CN117430839A - Automotive heat aging resistant glass fiber reinforced PP material and preparation method thereof - Google Patents
Automotive heat aging resistant glass fiber reinforced PP material and preparation method thereof Download PDFInfo
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- CN117430839A CN117430839A CN202311611937.8A CN202311611937A CN117430839A CN 117430839 A CN117430839 A CN 117430839A CN 202311611937 A CN202311611937 A CN 202311611937A CN 117430839 A CN117430839 A CN 117430839A
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- glass fiber
- titanium dioxide
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- aging
- fiber reinforced
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 170
- 239000000463 material Substances 0.000 title claims abstract description 69
- 230000032683 aging Effects 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000004743 Polypropylene Substances 0.000 claims abstract description 95
- 229920001155 polypropylene Polymers 0.000 claims abstract description 82
- -1 polypropylene Polymers 0.000 claims abstract description 44
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 102
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 94
- 238000002156 mixing Methods 0.000 claims description 69
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 239000004408 titanium dioxide Substances 0.000 claims description 47
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 46
- 238000001035 drying Methods 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000001914 filtration Methods 0.000 claims description 32
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 31
- 238000001291 vacuum drying Methods 0.000 claims description 31
- 239000008367 deionised water Substances 0.000 claims description 29
- 229910021641 deionized water Inorganic materials 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 24
- 239000012965 benzophenone Substances 0.000 claims description 20
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 17
- 229920001721 polyimide Polymers 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- 239000004642 Polyimide Substances 0.000 claims description 16
- 239000003999 initiator Substances 0.000 claims description 14
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 14
- 239000011347 resin Substances 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 14
- 239000003963 antioxidant agent Substances 0.000 claims description 12
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 10
- 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 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- 238000003878 thermal aging Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- MTEZSDOQASFMDI-UHFFFAOYSA-N 1-trimethoxysilylpropan-1-ol Chemical compound CCC(O)[Si](OC)(OC)OC MTEZSDOQASFMDI-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 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 claims description 2
- 239000000155 melt Substances 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 42
- 238000012360 testing method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 15
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000004611 light stabiliser Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000008366 benzophenones Chemical class 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 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 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical class C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 102220040412 rs587778307 Human genes 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2451/00—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers
- C08J2451/06—Characterised by the use of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
- C08J2479/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2479/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
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- Chemical & Material Sciences (AREA)
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- Health & Medical Sciences (AREA)
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Abstract
The invention relates to the technical field of polypropylene materials, and particularly discloses a heat-resistant aging glass fiber reinforced PP material for a vehicle and a preparation method thereof.
Description
Technical Field
The invention relates to the technical field of polypropylene materials, in particular to a heat aging resistant glass fiber reinforced PP material for a vehicle and a preparation method thereof.
Background
Polypropylene is a semi-crystalline thermoplastic plastic, colorless, nontoxic, light in weight and low in price, has excellent chemical stability, wear resistance and mechanical properties, is widely used as one of five general plastics in the fields of automobiles, electric appliances, buildings, packaging, food industry and the like, is easy to process and mold, and has excellent plasticity. However, polypropylene contains unstable tertiary carbon groups, has general heat resistance, is sensitive to the action of oxygen, and has poor ultraviolet resistance especially at higher temperatures. When the polypropylene is applied to the field of automobiles, the automobiles can be continuously irradiated by high temperature and ultraviolet rays in high-temperature weather, so that parts are aged.
