CN114773727A - 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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- CN114773727A CN114773727A CN202210385033.7A CN202210385033A CN114773727A CN 114773727 A CN114773727 A CN 114773727A CN 202210385033 A CN202210385033 A CN 202210385033A CN 114773727 A CN114773727 A CN 114773727A
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- graft
- maleic anhydride
- composite material
- glycidyl methacrylate
- polypropylene composite
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 74
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 71
- -1 Polypropylene Polymers 0.000 title claims abstract description 70
- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 48
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002667 nucleating agent Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 8
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000012802 nanoclay Substances 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 239000000110 cooling liquid Substances 0.000 abstract description 32
- 229920005989 resin Polymers 0.000 abstract description 28
- 239000011347 resin Substances 0.000 abstract description 28
- 239000003365 glass fiber Substances 0.000 abstract description 22
- 230000032683 aging Effects 0.000 abstract description 19
- 230000014759 maintenance of location Effects 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000002826 coolant Substances 0.000 description 10
- 239000000155 melt Substances 0.000 description 8
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 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 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000011208 reinforced composite material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 102200017650 rs28383586 Human genes 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C08L23/12—Polypropene
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01P—COOLING OF MACHINES OR ENGINES IN GENERAL; COOLING OF INTERNAL-COMBUSTION ENGINES
- F01P11/00—Component parts, details, or accessories not provided for in, or of interest apart from, groups F01P1/00 - F01P9/00
-
- 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
- C08K2201/011—Nanostructured additives
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polypropylene composite material and a preparation method and application thereof, belonging to the technical field of high polymer materials. The polypropylene composite material comprises the following components in parts by weight: 30-70 parts of polypropylene resin; 20-40 parts of glass fiber; 3-5 parts of a polar graft; 0.1-1 part of nucleating agent; the polar graft is a mixture of a maleic anhydride graft and a glycidyl methacrylate graft, and the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1-3): 1. The invention effectively improves the cooling liquid resistance and the thermal oxidation aging resistance of the polypropylene composite material, and can well meet the requirements of the water chamber material of the automobile radiator. The tensile strength retention rate of the material in the cooling liquid at 140 ℃/1000h is more than 90 percent, and the tensile strength retention rate under the thermo-oxidative aging resistant condition at 140 ℃/1000h is 95 percent.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and in particular relates to a polypropylene composite material as well as a preparation method and application thereof.
Background
The automobile cooling system in the automobile heat management system mainly plays a role of cooling an engine system, the main components of the cooling medium cooling liquid in the water chamber are water and glycol, and in cold winter, the water in the water chamber is easy to cool and freeze when the automobile is parked overnight, so that the volume is increased, the radiator is cracked, and the engine is frozen. The cooling in the water chamber is kept in a liquid state in cold seasons, and the heat dissipation function of the water chamber is maintained. Furthermore, the coolant prepared by chemical components such as glycol has excellent low temperature resistance and high temperature resistance, and the coolant can be boiled at the temperature close to 200 ℃. In summer, the cooling liquid is filled in the water chamber, so that a driver can not be troubled by boiling.
The traditional radiator water chamber is made of metal, but with the technical improvement of a thermal management system and the revolutionary change of a power system of a new energy vehicle, new opportunities are brought to the light weight of the water chamber.
The prior art discloses a glass fiber reinforced PP/PA66 composite material for a water chamber of a new energy automobile, which is composed of polypropylene resin, PA66 resin, glass fiber and a compatilizer, and meets the working condition that parts of the water chamber are contacted with high-temperature cooling liquid for a long time. However, since the main component of the cooling liquid is ethylene glycol and the temperature fluctuation of the cooling liquid is large, the cooling liquid can reduce the mechanical properties, especially the tensile strength, of the PP/PA66 composite material under the long-term soaking of the cooling liquid. Although the tensile strength of the composite material in the prior art can be 86% of that at normal temperature after the composite material is soaked in cooling liquid at 120 ℃ for 1000h, the material still cannot meet the existing requirement, the tensile strength retention of the material after the composite material is soaked in the cooling liquid for a long time still needs to be further improved, and the improvement of the thermal oxygen aging resistance of the material in hot air for a long time is not involved.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defect and the defect that the tensile strength retention rate of the existing glass fiber reinforced composite material is low after the glass fiber reinforced composite material is soaked in cooling liquid for a long time, and provides a polypropylene composite material.
The invention also aims to provide a preparation method of the polypropylene composite material.
The invention also aims to provide the application of the polypropylene composite material in the preparation of the water chamber material of the automobile radiator.
