CN114752152A - 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
- Publication number
- CN114752152A CN114752152A CN202210623967.XA CN202210623967A CN114752152A CN 114752152 A CN114752152 A CN 114752152A CN 202210623967 A CN202210623967 A CN 202210623967A CN 114752152 A CN114752152 A CN 114752152A
- Authority
- CN
- China
- Prior art keywords
- carbon fiber
- calcium carbonate
- nano calcium
- polypropylene
- modified carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 130
- 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 65
- -1 polypropylene Polymers 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000011049 filling Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 52
- 239000004917 carbon fiber Substances 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 150000001721 carbon Chemical class 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 13
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 229920001911 maleic anhydride grafted polypropylene Polymers 0.000 claims description 10
- 238000002791 soaking 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 8
- 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
- 230000003647 oxidation Effects 0.000 claims description 6
- 238000007254 oxidation reaction Methods 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
- 230000003179 granulation Effects 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 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
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- 229920001577 copolymer Polymers 0.000 claims description 2
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 2
- 238000001125 extrusion Methods 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
- 238000005728 strengthening Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 9
- 229920005606 polypropylene copolymer Polymers 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 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 Chemical group 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
- 239000013078 crystal Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002105 nanoparticle Substances 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
- 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
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
-
- 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
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- 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
- 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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K7/06—Elements
-
- 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
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 a compatilizer. The invention takes polypropylene as matrix resin, nano calcium carbonate as main toughening filler, carbon fiber is chemically treated and then the nano calcium carbonate is deposited on the surface, and the compatilizer is mutually combined with the nano calcium carbonate filler and the polypropylene resin to play a role in strengthening 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, has the characteristics of low density, easiness in molding, low price, rich sources and the like, and is particularly widely applied. However, PP is difficult to be used as an engineering material due to its low modulus and poor impact strength. Therefore, extensive and intensive research is carried out on the modification of PP at home and abroad, and the Nano-particle toughened PP is one of the current research hotspots, in particular to 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 a beta crystal form which is beneficial to improving the toughness of the composite material. Can effectively improve the toughness of the PP composite material.
Although the nano calcium carbonate can effectively improve the impact toughness of the polypropylene and also can improve the rigidity to a certain extent, the rigidity and the strength of the polypropylene still can hardly reach the use level of high-strength engineering plastics. The rigidity and the strength of the PP can be greatly improved by adopting a fiber reinforcement mode. Compared with common fiber materials such as glass fiber and the like, Carbon Fiber (CF) is a reinforced 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 although the CF rigid material can greatly improve the rigidity mechanical indexes such as tensile strength, flexural modulus and the like of the composite material, the fracture is brittle fracture, and the improvement on the toughness indexes such as impact strength and the like of the material is small.
It can be seen from the above prior art that the carbon fiber reinforcement and the nano calcium carbonate toughening have complementarity for improving 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 high-toughness modification of the polypropylene composite material. However, the interfaces of the carbon fiber, the nano calcium carbonate and the polypropylene are mutually incompatible, and the carbon fiber, the nano calcium carbonate and the polypropylene are difficult to combine with each other even if corresponding compatilizers are added, so that the comprehensive performance of the composite material is influenced. Therefore, the technical problem to be solved is to realize the uniform dispersion and interface compatibility of the carbon fiber and the high-filling nano calcium carbonate in the PP matrix by carrying out surface modification on the carbon fiber.
Disclosure of Invention
In view of the above, the 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 100 parts of polypropylene, 1-10 parts of modified carbon fiber, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer by mass. Wherein the modified carbon fiber is prepared by the following method:
(1) soaking the carbon fiber in concentrated nitric acid for liquid-phase oxidation, treating at 90-120 ℃ for 60 minutes, washing and drying;
(2) soaking the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, ultrasonically stirring, controlling the 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 of the modified carbon fiber in a crystallization manner.
Preferably, the polypropylene is homo-polypropylene and/or co-polypropylene;
preferably, the compatilizer 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, placing the mixture in a main feeding cylinder of a granulator, and blending with 1-10 parts of modified carbon fibers for granulation and 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 then are granulated by the double-screw granulator, the temperature of the first zone of the double-screw granulator is 200-210 ℃, the temperature of the second zone of the double-screw granulator is 205-210 ℃, the temperature of the third zone of the double-screw granulator is 210-215 ℃, the temperature of the fourth zone of the double-screw granulator is 215-220 ℃, the temperature of the fifth zone of the double-screw granulator is 220-225 ℃, the temperature of the sixth zone of the double-screw granulator is 220-230 ℃, and the temperature of the head of the double-screw granulator is 230-235 ℃.
