CN114773727B - 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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- CN114773727B CN114773727B CN202210385033.7A CN202210385033A CN114773727B CN 114773727 B CN114773727 B CN 114773727B CN 202210385033 A CN202210385033 A CN 202210385033A CN 114773727 B CN114773727 B CN 114773727B
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- composite material
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- maleic anhydride
- glycidyl methacrylate
- polypropylene
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 73
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 70
- -1 Polypropylene Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 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
- 229920005989 resin Polymers 0.000 claims abstract description 32
- 239000011347 resin Substances 0.000 claims abstract description 32
- 239000003365 glass fiber Substances 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002667 nucleating agent Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000004712 Metallocene polyethylene (PE-MC) Substances 0.000 claims description 8
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 239000012802 nanoclay Substances 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000110 cooling liquid Substances 0.000 abstract description 38
- 230000032683 aging Effects 0.000 abstract description 21
- 230000014759 maintenance of location Effects 0.000 abstract description 17
- 239000002861 polymer material Substances 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000000155 melt Substances 0.000 description 7
- 230000001590 oxidative effect Effects 0.000 description 7
- 239000003963 antioxidant agent Substances 0.000 description 6
- 230000003078 antioxidant effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229920001169 thermoplastic Polymers 0.000 description 5
- 239000004416 thermosoftening plastic Substances 0.000 description 5
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000002826 coolant Substances 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 description 2
- 241000218691 Cupressaceae Species 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012809 cooling fluid 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
- 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
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002530 phenolic antioxidant 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
- 230000009257 reactivity Effects 0.000 description 1
- 239000011208 reinforced composite material Substances 0.000 description 1
- 102200017650 rs28383586 Human genes 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—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
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- 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, a preparation method and application thereof, and belongs 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 polar grafts; 0.1-1 part of nucleating agent; wherein the polar graft is a mixture of maleic anhydride graft and 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 thermo-oxidative aging resistance of the polypropylene composite material, and can well meet the requirements of water chamber materials of the automobile radiator. The material has a tensile strength retention rate of more than 90% in 140 ℃/1000h cooling liquid and a tensile strength retention rate of 95% under 140 ℃/1000h thermo-oxidative aging conditions.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene composite material and a preparation method and application thereof.
Background
The automobile cooling system in the automobile thermal management system mainly plays a role in cooling an engine system, the main components of cooling medium cooling liquid of the water chamber are water and glycol, and in cold winter, the water in the water chamber is easy to cool and freeze during a night stop, so that the volume is increased to crack the radiator and freeze the engine. 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. Moreover, the cooling liquid prepared by using chemical components such as glycol has the characteristics of low temperature resistance and high temperature resistance, and can be boiled at the temperature close to 200 ℃. The cooling liquid is filled in the water chamber in summer, so that a driver cannot be bothered 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, a new opportunity is 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 consists of polypropylene resin, PA66 resin, glass fiber and a compatilizer, and meets the working condition that water chamber parts 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 condition that the cooling liquid is soaked for a long time. Although the tensile strength of the composite material in the prior art can be 86% of the tensile strength at normal temperature after the composite material is soaked in a cooling liquid at 120 ℃ for 1000 hours, the material still cannot meet the existing requirements, the retention rate of the tensile strength of the composite material after the composite material is soaked in the cooling liquid for a long time is still to be further improved, and the improvement of the thermal-oxidative aging resistance of the composite material in hot air for a long time is not involved.
Disclosure of Invention
The invention aims to overcome the defect and the defect of low retention rate of tensile strength of the traditional glass fiber reinforced composite material after being soaked in cooling liquid for a long time, and provides a polypropylene composite material, which effectively improves the cooling liquid resistance of the composite material and simultaneously improves the thermo-oxidative aging resistance through the synergistic effect of maleic anhydride grafts and glycidyl methacrylate grafts in a specific proportion.
It is still another object of the present invention to provide a method for preparing a polypropylene composite.
The invention further aims to provide an application of the polypropylene composite material in preparing a water chamber material of an automobile radiator.
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:
wherein the polar graft is a mixture of maleic anhydride graft and glycidyl methacrylate graft, and the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1-3): 1.