The above purpose of the invention is realized by the following technical scheme:
the polypropylene composite material comprises the following components in parts by weight:
the polar graft is a mixture of a maleic anhydride graft and a glycidyl methacrylate graft, and the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1-3): 1.
Wherein, it is required to be noted that:
in the invention, the coolant resistance refers to the ratio of the tensile strength of the composite material after being soaked in the automobile coolant at high temperature (140 ℃) for a long time (1000h) to the tensile strength of the composite material in the air at normal temperature, namely the tensile strength retention rate is higher, namely the coolant resistance is better.
In the invention, the thermal oxidative aging resistance refers to the ratio of the tensile strength of the composite material in hot air (140 ℃) for a long time (1000h) to the tensile strength of the composite material in air at normal temperature, namely the tensile strength retention rate is higher, namely the thermal oxidative aging resistance is better.
The polypropylene resin is thermoplastic, the maleic anhydride graft can perform thermosetting reaction with the glycidyl methacrylate graft to form a physical interpenetrating network with the thermoplastic polypropylene resin, so that a thermoplastic system and a thermosetting system are combined more tightly, and the maleic anhydride graft and the glycidyl methacrylate graft can have good compatibility with glass fiber, so that the corrosion of solvents such as ethylene glycol in cooling liquid to an interface at high temperature can be reduced, and the cooling liquid resistance and the thermal oxygen aging resistance of the composite material can be improved.
The nucleating agent has the functions of improving the crystallinity of the matrix polypropylene resin and improving the compactness of the polypropylene composite material, thereby improving the cooling liquid resistance of the composite material.
In a particular embodiment, the maleic anhydride grafts of the present invention may be maleic anhydride grafted polypropylene.
The dosage of the polar graft is too small, the polar graft is difficult to improve the compatibility of the polypropylene resin and the glass fiber, and the debonding phenomenon exists between the glass fiber and the matrix resin, so that the mechanical properties such as tensile strength and the like at normal temperature are obviously reduced; although the maleic anhydride graft can also perform a thermosetting reaction with the glycidyl methacrylate graft, the maleic anhydride graft can perform a thermosetting reaction with the glycidyl methacrylate graft in a relatively small amount, and the maleic anhydride graft is not tightly bonded with the physical interpenetrating network formed by the thermoplastic polypropylene resin, so that the cooling liquid easily enters the interface of the composite material, and the composite material is corroded by the cooling liquid, and thus, the cooling liquid resistance of the composite material cannot be effectively improved.
The use amount of the polar graft is large, although the compatibility of the polypropylene resin and the glass fiber can be improved, the mechanical properties such as tensile strength and the like at normal temperature cannot be obviously reduced, when the material is soaked in a high-temperature cooling liquid for a long time, the thermal degradation half-life period of polypropylene can be shortened by excessive maleic anhydride, and therefore, the performance of the cooling liquid resistance and the thermal oxygen aging resistance can be reduced.
When the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is too low, the content of the glycidyl methacrylate graft is too high, the maleic anhydride and the epoxy group cannot react effectively, and an interpenetrating network is not formed, so that the performance of the cooling liquid resistance is reduced.
When the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is too large, the content of maleic anhydride is large, and mechanical properties such as normal-temperature tensile strength of the composite material are not reduced too much, but the residual maleic anhydride reduces the oxidation half-life of polypropylene, so that the thermal-oxidative aging resistance is reduced.
Preferably, in order to further improve the coolant resistance and thermo-oxidative aging resistance of the polypropylene composite,
the paint comprises the following components in parts by weight:
in order to further improve the cooling liquid resistance and the thermal oxidation aging resistance of the composite material, the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is preferably (1.5-2.5): 1.
In order to further improve the compatibility, interface compatibility, normal-temperature tensile strength, coolant resistance and thermo-oxidative aging resistance of the polypropylene resin and the glass fiber in the composite material, the mass grafting ratio of maleic anhydride in the maleic anhydride graft is preferably 0.7-1.3%.
The mass grafting ratio of maleic anhydride in the maleic anhydride graft can be determined by Fourier Infrared Spectroscopy (FTIR) testing.
Preferably, the maleic anhydride graft is maleic anhydride grafted polypropylene.
In order to further improve the cooling liquid resistance and the thermal oxidation aging resistance of the composite material, the mass grafting ratio of glycidyl methacrylate in the glycidyl methacrylate graft is preferably 0.5-0.8%.
The mass grafting ratio of glycidyl methacrylate in the glycidyl methacrylate graft can be obtained by fourier infrared spectroscopy (FTIR) test.
