CN104151708A - Carbon fiber strengthened polypropylene composite material and preparation method thereof - Google Patents
Carbon fiber strengthened polypropylene composite material and preparation method thereof Download PDFInfo
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- CN104151708A CN104151708A CN201410410747.4A CN201410410747A CN104151708A CN 104151708 A CN104151708 A CN 104151708A CN 201410410747 A CN201410410747 A CN 201410410747A CN 104151708 A CN104151708 A CN 104151708A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a carbon fiber strengthened polypropylene composite material and a preparation method thereof. The carbon fiber strengthened polypropylene composite material comprises the following raw materials: 39-97 parts of polypropylene, 1-40 parts of carbon fiber, 1-8 parts of modifier and 1-10 parts of compatilizer, and the modifier comprises a tetrafluoroborate ionic liquid. The modifier containing the tetrafluoroborate ionic liquid enables surface modification of the carbon fiber, carbon fiber modification effect can be greatly increased. The modified carbon fiber is added in polypropylene, enhance effect of carbon fiber to polypropylene is increased, the composite material has high tensile strength, high flexural modulus, strong notch impact strength and high comprehensive mechanical property.
Description
Technical field
The present invention relates to the technical field of carbon fiber, relate in particular to a kind of carbon fiber reinforced polypropylene compound material and preparation method thereof.
Background technology
Carbon fiber (carbon fiber is called for short CF) is the high strength of a kind of carbon content more than 95%, the tencel material of high modulus fibre.It is to be piled up along fiber axial direction due and formed by organic fibres such as flake graphite crystallites, through carbonization and graphitization processing and the micro crystal graphite material obtaining.Carbon fiber " soft outside but hard inside ", quality is lighter than metallic aluminium, but intensity is higher than iron and steel, and has characteristic corrosion-resistant, high-modulus, defence and military and civilian aspect be all important materials.
Because carbon fiber has high strength, low density, high-temperature resistant, the advantage such as water-fast, corrosion-resistant, can be used as a kind of good strongthener.Carbon fiber is added into the high polymer composite material that superpolymer is enhanced, can obviously improves the over-all properties of superpolymer.
Polypropylene (PP), is a kind of thermoplastic resin being made by propylene polymerization, and the absolute value of Mechanical Properties of PP is higher than polyethylene, thereby the market share in plastic industry progressively improves.In prior art carbon fiber Reinforced Polypropylene material due to carbon fiber and polyacrylic consistency poor, for improve carbon fiber in polypropylene the associativity in mutually, conventionally to carry out surface modification to carbon fiber.In prior art, be often subject to the effects limit such as properties-correcting agent, the mechanical property of the carbon fiber Reinforced Polypropylene of preparation is poor.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of carbon fiber reinforced polypropylene compound material, and this matrix material has good mechanical property.
A kind of carbon fiber reinforced polypropylene compound material, its raw material comprises 39～97 parts of polypropylene, 1～40 part of carbon fiber, 1～8 part of properties-correcting agent and 1～10 part of compatilizer according to mass parts, and described properties-correcting agent comprises tetrafluoroborate ion liquid.
Properties-correcting agent in the present invention is specially tetrafluoroborate ion liquid or the mixture with polyacrylonitrile.A tetrafluoro borate is a kind of in a tetrafluoro borate that contains vinyl imidazole base, propenyl imidazolyl, acrylonitrile group imidazolyl, styryl imidazolyl, epoxy group(ing) imidazolyl or at least two kinds.What deserves to be explained is, described each substituent tetrafluoroborate ion liquid here all adopts can be bought on market, and the present invention does not do any improvement for it.
Wherein, raw material also comprises in 0.05～3 part of processing aid of raw material total mass.Processing aid is oxidation inhibitor, lubricant and photostabilizer.
Raw material of the present invention is not limited to said components, and other the conventional component in this area is also suitable for being added in this programme, does not repeat them here.
Wherein, carbon fiber is PAN-based carbon fiber or asphalt base carbon fiber.
Preferably, described polypropylene is homo-polypropylene and/or Co-polypropylene;
Preferably, compatilizer is a kind of in polypropylene grafted maleic anhydride, Research of Grafting Malaic Anhydride Onto Polyethylene, ethylene-octene grafted maleic anhydride and ethene-vinyl acetate grafted maleic anhydride or at least two kinds;
Preferably, described oxidation inhibitor is a kind of in antioxidant 1010, irgasfos 168, oxidation inhibitor 1098 or at least two kinds;
Preferably, lubricant stearic acid zinc and/or aluminum stearate.