The method comprises the steps of firstly carrying out oxidation treatment on the surface of the carbon fiber to ensure that the inert surface of the carbon fiber is rich in electronegative groups such as carboxyl, hydroxyl and epoxy, absorbing calcium ions in a saturated calcium hydroxide solution, and further forming nano calcium carbonate precipitates with introduced carbon dioxide gas. The modified carbon fiber surface is deposited with a layer of nano calcium carbonate particles, the nano calcium carbonate particles can interact with nano calcium carbonate filler and compatilizer in a polypropylene matrix to improve the dispersion effect, meanwhile, the nano calcium carbonate particles have the sand bag effect, and the stress response of the carbon fiber surface is converted from rigidity to toughness, so that the rigidity and toughness mechanical properties 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 has a synergistic modification effect on the polypropylene, and the high-rigidity high-toughness modified PP-based composite material is obtained, so that the PP-based composite material has the use value of a high-performance engineering material.
2. The carbon fiber surface is deposited with the nano calcium carbonate, so that the carbon fiber surface has the effect of toughness enhancement while maintaining the excellent modification and enhancement effect, and can interact with the highly filled nano calcium carbonate to improve the dispersibility and the enhancement effect.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples.
Example 1
The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprises the following raw materials in parts by mass:
soaking carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 110 deg.C for 60 min, washing, and drying; soaking the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, ultrasonically 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 are crystallized and grown on the surface of the modified carbon fiber.
The method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine at a high speed for 5 minutes, placing the mixture into a main feeding cylinder of a double-screw extruder, feeding modified carbon fibers into the main feeding cylinder from a fiber inlet, granulating the mixture by the double-screw extruder, wherein the temperature of a first zone of the screw extruder is 200 ℃, the temperature of a second zone of the screw extruder is 205 ℃, the temperature of a third zone of the screw extruder is 210 ℃, the temperature of a fourth zone of the screw extruder is 215 ℃, the temperature of a fifth zone of the screw extruder is 220 ℃, the temperature of a sixth zone of the screw extruder is 220 ℃, the temperature of a machine head of the double-screw extruder is 230 ℃, cooling extruded strips to room temperature through a circulating water tank, drying the extruded strips by a blower, and then feeding the extruded strips into a granulator for granulation to obtain the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
Example 2
The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprises the following raw materials in parts by mass:
soaking carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 90 deg.C for 60 min, washing, and drying; soaking the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, ultrasonically 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 are crystallized and grown on the surface of the modified carbon fiber.
The method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine at a high speed for 5 minutes, placing the mixture into a main feeding cylinder of a double-screw extruder, feeding modified carbon fibers into the double-screw extruder from a fiber inlet, granulating the mixture by the double-screw extruder, wherein the first-zone temperature of the screw extruder is 210 ℃, the second-zone temperature of the screw extruder is 210 ℃, the third-zone temperature of the screw extruder is 215 ℃, the fourth-zone temperature of the screw extruder is 220 ℃, the fifth-zone temperature of the screw extruder is 225 ℃, the sixth-zone temperature of the screw extruder is 230 ℃ and the head temperature of the double-screw extruder is 235 ℃, cooling extruded strips to room temperature through a circulating water tank, drying the extruded strips by a blower, then granulating the extruded strips by a granulator, and drying the extruded strips by the blower, finally granulating the extruded strips by the granulator to obtain the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
Example 3
The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprises the following raw materials in parts by mass:
soaking the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 120 ℃ for 60 minutes, washing and drying; soaking the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, ultrasonically 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 are crystallized and grown on the surface of the modified carbon fiber.
