CN112126165A - Polypropylene composite material with self-repairing performance after high-temperature aging and preparation method thereof - Google Patents
Polypropylene composite material with self-repairing performance after high-temperature aging and preparation method thereof Download PDFInfo
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- CN112126165A CN112126165A CN202011032296.7A CN202011032296A CN112126165A CN 112126165 A CN112126165 A CN 112126165A CN 202011032296 A CN202011032296 A CN 202011032296A CN 112126165 A CN112126165 A CN 112126165A
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- 239000002131 composite material Substances 0.000 title claims abstract description 68
- -1 Polypropylene Polymers 0.000 title claims abstract description 62
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 57
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 57
- 230000032683 aging Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000002667 nucleating agent Substances 0.000 claims abstract description 33
- 150000007970 thio esters Chemical class 0.000 claims abstract description 29
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 26
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 229920001971 elastomer Polymers 0.000 claims abstract description 16
- 239000000806 elastomer Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001577 copolymer Polymers 0.000 claims description 4
- 239000004611 light stabiliser Substances 0.000 claims description 3
- FGHOOJSIEHYJFQ-UHFFFAOYSA-N (2,4-ditert-butylphenyl) dihydrogen phosphite Chemical compound CC(C)(C)C1=CC=C(OP(O)O)C(C(C)(C)C)=C1 FGHOOJSIEHYJFQ-UHFFFAOYSA-N 0.000 claims description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- 229920002943 EPDM rubber Polymers 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 2
- VSVVZZQIUJXYQA-UHFFFAOYSA-N [3-(3-dodecylsulfanylpropanoyloxy)-2,2-bis(3-dodecylsulfanylpropanoyloxymethyl)propyl] 3-dodecylsulfanylpropanoate Chemical compound CCCCCCCCCCCCSCCC(=O)OCC(COC(=O)CCSCCCCCCCCCCCC)(COC(=O)CCSCCCCCCCCCCCC)COC(=O)CCSCCCCCCCCCCCC VSVVZZQIUJXYQA-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- JKBYAWVSVVSRIX-UHFFFAOYSA-N octadecyl 2-(1-octadecoxy-1-oxopropan-2-yl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)SC(C)C(=O)OCCCCCCCCCCCCCCCCCC JKBYAWVSVVSRIX-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000006399 behavior Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 27
- 230000014759 maintenance of location Effects 0.000 description 22
- 229920005606 polypropylene copolymer Polymers 0.000 description 11
- 239000003365 glass fiber Substances 0.000 description 5
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000002195 synergetic effect Effects 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 238000005844 autocatalytic reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- XXHCQZDUJDEPSX-KNCHESJLSA-L calcium;(1s,2r)-cyclohexane-1,2-dicarboxylate Chemical compound [Ca+2].[O-]C(=O)[C@H]1CCCC[C@H]1C([O-])=O XXHCQZDUJDEPSX-KNCHESJLSA-L 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 229920005992 thermoplastic resin Polymers 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
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0083—Nucleating agents promoting the crystallisation of the polymer matrix
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The invention relates to a polypropylene composite material with self-repairing performance after high-temperature aging and a preparation method thereof. The composite material comprises the following components in percentage by weight: 47.6 to 89.0 percent of polypropylene, 0 to 20 percent of elastomer, 10 to 30 percent of talcum powder, 0.2 to 0.4 percent of nucleating agent, 0.4 to 1.0 percent of antioxidant, 0.2 to 0.6 percent of weather resistant agent and 0.2 to 0.4 percent of thioester. The composite material has no degradation and other behaviors after long-time aging, can realize self-repairing of performance after high-temperature aging, and can be widely used for large-area decorative parts of automobiles, household appliances and the like.
Description
Technical Field
The invention belongs to the field of polypropylene materials and preparation thereof, and particularly relates to a polypropylene composite material with self-repairing performance after high-temperature aging and a preparation method thereof.
Background
Compared with other general thermoplastic resins, the polypropylene resin has the advantages of small relative density, low price, good processing performance, good comprehensive performance and the like, but in the using and processing process of the polypropylene material, due to the action of mechanical stress and heat, carbon-hydrogen bonds or carbon-carbon bonds are easy to break to form macromolecular alkyl radicals, under the condition of oxygen, the alkyl radicals and the oxygen react to form hydroperoxide, the hydroperoxide has the autocatalysis effect on the oxidation reaction to form more alkyl radicals, and the cycle is repeated, so that the polypropylene material is continuously decomposed, the performance is greatly reduced, and the requirements cannot be met. And the polypropylene material is a semi-crystalline material, and can form secondary crystallization under the action of high temperature, so that the crystallinity is increased, and the toughness of the material is greatly reduced.