Another aspect of the invention provides a kind of preparation method of carbon fiber reinforced polypropylene compound material, adopts the carbon fiber reinforced polypropylene compound material that this preparation method makes to have good mechanical property.
The preparation method of above-mentioned carbon fiber reinforced polypropylene compound material, comprises the following steps:
(1) 1～8 mass parts properties-correcting agent is carried out to surface modification to 1～40 mass parts carbon fiber, obtain modified carbon fiber;
(2) described modified carbon fiber is carried out under the condition of rayed or heating to preliminary prepolymerization, obtain carbon fiber performed polymer;
(3) insert after the raw material that comprises 39～97 mass parts polypropylene, 1～40 mass parts carbon fiber, 1～10 mass parts compatilizer and described carbon fiber performed polymer is mixed and in tablets press, carry out granulating and forming.
Be understandable that, " mass parts " described in above-mentioned steps all refers to the total mass in the raw materials of carbon fiber reinforced polypropylene compound material.
Wherein, the mode of surface modification described in step (1) is that carbon fiber is inserted in the diluent of properties-correcting agent and flooded, or the diluent of properties-correcting agent is sprayed to carbon fiber surface;
Preferably, the thinner of the diluent of described properties-correcting agent is a kind of in water, methyl alcohol, ethanol, propyl alcohol, butanone, toluene or at least two kinds.Certainly other organic solvents that can be used for diluting tetrafluoroborate ion liquid can be applicable to the present invention.
Preferably, the mass concentration of the diluent of described properties-correcting agent is 10～80%, more preferably 20～50%.Can be for understood by one of ordinary skill in the art, " mass concentration of the diluent of properties-correcting agent " refers to properties-correcting agent and accounts for the percentage ratio of diluent total mass here.
Wherein, between step (1) neutralization procedure (2), also comprise the carbon fiber after modification is dried;
Preferably, described drying mode is 50～120 DEG C of oven dry.
Wherein, rayed described in step (2) is for adopting UV-irradiation or heating prepolymerization mode;
Preferably, the light intensity of described UV-irradiation is no more than 2KW;
Preferably, the time of described UV-irradiation is 2～15min;
Preferably, the equipment of heating is microwave oven or baking oven;
Preferably, the power of described microwave oven is 150～500W;
Preferably, the time of described microwave-oven-heating is for being no more than 20min;
Preferably, the Heating temperature of described baking oven is 80～120 DEG C;
Preferably, be 0.5～2h the heat-up time of described baking oven.
Wherein, described in step (3), mix and adopt homogenizer to mix 3～5min;
Preferably; described tablets press uses dual-screw-stem machine tablets press; described dual-screw-stem machine tablets press Yi district temperature is 200～210 DEG C; described dual-screw-stem machine tablets press Er district temperature is 205～210 DEG C; described dual-screw-stem machine tablets press San district temperature is 210～215 DEG C; described dual-screw-stem machine tablets press Si district temperature is 215～220 DEG C; described dual-screw-stem machine tablets press Wu district temperature is 220～225 DEG C; described dual-screw-stem machine tablets press Liu district temperature is 220～230 DEG C, and the head temperature of described dual-screw-stem machine tablets press is 230～235 DEG C.
The routine operation that is operating as polypropylene field of granulation, those skilled in the art can also can not obtain relevant technical intelligence by loading of the present invention, do not repeat them here.
The present invention uses the properties-correcting agent that contains tetrafluoroborate ion liquid to carry out surface modification to carbon fiber, has greatly improved carbon fiber modifying effect.Carbon fiber after modification is added into after polypropylene, can increases carbon fiber to polyacrylic reinforced effects, make matrix material there is higher tensile strength, larger modulus in flexure and stronger notched Izod impact strength, there is higher comprehensive mechanical property.
Embodiment
Further illustrate technical scheme of the present invention below in conjunction with embodiment.
