CN114752152B - Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof - Google Patents
Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 126
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 68
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 68
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 63
- -1 polypropylene Polymers 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000011049 filling Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title abstract description 17
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 49
- 239000004917 carbon fiber Substances 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 150000001721 carbon Chemical class 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 239000000945 filler Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 abstract description 3
- 239000011347 resin Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229920005606 polypropylene copolymer Polymers 0.000 description 5
- 230000003014 reinforcing effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000003938 response to stress Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
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- 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
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
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- 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
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- 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
- C08J2323/14—Copolymers of propene
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- 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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- C08K2003/265—Calcium, strontium or barium carbonate
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Abstract
The invention discloses a modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and a preparation method thereof. The raw materials of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprise, by mass, 100 parts of polypropylene, 1-10 parts of modified carbon fibers, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer. According to the invention, polypropylene is used as matrix resin, nano calcium carbonate is used as main toughening filler, nano calcium carbonate is deposited on the surface of the carbon fiber after chemical treatment, and the compatilizer is combined with the nano calcium carbonate filler and the polypropylene resin to play a role in enhancing rigidity, so that the composite material has excellent comprehensive mechanical properties.
Description
Technical Field
The invention relates to the technical field of reinforced polypropylene composite materials, in particular to a modified carbon fiber reinforced high-filling nano calcium carbonate reinforced polypropylene composite material and a preparation method thereof.
Background
Polypropylene (PP) is an important general thermoplastic material, and has the characteristics of small density, easiness in forming, low price, rich sources and the like, and is particularly widely applied. However, PP is difficult to use as an engineering material due to its low modulus and poor impact strength. Therefore, the modification of PP is widely and deeply studied at home and abroad, and the nanoparticle toughening PP is one of the current research hot spots, especially Nano calcium carbonate (Nano-CaCO) 3 ) Toughening PP. The addition of the nano calcium carbonate changes the crystallization condition of the composite material and can induce the formation of beta crystal forms which are beneficial to improving the toughness of the composite material. The toughness of the PP composite material can be effectively improved.
Although nano calcium carbonate can effectively improve the impact toughness and rigidity of polypropylene to a certain extent, the rigidity and strength still hardly reach the use level of high-strength engineering plastics. The rigidity and strength of the PP can be greatly improved by adopting a fiber reinforcement mode. Compared with common fiber materials such as glass fiber, the Carbon Fiber (CF) is a reinforcing material with excellent performance, and has the advantages of high modulus, high strength, good corrosion resistance, small density and the like. However, research shows that the CF as a rigid material can greatly improve the rigidity mechanical indexes such as the tensile strength, the flexural modulus and the like of the composite material, and the fracture is still brittle fracture, so that the improvement on the toughness indexes such as the impact strength and the like of the material is small.
The prior art shows that the carbon fiber reinforcement and the nano calcium carbonate toughening have complementarity to improve the comprehensive mechanical properties of the polypropylene composite material, and the combination of the carbon fiber reinforcement and the nano calcium carbonate toughening can realize the high-strength and high-toughness modification of the polypropylene composite material. However, because the interfaces of the carbon fiber, the nano calcium carbonate and the polypropylene are mutually incompatible, even if the corresponding compatilizer is added, the carbon fiber, the nano calcium carbonate and the polypropylene are difficult to combine with each other, and the comprehensive performance of the composite material is affected. Therefore, the surface modification of the carbon fiber, the uniform dispersion of the carbon fiber and the high-filling nano calcium carbonate in the PP matrix and the interfacial compatibility are technical problems to be solved urgently.
Disclosure of Invention
In view of the above, the present invention provides a modified carbon fiber reinforced high-filling nano calcium carbonate reinforced polypropylene composite material, which has excellent mechanical comprehensive properties.
The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material is characterized by comprising, by mass, 100 parts of polypropylene, 1-10 parts of modified carbon fiber, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer. Wherein the modified carbon fiber is prepared by the following method:
(1) Immersing the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating for 60 minutes at 90-120 ℃, washing and drying;
(2) Immersing the carbon fiber with oxidized surface in saturated calcium hydroxide solution, injecting carbon dioxide gas into the reactor, carrying out ultrasonic stirring, controlling bubbling speed to react for 30-120 minutes, taking out the carbon fiber, washing and drying to obtain the modified carbon fiber, wherein nano calcium carbonate particles grow on the surface crystal of the modified carbon fiber.