Chinese patent CN103059420B discloses a light aging resistant polypropylene material and preparation method thereof, comprising the following components in parts by weight: 30-80 parts of polypropylene, 5-10 parts of ethylene propylene diene monomer, 10-25 parts of talcum powder, 5-10 parts of glass fiber and 0.2-0.8 part of composite light stabilizer; the polypropylene material has higher light aging resistance, can be easily processed into parts with various shapes by an injection molding process, can be used for manufacturing automobile sealing parts, various operating handles, handles and the like, but has poor dispersibility among all raw materials and influences the comprehensive performance of the polypropylene material by directly melt blending, extruding and granulating polypropylene, ethylene propylene diene monomer rubber, talcum powder, glass fiber and a composite light stabilizer. Chinese patent CN102010545B discloses a black filled polypropylene composite material with thermal oxidative aging resistance and a preparation method thereof, wherein the composite material comprises 50-75% of polypropylene, 10-40% of filling, 0-15% of elastomer, 0.5-2% of acid absorbent, 0.7-1.5% of composite antioxidant, 0.2-0.6% of processing aid, 0.4-0.8% of carbon black and 0.2-0.8% of white mineral oil, and the thermal oxidative aging resistance of polypropylene is improved by adding the acid absorbent to absorb acidic substances on the surface of the carbon black and the antioxidant containing multiple reactive functional groups, so that the thermal oxidative aging resistance of the system is improved, but the antioxidant or the light stabilizer is directly dispersed in the material system, and the short-term aging resistance is good, but under the long-term actions of heat, oxygen and light, the antioxidant or the light stabilizer has precipitation problems, so that the aging resistance of the polypropylene product is greatly reduced.
Therefore, how to improve the ageing resistance of the PP material and how to prepare the heat-aging-resistant glass fiber reinforced PP material for the vehicle become the key point of research.
Disclosure of Invention
In order to solve the technical problems, the invention provides the heat aging resistant glass fiber reinforced PP material for the vehicle and the preparation method thereof, and solves the general problem of the heat aging resistant performance of the PP material.
In order to achieve the above purpose, the invention discloses a preparation method of a glass fiber reinforced PP material for a vehicle, which comprises the following steps:
modifying glass fiber by using gamma-aminopropyl triethoxy silane, and obtaining amino glass fiber after modification;
dispersing nano titanium dioxide into absolute ethyl alcohol by ultrasonic, adding gamma-glycidol ether oxypropyl trimethoxy silane after uniform dispersion, uniformly mixing, reacting, filtering after the reaction is finished, washing by using absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide, reacting, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain titanium dioxide modified glass fiber;
fourthly, ultrasonically dispersing the titanium dioxide modified glass fiber into toluene, adding 2-hydroxy-4-chloroacetate-benzophenone after uniform dispersion, reacting in a nitrogen atmosphere, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain the modified glass fiber;
dispersing the modified glass fiber into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator, uniformly mixing, reacting in a nitrogen atmosphere, steaming in a rotary way after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fiber;
and step six, mixing the polypropylene resin, the heat-aging-resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant, carrying out melt blending, extruding and cooling to obtain the heat-aging-resistant glass fiber reinforced PP material for the vehicle.
Preferably, the specific preparation steps of the aminated glass fiber in the first step are as follows: mixing deionized water and glass fiber uniformly, adding gamma-aminopropyl triethoxysilane, washing the deionized water, the glass fiber and the gamma-aminopropyl triethoxysilane according to the mass ratio of 4200-6000:100:36-45, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 70-80 ℃ for 3-5h, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12h to obtain the aminated glass fiber.
Preferably, in the second step, the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 2500-3500:100:40-55.
Preferably, the temperature of the reaction in the second step is 60-65 ℃ and the reaction time is 2-4h.
Preferably, in the third step, the mass ratio of the 1, 4-dioxane, the aminated glass fiber and the epoxidized titanium dioxide is 4800-5200:100:18-30.
Preferably, the temperature of the reaction in the third step is 85-95 ℃ and the reaction time is 18-24h.
Preferably, in the fourth step, the mass ratio of the titanium dioxide modified glass fiber, toluene and 2-hydroxy-4-chloroacetate-benzophenone is 100:1800-2500:24-30.
Preferably, the temperature of the reaction in the step four is 85-95 ℃, and the reaction time is 9-12h.
Preferably, in the fifth step, the mass ratio of the modified glass fiber, the toluene, the styrene, the acrylonitrile and the initiator is 100:700-900:12-25:15-30:1-3.
