CN110951244A - Waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and preparation method thereof - Google Patents
Waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a preparation method of a waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material, which comprises the following steps: (1) preparing and recovering carbon fibers; (2) preparing raw materials; (3) putting the carrier and the additive in the step (2) into a high-speed mixer, and mixing for 5min to obtain a mixture A; (4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recovered carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder; (5) and (5) bracing, cooling, granulating and drying to obtain a finished product. The invention also provides a composite material prepared by the method. The invention adopts a unique formula and a preparation process, the expensive carbon fiber and CFRP are effectively recycled, and the prepared regenerated reinforced recycled carbon fiber thermoplastic composite material has heat conduction and electric conduction performance and can be widely applied to the industrial field.
Description
Technical Field
The invention relates to the technical field of waste recovery and composite material preparation, in particular to a waste plastic regeneration enhanced type recovered carbon fiber thermoplastic composite material and a preparation method thereof.
Background
As a chemical product, the plastic brings convenience to daily life of human beings, and simultaneously brings great influence to the global environment due to the defect of deadly and difficult degradation. If the waste plastics can not be reasonably arranged, the problems of serious environmental pollution and the like can be caused, and simultaneously, huge resource waste is caused. At present, the total consumption of plastics in China accounts for 1/4 of the total amount of the world, but the recycling rate is low. Moreover, the recovery rate and the regeneration utilization rate of the waste plastics are obviously reduced. Therefore, great support should be given to the recycling of waste plastics and the development of industrialization thereof.
Waste plastics are classified and recycled, and are physically or chemically modified in a proper way to improve the performance of the waste plastics, and then particles of the waste plastics are obtained, which is an important step in the waste plastics recycling technology. Compared with the traditional direct landfill or incineration process and the like, the waste plastic recycling method can replace part of new materials in the plastic industry through modification and doping methods, not only can reduce the enterprise cost, but also is an effective resource recycling method.
Carbon fiber reinforced resin based Composites (CFRP) are composites of carbon fibers as reinforcement and a resin as matrix, usually a thermosetting resin or a thermoplastic resin. The CFRP composite material has the excellent performances of high specific strength, high specific rigidity, good corrosion resistance and the like, and has wide engineering application and steady growth in the fields of aerospace, sports equipment, wind power generation and the like. It is expected that the global demand for carbon fiber will reach 11.2 million tons by 2020, of which more than 60% will be applied in the industrial field.
The increase of the CFRP output also brings the increase of wastes, and in the processes of production, preparation, assembly and equipment maintenance replacement of the carbon fiber composite material, the production accounts for 30-50% of the total amount of the wastes, so that a large amount of CFRP wastes are generated. And the CFRP waste has high corrosion resistance and weather resistance and is not easy to decompose, and the direct landfill or incineration can cause great pressure on the environment. The two methods also cause waste of expensive carbon fiber resources, so how to effectively recycle CFRP becomes a new problem in the composite material industry and society.
The Chinese patent application No. 201811018435.3 discloses a conductive carbon fiber composite material and a preparation method thereof, wherein the conductive carbon fiber composite material comprises the following components in percentage by weight: the composite material comprises, by weight, 630-50% of PA, 20-35% of carbon fiber, 20-30% of a recycled waste composite material, 1-2% of a reinforcing agent, 0.3-1.8% of a coupling agent, 0.1-2% of a heat stabilizer, 0.1-0.35% of an antioxidant, 0.2-5.5% of a flame retardant, 5-10% of conductive particles and 1-2% of zinc stearate, and the waste recycled from automobiles is added into the composite material, so that the cost is reduced, and the environmental protection requirement is met; the conductive particles are added into the base material, so that the composite material has a good conductive effect.
However, the above scheme can only effectively recycle the PA material, but cannot effectively recycle the CFRP; and the comprehensive performance of the prepared material is reduced, and the heat-conducting property can not be considered at the same time, so that the environment-friendly and market requirements can not be better met.
Disclosure of Invention
In view of the above disadvantages, the present invention aims to provide a waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and a preparation method thereof, so as to solve the problem of the reduction of the recycling performance of waste plastics, and effectively recycle expensive carbon fibers and CFRP, and the prepared waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material has heat conductivity and electrical conductivity, and can be widely applied in the industrial field to meet the market and environmental protection requirements.