Preferably, the polypropylene is homo-polypropylene and/or co-polypropylene;
preferably, the compatibilizer is one or at least two of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer, and maleic anhydride grafted ethylene-vinyl acetate copolymer;
the invention also provides a preparation method of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material, and the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material prepared by the preparation method has excellent mechanical comprehensive properties.
The preparation method of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprises the following steps:
mixing 100 parts of polypropylene, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer raw materials, and then placing the mixture into a main feeding cylinder of a granulator to be mixed with 1-10 parts of modified carbon fiber for granulation extrusion. Wherein, the raw material mixing method adopts a high-speed stirrer to mix for 3-5 min;
preferably, the granulator uses a double-screw granulator, the modified carbon fibers enter from a fiber inlet and are granulated by the double-screw granulator, the temperature of one region of the double-screw granulator is 200-210 ℃, the temperature of two regions of the double-screw granulator is 205-210 ℃, the temperature of three regions of the double-screw granulator is 210-215 ℃, the temperature of four regions of the double-screw granulator is 215-220 ℃, the temperature of five regions of the double-screw granulator is 220-225 ℃, the temperature of six regions of the double-screw granulator is 220-230 ℃, and the temperature of a machine head of the double-screw granulator is 230-235 ℃.
Firstly, oxidizing the surface of carbon fiber to make the inert surface of the carbon fiber rich in carboxyl, hydroxyl, epoxy and other electronegative groups, adsorbing calcium ions in saturated calcium hydroxide solution, and further forming nano calcium carbonate precipitate with the introduced carbon dioxide gas. The modified carbon fiber surface is deposited with a layer of nano calcium carbonate particles, which can interact with nano calcium carbonate filler and compatilizer in the polypropylene matrix to improve the dispersion effect, and meanwhile, the modified carbon fiber surface has the sand bag effect of the nano calcium carbonate particles, and the stress response of the carbon fiber surface is changed from rigidity to toughness, so that the rigidity and toughness mechanical property of the whole system are improved. Therefore, the invention has the following beneficial effects:
1. the addition of the nano calcium carbonate and the modified carbon fiber plays a role in synergistic modification on polypropylene, and the high-rigidity and high-toughness modified PP-based composite material is obtained, so that the composite material has the use value of high-performance engineering materials.
2. The nano calcium carbonate is deposited on the surface of the carbon fiber, so that the carbon fiber has the toughness reinforcing effect while maintaining the excellent modification reinforcing effect, and can interact with the highly filled nano calcium carbonate to improve the dispersibility and reinforcing effect.
Detailed Description
The technical scheme of the invention is further described below by combining examples.
Example 1
The preparation raw materials of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprise the following components in parts by mass:
immersing the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 110 ℃ for 60 minutes, washing and drying; immersing the carbon fiber with oxidized surface in saturated calcium hydroxide solution, injecting carbon dioxide gas into the reactor, carrying out ultrasonic stirring, controlling the bubbling speed to be 20ml/min, reacting for 60 minutes, taking out the carbon fiber, washing and drying to obtain the modified carbon fiber, wherein nano calcium carbonate particles grow on the surface crystals of the modified carbon fiber.
The preparation method comprises the steps of mixing the copolymer polypropylene, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, enabling modified carbon fibers to enter from a fiber inlet, and granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 200 ℃, the temperature of a second area of the screw extruder is 205 ℃, the temperature of a third area of the screw extruder is 210 ℃, the temperature of a fourth area of the screw extruder is 215 ℃, the temperature of a fifth area of the screw extruder is 220 ℃, the temperature of a sixth area of the screw extruder is 220 ℃, the temperature of a machine head is 230 ℃, and an extruded strip is cooled to room temperature through a circulating water tank, and enters a granulator for granulating after being dried by a blower, so that the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material is obtained.
Example 2
The preparation raw materials of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprise the following components in parts by mass:
immersing the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 90 ℃ for 60 minutes, washing and drying; immersing the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, carrying out ultrasonic stirring, controlling the bubbling speed to be 30ml/min, reacting for 90 minutes, taking out the carbon fiber, washing and drying to obtain the modified carbon fiber, wherein nano calcium carbonate particles grow on the surface crystals of the modified carbon fiber.