Preferably, the glycidyl methacrylate graft is glycidyl methacrylate grafted metallocene polyethylene.
The glycidyl methacrylate grafted metallocene polyethylene has higher reaction activity and is easier to react with maleic anhydride grafts, so the glycidyl methacrylate grafted metallocene polyethylene is easier to form physical interpenetrating network combination with thermoplastic polypropylene resin, and the cooling liquid resistance and the thermal oxygen aging resistance are improved.
Preferably, the nucleating agent is nanoclay or nanocalcium carbonate.
In order to further improve the mechanical property and the thermal-oxidative aging property of the composite material, preferably, the melt mass flow rate of the polypropylene resin is 10-100 g/10min, the test condition is 230 ℃ and 2.16kg, and the test standard is ISO 1133-2011.
Still more preferably, the melt mass flow rate of the polypropylene resin is 40 to 70g/10 min.
The polypropylene resin is homo-polypropylene or co-polypropylene.
Preferably, the glass fibers are alkali-free chopped strand glass fibers.
In practical application, auxiliary agents such as antioxidants and the like can be added according to the actual performance requirements.
Wherein, the paint also comprises 0.2 to 2 parts of antioxidant by weight.
The antioxidant may be selected from hindered phenols and/or phosphites.
The antioxidant can improve the antioxidant effect of the polypropylene composite material.
The polypropylene composite material can be prepared by adopting a common plastic material preparation method, and specifically comprises the following steps: and uniformly mixing the components, performing melt extrusion at 160-200 ℃ through a double-screw extruder, granulating, and drying to obtain the polypropylene composite material.
The polypropylene composite material prepared by the invention has good cooling liquid resistance and thermal oxidation aging resistance, can be widely applied to preparation of plastic products, and particularly protects the application of the polypropylene composite material in preparation of automobile radiator water chamber materials.
Compared with the prior art, the invention has the beneficial effects that:
the invention discloses a polypropylene composite material, which comprises polypropylene resin, glass fiber, maleic anhydride graft, glycidyl methacrylate graft and nucleating agent, wherein the cooling liquid resistance and thermal oxygen aging resistance of the polypropylene composite material are effectively improved through the combined synergistic effect of the maleic anhydride graft and the glycidyl methacrylate graft, and the requirement of a water chamber material of an automobile radiator can be well met.
The retention rate of the tensile strength of the polypropylene composite material in the cooling liquid at 140 ℃/1000h is more than 90%, and the retention rate of the tensile strength of the polypropylene composite material under the thermo-oxidative aging resistant condition at 140 ℃/1000h is more than 95%.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the present invention is not limited to the examples in any way. The starting reagents employed in the examples of the present invention are, unless otherwise specified, those that are conventionally purchased.
The polypropylene resin 1 is homopolymerized polypropylene resin PPH-Z30S, the melt mass flow rate is 30g/10min, and the medium petrochemical property and the sea-land petrochemical property are realized;
the polypropylene resin 2 is homopolymerized polypropylene resin PP T03, the melt mass flow rate is 3g/10min, and the medium petrochemical property and the sea petrochemical property are realized;
the polypropylene resin 3 is homo-polypropylene resin MH7900, the melt mass flow rate is 150g/10min, and the LG chemistry is adopted;
the polypropylene resin 4 is copolymerized polypropylene resin M60T, the melt mass flow rate is 60g/10min, and the melt is petrochemical;
the polypropylene resin 5 is copolymerized polypropylene resin BX3920, the melt mass flow rate is 100g/10min, and SK chemistry is performed;
the alkali-free chopped glass fiber is commercially available, and the same glass fiber is adopted in a parallel experiment;
the maleic anhydride graft 1 is maleic anhydride grafted polypropylene CA100, the mass grafting rate of maleic anhydride is 1.0 percent, and Achima;
the maleic anhydride graft 2 is maleic anhydride grafted polypropylene PC-1, the mass grafting rate of the maleic anhydride is 0.5 percent, and the south China sea cypress is morning;
maleic anhydride graft 3 is maleic anhydride grafted polypropylene QE800, the mass grafting rate of maleic anhydride is 1.3%, and the three-well chemistry is carried out;
the maleic anhydride graft 4 is maleic anhydride grafted polypropylene PC-3, the mass grafting rate of the maleic anhydride is 0.7 percent, and the grafting rate of the maleic anhydride is 0.7 percent;
maleic anhydride graft 5 is maleic anhydride grafted polypropylene QE810, the mass grafting rate of maleic anhydride is 1.5%, and the three-well chemistry is carried out;
the glycidyl methacrylate graft 1 is glycidyl methacrylate grafted metallocene polyethylene E515, the mass grafting rate of the glycidyl methacrylate is 0.6 percent, and Ning wave energy is light;
the glycidyl methacrylate graft 2 is glycidyl methacrylate grafted metallocene polyethylene E513, the mass grafting rate of the glycidyl methacrylate is 0.2 percent, and the light of the Ning wave energy is utilized;
the glycidyl methacrylate graft 3 is glycidyl methacrylate grafted metallocene polyethylene 2022, the mass grafting rate of the glycidyl methacrylate is 1.2%, and the DuPont chemical reaction is adopted;
the glycidyl methacrylate graft 4 is POE grafted by glycidyl methacrylate, the trademark is N416, the mass grafting rate of the glycidyl methacrylate is 0.6 percent, and the DuPont chemical is adopted;
the glycidyl methacrylate graft 5 is glycidyl methacrylate grafted metallocene polyethylene E518, the mass grafting rate of the glycidyl methacrylate is 0.8 percent, and Ning wave energy is light;
the nucleating agent 1 is nano clay which is sold in the market and adopts the same nucleating agent in parallel experiments;
antioxidant: hindered phenol antioxidant and phosphite antioxidant in a ratio of 1:1, commercially available and the same for all examples and comparative examples.
