CN115584087B - 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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- CN115584087B CN115584087B CN202211215106.4A CN202211215106A CN115584087B CN 115584087 B CN115584087 B CN 115584087B CN 202211215106 A CN202211215106 A CN 202211215106A CN 115584087 B CN115584087 B CN 115584087B
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 89
- -1 Polypropylene Polymers 0.000 title claims abstract description 88
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 87
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 68
- 239000011347 resin Substances 0.000 claims abstract description 68
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 31
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 31
- 239000004677 Nylon Substances 0.000 claims abstract description 29
- 229920001778 nylon Polymers 0.000 claims abstract description 29
- 238000012360 testing method Methods 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 20
- 239000000155 melt Substances 0.000 claims abstract description 13
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 8
- 238000003860 storage Methods 0.000 claims abstract description 8
- 239000002828 fuel tank Substances 0.000 claims description 26
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- 239000000446 fuel Substances 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 8
- 229920005672 polyolefin resin Polymers 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 5
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 2
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 2
- 230000006353 environmental stress Effects 0.000 abstract description 25
- 238000005336 cracking Methods 0.000 abstract description 23
- 230000004888 barrier function Effects 0.000 abstract description 19
- 239000000295 fuel oil Substances 0.000 abstract description 16
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920005992 thermoplastic resin Polymers 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- FEHDLMJLTHKGJQ-UHFFFAOYSA-N C1(CC(=O)OC(C2=CC=CC=C2)O1)=O.N1=NN=CC=C1 Chemical compound C1(CC(=O)OC(C2=CC=CC=C2)O1)=O.N1=NN=CC=C1 FEHDLMJLTHKGJQ-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
- C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/06—Properties of polyethylene
- C08L2207/066—LDPE (radical process)
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Cooling, Air Intake And Gas Exhaust, And Fuel Tank Arrangements In Propulsion Units (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, 42-76 parts of polypropylene resin; 10-20 parts of low-density polyethylene; 10-30 parts of nylon resin; 3-5 parts of compatilizer; 1-3 parts of processing aid; the melt strength of the polypropylene resin is 90-200 mN, and the test condition is 210 ℃; the elongation at break of the nylon resin after reaching the moisture absorption balance is more than or equal to 80 percent, and the test conditions of the moisture absorption balance are as follows: the temperature is-40 ℃, the relative humidity is 50%, and the storage time is 72h. Through the synergistic effect of polypropylene, low-density polyethylene resin and nylon resin with certain melt strength, the polypropylene composite material not only has excellent fuel oil barrier property, but also effectively improves the environmental stress cracking resistance of the polypropylene composite material.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a polypropylene composite material, a preparation method and application thereof.
Background
In the field of automotive manufacturing, fuel tanks are particularly devices for storing fuel oil on machines driven by diesel or petrol engines. In order to realize the light weight of automobiles, plastic fuel tanks are mostly adopted to contain gasoline in the existing automobile manufacturing process.
Materials used as plastic fuel tanks need to have good barrier properties or low permeability to fuel. In addition, the automobile fuel tank is in vibration condition caused by road condition jolting for a long time, and needs to load automobile fuel containing various different components at higher temperature for a long time, and has higher requirements on the environmental stress cracking resistance of materials in such complex use environment for a long time.
Compared with other general thermoplastic resins, the polypropylene material has the advantages of small relative density, low price, good processability, good comprehensive performance and the like, and is often used for automobile decorative parts. However, the polypropylene material has the defects of poor fuel oil barrier property, poor environmental stress cracking resistance and the like, and greatly limits the application of the polypropylene material to fuel oil and other parts contacted with fuel oil.
The prior art discloses a low permeability plastic fuel tank shell material comprising thermoplastic resins such as polyethylene, polypropylene and polyamide, and a plastic fuel tank prepared by mixing the thermoplastic resins and thermoplastic polyesters has low permeability. However, it does not address the environmental stress cracking problem that current fuel tanks need to address.