The following are to be described:
in the invention, the cooling liquid resistance refers to the ratio of the tensile strength of the composite material after being soaked in the high-temperature (140 ℃) automobile cooling liquid for a long time (1000 h) to the tensile strength of the composite material in the air at normal temperature, namely the tensile strength retention rate is higher, namely the cooling liquid 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 (1000 hours) to the tensile strength of the composite material in air at normal temperature, namely, the retention rate of the tensile strength is higher, namely, the thermal-oxidative aging resistance is better.
The polypropylene resin is thermoplastic, the maleic anhydride graft can react with the glycidyl methacrylate graft in a thermosetting way, and a physical interpenetrating network is formed with the thermoplastic polypropylene resin, so that the thermoplastic system and the thermosetting system are combined more tightly, and the maleic anhydride graft and the glycidyl methacrylate graft can have good compatibility with glass fibers, so that the corrosion of solvents such as glycol in cooling liquid to interfaces at high temperature can be reduced, and the cooling liquid resistance and the thermo-oxidative 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 the compactness of the polypropylene composite material, thereby improving the cooling liquid resistance of the composite material.
In a specific embodiment, the maleic anhydride graft of the present invention may be a 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 are obviously reduced at normal temperature; although the maleic anhydride graft can react with the glycidyl methacrylate graft in a thermosetting way, the maleic anhydride graft can react with the glycidyl methacrylate graft in a thermosetting way in a small amount, so that the maleic anhydride graft is not tightly combined with a physical interpenetrating network formed by thermoplastic polypropylene resin, and cooling liquid easily enters the interface of the composite material, so that the composite material is corroded by the cooling liquid, and the cooling liquid resistance of the composite material cannot be effectively improved.
The polar graft has larger dosage, and the compatibility of the polypropylene resin and the glass fiber can be improved, and the mechanical properties such as tensile strength at normal temperature are not obviously reduced, but when the material is soaked in high-temperature cooling liquid for a long time, the thermal degradation half life of the polypropylene is shortened by excessive maleic anhydride, so that the cooling liquid resistance and the thermal oxidative aging resistance are reduced.
When the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is too small, the content of the glycidyl methacrylate graft is too large, the maleic anhydride and the epoxy group cannot react effectively, an interpenetrating network is not formed, and 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 although mechanical properties such as normal-temperature tensile strength of the composite material are not reduced too much, the residual maleic anhydride can reduce the oxidation half-life of polypropylene, so that the thermo-oxidative aging resistance can be reduced.
Preferably, in order to further improve the cooling fluid resistance and the thermo-oxidative aging resistance of the polypropylene composite,
the composite material comprises the following components in parts by weight:
in order to further improve the cooling liquid resistance and the thermal oxidative aging resistance of the composite material, it is preferable that the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1.5 to 2.5): 1.
In order to further improve the compatibility, interfacial compatibility, normal temperature tensile strength, cooling liquid resistance and thermo-oxidative aging resistance of the polypropylene resin and glass fiber in the composite material, preferably, the mass grafting rate of maleic anhydride in the maleic anhydride graft is 0.7-1.3%.
The mass grafting ratio of maleic anhydride in the maleic anhydride graft can be obtained by a fourier infrared spectrometer (FTIR) test.
Preferably, the maleic anhydride graft is maleic anhydride grafted polypropylene.
In order to further improve the cooling liquid resistance and the thermal oxidative aging resistance of the composite material, it is preferable that the mass grafting ratio of the glycidyl methacrylate in the glycidyl methacrylate graft is 0.5 to 0.8%.
The mass grafting ratio of the glycidyl methacrylate in the glycidyl methacrylate graft can be obtained by a Fourier infrared spectrometer (FTIR) test.
Preferably, the glycidyl methacrylate graft is a glycidyl methacrylate grafted metallocene polyethylene.
The glycidyl methacrylate grafted metallocene polyethylene has higher reactivity, and is easier to react with maleic anhydride grafts, so that the glycidyl methacrylate grafted metallocene polyethylene is easier to form a physical interpenetrating network combination with thermoplastic polypropylene resin, thereby being beneficial to improving the cooling liquid resistance and the thermal oxidative aging resistance.
Preferably, the nucleating agent is a nanoclay or a nano calcium 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 ℃,2.16kg, and the test standard is ISO 1133-2011.