The technical scheme adopted by the invention to achieve the aim is as follows:
a preparation method of a waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material is characterized by comprising the following steps:
(1) preparing and recovering carbon fibers:
(2) preparing raw materials, namely preparing the following raw materials in percentage by mass:
1-50% of recycled carbon fiber
25-68% of carrier
10 to 30 percent of recycled plastic particles
1-15% of an additive;
(3) putting the carrier and the additive in the step (1) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recycled carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-320 ℃, and the screw rotation speed is 150-300 r/min);
(5) and (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
As a further improvement of the present invention, the preparation method of the recycled carbon fiber in the step (1) comprises:
A. placing the recovered carbon fiber leftover materials in a muffle furnace, heating to 400-650 ℃ at a heating rate of 5-25 ℃/min, preserving heat for 30-240 min, and naturally cooling to room temperature;
B. soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 50-60 ℃ for 1-4 hours, and drying to obtain recovered carbon fiber;
as a further improvement of the invention, the carbon fiber leftover materials taken in the step A are in the form of one or a combination of more of continuous fibers, long fibers, short fibers, powder fibers or fiber fabrics.
As a further improvement of the invention, the carrier comprises one or a combination of several of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyformaldehyde, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
As a further improvement of the invention, the recycled plastic particles comprise one or more of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyformaldehyde, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
As a further improvement of the invention, the additives include a dispersant, an antioxidant, and a coupling agent.
As a further improvement of the invention, the dispersant comprises one of polyethylene wax, polypropylene wax and EVA wax.
As a further improvement of the invention, the antioxidant comprises one or a combination of several of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant CA, antioxidant TNP and antioxidant MB.
As a further improvement of the invention, the coupling agent comprises one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
A waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material is prepared by any one of the preparation methods.
The invention has the beneficial effects that:
(1) according to the waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material and the preparation method thereof, the problem of reduction of recycling performance of waste plastics can be solved by adopting a unique formula and a unique preparation process, expensive carbon fibers and CFRP are effectively recycled, and the prepared waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material has heat conduction and electric conduction performance, can be widely applied to the industrial field and meets the market and environmental protection requirements.
(2) The preparation method and the material provided by the invention can fully utilize recycled waste plastics to be added into the composite material, reduce the cost, relieve the environmental protection pressure, solve the problem of waste of carbon fiber scraps, and simultaneously enable the prepared composite material to have electric conductivity and heat conductivity.
The foregoing is a summary of the technical solutions of the present invention, and the present invention is further described below with reference to specific embodiments.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the intended purposes, the following detailed description of the embodiments of the present invention is given with reference to the preferred embodiments.
Example 1
The preparation method of the waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material provided by the embodiment comprises the following steps:
(1) preparing the recycled carbon fiber:
A. placing the recovered short carbon fiber board leftover material in a muffle furnace, heating to 650 ℃ at the heating rate of 25 ℃/min, preserving heat for 240min, and naturally cooling to room temperature;
B. and B, soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 60 ℃ for 4 hours, and drying to obtain the recycled carbon fiber.
(2) Preparing raw materials, namely preparing the following raw materials in percentage by mass:
(3) putting the carrier and the additive in the step (2) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recovered carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder; (reaction temperature 260 ~ 280 ℃ screw rotation speed is 300r/min)
(5) And (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
The preparation method of the recycled carbon fiber in the step (1) comprises the following steps:
A. placing the recovered carbon fiber leftover materials in a muffle furnace, heating to 400-650 ℃ at a heating rate of 5-25 ℃/min, preserving heat for 30-240 min, and naturally cooling to room temperature;
B. soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 50-60 ℃ for 1-4 hours, and drying to obtain recovered carbon fiber;
the carbon fiber leftover materials taken in the step A are in one or a combination of more of continuous fibers, long fibers, short fibers, powder fibers or fiber fabrics.
The carrier is one or a combination of more of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyformaldehyde, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
The recycled plastic particles are one or a combination of more of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyformaldehyde, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
The additives include dispersants, antioxidants, and coupling agents.
The dispersing agent is specifically one of polyethylene wax, polypropylene wax and EVA wax.
The antioxidant is one or a combination of more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant CA, antioxidant TNP and antioxidant MB.
The coupling agent is one of silane coupling agent, titanate coupling agent and aluminate coupling agent.
A waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material is prepared by the preparation method.
The invention adds the recycled waste plastics into the composite material, reduces the cost and the environmental protection pressure, solves the problem of waste of carbon fiber leftover materials, enhances the performance of the prepared composite material, and ensures that the composite material has electric conduction and heat conduction performances.
Example 2
The waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and the preparation method thereof provided by the embodiment are basically the same as those of the embodiment 1, and the differences are as follows:
the preparation method of the waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material comprises the following steps:
(1) preparing the recycled carbon fiber:
A. placing the recovered leftover materials of the continuous carbon fiber plate in a muffle furnace, heating to 400 ℃ at the heating rate of 5 ℃/min, preserving heat for 30min, and naturally cooling to room temperature;
B. and B, soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 50 ℃ for 1 hour, and drying to obtain the recycled carbon fiber.