Disclosure of Invention
The invention aims to overcome the defect and the defect of poor environmental stress cracking resistance of the traditional polypropylene composite material, and provides the polypropylene composite material, which has excellent fuel oil barrier property and effectively improves the environmental stress cracking resistance of the polypropylene composite material through the synergistic effect of polypropylene, low-density polyethylene resin and nylon resin with certain melt strength.
It is still another object of the present invention to provide a method for preparing a polypropylene composite.
Another object of the invention is to provide an application of the polypropylene composite material in the preparation of an automobile fuel tank, a fuel feeding pipeline or a motorcycle fuel tank.
It is a further object of the present invention to provide a fuel tank.
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:
The melt strength of the polypropylene resin is 90-200 mN, and the test condition is 210 ℃;
the elongation at break of the nylon resin after reaching the moisture absorption balance is more than or equal to 80 percent, and the test conditions of the moisture absorption balance are as follows: the temperature is-40 ℃, the relative humidity is 50%, and the storage time is 72h.
The following are to be described: the polypropylene composite material provided by the invention has excellent fuel oil barrier property through the polypropylene resin, the low-density polyethylene resin and the nylon resin with certain melt strength, and the environmental stress cracking resistance of the polypropylene composite material is effectively improved.
In the invention, the test condition of the melt strength is 210 ℃, and the test method is to measure the tensile rheological property on a Rheotens71.97 type extrusion type melt tensile rheometer. The method comprises the steps of continuously feeding by adopting a RheoGraph < 600 > high-pressure capillary rheometer, wherein the diameter of a plunger of the capillary rheometer is 12mm, the moving speed of the plunger is 0.5mm/s, the diameter of a capillary is 2mm, the length-diameter ratio is 30, the extrusion speed of a melt at an outlet of the capillary is 18mm/s, a clamping roller rotates in a linear acceleration mode, the acceleration is 10mm/s 2, the stretching distance is 100mm, and the distance between the clamping rollers is 0.2mm.
The elongation at break test standard is ISO 527-2012, the stretching speed is 50mm/min, and the test temperature is-40 ℃.
The action mechanism of each component of the polypropylene composite material is as follows:
the polypropylene resin has excellent oil resistance, heat resistance and processability, and the melt strength of the polypropylene resin can meet the blow molding requirement of an automobile fuel tank, so that the molding of a fuel tank product is ensured.
The low-density polyethylene and the polypropylene both contain ethylene monomers and have good compatibility. Moreover, the low-density polyethylene has higher crystallinity, so that the low-density polyethylene has good synergistic effect on the barrier property of fuel oil. In addition, the molecular structure of the low-density polyethylene is formed by ethylene, the crystallization area is smaller, and the molecular chain is easy to stretch in a certain space, so that the low-density polyethylene has good environmental stress cracking resistance.
However, too much amount of low density polyethylene can significantly reduce the heat distortion temperature of the composite.
The nylon resin has strong polarity and good barrier property to fuel oil, and the nylon resin still has higher elongation at break, which can reach moisture absorption balance at low temperature, effectively overcomes the defect of obvious performance change of nylon after water absorption, has larger molecular chain action space and better environmental stress cracking resistance, can form effective synergistic effect with low-density polyethylene, and improves the environmental stress cracking resistance of the composite material. Further, the nylon resin has a high heat distortion temperature, and therefore, the heat resistance of the composite material can be improved.
However, excessive amounts of nylon resin can result in failure of the composite to form.
The compatibilizing agent serves to improve the compatibility of the polypropylene resin, the low-density polyethylene resin and the nylon resin.
In order to further improve the environmental stress cracking resistance and the thermal deformation temperature of the material, preferably, the elongation at break of the nylon resin after reaching the moisture absorption balance is 90-100%.
In addition, the high elongation at break of the nylon resin can improve the impact resistance of the composite material at low temperature and can improve the energy of the composite material at the time of low-temperature multiaxial impact maximum load.
In order to further improve the environmental stress cracking resistance of the composite material, preferably, the low-density polyethylene has a melt index of 1-3 g/10min, a test condition of 190 ℃ and 2.16kg, and a test standard of ISO1133-1-2011.