Examples 1 to 23
The polypropylene composite material comprises the following components in parts by weight:
a polypropylene resin; glass fibers; maleic anhydride grafts; glycidyl methacrylate grafts and nucleating agents; wherein the specific contents of each component are shown in the following table 1.
TABLE 1 composition of Polypropylene composite (in parts by weight) of the examples
TABLE 1
TABLE 1
| Components | 19 | 20 | 21 | 22 | 23 |
| Polypropylene resin 1 | 55 | 55 | 55 | 55 | 55 |
| Alkali-free chopped glass fiber | 30 | 30 | 30 | 30 | 30 |
| Maleic anhydride graft 1 | 2.4 | 2.86 | 2.6 | 2.6 | |
| Maleic anhydride graft 4 | 2.6 | ||||
| Maleic anhydride graft 5 | 2.6 | ||||
| Glycidyl methacrylate graft 1 | 1.6 | 1.14 | 1.4 | 1.4 | |
| Glycidyl methacrylate graft 5 | 1.4 | ||||
| Nucleating agent 1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant agent | 1 | 1 | 1 | 1 | 1 |
The preparation method of the polypropylene composite material comprises the following steps:
s1, weighing all components except glass fiber according to weight, adding the components into a high-speed mixer, mixing for 3-5 minutes, adding the components into a double-screw extruder with the length-diameter ratio of 30: 1-50: 1, melting, mixing and dispersing, and plasticizing through the double-screw extruder, wherein the set temperature of the double-screw extruder is 160-200 ℃, and the rotating speed of a screw is 350-450 revolutions per minute;
the second step is that: adding glass fiber from a side feeding port of a double-screw extruder, setting the temperature of a screw cylinder of the side feeding port at 180 ℃, and carrying out traction, cooling, granulating and drying to obtain the polypropylene composite material.
Comparative examples 1 to 5
The polypropylene composite material comprises the following components in specific content as shown in the following table 2.
TABLE 2 comparative polypropylene composite compositions (in parts by weight)
| Components | 1 | 2 | 3 | 4 | 5 |
| Polypropylene resin 1 | 55 | 55 | 55 | 55 | 55 |
| Alkali-free chopped glass fiber | 30 | 30 | 30 | 30 | 30 |
| Maleic anhydride graft 1 | / | 0.8 | 4 | 1 | 3.2 |
| Glycidyl methacrylate graft 1 | / | 0.4 | 2 | 3 | 0.8 |
| Nucleating agent 1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Antioxidant agent | 1 | 1 | 1 | 1 | 1 |
The preparation method of the polypropylene composite material comprises the following steps:
s1, weighing all components except glass fiber according to weight, adding the components into a high-speed mixer, mixing for 3-5 minutes, adding the components into a double-screw extruder with the length-diameter ratio of 30: 1-50: 1, melting, mixing and dispersing, and plasticizing through the double-screw extruder, wherein the set temperature of the double-screw extruder is 160-200 ℃, and the rotating speed of a screw is 350-450 revolutions per minute;
the second step: adding glass fiber from a side feeding port of a double-screw extruder, setting the temperature of a screw cylinder of the side feeding port to be 180 ℃, and carrying out traction, cooling, grain-sized dicing and drying to obtain the polypropylene composite material.