Preferably, the temperature of the reaction in the step five is 75-85 ℃, and the reaction time is 12-15h.
Preferably, the initiator in the fifth step is azobisisobutyronitrile.
Preferably, in the sixth step, the mass ratio of the polypropylene resin, the heat aging resistant glass fiber, the polyimide, the maleic anhydride grafted polypropylene and the antioxidant is 100:15-25:10-15:2-5:0.1-0.3.
Preferably, the melt blending in the step six is performed in a double-screw extruder, five temperature areas are arranged in the double-screw extruder according to the advancing direction of materials, the temperatures of the temperature areas are 120-135 ℃, 140-155 ℃, 160-170 ℃, 175-185 ℃, 190-205 ℃ respectively, and the rotating speed of the double-screw extruder is 120-130rpm.
Preferably, the antioxidant in the sixth step comprises one or two of antioxidant 168, antioxidant 1010 and antioxidant 1076.
Preferably, the preparation method of the automotive heat-aging-resistant glass fiber reinforced PP material is used for preparing the automotive heat-aging-resistant glass fiber reinforced PP material.
The glass fiber is an inorganic nonmetallic material, has low price, has the advantages of high strength, chemical corrosion resistance, high temperature resistance, flame retardance and the like, and the polypropylene (PP) is a crystalline polymer, has excellent mechanical property, impact resistance and chemical corrosion resistance, and has excellent comprehensive performance, excellent heat resistance and ageing resistance, and the strength and rigidity of the material can be improved by using the glass fiber as a reinforcing body of the PP composite material. The nano titanium dioxide has excellent mechanical properties, and has large specific surface area and surface energy due to small size, so that the nano titanium dioxide can keep good stability and thermal ageing resistance in a high-temperature environment. Meanwhile, the nano titanium dioxide has small size, high light refraction and high light activity, light can penetrate through the particle surface of the nano titanium dioxide, the reflection and scattering properties of ultraviolet rays in a long wave region are not obvious, the absorption properties of the ultraviolet rays in a medium wave region are obviously enhanced, and the nano titanium dioxide has excellent ultraviolet aging resistance. The polyimide resin has excellent high temperature resistance and mechanical property, and the polyimide can be used as a reinforcing agent in polypropylene, so that the mechanical properties of the polypropylene such as tensile strength, bending strength, impact strength and the like can be obviously improved, and the thermal stability of the polypropylene is improved.
According to the invention, gamma-aminopropyl triethoxysilane is used for modifying glass fiber, amino is introduced to the surface of the glass fiber to obtain aminated glass fiber, gamma-glycidol ether oxypropyl trimethoxysilane is used for modifying nano titanium dioxide, and epoxy groups are introduced to the surface of nano titanium dioxide to obtain epoxidized titanium dioxide. The amino group on the aminated glass fiber reacts with the epoxy group on the epoxidized titanium dioxide, the epoxy ring is opened, and the hydroxyl group is introduced to obtain the titanium dioxide modified glass fiber. The hydroxyl on the titanium dioxide modified glass fiber and the chlorine atom on the 2-hydroxy-4-chloroacetate-diphenyl ketone are subjected to substitution reaction, and alkenyl and diphenyl ketone derivatives are introduced to obtain the modified glass fiber. The alkenyl, the styrene and the acrylonitrile on the modified glass fiber are polymerized under the action of an initiator to obtain the heat-aging-resistant glass fiber. And mixing the polypropylene resin, the heat-aging-resistant glass fiber, the polyimide, the maleic anhydride grafted polypropylene and the antioxidant, and carrying out melt blending to obtain the heat-aging-resistant glass fiber reinforced PP material for the vehicle.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, through the synergistic effect of the glass fiber and the nano titanium dioxide, the agglomeration of the glass fiber and the nano titanium dioxide is effectively avoided, the nano titanium dioxide can be uniformly dispersed in a polypropylene matrix, and meanwhile, the nano titanium dioxide has excellent ultraviolet aging resistance, so that the aging resistance of the matrix is improved. The benzophenone derivative introduced on the glass fiber can absorb high-energy ultraviolet light, convert the light energy into heat energy for release or convert the heat energy into other harmless energy for release, further improve the effect of ultraviolet absorption, effectively avoid