Embodiment 1
The raw materials of carbon fiber reinforced polypropylene compound material is according to mass parts, and it is composed as follows:
Carbon fiber is inserted in the alcohol dilution liquid of 10% propenyl tetrafluoroborate ionic liquid and flood, after complete wetting, filter out carbon fiber.To be to be dried at 50 DEG C through the carbon fiber of aforesaid way processing, and carry out preliminary prepolymerization in baking oven, oven temperature be controlled at 80 DEG C, and the time is 0.5～2 hour, obtains carbon fiber performed polymer.
Polypropylene, properties-correcting agent, compatilizer and processing aid are mixed after 3～5 minutes in high speed machine high speed; carbon fiber is entered from entering fine mouthful; then carry out granulation through dual-screw-stem machine; wherein screw machine Yi district temperature is that 200 DEG C, two district's temperature are that 205 DEG C, three district's temperature are that 210 DEG C, four district's temperature are that 215 DEG C, five district's temperature are that 220 DEG C, six district's temperature are that 220 DEG C, head temperature are 230 DEG C; extrude bar and be cooled to room temperature by circulating water channel; after blower is dry, enter dicing machine granulation, obtain a kind of carbon fiber reinforced polypropylene composite material.
Embodiment 2
The raw materials of carbon fiber reinforced polypropylene compound material is according to mass parts, and it is composed as follows:
The alcohol dilution liquid of 80% propenyl tetrafluoroborate ionic liquid is evenly sprayed in carbon fiber surface when the stirrer high speed rotating.To be to be dried at 120 DEG C through the carbon fiber of aforesaid way processing, and carry out preliminary prepolymerization under UV-light, the prepolymerized light intensity of UV-light be no more than 2KW, and irradiation time is 2 minutes, obtains carbon fiber performed polymer.
Polypropylene, properties-correcting agent, compatilizer and processing aid are mixed after 5 minutes in high speed machine high speed; carbon fiber is entered from entering fine mouthful; then carry out granulation through dual-screw-stem machine; wherein screw machine Yi district temperature is that 210 DEG C, two district's temperature are that 210 DEG C, three district's temperature are that 215 DEG C, four district's temperature are that 220 DEG C, five district's temperature are that 225 DEG C, six district's temperature are that 230 DEG C, head temperature are 235 DEG C; extrude bar and be cooled to room temperature by circulating water channel; after blower is dry, enter dicing machine granulation, obtain a kind of carbon fiber reinforced polypropylene composite material.
Embodiment 3
The raw materials of carbon fiber reinforced polypropylene compound material is according to mass parts, and it is composed as follows:
Carbon fiber is inserted in the water diluent of 35% propenyl tetrafluoroborate ionic liquid and flood, after complete wetting, filter out carbon fiber.To be to be dried at 85 DEG C through the carbon fiber of above-mentioned two kinds of mode processing, and carry out preliminary prepolymerization in microwave oven, the power of microwave oven be 150W, is placed in the 20 minutes reaction times of microwave oven, obtains carbon fiber performed polymer.
Polypropylene, properties-correcting agent, compatilizer and processing aid are mixed after 4 minutes in high speed machine high speed; carbon fiber is entered from entering fine mouthful; then carry out granulation through dual-screw-stem machine; wherein screw machine Yi district temperature is that 205 DEG C, two district's temperature are that 207 DEG C, three district's temperature are that 218 DEG C, four district's temperature are that 218 DEG C, five district's temperature are that 223 DEG C, six district's temperature are that 225 DEG C, head temperature are 232 DEG C; extrude bar and be cooled to room temperature by circulating water channel; after blower is dry, enter dicing machine granulation, obtain a kind of carbon fiber reinforced polypropylene composite material.
Embodiment 4
The raw materials of carbon fiber reinforced polypropylene compound material is according to mass parts, and it is composed as follows:
The alcohol dilution liquid of 45% propenyl tetrafluoroborate ionic liquid is evenly sprayed in carbon fiber surface when the stirrer high speed rotating.To be to be dried at 70 DEG C through the carbon fiber of aforesaid way processing, and carry out preliminary prepolymerization under UV-light, the prepolymerized light intensity of UV-light be no more than 2KW, and irradiation time is 8 minutes, obtains carbon fiber performed polymer.