The automobile decorative parts have anti-aging requirements, and the performance of the material cannot be obviously attenuated after aging, and general research only ensures that the material is not obviously degraded after the material acts at a certain temperature and time, and rarely relates to the retention rate of the material performance.
Chinese patent CN102924815A discloses a continuous long glass fiber reinforced polypropylene compound, which comprises, by weight, 34-78% of polypropylene, 0-2% of a heat stabilizer, 0-2% of a light stabilizer, 0-2% of a special nucleating agent for polypropylene, 2-10% of a compatilizer, and 20-50% of continuous long glass fiber. The composite material has high rigidity, high heat resistance, high dimensional stability, weather resistance and the like, but the performance retention rate of the composite material after high-temperature aging is lower.
Disclosure of Invention
The invention aims to solve the technical problem of providing a polypropylene composite material with self-repairing performance after high-temperature aging and a preparation method thereof, so as to overcome the defect of low performance retention rate of the polypropylene composite material after high-temperature aging in the prior art.
The invention provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in percentage by weight: 47.6 to 89.0 percent of polypropylene, 0 to 20 percent of elastomer, 10 to 30 percent of talcum powder, 0.2 to 0.4 percent of nucleating agent, 0.4 to 1.0 percent of antioxidant, 0.2 to 0.6 percent of weather resistant agent and 0.2 to 0.4 percent of thioester.
The polypropylene is copolymerized polypropylene, and the comonomer of the copolymerized polypropylene is ethylene.
The elastomer is at least one of polybutadiene rubber, ethylene-butylene copolymer, ethylene-octene copolymer and ethylene-propylene-diene rubber.
The particle size of the talcum powder is 1-50 mu m, and the weight percentage of the silicon dioxide is 60-90%.
The nucleating agent is a beta-type nucleating agent.
The beta-nucleating agent is one or more of a fused ring compound with a quasi-planar structure, a salt of a group IIA metal element and a dicarboxylic acid compound thereof, and aromatic diamide.
The antioxidant is a compound of any two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
The weather resisting agent is one or more of hindered amine, benzotriazole, benzophenone and triazine benzylidene malonate light stabilizers.
The thioester is one of pentaerythritol tetrakis (3-lauryl thiopropionate) and dioctadecyl thiodipropionate.
The invention also provides a preparation method of the polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following steps:
uniformly mixing polypropylene, elastomer, talcum powder, nucleating agent, antioxidant, weather-resistant agent and thioester, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating to obtain the polypropylene composite material.
The mixing is carried out in a mixer at a temperature of 60-70 deg.C and a speed of 120-.
The temperature of the double-screw extruder from the feeding section to the head is 175-: 1.
the invention also provides application of the polypropylene composite material with self-repairing performance after high-temperature aging in high-temperature aging self-repairing.
The high-temperature aging condition of the invention is 150 ℃ storage for 1000 h.
Advantageous effects
The nucleating agent and the thioester have a synergistic effect, so that the polypropylene composite material can be self-repaired after being aged at high temperature, and the composite material is free from degradation and other behaviors after being aged at high temperature.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The raw materials used in the invention are as follows:
copolymerized polypropylene: seashell brand in EP 548R;
elastomer: POE ENGAGE 7467 dow;
nucleating agent: HPN-20E Milliken;
talc powder: 777A adding 3000 mesh;
an antioxidant A: antioxidant 1010 basf;
and (3) antioxidant B: antioxidant 168 basf;
weather resisting agent: UV-3808PP5 Cyanid;
thio ester: the antioxidant 412S is Kehai.
Example 1
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 88.5 parts of polypropylene copolymer, 10 parts of talcum powder, 0.2 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather resistant agent and 0.3 part of thioester.
The preparation method of the composite material comprises the following steps: adding all the components into a mixer and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, the time is 30 min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 175 ℃, 190 ℃, 185 ℃, 180 ℃ in sequence, the rotation speed of the screw is 180 r/min, and the length-diameter ratio of the screw is 40: 1.
example 2
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 78.5 parts of polypropylene copolymer, 10 parts of elastomer, 10 parts of talcum powder, 0.2 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather-resistant agent and 0.3 part of thioester.