Still more preferably, the polypropylene resin has a melt mass flow rate of 40 to 70g/10min.
The polypropylene resin is homo-polypropylene or co-polypropylene.
Preferably, the glass fibers are alkali-free chopped glass fibers.
In practical application, additives such as an antioxidant and the like can be added according to the actual performance requirement.
Wherein, the composition 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 of the invention 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 and granulation at 160-200 ℃ by a double-screw extruder, and drying to obtain the polypropylene composite material.
The polypropylene composite material prepared by the invention has good cooling liquid resistance and thermal oxidative aging resistance, can be widely applied to the preparation of plastic products, and particularly protects the application of the polypropylene composite material in the preparation of water chamber materials of automobile radiators.
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 combination synergistic effect of the maleic anhydride graft and the glycidyl methacrylate graft effectively improves the cooling liquid resistance and the thermo-oxidative aging resistance of the polypropylene composite material, and can well meet the requirements of water chamber materials of automobile radiators.
The tensile strength retention rate of the polypropylene composite material in 140 ℃/1000h cooling liquid is more than 90%, and the tensile strength retention rate under 140 ℃/1000h thermo-oxidative aging resistant condition is more than 95%.
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 polypropylene resin 1 is homopolymerized polypropylene resin PPH-Z30S, the melt mass flow rate is 30g/10min, and the polypropylene resin is middle petrochemical and Zhenhai petrochemical;
the polypropylene resin 2 is homopolymerized polypropylene resin PP T03, the melt mass flow rate is 3g/10min, and the polypropylene resin is middle petrochemical sea-level petrochemical;
the polypropylene resin 3 is homo-polypropylene resin MH7900, the melt mass flow rate is 150g/10min, LG chemistry;
the polypropylene resin 4 is copolymerized polypropylene resin M60T, the melt mass flow rate is 60g/10min, and the polypropylene resin is medium petrochemical;
the polypropylene resin 5 is a copolymerized polypropylene resin BX3920, the melt mass flow rate is 100g/10min, and SK chemistry is carried out;
alkali-free chopped glass fibers are commercially available, and the same type of glass fibers are adopted in parallel experiments;
the maleic anhydride graft 1 is maleic anhydride grafted polypropylene CA100, the mass grafting rate of maleic anhydride is 1.0%, and the grafting rate of the maleic anhydride is Acomat;
the maleic anhydride graft 2 is maleic anhydride grafted polypropylene PC-1, and the mass grafting rate of maleic anhydride is 0.5 percent, and the south China sea cypress morning;
the 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 adopted;
the maleic anhydride graft 4 is maleic anhydride grafted polypropylene PC-3, and the mass grafting rate of maleic anhydride is 0.7 percent, and the south China sea cypress morning;
the 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 adopted;
the glycidyl methacrylate graft 1 is a glycidyl methacrylate grafted metallocene polyethylene E515, the mass grafting rate of the glycidyl methacrylate is 0.6%, and the light of wave energy is turned on;
the glycidyl methacrylate graft 2 is glycidyl methacrylate grafted metallocene polyethylene E513, the mass grafting rate of the glycidyl methacrylate is 0.2%, and the light of wave energy is turned on;
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 chemistry;
the glycidyl methacrylate graft 4 is glycidyl methacrylate grafted POE, the brand is N416, the mass grafting rate of the glycidyl methacrylate is 0.6%, and the DuPont chemical;
the glycidyl methacrylate graft 5 is glycidyl methacrylate grafted metallocene polyethylene E518, the mass grafting rate of the glycidyl methacrylate is 0.8%, and the light of wave energy is turned on;
the nucleating agent 1 is nano clay, is commercially available, and adopts the same nucleating agent in parallel experiments;
an antioxidant: hindered phenolic antioxidants and phosphite antioxidants 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 the components are shown in Table 1 below.
Table 1 Polypropylene composite material compositions (in parts by weight) of the examples
Table 1, below
Table 1, below
| Component (A) | 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 | 1 | 1 | 1 | 1 | 1 |
The preparation method of the polypropylene composite material specifically comprises the following steps:
s1, weighing all components except glass fibers 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, plasticizing by the double-screw extruder, wherein the temperature of the double-screw extruder is 160-200 ℃, and the screw rotating speed is 350-450 rpm;
and a second step of: 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 180 ℃, and obtaining the polypropylene composite material after traction, cooling, granulating and drying.