Polypropylene, properties-correcting agent, compatilizer and processing aid are mixed after 4 minutes in high speed machine high speed; carbon fiber is entered from entering fine mouthful; then carry out granulation through dual-screw-stem machine; wherein screw machine Yi district temperature is that 205 DEG C, two district's temperature are that 208 DEG C, three district's temperature are that 213 DEG C, four district's temperature are that 218 DEG C, five district's temperature are that 222 DEG C, six district's temperature are that 225 DEG C, head temperature are 232 DEG C; extrude bar and be cooled to room temperature by circulating water channel; after blower is dry, enter dicing machine granulation, obtain a kind of carbon fiber reinforced polypropylene composite material.
Embodiment 5
The raw materials of carbon fiber reinforced polypropylene compound material is according to mass parts, and it is composed as follows:
Except above-mentioned condition, other are with embodiment 4.
The carbon fiber reinforced polypropylene compound material that embodiment 1～5 is obtained is carried out the test of tensile strength, flexural strength, modulus in flexure and notched Izod impact strength, what deserves to be explained is, these tests are the familiar means of testing of those skilled in the art, and concrete testing method does not repeat at this.Its test result is as following table:
Table 1
Applicant's statement, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of ancillary component, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (10)
1. a carbon fiber reinforced polypropylene compound material, is characterized in that, its raw material comprises 39～97 parts of polypropylene, 1～40 part of carbon fiber, 1～8 part of properties-correcting agent and 1～10 part of compatilizer according to mass parts, and described properties-correcting agent comprises tetrafluoroborate ion liquid.
2. carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described properties-correcting agent is the mixture of tetrafluoroborate ion liquid and polyacrylonitrile.
3. carbon fiber reinforced polypropylene compound material according to claim 2, it is characterized in that, described tetrafluoroborate ion liquid is a kind of in the tetrafluoroborate ion liquid that contains vinyl imidazole base, propenyl imidazolyl, acrylonitrile group imidazolyl, styryl imidazolyl, epoxy group(ing) imidazolyl or at least two kinds.
4. carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, its raw material also comprises in 0.05～3 part of processing aid of raw material total mass;
Preferably, described processing aid is oxidation inhibitor, lubricant and photostabilizer.
Preferably, described lubricant is Zinic stearas and/or aluminum stearate.
5. carbon fiber reinforced polypropylene compound material according to claim 1, is characterized in that, described carbon fiber is PAN-based carbon fiber or asphalt base carbon fiber;
Preferably, described polypropylene is homo-polypropylene and/or Co-polypropylene;
Preferably, compatilizer is a kind of in polypropylene grafted maleic anhydride, Research of Grafting Malaic Anhydride Onto Polyethylene, ethylene-octene grafted maleic anhydride and ethene-vinyl acetate grafted maleic anhydride or at least two kinds;
Preferably, described oxidation inhibitor is a kind of in antioxidant 1010, irgasfos 168, oxidation inhibitor 1098 or at least two kinds.
6. prepare a method for carbon fiber reinforced polypropylene compound material as claimed in claim 1, it is characterized in that, comprise the following steps:
(1) 1～8 mass parts properties-correcting agent is carried out to surface modification to 1～40 mass parts carbon fiber, obtain modified carbon fiber;
(2) described modified carbon fiber is carried out under the condition of rayed or heating to preliminary prepolymerization, obtain carbon fiber performed polymer;
(3) insert after the raw material that comprises 39～97 mass parts polypropylene, 1～10 mass parts compatilizer and described carbon fiber performed polymer is mixed and in tablets press, carry out granulating and forming.
7. method according to claim 6, is characterized in that, the mode of surface modification described in step (1) is that carbon fiber is inserted in the diluent of properties-correcting agent and flooded, or the diluent of properties-correcting agent is sprayed to carbon fiber surface;
Preferably, the thinner of the diluent of described properties-correcting agent is a kind of in water, methyl alcohol, ethanol, propyl alcohol, butanone, toluene or at least two kinds;
Preferably, the mass concentration of the diluent of described properties-correcting agent is 10～80%, more preferably 20～50%.
8. method according to claim 6, is characterized in that, also comprises modified carbon fiber dry between step (1) neutralization procedure (2);
Preferably, described drying mode is 50～120 DEG C of oven dry.
9. method according to claim 6, is characterized in that, rayed described in step (2) is for adopting UV-irradiation;
Preferably, the light intensity of described UV-irradiation is no more than 2KW;
Preferably, the time of described UV-irradiation is 2～15min;
Preferably, the equipment of heating is baking oven or microwave oven;
Preferably, the power of described microwave oven is 150～500W;
Preferably, the time of described microwave oven is for being no more than 20min;
Preferably, the Heating temperature of described baking oven is 80～120 DEG C;
Preferably, be 0.5～2h the heat-up time of described baking oven.