The preparation method of the composite material comprises the following steps: adding all the components into a mixer and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, the time is 30 min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 175 ℃, 190 ℃, 185 ℃, 180 ℃ in sequence, the rotation speed of the screw is 180 r/min, and the length-diameter ratio of the screw is 40: 1.
example 3
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 68.3 parts of polypropylene copolymer, 30 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather resistant agent and 0.3 part of thioester.
The preparation method of the composite material comprises the following steps: adding all the components into a mixer and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, the time is 30 min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 185 ℃, 200 ℃, 1195 ℃, 195 ℃, 190 ℃, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
example 4
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 58.3 parts of polypropylene copolymer, 10 parts of elastomer, 30 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather-resistant agent and 0.3 part of thioester.
The preparation method of the composite material comprises the following steps: adding all the components into a mixer and uniformly mixing. Wherein the temperature of the mixer is 63 ℃, the rotating speed of the mixer is 130 r/min, the time is 30 min, and then the mixed materials are added into a double-screw extruder for extrusion, cooling, granulation and packaging. The temperature of the extruder from the feeding section to the head is 185 ℃, 200 ℃, 195 ℃, 190 ℃, the rotation speed of the screw is 180 r/min, the length-diameter ratio of the screw is 40: 1.
example 5
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 58.4 parts of polypropylene copolymer, 10 parts of elastomer, 30 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather-resistant agent and 0.2 part of thioester.
The above composite material was prepared in the same manner as in example 4.
Example 6
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 58.2 parts of polypropylene copolymer, 10 parts of elastomer, 30 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather-resistant agent and 0.4 part of thioester.
The above composite material was prepared in the same manner as in example 4.
Example 7
The embodiment provides a polypropylene composite material with self-repairing performance after high-temperature aging, which comprises the following components in parts by weight: 58.2 parts of polypropylene copolymer, 20 parts of elastomer, 20 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.2 part of weather-resistant agent and 0.4 part of thioester.
The above composite material was prepared in the same manner as in example 4.
Comparative example 1
According to example 1, this comparative example provides a polypropylene composite and a method for preparing the same, wherein the weight part of the polypropylene copolymer is changed to 88.7 parts without adding a nucleating agent, and the rest is the same as that of example 1.
Comparative example 2
This comparative example provides a polypropylene composite and a process for preparing the same according to example 1, except that the weight part of the copolymerized polypropylene is changed to 88.8 parts without adding thioester, and the rest is the same as in example 1.
Comparative example 3
According to example 2, this comparative example provides a polypropylene composite and a method for preparing the same, wherein 78.7 parts by weight of polypropylene copolymer is used instead of the nucleating agent, and the rest is the same as example 2.
Comparative example 4
This comparative example provides a polypropylene composite and a process for preparing the same according to example 2, except that the weight part of the copolymerized polypropylene is changed to 78.8 parts without adding thioester, and the rest is the same as in example 2.
Comparative example 5
According to example 3, this comparative example provides a polypropylene composite and a method for preparing the same, wherein the weight part of the polypropylene copolymer is changed to 68.7 parts without adding a nucleating agent, and the rest is the same as that of example 3.
Comparative example 6
This comparative example provides a polypropylene composite and a process for preparing the same according to example 3, except that the weight part of the copolymerized polypropylene is changed to 68.6 parts without adding thioester, and the rest is the same as in example 3.
Comparative example 7
According to example 4, this comparative example provides a polypropylene composite and a method for preparing the same, wherein the weight part of the polypropylene copolymer is changed to 58.7 parts without adding a nucleating agent, and the rest is the same as that of example 4.
Comparative example 8
This comparative example provides a polypropylene composite and a method of making the same according to example 4, except that 58.6 parts by weight of the copolymerized polypropylene is used instead of the thioester, and the remainder is the same as in example 4.
Comparative example 9
According to the chinese patent CN102924815A, the present comparative example provides a long glass fiber reinforced polypropylene composite material, which comprises the following components in parts by weight: 44.3 parts of polypropylene, 30 parts of talcum powder, 0.4 part of nucleating agent, 0.4 part of antioxidant A, 0.4 part of antioxidant B, 0.3 part of thioester, 4 parts of maleic anhydride grafted polypropylene, 20 parts of continuous long glass fiber Tufrov 4575(PPG company) and 0.2 part of weather-resistant agent. The composite was prepared in the same manner as in example 3.
The polypropylene composites of examples 1-5 and comparative examples 1-9 were subjected to the following performance tests, and the results are shown in Table 1.
(1) Tensile strength: ISO 527 tensile speed 50 mm/min.