In order to further improve the fuel barrier properties of the composite, the crystallinity of the low density polyethylene is preferably 15% to 25% by differential scanning calorimetry.
Preferably, the compatilizer is one or more of maleic anhydride grafted polypropylene, glycidyl methacrylate grafted polypropylene or ethylene-methyl acrylate-glycidyl methacrylate copolymer.
Still more preferably, the compatibilizer is maleic anhydride grafted polypropylene.
Preferably, the melt strength of the polypropylene resin is 100 to 150mN, and the test condition is 210 ℃.
The higher the melt strength is, the toughness, fuel oil barrier property, maximum load energy and environmental stress cracking resistance of the material are improved, but the thermal deformation temperature is reduced.
Preferably, the processing aid is one or more of an antioxidant, a weather-resistant agent or toner.
Preferably, the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
The antioxidant can improve the antioxidation effect of the composite material.
Preferably, the weather-proof agent is one or more of hindered amine, benzotriazole, benzophenone or triazine benzylidene malonate.
The weather-proof agent can improve the light resistance of the composite material.
The invention also provides a preparation method of the polypropylene composite material, which comprises the following steps:
s1, mixing polypropylene resin, low-density polyethylene resin and a compatilizer, extruding at 180-195 ℃ through a double-screw extruder, and granulating to obtain polar polyolefin resin;
s2, uniformly mixing the polar polyolefin resin and other components, performing melt extrusion and granulation at 200-230 ℃ through a double-screw extruder, and drying to obtain the polypropylene composite material.
According to the invention, the polar polyolefin resin is prepared by mixing the polypropylene resin, the low-density polyethylene resin and the compatilizer, and the compatilizer improves the compatibility between the nonpolar polyolefin resin and the nylon, so that the fuel oil barrier property and the environmental stress cracking resistance of the composite material are improved.
The polypropylene composite material prepared by the invention has good fuel oil barrier property and environmental stress cracking 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 automobile fuel tanks, oil adding pipelines or motorcycle oil tanks.
The invention also provides an automobile fuel tank which is made of the polypropylene composite material.
The preparation method of the automobile fuel tank can be blow molding.
Compared with the prior art, the invention has the beneficial effects that:
The invention discloses a polypropylene composite material, which comprises polypropylene resin, low-density polyethylene, nylon resin, a compatilizer and a processing aid, wherein the polypropylene composite material has excellent fuel oil barrier property and effectively improves the environmental stress cracking resistance of the polypropylene composite material through the synergistic effect of polypropylene with certain melt strength, low-density polyethylene resin and nylon resin.
The polypropylene composite material has good fuel oil barrier property, reduces the average permeation quantity of fuel oil to 9-13 g in 24h, has long environmental stress cracking resistance time, can reach 7-11 h, has excellent heat resistance, high heat deformation temperature of 96-107 ℃, is anti-collision, has the energy of 21-28J under the maximum load, and can meet the use requirement of an automobile fuel tank.
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.