Result detection
The polypropylene composites of the above examples and comparative examples were injection molded to produce standard bars and tested by the following performance test methods:
(1) tensile strength: according to the method of ISO 527-2011, the drawing speed is 10 mm/min.
(2) The retention rate of the thermal-oxidative aging resistant tensile strength performance is as follows:
ISO 188, 140 ℃ of experiment temperature and 1000 hours of experiment period.
(3) The retention rate of the tensile strength performance of the cooling liquid resistance is as follows:
a) experimental medium: LLC coolant (specialty coolant produced daily);
b) the temperature of the experimental medium is 140 ℃, and the experimental period is 1000 hours.
The specific test results of the examples are shown in table 3 below:
TABLE 3
TABLE 3
| Performance testing | 19 | 20 | 21 | 22 | 23 |
| Tensile Strength (MPa) | 98 | 97 | 99 | 98 | 99 |
| Tensile strength retention (%) | 98 | 98 | 97 | 94 | 96 |
| Retention of tensile Strength Property (%) against Cooling liquid | 97 | 96 | 95 | 94 | 97 |
The specific test results of each proportion are shown in the following table 4:
| performance test | 1 | 2 | 3 | 4 | 5 |
| Tensile Strength (MPa) | 64 | 76 | 96 | 83 | 95 |
| Tensile strength property retention ratio (%) of thermo-oxidative aging resistant liquid | 85 | 96 | 89 | 93 | 87 |
| Retention of tensile Strength Property (%) against Cooling liquid | 82 | 86 | 89 | 87 | 84 |
From the above data, it can be seen that the polypropylene composite material of the present invention has a tensile strength retention rate of 90% or more in the cooling liquid at 140 ℃/1000h, and a tensile strength retention rate of 95% under the thermo-oxidative aging resistant condition at 140 ℃/1000 h.
The composite material of the invention has higher retention rate of impact strength, flexural modulus and flexural strength after being soaked in high-temperature cooling liquid for a long time and in hot air for a long time.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
the polar graft is a mixture of a maleic anhydride graft and a glycidyl methacrylate graft, and the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1-3): 1.
2. The polypropylene composite material as claimed in claim 1, comprising the following components in parts by weight:
3. the polypropylene composite of claim 1, wherein the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1.5-2.5): 1.
4. The polypropylene composite according to claim 1, wherein the mass graft ratio of maleic anhydride in the maleic anhydride graft is 0.7 to 1.3%.
5. The polypropylene composite of claim 4, wherein the maleic anhydride graft is maleic anhydride grafted polypropylene.
6. The polypropylene composite according to claim 1, wherein the glycidyl methacrylate graft has a mass graft ratio of glycidyl methacrylate of 0.5 to 0.8%.
7. The polypropylene composite of claim 6, wherein the glycidyl methacrylate graft is glycidyl methacrylate grafted metallocene polyethylene.
8. The polypropylene composite of claim 1, wherein the nucleating agent is nanoclay and/or nanocalcium carbonate.
9. A method for preparing the polypropylene composite material as claimed in any one of claims 1 to 8, comprising the steps of:
the components are uniformly mixed, and the polypropylene composite material is obtained by melt extrusion, granulation and drying at 160-200 ℃ through a double-screw extruder.
10. The application of the polypropylene composite material as claimed in any one of claims 1 to 8 in preparation of a water chamber material of an automobile radiator.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116041845A (en) * | 2022-12-23 | 2023-05-02 | 上海金发科技发展有限公司 | Polypropylene composite material and preparation method and application thereof |
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| CN110845792A (en) * | 2019-10-23 | 2020-02-28 | 上海金发科技发展有限公司 | Polypropylene composition for automobile water chamber and preparation method thereof |
| CN112300494A (en) * | 2020-11-23 | 2021-02-02 | 上海金发科技发展有限公司 | Alcoholysis-resistant chopped glass fiber reinforced polypropylene polymer and preparation method thereof |
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| CN104927193A (en) * | 2015-06-15 | 2015-09-23 | 上海俊尓新材料有限公司 | Glass fiber reinforcing propathene composite material for high-rigidity car structural member and preparing method thereof |
| CN110845792A (en) * | 2019-10-23 | 2020-02-28 | 上海金发科技发展有限公司 | Polypropylene composition for automobile water chamber and preparation method thereof |
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| CN116041845A (en) * | 2022-12-23 | 2023-05-02 | 上海金发科技发展有限公司 | Polypropylene composite material and preparation method and application thereof |
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