30s under the condition of the pressure of 50-55 MPa.
8. Use of a thermoplastic composite according to any one of claims 1 to 4, characterized in that: the thermoplastic composite material is used for preparing an automobile engine hood.
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EP3006507A1 (en) * | 2014-10-10 | 2016-04-13 | Ems-Patent Ag | Reinforced polyamide moulding material and injection moulding parts made from the same |
CN109181104A (en) * | 2018-08-20 | 2019-01-11 | 马鞍山卓凡新材料科技有限公司 | A kind of glass fiber reinforced polypropylene composite material resistant to high temperature |
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CN103183894A (en) * | 2011-12-29 | 2013-07-03 | 辽宁辽杰科技有限公司 | Continuous glass fiber reinforced polypropylene resin composite material and preparation method thereof |
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EP3006507A1 (en) * | 2014-10-10 | 2016-04-13 | Ems-Patent Ag | Reinforced polyamide moulding material and injection moulding parts made from the same |
CN109181104A (en) * | 2018-08-20 | 2019-01-11 | 马鞍山卓凡新材料科技有限公司 | A kind of glass fiber reinforced polypropylene composite material resistant to high temperature |
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