Polypropylene resin 1: PP3010, melt strength 147mN, china table plastic;
polypropylene resin 2: PPH-T03, melt strength 76mN, medium petrochemical;
polypropylene resin 3: PP1101, melt strength 262mN, chinese plateau;
Polypropylene resin 4: AS164, melt strength 200mN, freshly-added polyolefin;
polypropylene resin 5: k8003, melt strength 170mN, taiwan petrochemical;
polypropylene resin 6: PP 17112, melt strength 130mN, sha Bike;
Polypropylene resin 7: PP 140HMS, melt strength 100mN, nordic chemical;
Low density polyethylene 1: LDPE 2426H with a melt index of 1.8g/10min and a crystallinity of 20% and a luxuriant petrochemical appearance;
Low density polyethylene 2: LDPE 2420D with a melt index of 0.4g/10min and a crystallinity of 30% and a luxuriant petrochemical appearance;
low density polyethylene 3: PEM 2440, melt index 4g/10min, crystallinity 10%, dandall;
Nylon resin 1: adsint PA12, the elongation at break after reaching the moisture absorption equilibrium is 90%, the test conditions of the moisture absorption equilibrium: the temperature is-40 ℃, the relative humidity is 50%, the storage time is 72 hours, and the Pasteur;
nylon resin 2: PA 12H, 100% elongation at break after moisture absorption equilibrium is reached, test conditions for moisture absorption equilibrium: the temperature is-40 ℃, the relative humidity is 50%, the storage time is 72h, and the Bada AG;
Nylon resin 3: inColor TM PA12, elongation at break after reaching moisture absorption equilibrium of 80%, test conditions of moisture absorption equilibrium: the temperature is-40 ℃, the relative humidity is 50%, the storage time is 72h, and the American;
Nylon resin 4: PA6 a 1000, elongation at break after reaching moisture absorption equilibrium is 120%, test conditions for moisture absorption equilibrium: the temperature is-40 ℃, the relative humidity is 50%, the storage time is 72 hours, and the medicine is Mokang;
nylon resin 5: A3K, the elongation at break after reaching the moisture absorption equilibrium is 40%, and the test conditions of the moisture absorption equilibrium are as follows: the temperature is-40 ℃, the relative humidity is 50%, the storage time is 72 hours, and the Pasteur;
compatibilizer 1: maleic anhydride grafted polypropylene, CA100, alcma;
compatibilizer 2: ethylene-methyl acrylate-glycidyl methacrylate copolymer, AX8900, alcma;
an antioxidant: the mass ratio of the hindered phenol antioxidant to the phosphite antioxidant is 1:1, commercially available and all examples and comparative examples are the same;
weather-resistant agent: hindered amine weatherproofing agents are commercially available and are the same for all examples and comparative examples.
Examples 1 to 13
The polypropylene composite material comprises the following components in parts by weight: a polypropylene resin; a low density polyethylene; nylon resin; a compatibilizer; a processing aid; the processing aid is an antioxidant and a weather-proof agent; 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
| Component (A) | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 |
| Polypropylene resin 1 | 59 | / | / | / | / |
| Polypropylene resin 4 | / | 59 | / | / | / |
| Polypropylene resin 5 | / | / | 59 | / | / |
| Polypropylene resin 6 | / | / | / | 59 | / |
| Polypropylene resin 7 | / | / | / | / | 59 |
| Low density polyethylene 1 | 15 | 15 | 15 | 15 | 15 |
| Compatibilizing agent 1 | / | 4 | 4 | 4 | 4 |
| Compatibilizer 2 | 4 | / | / | / | / |
| Nylon resin 1 | 20 | 20 | 20 | 20 | 20 |
| Antioxidant | 2 | 2 | 2 | 2 | 2 |
The preparation method of the polypropylene composite material comprises the following steps:
s1, mixing polypropylene resin, low-density polyethylene resin and a compatilizer, extruding at 180-195 ℃ through a double-screw extruder, and granulating to obtain polar polyolefin resin;
s2, uniformly mixing the polar polyolefin resin and other components, performing melt extrusion and granulation at 200-230 ℃ through a double-screw extruder, and drying to obtain the polypropylene composite material.
Comparative examples 1 to 7
The polypropylene composite material comprises the following components in parts by weight: a polypropylene resin; a low density polyethylene; nylon resin; a compatibilizer; a processing aid; the processing aid is an antioxidant and a weather-proof agent; wherein the specific contents of the components are shown in Table 2 below.
Table 2 Polypropylene composite compositions (in parts by weight) of the respective comparative examples
| Component (A) | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| Polypropylene resin 1 | / | / | 59 | 59 | 59 | 59 | 59 |
| Polypropylene resin 2 | 59 | / | / | / | / | / | / |
| Polypropylene resin 3 | / | 59 | / | / | / | / | / |
| Low density polyethylene 1 | 15 | 15 | 15 | / | 15 | 30 | 15 |
| Compatibilizing agent | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Nylon resin 1 | 20 | 20 | / | 20 | / | 20 | 45 |
| Nylon resin 5 | / | / | 20 | / | / | / | / |
| Antioxidant | 2 | 2 | 2 | 2 | 2 | 2 | 2 |
The preparation method of the polypropylene composite material is the same as that of example 1, and is not repeated here.