precipitation of the micromolecular benzophenone derivative and improve the ultraviolet aging resistance of the matrix. The hydroxyl groups on the modified glass fiber, the carbonyl groups and the hydroxyl groups on the polyimide can form hydrogen bonds to form acting force, so that the compatibility and the dispersibility are improved, and the comprehensive performance of the matrix is improved. Styrene and acrylonitrile are used as monomers, and the modified glass fiber is polymerized under the action of an initiator, so that the introduced acrylonitrile and styrene can slow down the aging rate of polypropylene, and meanwhile, the acrylonitrile can undergo a grafting reaction with the polypropylene due to the existence of cyano groups, so that the anti-aging purpose is achieved. Acrylonitrile can also be used to reinforce polypropylene, which can significantly improve the strength and toughness of polypropylene, making it have better mechanical properties. In addition, styrene can also improve the processability of polypropylene, making it easier to process. After the acrylonitrile and the styrene are polymerized, the polypropylene has better compatibility with the polypropylene, and the rigidity and the strength of the polypropylene can be effectively improved. The automotive heat-aging-resistant glass fiber reinforced PP material obtained by melt blending the polypropylene resin, the heat-aging-resistant glass fiber, the polyimide, the maleic anhydride grafted polypropylene and the antioxidant is a high-performance composite material, has excellent heat resistance and ageing resistance, and is suitable for manufacturing automobile parts.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by those skilled in the art without making any inventive effort based on the embodiments of the present invention are within the scope of protection of the present invention.
Example 1
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
uniformly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 4200:100:36, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 70 ℃ for 5 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxysilane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 2500:100:40, uniformly mixing, reacting at 60 ℃ for 4 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 4800:100:18, reacting at 85 ℃ for 24 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fibers into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fibers to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:1800:24, reacting in a nitrogen atmosphere at the temperature of 85 ℃ for 12 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at the temperature of 60 ℃ for 12 hours to obtain modified glass fibers;
dispersing modified glass fibers into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fibers to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:700:12:15:1, reacting in a nitrogen atmosphere at the temperature of 75 ℃ for 15 hours, performing rotary steaming after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fibers;
step six, mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:15:10:2:0.1, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 120 ℃ and 140 ℃, 160 ℃, 175 ℃ and 190 ℃, the rotating speed of the double-screw extruder is 120rpm, extruding, and cooling to obtain the heat aging resistant glass fiber reinforced PP material for the vehicle.
Example 2
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
uniformly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 4800:100:40, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 75 ℃ for 4 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxy silane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxy silane is 2800:100:45, uniformly mixing, reacting at 62 ℃ for 3 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 4950:100:22, reacting at 90 ℃ for 20 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fiber into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2100:26, reacting in a nitrogen atmosphere at 90 ℃ for 10 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain modified glass fiber;
dispersing modified glass fibers into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fibers to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:750:18:20:1.8, reacting in a nitrogen atmosphere at the temperature of 80 ℃ for 13 hours, performing rotary steaming after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fibers;
step six, mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:18:12:3:0.15, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 125 ℃, 145 ℃, 165 ℃, 180 ℃ and 195 ℃, the rotating speed of the double-screw extruder is 125rpm, extruding, and cooling to obtain the heat aging resistant glass fiber reinforced PP material for the vehicle.