The method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene at a high speed in a high-speed machine for 5 minutes, placing the mixture into a main feeding cylinder of a double-screw extruder, feeding modified carbon fibers from a fiber inlet, granulating by the double-screw extruder, wherein the temperature of a first zone of the screw extruder is 210 ℃, the temperature of a second zone of the screw extruder is 210 ℃, the temperature of a third zone of the screw extruder is 215 ℃, the temperature of a fourth zone of the screw extruder is 220 ℃, the temperature of a fifth zone of the screw extruder is 225 ℃, the temperature of a sixth zone of the screw extruder is 230 ℃, the temperature of a machine head of the double-screw extruder is 235 ℃, cooling extruded strips to room temperature through a circulating water tank, drying the extruded strips through a blower, and granulating in a granulator to obtain 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 portions of polypropylene copolymer
10 parts of carbon fiber
5 parts of maleic anhydride grafted polypropylene
Mixing the polypropylene copolymer and the maleic anhydride grafted polypropylene at a high speed in a high-speed machine for 5 minutes, placing the mixture in a main feeding cylinder of a double-screw extruder, feeding carbon fibers from a fiber inlet, and then granulating by the double-screw extruder, wherein the temperature of a first zone of the screw extruder is 210 ℃, the temperature of a second zone of the screw extruder is 210 ℃, the temperature of a third zone of the screw extruder is 215 ℃, the temperature of a fourth zone of the screw extruder is 220 ℃, the temperature of a fifth zone of the screw extruder is 225 ℃, the temperature of a sixth zone of the screw extruder is 230 ℃ and the temperature of a machine head of the screw extruder is 235 ℃, cooling extruded strips to room temperature through a circulating water tank, drying the extruded strips through a blower, feeding the dried strips into a granulator for granulation, and obtaining 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 portions of polypropylene copolymer
20 portions of nano calcium carbonate
5 parts of maleic anhydride grafted polypropylene
Mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene in a high-speed machine at a high speed for 5 minutes, then placing the mixture into a main feeding cylinder of a double-screw extruder, and granulating by the double-screw extruder, wherein the temperature of a first zone of the screw extruder is 210 ℃, the temperature of a second zone of the screw extruder is 210 ℃, the temperature of a third zone of the screw extruder is 215 ℃, the temperature of a fourth zone of the screw extruder is 220 ℃, the temperature of a fifth zone of the screw extruder is 225 ℃, the temperature of a sixth zone of the screw extruder is 230 ℃ and the temperature of a machine head of the screw extruder is 235 ℃, cooling the extruded strips to room temperature by a circulating water tank, drying the extruded strips by a blower, then granulating the extruded strips by a granulator, drying the extruded strips by the circulating water tank to room temperature, and granulating the extruded strips by the blower, thus obtaining the high-filling nano calcium carbonate polypropylene composite material.
Comparative example 3
The carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material comprises the following raw materials in parts by mass:
the method comprises the steps of mixing the polypropylene copolymer, the nano calcium carbonate and the maleic anhydride grafted polypropylene at a high speed in a high-speed machine for 5 minutes, placing the mixture into a main feeding cylinder of a double-screw extruder, feeding the carbon fibers from a fiber inlet, and then granulating by the double-screw extruder, wherein the temperature of a first zone of the screw extruder is 210 ℃, the temperature of a second zone of the screw extruder is 210 ℃, the temperature of a third zone of the screw extruder is 215 ℃, the temperature of a fourth zone of the screw extruder is 220 ℃, the temperature of a fifth zone of the screw extruder is 225 ℃, the temperature of a sixth zone of the screw extruder is 230 ℃, the temperature of a machine head of the screw extruder is 235 ℃, cooling extruded strips to room temperature through a circulating water tank, drying the extruded strips through a blower, then granulating the extruded strips through a granulator, and finally granulating the extruded strips to obtain the carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material.
And (3) mechanical property test comparison:
the examples 1-3 are modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite materials prepared according to the formula and the process, the comparative example 1 is an unmodified carbon fiber direct blending reinforced polypropylene material, the comparative example 2 is a high-filling nano calcium carbonate polypropylene composite material without carbon fiber, and the comparative example 3 is the blending of unmodified carbon fiber, high-filling nano calcium carbonate and polypropylene.
As can be seen from the table above, the sample of comparative example 1 is carbon fiber reinforced PP, the tensile strength and the bending strength of the rigidity mechanical index of the sample are obviously improved compared with pure PP (20-30 MPa), but the notch impact strength is small; the comparative example 2 is a high-filling (20%) nano calcium carbonate polypropylene composite material, the toughness notch impact strength of which is greatly improved, but the tensile strength and the bending strength of which are slightly changed or even slightly reduced compared with pure PP; under the same conditions of other process formulas, the reinforcing effect of the carbon fiber in the example 3 is obviously improved in rigidity and toughness strength compared with the reinforcing effect of the carbon fiber which is not modified in 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 the polypropylene, and the high-rigidity high-toughness modified PP-based composite material is obtained, so that the PP-based composite material has the use value of a high-performance engineering material.
The applicant states that the present invention is illustrated by the above examples to show the detailed process equipment and process flow of the present invention, but the present invention is not limited to the above detailed process equipment and process flow, i.e. it does not mean that the present invention must be implemented by relying on the above detailed process equipment and process flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (5)
1. The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material is characterized by comprising 100 parts of polypropylene, 1-10 parts of modified carbon fiber, 15-30 parts of nano calcium carbonate and 1-5 parts of compatilizer by mass.
2. The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material according to claim 1, wherein the modified carbon fiber is prepared by the following method:
(1) soaking the carbon fiber in concentrated nitric acid for liquid phase oxidation, treating at 90-120 ℃ for 60 minutes, washing and drying;
(2) soaking the carbon fiber with the oxidized surface in a saturated calcium hydroxide solution, injecting carbon dioxide gas into a reactor, ultrasonically stirring, controlling the 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 of the modified carbon fiber in a crystallization manner.