Result detection
The polypropylene composite materials of the above examples and comparative examples were subjected to a blow molding apparatus at a temperature of 200 to 220℃to prepare fuel tanks.
The fuel tanks of the above examples and comparative examples were tested by the following performance test methods:
(1) Workability: and observing whether the oil tank can be molded smoothly.
(2) Fuel barrier properties: 50wt% of aromatic hydrocarbon-containing fuel is injected into a fuel tank, the total mass M0 of the fuel tank and the fuel is weighed, the total mass M1 of the fuel tank and the fuel at the moment is weighed after the fuel tank and the fuel are placed in an environment of 40 ℃ for 56 days, and finally the average seepage quantity delta M of the fuel per day is obtained, wherein delta M= (M0-M1)/56. The smaller Δm indicates the better fuel barrier properties of the material.
(3) Environmental stress cracking resistance: the test standard is ASTM D1693-2015F 50, the test temperature is 50 ℃, and the test medium is 10% nonylphenol polyoxyethylene ether (TX 10). The longer the environmental stress crack resistance time is, the better the environmental stress crack resistance is.
(4) Maximum load energy: the test standard is ASTM D3763-1986, test temperature-40℃speed 7m/s. The greater the maximum load energy, the better the impact resistance of the material at low temperatures.
(5) Heat distortion temperature: the test standard is ISO75-2013, and the load is 0.45Mpa. The higher the heat distortion temperature, the better the heat resistance.
The specific test results for each example are set forth in Table 3 below:
TABLE 3 Table 3
| Sequence number | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 |
| Workability(s) | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Formable into shape |
| Barrier property (g/24 h) | 10 | 11 | 11 | 13 | 13 | 11 | 10 |
| Heat distortion temperature (DEG C) | 105 | 105 | 103 | 98 | 105 | 96 | 104 |
| Energy at maximum load (J) | 25 | 25 | 21 | 23 | 22 | 20 | 22 |
| Environmental stress cracking resistance (h) | 10 | 9 | 8 | 9 | 8 | 9 | 7 |
Table 3 shows the sequence
| Sequence number | Example 8 | Example 9 | Example 10 | Example 11 | Example 12 | Example 13 |
| Workability(s) | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Formable into shape |
| Barrier property (g/24 h) | 13 | 11 | 13 | 12 | 10 | 9 |
| Heat distortion temperature (DEG C) | 105 | 103 | 100 | 103 | 106 | 107 |
| Energy at maximum load (J) | 22 | 24 | 28 | 27 | 24 | 23 |
| Environmental stress cracking resistance (h) | 7 | 9 | 11 | 10 | 10 | 9 |
The specific test results of each comparative example are shown in table 4 below.
TABLE 4 Table 4
| Sequence number | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 |
| Workability(s) | Non-formable | Non-formable | Formable into shape | Formable into shape | Formable into shape | Formable into shape | Non-formable |
| Barrier property (g/24 h) | / | / | 11 | 14 | 20 | 12 | / |
| Heat distortion temperature (DEG C) | / | / | 104 | 104 | 85 | 88 | |
| Energy at maximum load (J) | / | / | 20 | 22 | 18 | 21 | / |
| Environmental stress cracking resistance (h) | / | / | 5 | 4 | 6 | 9 | / |
From the data, the polypropylene composite material has good fuel barrier property, the average permeation quantity of fuel oil is reduced to 9-13 g in 24h, the environmental stress cracking resistance time is long, the environmental stress cracking resistance time can reach 7-11 h, the heat resistance is excellent, the thermal deformation temperature is 96-107 ℃, the collision resistance is realized, the energy under the maximum load is 21-28J, and the use requirement of an automobile fuel tank can be met.