(2) Flexural modulus: ISO 178 bending speed 2 mm/min.
(3) Notch impact: ISO 179 pendulum energy 1J.
After the polypropylene composite materials in examples 1-5 and comparative examples 1-9 were stored at 150 ℃ for 1000 hours, the tensile strength, flexural modulus and notch impact were measured according to the above method, and the retention rate was calculated; and observing the surface of the sample bar, judging whether the chalking phenomenon exists or not, and if the chalking phenomenon exists, judging the sample bar to be degraded.
TABLE 1 results of the Performance test of examples and comparative examples
As can be seen from Table 1, the composite materials in comparative example 1 and comparative example 5, which are not added with the nucleating agent, have tensile strength retention, flexural modulus retention and notched impact retention that are significantly lower than those of the composite materials in example 1 and example 3. The composites of comparative examples 2 and 6, to which no thioester was added, also exhibited significantly lower retention of tensile strength, flexural modulus and notched impact than the composites of examples 1 and 3. In the presence of the elastomer, the composite materials in the comparative examples 3 and 7 are not added with a nucleating agent, and the tensile strength retention rate, the flexural modulus retention rate and the notch impact retention rate of the composite materials are obviously lower than those of the composite materials in the examples 2 and 4. In the presence of the elastomer, the tensile strength retention, the flexural modulus retention and the notched impact retention of the composites in comparative examples 4 and 8, to which no thioester was added, were significantly lower than those of the composites in examples 2 and 4. Therefore, no matter whether an elastomer exists or not, the talcum powder of the filling system is low or high, the nucleating agent and the thioester have a synergistic effect, so that the performance retention rate of the polypropylene composite material after aging is maintained to be more than 95%, the composite material is not degraded after high-temperature aging, the nucleating agent or the thioester is not added, namely, the synergistic effect between the nucleating agent and the thioester is avoided, the performance retention rate of the composite material after aging is maintained to be less than 80%, and the composite material is obviously degraded under the condition that the thioester is not added after high-temperature aging. In addition, although the composite material in comparative example 9 is added with the nucleating agent and the thioester, the tensile strength retention rate, the flexural modulus retention rate and the notched impact retention rate of the composite material are obviously lower than those of the composite material in example 3, and the material is also degraded after high-temperature aging, because the maleic anhydride grafted polypropylene and the continuous long glass fiber added into the composite material influence the action between the nucleating agent and the thioester, so that the tensile strength retention rate, the flexural modulus retention rate, the notched impact retention rate and the degradation condition are influenced.
Claims (9)
1. The self-repairing polypropylene composite material with the performance after high-temperature aging is characterized by comprising the following components in percentage by weight: 47.6 to 89.0 percent of polypropylene, 0 to 20 percent of elastomer, 10 to 30 percent of talcum powder, 0.2 to 0.4 percent of nucleating agent, 0.4 to 1.0 percent of antioxidant, 0.2 to 0.6 percent of weather resistant agent and 0.2 to 0.4 percent of thioester.
2. The composite material of claim 1, wherein the polypropylene is a co-polypropylene and the co-monomer of the co-polypropylene is ethylene.
3. The composite material of claim 1, wherein the elastomer is at least one of polybutadiene rubber, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-diene rubber; the particle size of the talcum powder is 1-50 μm, and the weight percentage of the silicon dioxide is 60-90%.
4. The composite material as claimed in claim 1, wherein the nucleating agent is a β -type nucleating agent, and the β -type nucleating agent is one or more of a fused ring compound with a quasi-planar structure, a salt of a group IIA metal element and a dicarboxylic acid compound thereof, and an aromatic diamide; the antioxidant is a compound of any two of tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and N-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate.
5. The composite material of claim 1, wherein the weather resistant agent is one or more of hindered amine, benzotriazole, benzophenone and triazine benzylidene malonate light stabilizers.
6. The composite material of claim 1, wherein the thio-ester is one of pentaerythritol tetrakis (3-laurylthiopropionate) and dioctadecyl thiodipropionate.
7. A method of making the composite material of claim 1, comprising:
uniformly mixing polypropylene, elastomer, talcum powder, nucleating agent, antioxidant, weather-resistant agent and thioester, adding the mixed material into a double-screw extruder for extrusion, cooling and granulating to obtain the polypropylene composite material.
8. The method as claimed in claim 7, wherein the temperature of the twin-screw extruder is, in order from the feeding section to the head, 175-: 1.
9. use of the composite of claim 1 for self-healing after high temperature aging.
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