Example 3
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
uniformly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 5500:100:42, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 75 ℃ for 4 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxysilane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 3200:100:50, uniformly mixing, reacting at 62 ℃ for 3 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 5100:100:26, reacting at 90 ℃ for 22 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fiber into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2100:26, reacting in a nitrogen atmosphere at 90 ℃ for 10 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain modified glass fiber;
dispersing modified glass fibers into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fibers to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:750:18:20:1.8, reacting in a nitrogen atmosphere at the temperature of 80 ℃ for 13 hours, performing rotary steaming after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fibers;
step six, mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:18:12:3:0.15, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 125 ℃, 145 ℃, 165 ℃, 180 ℃ and 195 ℃, the rotating speed of the double-screw extruder is 125rpm, extruding, and cooling to obtain the heat aging resistant glass fiber reinforced PP material for the vehicle.
Example 4
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
uniformly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 5500:100:42, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 75 ℃ for 4 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxysilane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 3200:100:50, uniformly mixing, reacting at 62 ℃ for 3 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 5100:100:26, reacting at 90 ℃ for 22 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fiber into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2400:28, reacting in a nitrogen atmosphere at 90 ℃ for 11 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain modified glass fiber;
dispersing modified glass fibers into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fibers to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:850:22:25:2.5, reacting in a nitrogen atmosphere at the temperature of 80 ℃ for 14 hours, performing rotary steaming after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fibers;
step six, mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:22:14:4:0.25, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 130 ℃, 150 ℃, 165 ℃, 180 ℃ and 200 ℃, the rotating speed of the double-screw extruder is 125rpm, extruding, and cooling to obtain the heat aging resistant glass fiber reinforced PP material for the vehicle.
Example 5
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
step one, after evenly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 6000:100:45, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 80 ℃ for 3 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxysilane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 3500:100:55, uniformly mixing, reacting at 65 ℃ for 2 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 5200:100:30, reacting at 95 ℃ for 18 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fiber into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2500:30, reacting in a nitrogen atmosphere at the temperature of 95 ℃ for 9 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at the temperature of 60 ℃ for 12 hours to obtain modified glass fiber;
dispersing modified glass fibers into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fibers to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:900:25:30:3, reacting in a nitrogen atmosphere at the temperature of 85 ℃ for 12 hours, steaming in a rotary way after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fibers;
step six, mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:25:15:5:0.3, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 135 ℃, 155 ℃, 170 ℃, 185 ℃ and 205 ℃, the rotating speed of the double-screw extruder is 130rpm, extruding, and cooling to obtain the heat aging resistant glass fiber reinforced PP material for the vehicle.
Comparative example 1
The preparation method of the glass fiber reinforced PP material for the automobile heat aging resistance comprises the following steps:
firstly, ultrasonically dispersing glass fibers into toluene, after uniformly dispersing, adding 2-hydroxy-4-chloroacetate-benzophenone, wherein the mass ratio of the glass fibers to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2400:28, reacting in a nitrogen atmosphere at the temperature of 90 ℃ for 11 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain modified glass fibers;
secondly, ultrasonically dispersing the modified glass fiber into toluene, adding styrene, acrylonitrile and an initiator azodiisobutyronitrile, and uniformly mixing, wherein the mass ratio of the modified glass fiber to the toluene to the styrene to the acrylonitrile to the azodiisobutyronitrile is 100:850:22:25:2.5, reacting in a nitrogen atmosphere at the temperature of 80 ℃ for 14 hours, performing rotary evaporation after the reaction is finished, and drying in a vacuum drying oven at the temperature of 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fiber;
mixing polypropylene resin, heat aging resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:22:14:4:0.25, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 130 ℃, 150 ℃, 165 ℃, 180 ℃ and 200 ℃, the rotating speed of the double-screw extruder is 125rpm, extruding, and cooling to obtain the reinforced PP material.
Comparative example 2
The preparation method of the reinforced PP material comprises the following steps:
uniformly mixing deionized water and glass fiber, adding gamma-aminopropyl triethoxysilane, wherein the mass ratio of the deionized water to the glass fiber to the gamma-aminopropyl triethoxysilane is 5500:100:42, stirring and mixing, adjusting the pH to 3 by using an acetic acid solution, wherein the concentration of the acetic acid solution is 1mol/L, reacting at 75 ℃ for 4 hours, filtering after the reaction is finished, washing by using deionized water, and drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the aminated glass fiber;
dispersing nano titanium dioxide into absolute ethyl alcohol in an ultrasonic manner, adding gamma-glycidoxypropyl trimethoxysilane after dispersing uniformly, wherein the mass ratio of the absolute ethyl alcohol to the nano titanium dioxide to the gamma-glycidoxypropyl trimethoxysilane is 3200:100:50, uniformly mixing, reacting at 62 ℃ for 3 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide in a mass ratio of 5100:100:26, reacting at 90 ℃ for 22 hours, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the titanium dioxide modified glass fiber;
dispersing titanium dioxide modified glass fiber into toluene by ultrasonic, adding 2-hydroxy-4-chloroacetate-benzophenone after dispersing uniformly, wherein the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:2400:28, reacting in a nitrogen atmosphere at 90 ℃ for 11 hours, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain modified glass fiber;
mixing polypropylene resin, modified glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant 1010 in a mass ratio of 100:22:14:4:0.25, carrying out melt blending, and carrying out melt blending in a double-screw extruder, wherein the double-screw extruder is provided with five temperature areas according to the advancing direction of materials, the temperature of the temperature areas is 130 ℃, 150 ℃, 165 ℃, 180 ℃ and 200 ℃, the rotating speed of the double-screw extruder is 125rpm, extruding and cooling to obtain the reinforced PP material.
The glass fibers used in the examples and comparative examples of the present invention were purchased from Mount Taishan glass fiber Co., ltd., model number T439; the nano titanium dioxide is purchased from Xuancheng Jinrui new material Co., ltd, the model is JR05, and the average grain diameter is 5nm; polypropylene is purchased from China petroleum Daqing petrochemical company, and the model is T30S; maleic anhydride grafted polypropylene is purchased from Shanghai, a new technology development Co., ltd, model CMG9801; polyimide was purchased from the japanese triple well chemical under the model PIPL6200; other non-illustrated materials and reagents are commercially available.
The PP materials prepared in examples 1-5 and comparative examples 1-2 were used as samples for performance testing, and the performance testing of the relevant samples was as follows:
(1) Mechanical property test: preparing samples with the dimensions of 80mm multiplied by 10mm multiplied by 4mm into sample bars respectively, testing the mechanical properties of the sample bars, testing the tensile strength of the sample bars on a WDW-1000G universal testing machine, testing each sample for 5 times, and taking an average value; the corresponding data for the test are shown in table 1:
TABLE 1
According to the test results of Table 1, the PP materials prepared in examples 1 to 5 of the present invention have excellent mechanical properties. The glass fiber and the nano titanium dioxide have excellent mechanical properties, the agglomeration of the glass fiber and the nano titanium dioxide is effectively avoided through modification, the glass fiber and the nano titanium dioxide can be uniformly dispersed in a polypropylene matrix, the mechanical properties of the matrix can be effectively improved through synergistic effect, and meanwhile, the polypropylene is modified through acrylonitrile and styrene, so that the obtained PP material has excellent tensile strength. Wherein, the tensile strength of the PP material corresponding to the example 5 can reach 72.3MPa. In comparative example 1, the hydroxyl group on the glass fiber directly reacts with the chlorine atom on the 2-hydroxy-4-chloroacetate-benzophenone to obtain the modified glass fiber, the alkenyl group is introduced to perform polymerization reaction, nano titanium dioxide is not introduced, the mechanical property is reduced, and the tensile strength is 63.1MPa. In comparative example 2, the titanium dioxide modified glass fiber and 2-hydroxy-4-chloroacetate-benzophenone are reacted to obtain a modified glass fiber, and the modified glass fiber is directly added into a polypropylene resin matrix, so that acrylonitrile and styrene are not introduced, the mechanical properties are greatly reduced, the tensile strength is greatly reduced, and the tensile strength is 56.4MPa.