The preparation method comprises the steps of mixing the copolymer polypropylene, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, then enabling modified carbon fibers to enter from a fiber inlet, and granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 210 ℃, the temperature of a second area of the screw extruder is 210 ℃, the temperature of a third area of the screw extruder is 215 ℃, the temperature of a fourth area of the screw extruder is 220 ℃, the temperature of a fifth area of the screw extruder is 225 ℃, the temperature of a sixth area of the screw extruder is 230 ℃, the temperature of a machine head is 235 ℃, extruding strips are cooled to room temperature by a circulating water tank, and then enter a granulator for granulating after being dried by the blower, and finally obtaining the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
Example 3
The preparation raw materials of the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprise the following components in parts by mass:
immersing the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 120 ℃ for 60 minutes, washing and drying; immersing the carbon fiber with oxidized surface in saturated calcium hydroxide solution, injecting carbon dioxide gas into the reactor, carrying out ultrasonic stirring, controlling the bubbling speed to be 30ml/min, reacting for 120 minutes, taking out the carbon fiber, washing and drying to obtain the modified carbon fiber, wherein nano calcium carbonate particles grow on the surface crystals of the modified carbon fiber.
The preparation method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, allowing modified carbon fibers to enter from a fiber inlet, and granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 210 ℃, the temperature of a second area of the screw extruder is 210 ℃, the temperature of a third area of the screw extruder is 215 ℃, the temperature of a fourth area of the screw extruder is 220 ℃, the temperature of a fifth area of the screw extruder is 225 ℃, the temperature of a sixth area of the screw extruder is 230 ℃, the temperature of a machine head is 235 ℃, extruding strips are cooled to room temperature by a circulating water tank, and then enter a granulator for granulating after being dried by the circulating water tank, and finally obtaining the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
Comparative example 1
The carbon fiber reinforced propylene composite material comprises the following raw materials in parts by mass:
100 parts of polypropylene copolymer
10 parts of carbon fiber
Maleic anhydride grafted polypropylene 5 parts
The preparation method comprises the steps of mixing the polypropylene copolymer and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, feeding carbon fibers into the mixture from a fiber inlet, and granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 210 ℃, the temperature of a second area of the screw extruder is 210 ℃, the temperature of a third area of the screw extruder is 215 ℃, the temperature of a fourth area of the screw extruder is 220 ℃, the temperature of a fifth area of the screw extruder is 225 ℃, the temperature of a sixth area of the screw extruder is 230 ℃, the temperature of a machine head is 235 ℃, an extruded strip is cooled to room temperature by a circulating water tank, and then enters a granulator for granulating after being dried by a blower, the extruded strip is cooled to room temperature by the circulating water tank, and then enters the granulator for granulating to obtain the carbon fiber reinforced polypropylene composite material.
Comparative example 2
The preparation raw materials of the high-filling nano calcium carbonate polypropylene composite material comprise the following components in parts by mass:
100 parts of polypropylene copolymer
20 parts of nano calcium carbonate
Maleic anhydride grafted polypropylene 5 parts
Mixing the copolymer polypropylene, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 210 ℃, the temperature of a second area of the screw extruder is 210 ℃, the temperature of a third area of the screw extruder is 215 ℃, the temperature of a fourth area of the screw extruder is 220 ℃, the temperature of a fifth area of the screw extruder is 225 ℃, the temperature of a sixth area of the screw extruder is 230 ℃, the temperature of a machine head is 235 ℃, cooling an extruded strip to room temperature by a circulating water tank, drying by a blower, granulating by a granulator, cooling the extruded strip to room temperature by the circulating water tank, drying by the blower, and granulating by the granulator to obtain the high-filling nano calcium carbonate polypropylene composite material.
Comparative example 3
The preparation raw materials of the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprise the following components in parts by mass:
the preparation method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, allowing carbon fibers to enter from a fiber inlet, and granulating by the double-screw extruder, wherein the temperature of a first area of the screw extruder is 210 ℃, the temperature of a second area of the screw extruder is 210 ℃, the temperature of a third area of the screw extruder is 215 ℃, the temperature of a fourth area of the screw extruder is 220 ℃, the temperature of a fifth area of the screw extruder is 225 ℃, the temperature of a sixth area of the screw extruder is 230 ℃, the temperature of a head of the screw extruder is 235 ℃, an extruded strip is cooled to room temperature by a circulating water tank, and enters a granulator for granulating after being dried by the circulating water tank, and the extruded strip enters the granulator for granulating to obtain the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
Mechanical property test and comparison:
examples 1-3 are modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite materials prepared according to the formula and the process of the invention, comparative example 1 is an unmodified carbon fiber direct blending reinforced polypropylene material, comparative example 2 is a high-filling nano calcium carbonate polypropylene composite material without carbon fiber added, and comparative example 3 is an unmodified carbon fiber blended with high-filling nano calcium carbonate and polypropylene.
From the table above, the sample of comparative example 1 is carbon fiber reinforced PP, and the tensile strength and bending strength of the rigidity mechanical index are obviously improved compared with those of pure PP (20-30 MPa), but the notch impact strength is smaller; the comparative example 2 is a high-filling (20%) nano calcium carbonate polypropylene composite material, the toughness notch impact strength is greatly improved, but the tensile strength and the bending strength are slightly reduced and are not greatly changed compared with pure PP; under the same conditions of other process formulations, the reinforcing effect of the unmodified carbon fiber of the example 3 is obviously improved in rigidity and toughness strength compared with that of the comparative example 3. In conclusion, the technical scheme provided by the invention enables the nano calcium carbonate and the carbon fiber to have a synergistic modification effect on polypropylene, and the high-rigidity and high-toughness modified PP-based composite material is obtained, so that the PP-based composite material has the use value of high-performance engineering materials.
The applicant states that the detailed process equipment and process flows of the present invention are described by the above examples, but the present invention is not limited to, i.e., does not mean that the present invention must be practiced in dependence upon, the above detailed process equipment and process flows. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (4)
1. The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material is characterized by comprising, by mass, 100 parts of polypropylene, 1-10 parts of modified carbon fiber, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer:
wherein, the modified carbon fiber is prepared by the following method:
(1) Immersing the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating for 60 minutes at 90-120 ℃, washing and drying;
(2) Immersing the carbon fiber with oxidized surface in saturated calcium hydroxide solution, injecting carbon dioxide gas into the reactor, carrying out ultrasonic stirring, controlling bubbling speed to react for 30-120 minutes, taking out the carbon fiber, washing and drying to obtain the modified carbon fiber, wherein nano calcium carbonate particles grow on the surface crystal of the modified carbon fiber.
2. The modified carbon fiber reinforced high-filled nano calcium carbonate polypropylene composite material according to claim 1, wherein the polypropylene is homo-polypropylene and/or co-polypropylene.
3. The modified carbon fiber reinforced high-filled nano calcium carbonate polypropylene composite material according to claim 1, wherein the compatibilizer is one or more of a combination of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer, and maleic anhydride grafted ethylene-vinyl acetate copolymer.
4. A method for preparing the modified carbon fiber reinforced high-filled nano calcium carbonate polypropylene composite material according to claim 1, which is characterized by comprising the following steps:
mixing raw materials comprising 100 parts of polypropylene, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer, placing the raw materials in a main feeding cylinder of a granulator, and blending, granulating and extruding the raw materials with 1-10 parts of modified carbon fiber; the granulator uses a double-screw granulator, modified carbon fibers enter from a fiber inlet and are granulated by the double-screw granulator, wherein the temperature of one region of the double-screw granulator is 200-210 ℃, the temperature of two regions of the double-screw granulator is 205-210 ℃, the temperature of three regions of the double-screw granulator is 210-215 ℃, the temperature of four regions of the double-screw granulator is 215-220 ℃, the temperature of five regions of the double-screw granulator is 220-225 ℃, the temperature of six regions of the double-screw granulator is 220-230 ℃, and the temperature of a machine head of the double-screw granulator is 230-235 ℃.
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KR20080061077A (en) * | 2006-12-28 | 2008-07-02 | 호남석유화학 주식회사 | Fiber-reinforced polypropylene resin composition |
CN104151708A (en) * | 2014-08-20 | 2014-11-19 | 苏州德宝凯迪新材料有限公司 | Carbon fiber strengthened polypropylene composite material and preparation method thereof |
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CN104151708A (en) * | 2014-08-20 | 2014-11-19 | 苏州德宝凯迪新材料有限公司 | Carbon fiber strengthened polypropylene composite material and preparation method thereof |
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