It is to be understood that the above examples of the present invention are provided by way of illustration only and not by way of limitation of the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (10)
1. The polypropylene composite material is characterized by comprising the following components in parts by weight:
the melt strength of the polypropylene resin is 100-200 mN, and the test condition is 210 ℃;
the elongation at break of the nylon resin after reaching the moisture absorption balance is more than or equal to 80 percent, and the test conditions of the moisture absorption balance are as follows:
the temperature is-40 ℃, the relative humidity is 50%, and the storage time is 72h.
2. The polypropylene composite material of claim 1, wherein the nylon resin has an elongation at break of 90 to 100% after reaching moisture absorption equilibrium.
3. The polypropylene composite material according to claim 1, wherein the low density polyethylene has a melt index of 1-3 g/10min, a test condition of 190 ℃, 2.16kg, and a test standard of ISO 1133-1-2011.
4. The polypropylene composite of claim 1, wherein the low density polyethylene has a crystallinity of 15% to 25% by differential scanning calorimetry.
5. The polypropylene composite material according to claim 1, wherein the compatibilizer is one or more of maleic anhydride grafted polypropylene, glycidyl methacrylate grafted polypropylene, or ethylene-methyl acrylate-glycidyl methacrylate copolymer.
6. The polypropylene composite material according to claim 1, wherein the polypropylene resin has a melt strength of 100 to 150mN under a test condition of 210 ℃.
7. The polypropylene composite material according to claim 6, wherein the processing aid is one or more of an antioxidant, a weather-resistant agent or a toner, and the antioxidant is a hindered phenol antioxidant and/or a phosphite antioxidant.
8. The method for preparing the polypropylene composite material according to any one of claims 1 to 7, comprising the steps of:
s1, mixing polypropylene resin, low-density polyethylene resin and a compatilizer, extruding at 180-195 ℃ through a double-screw extruder, and granulating to obtain polar polyolefin resin;
s2, uniformly mixing the polar polyolefin resin and other components, performing melt extrusion and granulation at 200-230 ℃ through a double-screw extruder, and drying to obtain the polypropylene composite material.
9. Use of the polypropylene composite according to any one of claims 1 to 7 for the preparation of a fuel tank for a motor vehicle, a fuel line or a fuel tank for a motor vehicle.
10. An automotive fuel tank, characterized by being made of a material comprising the polypropylene composite according to any one of claims 1 to 7.
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|---|---|---|---|---|
| WO1991002027A1 (en) * | 1989-08-04 | 1991-02-21 | Tonen Sekiyukagaku K.K. | Thermoplastic resin composition used for multi-layered molding product |
| CN1315469A (en) * | 2000-03-30 | 2001-10-03 | 上海杰事杰新材料股份有限公司 | Material for fuel oil tank |
| CN102532868A (en) * | 2011-12-30 | 2012-07-04 | 杭州临安宏凯工程塑料有限公司 | Polyamide composite material, and preparation method and application thereof |
| CN112898659A (en) * | 2021-01-15 | 2021-06-04 | 安徽绿能技术研究院有限公司 | Low-permeability plastic fuel tank shell material and preparation method thereof |
| CN114957851A (en) * | 2022-03-29 | 2022-08-30 | 武汉金发科技有限公司 | Polypropylene composite material easy to absorb plastic and preparation method thereof |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1991002027A1 (en) * | 1989-08-04 | 1991-02-21 | Tonen Sekiyukagaku K.K. | Thermoplastic resin composition used for multi-layered molding product |
| CN1315469A (en) * | 2000-03-30 | 2001-10-03 | 上海杰事杰新材料股份有限公司 | Material for fuel oil tank |
| CN102532868A (en) * | 2011-12-30 | 2012-07-04 | 杭州临安宏凯工程塑料有限公司 | Polyamide composite material, and preparation method and application thereof |
| CN112898659A (en) * | 2021-01-15 | 2021-06-04 | 安徽绿能技术研究院有限公司 | Low-permeability plastic fuel tank shell material and preparation method thereof |
| CN114957851A (en) * | 2022-03-29 | 2022-08-30 | 武汉金发科技有限公司 | Polypropylene composite material easy to absorb plastic and preparation method thereof |
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