(2) And (3) ageing resistance test: preparing the prepared samples into sample bars with the dimensions of 80mm multiplied by 10mm multiplied by 4mm respectively, performing ultraviolet aging and thermal oxidation aging tests, respectively placing the samples in an ultraviolet aging test box and a thermal aging test box for 10 days of aging treatment, using a xenon lamp in the ultraviolet aging process, wherein the power is 35W, the temperature of the thermal aging test is 50 ℃, taking out the samples after the treatment is finished, performing the same mechanical property test as in table 1, testing 5 times for each sample, and taking an average value; the corresponding data for the test are shown in table 2:
TABLE 2
According to the test results of Table 2, the PP materials prepared in examples 1 to 5 of the present invention still have excellent mechanical properties after UV aging and thermal oxidative aging treatment. Wherein, the tensile strength of the PP material corresponding to the example 4 still can reach 60.2MPa after the ultraviolet aging treatment, and the tensile strength of the PP material corresponding to the example 5 still can reach 59.2MPa after the thermal oxidation aging treatment. The PP material corresponding to comparative example 1 had a tensile strength of 43.6MPa after UV aging treatment and a tensile strength of 50.3MPa after thermal oxidative aging treatment. The PP material corresponding to comparative example 2 had a tensile strength of 43.2MPa after UV aging treatment and a tensile strength of 42.4MPa after thermo-oxidative aging treatment. The modification of the PP material can obviously improve the ageing resistance of the PP material, and the heat aging resistance and the ultraviolet ageing resistance are improved.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The preparation method of the glass fiber reinforced PP material for the vehicle is characterized by comprising the following steps of:
modifying glass fiber by using gamma-aminopropyl triethoxy silane, and obtaining amino glass fiber after modification;
dispersing nano titanium dioxide into absolute ethyl alcohol by ultrasonic, adding gamma-glycidol ether oxypropyl trimethoxy silane after uniform dispersion, uniformly mixing, reacting, filtering after the reaction is finished, washing by using absolute ethyl alcohol, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain epoxidized titanium dioxide;
uniformly mixing 1, 4-dioxane, aminated glass fiber and epoxidized titanium dioxide, reacting, filtering after the reaction is finished, washing with deionized water, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain titanium dioxide modified glass fiber;
fourthly, ultrasonically dispersing the titanium dioxide modified glass fiber into toluene, adding 2-hydroxy-4-chloroacetate-benzophenone after uniform dispersion, reacting in a nitrogen atmosphere, filtering after the reaction is finished, washing with absolute ethyl alcohol, and drying at 60 ℃ for 12 hours to obtain the modified glass fiber;
dispersing the modified glass fiber into toluene by ultrasonic, adding styrene, acrylonitrile and an initiator, uniformly mixing, reacting in a nitrogen atmosphere, steaming in a rotary way after the reaction is finished, and drying in a vacuum drying oven at 60 ℃ for 12 hours to obtain the heat-aging-resistant glass fiber;
and step six, mixing the polypropylene resin, the heat-aging-resistant glass fiber, polyimide, maleic anhydride grafted polypropylene and an antioxidant, carrying out melt blending, extruding and cooling to obtain the heat-aging-resistant glass fiber reinforced PP material for the vehicle.
2. The preparation method of the automotive thermal aging resistant glass fiber reinforced PP material according to claim 1, wherein the mass ratio of the 1, 4-dioxane, the aminated glass fiber and the epoxidized titanium dioxide in the third step is 4800-5200:100:18-30.
3. The method for preparing the glass fiber reinforced PP material for the vehicle, according to claim 1, wherein the reaction temperature in the third step is 85-95 ℃ and the reaction time is 18-24 hours.
4. The preparation method of the automotive thermal aging resistant glass fiber reinforced PP material according to claim 1, wherein in the fourth step, the mass ratio of the titanium dioxide modified glass fiber to the toluene to the 2-hydroxy-4-chloroacetate-benzophenone is 100:1800-2500:24-30, the reaction temperature is 85-95 ℃, and the reaction time is 9-12h.