Comparative examples 1 to 5
A polypropylene composite material, wherein the specific content of each component is shown in the following Table 2.
Table 2 Polypropylene composite compositions (in parts by weight) of the respective comparative examples
| Component (A) | 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 | 1 | 1 | 1 | 1 | 1 |
The preparation method of the polypropylene composite material specifically comprises the following steps:
s1, weighing all components except glass fibers according to weight, adding the components into a high-speed mixer for mixing for 3-5 minutes, adding the components into a double-screw extruder with the length-diameter ratio of 30:1-50:1 for melt mixing and dispersing, and plasticizing the components through the double-screw extruder, wherein the temperature of the double-screw extruder is 160-200 ℃, and the screw speed is 350-450 rpm;
and a second step of: 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 180 ℃, and obtaining the polypropylene composite material after traction, cooling, granulating and drying.
Result detection
The polypropylene composites of the above examples and comparative examples were injection molded to give standard bars, which were tested by the following performance test methods:
(1) Tensile strength: the stretching speed was 10mm/min according to ISO 527-2011.
(2) The retention of the thermal oxidative aging resistance tensile strength properties was as follows:
ISO 188, 140℃test temperature, 1000 hours test period.
(3) The retention rate of the tensile strength performance of the cooling liquid resistance is as follows:
a) Experimental medium: LLC coolant (professional coolant of Nissan);
b) The temperature of the experimental medium is 140 ℃, and the experimental period is 1000 hours.
The specific test results for each example are set forth in Table 3 below:
table 3 shows the sequence
Table 3 shows the sequence
| Performance testing | 19 | 20 | 21 | 22 | 23 |
| Tensile Strength (MPa) | 98 | 97 | 99 | 98 | 99 |
| Retention of tensile Strength Property of thermo-oxidative aging liquid (%) | 98 | 98 | 97 | 94 | 96 |
| Retention of tensile strength properties of Cooling liquid (%) | 97 | 96 | 95 | 94 | 97 |
The specific test results of each comparative example are shown in table 4 below.
| Performance testing | 1 | 2 | 3 | 4 | 5 |
| Tensile Strength (MPa) | 64 | 76 | 96 | 83 | 95 |
| Retention of tensile Strength Property of thermo-oxidative aging liquid (%) | 85 | 96 | 89 | 93 | 87 |
| Retention of tensile strength properties of Cooling liquid (%) | 82 | 86 | 89 | 87 | 84 |
From the above data, it can be seen that the tensile strength retention of the polypropylene composite material of the present invention in 140 ℃/1000h cooling liquid is 90% or more, and the tensile strength retention under 140 ℃/1000h thermo-oxidative aging conditions is 95%.
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 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 (6)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
wherein the polar graft is a mixture of maleic anhydride graft and glycidyl methacrylate graft, and the weight ratio of the maleic anhydride graft to the glycidyl methacrylate graft is (1.5-2.5): 1;
the mass grafting rate of the glycidyl methacrylate in the glycidyl methacrylate graft is 0.6-0.8%;
the glycidyl methacrylate graft is glycidyl methacrylate grafted metallocene polyethylene;
the maleic anhydride graft is maleic anhydride grafted polypropylene.
2. The polypropylene composite material according to claim 1, comprising the following components in parts by weight:
50-60 parts of polypropylene resin;
25-35 parts of glass fiber;
4 to 4.5 portions of polar grafts;
0.3 to 0.6 portion of nucleating agent.
3. The polypropylene composite material according to claim 1, wherein the mass grafting ratio of maleic anhydride in the maleic anhydride graft is 0.7-1.3%.
4. The polypropylene composite material according to claim 1, wherein the nucleating agent is a nanoclay and/or a nano calcium carbonate.
5. The method for preparing the polypropylene composite material according to any one of claims 1 to 4, comprising the steps of:
and uniformly mixing the components, performing melt extrusion and granulation at 160-200 ℃ by a double-screw extruder, and drying to obtain the polypropylene composite material.
6. Use of the polypropylene composite material according to any one of claims 1 to 4 for the preparation of a radiator water chamber material for an automobile.
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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 |
| 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 |
| 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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