10. method according to claim 6, is characterized in that, mixes and adopt homogenizer to mix 3～5min described in step (3);
Preferably; described tablets press uses dual-screw-stem machine tablets press; described dual-screw-stem machine tablets press Yi district temperature is 200～210 DEG C; described dual-screw-stem machine tablets press Er district temperature is 205～210 DEG C; described dual-screw-stem machine tablets press San district temperature is 210～215 DEG C; described dual-screw-stem machine tablets press Si district temperature is 215～220 DEG C; described dual-screw-stem machine tablets press Wu district temperature is 220～225 DEG C; described dual-screw-stem machine tablets press Liu district temperature is 220～230 DEG C, and the head temperature of described dual-screw-stem machine tablets press is 230～235 DEG C.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104774437A (en) * | 2015-04-07 | 2015-07-15 | 北京汽车股份有限公司 | Carbon fibre reinforced polylactic acid composite material as well as preparation method and application thereof |
| CN105199234A (en) * | 2015-11-11 | 2015-12-30 | 贵州凯科特材料有限公司 | Carbon fiber reinforced polypropylene composite and preparation method thereof |
| CN105670162A (en) * | 2016-01-20 | 2016-06-15 | 苏州市景荣科技有限公司 | Preparation method of high-toughness antistatic PVC (polyvinyl chloride) composite sole material |
| CN106366405A (en) * | 2016-08-30 | 2017-02-01 | 盐城市艾斯特体育器材有限公司 | Polymer composition for manufacturing high-elasticity table tennis ball |
| CN114213751A (en) * | 2021-12-09 | 2022-03-22 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN114752152A (en) * | 2022-06-02 | 2022-07-15 | 福建师范大学泉港石化研究院 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
| US11780991B2 (en) | 2016-08-12 | 2023-10-10 | Dow Global Technologies Llc | Compositions comprising carbon fibers and at least one thermoplastic polyolefin elastomer |
| US11827776B2 (en) | 2016-08-12 | 2023-11-28 | Dow Global Technologies Llc | Propylene-based compositions comprising carbon fibers and a thermoplastic polyolefin elastomer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774437A (en) * | 2015-04-07 | 2015-07-15 | 北京汽车股份有限公司 | Carbon fibre reinforced polylactic acid composite material as well as preparation method and application thereof |
| CN105199234A (en) * | 2015-11-11 | 2015-12-30 | 贵州凯科特材料有限公司 | Carbon fiber reinforced polypropylene composite and preparation method thereof |
| CN105670162A (en) * | 2016-01-20 | 2016-06-15 | 苏州市景荣科技有限公司 | Preparation method of high-toughness antistatic PVC (polyvinyl chloride) composite sole material |
| CN105670162B (en) * | 2016-01-20 | 2018-05-11 | 林家豪 | A kind of preparation method of high tenacity anti-static PVC composite sole material |
| US11780991B2 (en) | 2016-08-12 | 2023-10-10 | Dow Global Technologies Llc | Compositions comprising carbon fibers and at least one thermoplastic polyolefin elastomer |
| US11827776B2 (en) | 2016-08-12 | 2023-11-28 | Dow Global Technologies Llc | Propylene-based compositions comprising carbon fibers and a thermoplastic polyolefin elastomer |
| CN106366405A (en) * | 2016-08-30 | 2017-02-01 | 盐城市艾斯特体育器材有限公司 | Polymer composition for manufacturing high-elasticity table tennis ball |
| CN114213751A (en) * | 2021-12-09 | 2022-03-22 | 福建师范大学泉港石化研究院 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| WO2023103081A1 (en) * | 2021-12-09 | 2023-06-15 | 福建师范大学泉港石化研究院 | Carbon fiber-reinforced polypropylene composite material and preparation method therefor |
| CN114752152A (en) * | 2022-06-02 | 2022-07-15 | 福建师范大学泉港石化研究院 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
| CN114752152B (en) * | 2022-06-02 | 2024-04-12 | 福建师范大学泉港石化研究院 | Modified carbon fiber reinforced high-filling nano calcium carbonate polypropylene composite material and preparation method thereof |
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| CN104151708B (en) | 2016-09-21 |
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