3. The modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material according to claim 1, wherein the polypropylene is homo-polypropylene and/or co-polypropylene.
4. The modified carbon fiber reinforced highly filled nano calcium carbonate polypropylene composite according to claim 1, wherein the compatibilizer is one or more of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene-octene copolymer, and maleic anhydride grafted ethylene-vinyl acetate copolymer.
5. A method for preparing the modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material as claimed in 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 mixture in a main feeding cylinder of a granulator, and blending the mixture with 1-10 parts of modified carbon fiber for granulation and extrusion; the granulator uses a double-screw granulator, modified carbon fibers enter from a fiber inlet, and then granulation is carried out through the double-screw granulator, the temperature of a first zone of the double-screw granulator is 200-210 ℃, the temperature of a second zone of the double-screw granulator is 205-210 ℃, the temperature of a third zone of the double-screw granulator is 210-215 ℃, the temperature of a fourth zone of the double-screw granulator is 215-220 ℃, the temperature of a fifth zone of the double-screw granulator is 220-225 ℃, the temperature of a sixth zone of the double-screw granulator is 220-230 ℃, and the temperature of a head of the double-screw granulator is 230-235 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210623967.XA CN114752152B (en) | 2022-06-02 | 2022-06-02 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210623967.XA CN114752152B (en) | 2022-06-02 | 2022-06-02 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114752152A true CN114752152A (en) | 2022-07-15 |
| CN114752152B CN114752152B (en) | 2024-04-12 |
Family
ID=82337077
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210623967.XA Active CN114752152B (en) | 2022-06-02 | 2022-06-02 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114752152B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2022
- 2022-06-02 CN CN202210623967.XA patent/CN114752152B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114752152B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105385124B (en) | Carbon fiber enhanced polylactic acid 3D printing material and preparation method thereof | |
| CN102181150B (en) | Waste carbon fiber reinforced nylon 6 composite material and preparation method thereof | |
| CN111087805B (en) | Supercritical fluid continuous extrusion high-performance recyclable PA (polyamide) foam material and preparation method thereof | |
| CN105153654A (en) | Fiber-reinforced polyester composition and preparation method thereof | |
| CN110791018A (en) | Modified sepiolite polymer composite material and preparation method and application thereof | |
| CN102146183B (en) | Beta nucleating agent for polypropylene, preparation method thereof, and beta polypropylene pipe special material prepared from same | |
| CN102942790A (en) | High temperature-resistant high-strength polyphenylene sulfide-based reactively reinforced and toughened composite material | |
| CN102776597A (en) | High-strength and high-modulus polyvinyl alcohol fiber and melt spinning method of high-strength and high-modulus polyvinyl alcohol fiber | |
| CN108467544B (en) | High-strength, high-rigidity and transparent modified polypropylene composite material and preparation method thereof | |
| CN101691445A (en) | Alcoholysis resistant PA66 composite material used for automobiles and preparation method thereof | |
| CN109337198B (en) | High-rigidity glass fiber reinforced polypropylene material and preparation equipment and preparation method thereof | |
| CN114507395A (en) | Corrosion-resistant glass fiber reinforced polypropylene material and preparation method thereof | |
| CN114752152B (en) | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof | |
| CN113788914A (en) | SEBS/AT composite toughening agent, preparation method thereof and high-performance PET/PA6 foam material | |
| CN111004436B (en) | Toughened isotactic polypropylene composite material and preparation method thereof | |
| CN112552595A (en) | High-strength high-toughness glass fiber reinforced polypropylene material and preparation method thereof | |
| CN106633710A (en) | Single-step-prepared halogen-free flame-resistant long glass fiber reinforced PLA composite material and preparation method thereof | |
| CN106854310A (en) | A kind of preparation method of PP composite material | |
| CN110669335A (en) | PA66 composite material with excellent fluidity and low-temperature toughness for cable ties and preparation method thereof | |
| CN114213686B (en) | Low-warpage glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN109206821B (en) | Polypropylene composite material and preparation method thereof | |
| CN104177793A (en) | PBT (polybutylene terephthalate) toughener as well as preparation method and application thereof | |
| CN111320869A (en) | High-temperature-resistant environment-friendly halogen-free fiber reinforced nylon 6T consumable for 3D printing and preparation method thereof | |
| JPS6042413A (en) | Glass fiber-reinforced polyolefin resin composition and its production | |
| CN109705430A (en) | The filling master batch preparation process of plastics tensile strength and elongation at break can be improved |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |