CN104292640A - Continuous carbon fiber reinforced polypropylene composite material with high wetting property and preparation method of continuous carbon fiber reinforced polypropylene composite material - Google Patents

Abstract

The invention relates to a continuous carbon fiber reinforced polypropylene composite material with high wetting property and a preparation method of the continuous carbon fiber reinforced polypropylene composite material. The preparation method of the continuous carbon fiber reinforced polypropylene composite material with high wetting property comprises the following steps: adding 60-95 parts by weight of polypropylene resin, 0.1-1 part by weight of a light stabilizer, 0.1-1 part by weight of an ultraviolet light absorber, 0.1-0.7 part of an antioxidant and 0.1-0.6 part of a lubricant into a high-speed mixer, and adding the mixed materials into a twin-screw extruder; adopting continuous carbon fiber reinforced polypropylene resin soaking equipment connected to an extrusion head to extrude melt extruded by the extruder into a soaking slot from a melt inlet of the soaking equipment; firstly introducing the continuous carbon fibers into a surface treatment chamber of the soaking equipment from a fiber inlet of the soaking equipment to perform surface treatment, and then introducing the continuous fibers into the soaking slot of the soaking equipment to sufficiently soak with polypropylene melt to obtain a mixture, and then, pulling out the mixture from a setting neck mould of the soaking equipment by virtue of a puller, and pelletizing the pulled-out mixture to obtain the continuous carbon fiber reinforced polypropylene composite material. Compared with the prior art, the continuous carbon fiber reinforced polypropylene composite material with high wetting property has the advantages that the process is simplified, the prepared composite material is excellent in mechanical performance, low in density and the like.

Description

Continuous carbon fiber reinforced polypropylene composite material with high wettability and preparation method thereof

technical field

The invention belongs to the technical field of polymer material recycling, and in particular relates to a highly wettable continuous carbon fiber reinforced polypropylene composite material and a preparation method thereof.

Background technique

Continuous fiber reinforced polypropylene composite material is a new type of composite material manufactured by special process with continuous fiber, such as glass fiber, carbon fiber, aramid fiber and other inorganic or organic fiber as reinforcement material, and polypropylene resin as matrix; Compared with long-fiber reinforced polypropylene composite materials, continuous fiber reinforced polypropylene composite materials have excellent properties such as light weight, high specific strength, high specific modulus, and good corrosion resistance. They are especially suitable for use in automobiles, aircraft, protection and Other applications requiring higher mechanical properties and weight savings are among the fastest growing materials in the composites market today.

However, the key to the preparation of continuous fiber reinforced polypropylene composites lies in the dispersion and impregnation of fibers. The quality of the fiber dispersion, whether the resin can completely infiltrate the fiber, and the compatibility between the fiber and the resin directly determine the performance of the final product. In order to solve the problem of fiber dispersion and impregnation, the Chinese invention patent CN1386778A adopts the powder impregnation method, that is, the fibers are dispersed through the yarn splitting device and then pulled into the impregnation tank. In the impregnation tank, the resin powder is dispersed on the fiber by overfrequency vibration to achieve melt impregnation. The problem that this method has is that production process is complicated, efficiency is low. In order to improve the compatibility of fiber and resin, in the Chinese invention patent CN102532864A, the resin, processing aid and compatibilizer are mixed uniformly in a high-speed mixer, and then added to a twin-screw extruder for extrusion, and then extruded The extrusion die head equipped with the machine head wraps and infiltrates the extruded resin mixture and the dispersed fibers to obtain a continuous fiber-reinforced resin composite material; in this method, the compatibilizer is first mixed in the resin, and then the compatibilizer is mixed The resin of the agent is used to infiltrate the fiber. Since there is no mixing effect in the process of infiltrating the fiber, if the content of the compatibilizer in the resin is low, it is easy to appear that there is no compatibilizer at the interface between the fiber and the resin, so its compatibility is improved. poor uniformity.

Carbon fiber is a kind of high-temperature-resistant fiber with high strength and modulus, and low density. These excellent characteristics endow carbon fiber composites with high mechanical properties, which are unmatched by other reinforced composite materials such as glass fibers. Widely used in aerospace, automobile industry, rail transit, new energy, sporting goods and other high-tech industries. Compared with other continuous fiber-reinforced composite materials, the composite material reinforced by continuous carbon fiber has higher mechanical properties and light weight, so it has a wide range of applications.

Contents of the invention

The object of the present invention is to provide a high wettability continuous carbon fiber reinforced polypropylene composite material and a preparation method thereof in order to overcome the defects of the above-mentioned prior art.

The purpose of the present invention can be achieved through the following technical solutions: a highly wettable continuous carbon fiber reinforced polypropylene composite material, characterized in that it comprises the following components by weight:

The fiber surface treatment agent has a content of 1-3% relative to the mass percentage of the continuous carbon fiber.

The polypropylene is homopolypropylene or copolymerized polypropylene.

The continuous carbon fiber is polyacrylonitrile-based carbon fiber or pitch-based carbon fiber.

The fiber surface treatment agent is silane coupling agent, titanate coupling agent, aluminate coupling agent, ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (AX8900), horse One or more of maic anhydride grafted polypropylene (PP-g-MAH) and acrylic acid grafted polypropylene (PP-g-AA).

The light stabilizer is bis(2,2,6,6-tetramethylphenyl piperidine) sebacate, bis(1,2,2,6,6-pentylmethyl-4-piperidine base) one or more of the sebacate salts.

The ultraviolet absorber is one or more of 2,2-dihydroxy-4-methyloxybenzophenone and 2-hydroxy-4-n-octyloxybenzophenone.

The antioxidant is one or more of antioxidant 1010, antioxidant 1076, antioxidant 1098, and antioxidant 168.

The lubricant is one or more of stearic acid, calcium stearate, zinc stearate and polyethylene wax.

A method for preparing a highly wettable continuous carbon fiber reinforced polypropylene composite material, characterized in that the method comprises the following steps:

(1) Add 60-95 parts of polypropylene resin, 0.1-1 part of light stabilizer, 0.1-1 part of ultraviolet absorber, 0.1-0.7 part of antioxidant, and 0.1-0.6 part of lubricant into the high-mixer, at room temperature Mix at high speed for 3-5 minutes and stop, then add the mixed material into the twin-screw extruder;

(2) Adopting the impregnation equipment of continuous fiber reinforced polypropylene resin connected to the extruder head, extruding the melt extruded from the extruder into the impregnation tank from the melt entrance of the impregnation equipment;

(3) The continuous carbon fiber first enters the surface treatment chamber of the impregnation equipment from the fiber inlet of the impregnation equipment, and the fiber surface treatment agent in the surface treatment chamber performs surface treatment on the continuous carbon fiber, and then the surface-treated carbon fiber enters the impregnation equipment immediately In the dipping tank, the carbon fibers are dispersed in the dipping tank and fully infiltrated with the polypropylene melt obtained in step (2);

(4) The carbon fibers obtained in step (3) fully soaked with polypropylene resin are pulled out from the shaping die of the impregnation equipment by a tractor, and pelletized by a pelletizer to obtain a composite material product.

The screw diameter of the twin-screw extruder is 50mm, the aspect ratio is 44:1, the temperature of the extruder is 180-220°C, and the dipping tank temperature of the dipping equipment is set at 220°C;

The carbon fiber content in the composite material product is controlled between 5-40% by adjusting the size of the sizing die of the impregnation equipment at 2-5mm and the rotating speed and feeding speed of the extruder; , so that the particle length of the final prepared continuous carbon fiber reinforced polypropylene composite product is controlled at 8-12 mm, and the particle size is controlled at 1-5 mm.

Compared with the prior art, the present invention realizes the continuous completion of fiber surface treatment, fiber dispersion and resin infiltration and compounding in one impregnation device, which simplifies the production process; the obtained composite material not only has good properties of carbon fiber and polypropylene Wettability, and the carbon fiber and polypropylene are treated with a surface treatment agent before infiltration, so that the two have a good interfacial bonding; the prepared continuous carbon fiber reinforced polypropylene composite material has excellent mechanical properties and low density. The composite material can Widely used in aerospace, automotive, machinery, electronic appliances, home appliances and other product components.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

In the following examples, the bending performance test standard is ASTM D790, and the unnotched impact strength test standard is ASTM D256.

Example 1

Weigh 60 parts of homopolypropylene, 0.1 part of light stabilizer bis(2,2,6,6-tetramethylphenylpiperidine) sebacate, 0.1 part of ultraviolet absorber 2,2-dihydroxy-4 - Methyloxybenzophenone, 0.3 parts of antioxidant 1010, 0.1 part of antioxidant 168, 0.1 part of lubricant stearic acid were mixed in a high mixer at room temperature for 5 minutes, and then added to a twin-screw extruder for extrusion , the obtained melt is extruded into the dipping tank of the dipping device from the melt inlet of the dipping device;

Continuous carbon fiber (Japan Toray Company, trade mark T300) is introduced from the fiber entrance of impregnation equipment, enters the surface treatment room of impregnation equipment, and the weight content of control surface treatment agent silane coupling agent KH550 relative to carbon fiber is 1%, then The carbon fibers treated with the surface treatment agent are introduced into the impregnation tank of the impregnation equipment to realize the dispersion of carbon fibers and compound with polypropylene resin; by selecting the size of the shaping die (2mm), at the same time adjust the main engine speed of the extruder to 13- 14HZ, feeding speed at 9-10HZ, control the continuous carbon fiber content at about 40%; adjust the speed of the pelletizer so that the length of the prepared continuous carbon fiber reinforced polypropylene composite material is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

Example 2

Weigh 80 parts of homopolypropylene, 0.5 part of light stabilizer di(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 0.5 part of ultraviolet absorber 2-hydroxy- 4-octyloxybenzophenone, 0.5 part of antioxidant 1076, 0.2 part of antioxidant 168, 0.3 part of lubricant calcium stearate were mixed in a high mixer at room temperature for 3 minutes, and then added to a twin-screw extruder Extrusion, extruding the melt from the melt inlet of the impregnation equipment into the impregnation tank of the impregnation equipment;

The continuous carbon fiber (Toray Corporation, Japan, brand T300J) is introduced from the fiber inlet of the impregnation equipment, and enters the surface treatment chamber of the impregnation equipment, and the surface treatment agent titanate coupling agent isopropyl triisodecanoyl titanate is controlled. The weight content relative to the carbon fiber is 2%, then the carbon fiber after the surface treatment agent is introduced into the dipping tank of the impregnating equipment, and the dispersion of the carbon fiber is realized and composited with the polypropylene resin; by selecting the size of the shaping die (4mm ), adjust the host speed of the extruder to 13-14HZ, feed speed at 9-10HZ, control the continuous carbon fiber content at about 20%; adjust the rotating speed of the pelletizer to make the prepared continuous carbon fiber reinforced polypropylene composite material The length is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

Example 3

Weigh 95 parts of copolymerized polypropylene, 1 part of light stabilizer bis(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 1 part of ultraviolet absorber 2-hydroxyl-4 -N-octyloxybenzophenone, 0.3 part of antioxidant 1098, 0.1 part of antioxidant 168, 0.6 part of lubricant polyethylene wax were mixed in a high mixer at room temperature for 5 minutes, and then added to a twin-screw extruder for extrusion , extruding the melt from the melt inlet of the impregnation equipment into the impregnation tank of the impregnation equipment;

The continuous carbon fiber (Japan Toray Company, brand T700S) is introduced from the fiber inlet of the impregnation equipment, enters the surface treatment chamber of the impregnation equipment, and controls the surface treatment agent aluminate coupling agent distearoyloxyisopropyl aluminate The weight content relative to the carbon fiber is 3%, then the carbon fiber after the surface treatment agent is introduced into the dipping tank of the dipping equipment, realizes the dispersion of the carbon fiber and carries out compounding with the polypropylene resin; By selecting the size of the shaping die (5mm ), adjust the host speed of the extruder to 15-16HZ, feed speed at 11-12HZ, control the continuous carbon fiber content at about 5%; adjust the rotating speed of the pelletizer to make the prepared continuous carbon fiber reinforced polypropylene composite material The length is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

Example 4

Weigh 70 parts of homopolypropylene, 0.5 part of light stabilizer di(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 0.5 part of ultraviolet absorber 2-hydroxy- 4-octyloxybenzophenone, 0.3 part of antioxidant 10010, 0.1 part of antioxidant 168, 0.6 part of lubricant zinc stearate were mixed in a high mixer at room temperature for 5 minutes, and then added to a twin-screw extruder Extrusion, extruding the melt from the melt inlet of the impregnation equipment into the impregnation tank of the impregnation equipment;

Continuous carbon fiber (Japan Toray Company, brand T800H) is introduced from the fiber inlet of the impregnation equipment, enters the surface treatment chamber of the impregnation equipment, and the weight content of the surface treatment agent AX8900 relative to the carbon fiber is controlled to be 2%. The treated carbon fiber is introduced into the impregnation tank of the impregnation equipment to realize the dispersion of carbon fiber and compound with polypropylene resin; by selecting the size of the shaping die (3mm) and adjusting the main engine speed of the extruder at 13-14HZ, feeding The speed is 8-9HZ, and the continuous carbon fiber content is controlled at about 30%; the speed of the pelletizer is adjusted so that the length of the prepared continuous carbon fiber reinforced polypropylene composite material is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

Example 5

Weigh 70 parts of copolymerized polypropylene, 0.5 part of light stabilizer bis(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 0.5 part of ultraviolet absorber 2-hydroxyl-4 -n-octyloxybenzophenone, 0.3 part of antioxidant 10010, 0.1 part of antioxidant 168, 0.5 part of lubricant calcium stearate were mixed at room temperature in a high mixer for 5 minutes, then added to a twin-screw extruder to extrude Extrude the melt from the melt inlet of the impregnation equipment into the impregnation tank of the impregnation equipment;

The continuous carbon fiber (Japan Toray Company, brand T300) is introduced from the fiber inlet of the impregnation equipment, enters the surface treatment chamber of the impregnation equipment, and the weight content of the surface treatment agent PP-MAH relative to the carbon fiber is controlled to be 2%. The carbon fiber treated with the treatment agent is introduced into the impregnation tank of the impregnation equipment to realize the dispersion of the carbon fiber and compound it with polypropylene resin; by selecting the size of the shaping die (3mm) and adjusting the main engine speed of the extruder to 13-14HZ, The feeding speed is 8-9HZ, and the continuous carbon fiber content is controlled at about 30%; the speed of the pelletizer is adjusted so that the length of the prepared continuous carbon fiber reinforced polypropylene composite material is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

Example 6

Weigh 80 parts of homopolypropylene, 0.5 part of light stabilizer di(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 0.5 part of ultraviolet absorber 2-hydroxy- 4-octyloxybenzophenone, 0.5 part of antioxidant 1076, 0.2 part of antioxidant 168, 0.3 part of lubricant calcium stearate were mixed in a high mixer at room temperature for 3 minutes, and then added to a twin-screw extruder Extrusion, extruding the melt from the melt inlet of the impregnation equipment into the impregnation tank of the impregnation equipment;

Continuous carbon fiber (Toray Corporation, Japan, brand T1000G) is introduced from the fiber inlet of the impregnation equipment, enters the surface treatment chamber of the impregnation equipment, and the weight content of the surface treatment agent PP-AA relative to the carbon fiber is controlled to be 3%. The carbon fiber treated with the treatment agent is introduced into the impregnation tank of the impregnation equipment to realize the dispersion of the carbon fiber and compound it with polypropylene resin; by selecting the size of the shaping die (4mm) and adjusting the main engine speed of the extruder to 13-14HZ, The feeding speed is 9-10HZ, and the continuous carbon fiber content is controlled at about 20%; the speed of the pelletizer is adjusted so that the length of the prepared continuous carbon fiber reinforced polypropylene composite material is about 10mm, and the particle size is about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Dip Tank 220°C.

comparative example

Weigh 100 parts of homopolypropylene, 0.5 part of light stabilizer di(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate, 0.5 part of ultraviolet absorber 2-hydroxy- 4-octyloxybenzophenone, 0.5 part of antioxidant 1076, 0.2 part of antioxidant 168, 0.3 part of lubricant calcium stearate were mixed in a high mixer at room temperature for 3 minutes, and then added to a twin-screw extruder Extrude, cool and cut into pellets to obtain a length of about 4mm and a particle size of about 3mm;

The diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio of the screw is 44:1, and the temperature of each zone of the twin-screw extruder is: 180°C in zone 1, 190°C in zone 2, 190°C in zone 3, 200°C in zone 4, 200°C in zone 5, Zone 6 210°C, Zone 7 210°C, Zone 8 220°C, Zone 9 220°C, Head 220°C.

The mechanical property test results of each embodiment are shown in Table 1 below:

Table 1 mechanical performance test results

From the analysis of the mechanical performance test results in the above table, it can be seen that the polypropylene composite material reinforced with continuous carbon fiber has high strength and excellent mechanical performance, which is suitable for use in occasions with high performance requirements.

The above description of the embodiments is for those of ordinary skill in the art to understand and apply the present invention. It is obvious that those skilled in the art can easily make various modifications to the embodiment, and apply the general principles described in this description to other embodiments without creative effort. Therefore, the present invention is not limited to the embodiments herein. Improvements and modifications made by those skilled in the art according to the disclosure of the present invention without departing from the scope of the present invention should fall within the protection scope of the present invention.

Claims (10)

1. A continuous carbon fiber reinforced polypropylene composite material with high wettability, characterized in that it comprises the following components by weight: The fiber surface treatment agent has a content of 1-3% relative to the mass percentage of the continuous carbon fiber. 2. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the polypropylene is homopolypropylene or copolymerized polypropylene. 3. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the continuous carbon fiber is polyacrylonitrile-based carbon fiber or pitch-based carbon fiber. 4. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the fiber surface treatment agent is a silane coupling agent, titanate coupling agent, aluminate coupling agent , Ethylene-methyl acrylate-glycidyl methacrylate random terpolymer (AX8900), maleic anhydride grafted polypropylene (PP-g-MAH), acrylic acid grafted polypropylene (PP-g-AA) one or more of the 5. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the light stabilizer is bis(2,2,6,6-tetramethylphenylpiperidine) sunflower One or more of diacid esters and di(1,2,2,6,6-pentylmethyl-4-piperidinyl) sebacate. 6. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the ultraviolet absorber is 2,2-dihydroxy-4-methyloxybenzophenone, 2 -One or more of hydroxy-4-n-octyloxybenzophenone. 7. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 1098, antioxidant 168 one or more of them. 8. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, wherein the lubricant is one of stearic acid, calcium stearate, zinc stearate, polyethylene wax species or more than one. 9. A preparation method of a high wettability continuous carbon fiber reinforced polypropylene composite material as claimed in claim 1, characterized in that, the method may further comprise the steps: (1) Add 60-95 parts of polypropylene resin, 0.1-1 part of light stabilizer, 0.1-1 part of ultraviolet absorber, 0.1-0.7 part of antioxidant, and 0.1-0.6 part of lubricant into the high-mixer, at room temperature Mix at high speed for 3-5 minutes and stop, then add the mixed material into the twin-screw extruder; (2) Adopting the impregnation equipment of continuous fiber reinforced polypropylene resin connected to the extruder head, extruding the melt extruded from the extruder into the impregnation tank from the melt entrance of the impregnation equipment; (3) The continuous carbon fiber first enters the surface treatment chamber of the impregnation equipment from the fiber inlet of the impregnation equipment, and the fiber surface treatment agent in the surface treatment chamber performs surface treatment on the continuous carbon fiber, and then the surface-treated carbon fiber enters the impregnation equipment immediately In the dipping tank, the carbon fibers are dispersed in the dipping tank and fully infiltrated with the polypropylene melt obtained in step (2); (4) The carbon fibers obtained in step (3) fully soaked with polypropylene resin are pulled out from the shaping die of the impregnation equipment by a tractor, and pelletized by a pelletizer to obtain a composite material product. 10. The highly wettable continuous carbon fiber reinforced polypropylene composite material according to claim 1, characterized in that, the screw diameter of the twin-screw extruder is 50mm, the length-to-diameter ratio is 44:1, and the extruder temperature 180-220°C, the dipping tank temperature of the dipping equipment is set at 220°C; The carbon fiber content in the composite material product is controlled between 5-40% by adjusting the size of the sizing die of the impregnation equipment at 2-5mm and the rotating speed and feeding speed of the extruder; , so that the particle length of the final prepared continuous carbon fiber reinforced polypropylene composite product is controlled at 8-12 mm, and the particle size is controlled at 1-5 mm.