5. The preparation method of the automotive thermal aging resistant glass fiber reinforced PP material according to claim 1, wherein the mass ratio of the modified glass fiber to the toluene to the styrene to the acrylonitrile to the initiator in the fifth step is 100:700-900:12-25:15-30:1-3, the reaction temperature is 75-85 ℃, and the reaction time is 12-15 hours.
6. The method for preparing the glass fiber reinforced PP material for vehicle thermal aging resistance according to claim 1, wherein the initiator in the fifth step is azobisisobutyronitrile.
7. The preparation method of the automotive heat-aging-resistant glass fiber reinforced PP material according to claim 1, wherein the mass ratio of the polypropylene resin to the heat-aging-resistant glass fiber to the polyimide to the maleic anhydride grafted polypropylene to the antioxidant in the sixth step is 100:15-25:10-15:2-5:0.1-0.3.
8. The method for preparing the glass fiber reinforced PP material for the vehicle according to claim 1, wherein the melt blending in the step six is performed in a twin-screw extruder, five temperature areas are arranged in the twin-screw extruder according to the advancing direction of materials, the temperatures of the temperature areas are 120-135 ℃, 140-155 ℃, 160-170 ℃, 175-185 ℃, 190-205 ℃ respectively, and the rotating speed of the twin-screw extruder is 120-130rpm.
9. The method for preparing the glass fiber reinforced PP material for vehicle thermal aging resistance according to claim 1, wherein the antioxidant in the sixth step comprises one or two of antioxidant 168, antioxidant 1010 and antioxidant 1076.
10. A heat aging resistant glass fiber reinforced PP material for vehicles, prepared by the preparation method of the heat aging resistant glass fiber reinforced PP material for vehicles according to any one of claims 1 to 9.
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| CN102226034A (en) * | 2011-05-10 | 2011-10-26 | 同济大学 | Preparation method of glass-fiber-reinforced epoxy resin composite material modified by circuit board recovered powder and nanoparticles |
| CN102863696A (en) * | 2012-09-28 | 2013-01-09 | 合肥杰事杰新材料股份有限公司 | Anti-ultraviolet-aging glass-fiber-reinforced polypropylene composite material and preparation method thereof |
| CN110591230A (en) * | 2019-10-15 | 2019-12-20 | 安徽强茗塑业科技有限公司 | Fiber-reinforced PP material and preparation method thereof |
| KR20200142188A (en) * | 2019-06-12 | 2020-12-22 | 단국대학교 산학협력단 | Method for preparing surface modified glass fiber and glass fiber reinforced polymeric composite material comprising the glass fiber |
| CN112151205A (en) * | 2020-09-25 | 2020-12-29 | 国网河南省电力公司周口供电公司 | Special high-toughness carbon fiber composite core rod for transmission conductor |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102226034A (en) * | 2011-05-10 | 2011-10-26 | 同济大学 | Preparation method of glass-fiber-reinforced epoxy resin composite material modified by circuit board recovered powder and nanoparticles |
| CN102863696A (en) * | 2012-09-28 | 2013-01-09 | 合肥杰事杰新材料股份有限公司 | Anti-ultraviolet-aging glass-fiber-reinforced polypropylene composite material and preparation method thereof |
| KR20200142188A (en) * | 2019-06-12 | 2020-12-22 | 단국대학교 산학협력단 | Method for preparing surface modified glass fiber and glass fiber reinforced polymeric composite material comprising the glass fiber |
| CN110591230A (en) * | 2019-10-15 | 2019-12-20 | 安徽强茗塑业科技有限公司 | Fiber-reinforced PP material and preparation method thereof |
| CN112151205A (en) * | 2020-09-25 | 2020-12-29 | 国网河南省电力公司周口供电公司 | Special high-toughness carbon fiber composite core rod for transmission conductor |
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