(2) Preparing raw materials, namely preparing the following raw materials in percentage by mass:
(3) putting the carrier and the additive in the step (2) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recovered carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder; (reaction temperature 160 ~ 190 ℃ screw rotation speed 150r/min)
(5) And (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
The preparation method of the recycled carbon fiber in the step (1) comprises the following steps:
A. placing the recovered carbon fiber leftover materials in a muffle furnace, heating to 400-650 ℃ at a heating rate of 5-25 ℃/min, preserving heat for 30-240 min, and naturally cooling to room temperature;
B. soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 50-60 ℃ for 1-4 hours, and drying to obtain recovered carbon fiber;
C. and performing electrochemical surface treatment on the recovered carbon fiber, and introducing active groups such as-C-OH and-COOH on the surface of the carbon fiber to further prepare the surface modified recovered carbon fiber.
Of course, other surface treatment methods can also be adopted to introduce active groups on the surface of the carbon fiber to prepare the surface-modified recycled carbon fiber.
The carbon fiber leftover materials taken in the step A are in one or a combination of more of continuous fibers, long fibers, short fibers, powder fibers or fiber fabrics; the continuous fibers are adopted in the embodiment, and other embodiments can be selected according to specific needs, so that the technical effects described in the invention can be achieved.
Example 3
The waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and the preparation method thereof provided by the embodiment are basically the same as those of the embodiment 1, and the differences are as follows:
the embodiment provides a preparation method of a waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material, which comprises the following steps:
(1) preparing the recycled carbon fiber:
A. placing the recovered leftover material of the long carbon fiber board in a muffle furnace, heating to 600 ℃ at the heating rate of 20 ℃/min, preserving heat for 150min, and naturally cooling to room temperature;
B. and B, soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 60 ℃ for 2 hours, and drying to obtain the recycled carbon fiber.
(2) Preparing raw materials, namely preparing the following raw materials in percentage by mass:
(3) putting the carrier and the additive in the step (2) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recovered carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder; (reaction temperature 290-320 ℃ screw rotation speed 200r/min)
(5) And (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
Example 4
The waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material and the preparation method thereof provided by the embodiment are basically the same as those of the embodiment 1, and the differences are as follows:
the embodiment provides a preparation method of a waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material, which comprises the following steps:
(1) preparing the recycled carbon fiber:
A. placing the recovered leftover material of the powder carbon fiber plate in a muffle furnace, heating to 500 ℃ at the heating rate of 10 ℃/min, preserving heat for 120min, and naturally cooling to room temperature;
B. and B, soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 55 ℃ for 2 hours, and drying to obtain the recycled carbon fiber.
(2) Preparing raw materials, namely preparing the following raw materials in percentage by mass:
(3) putting the carrier and the additive in the step (2) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recovered carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder; (reaction temperature 180 ~ 195 ℃ screw rotation speed 150r/min)
(5) And (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
In the above examples, the selection of the specific components and the ratios of the raw materials are merely examples, and in other examples, the technical effects described in the present invention can be achieved by selecting other specific components and ratios as necessary within the ranges described in the present invention. Therefore, embodiments of the present invention are not listed one by one.
Application example 1
The heat conductivity and surface resistivity of the waste plastic regeneration-enhanced recycled carbon fiber thermoplastic composite material prepared in the embodiments 1 to 4 were measured, and the results are shown in the following table.
| Sample (I) | Thermal conductivity (W/(m × k)) | Surface resistivity (omega) |
| Example 1 | 7.2 | 220 |
| Example 2 | 2.1 | 3.5×104 |
| Example 3 | 1.2 | 4.9×104 |
| Example 4 | 0.3 | 5.4×105 |
It can be seen that the waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material prepared in the embodiments 1 to 4 of the invention has good electric conductivity and heat conductivity.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that the technical features similar to or similar to the above-described embodiment of the present invention are all within the protective scope of the present invention.
Claims (10)
1. A preparation method of a waste plastic regeneration enhanced type recycled carbon fiber thermoplastic composite material is characterized by comprising the following steps:
(1) preparing and recovering carbon fibers:
(2) preparing raw materials, namely preparing the following raw materials in percentage by mass:
1-50% of recycled carbon fiber
25-68% of carrier
10 to 30 percent of recycled plastic particles
1-15% of an additive;
(3) putting the carrier and the additive in the step (1) into a high-speed mixer, and mixing for 5min to obtain a mixture A;
(4) adding the mixture A obtained in the step (3) into a double-screw extruder from a main feeding port, adding the recycled carbon fibers obtained in the step (1) into the double-screw extruder from a side feeding port, and performing melt extrusion through the double-screw extruder (the reaction temperature is 160-320 ℃, and the screw rotation speed is 150-300 r/min);
(5) and (3) bracing, cooling, granulating and drying to obtain a finished product of the recycled carbon fiber master batch for reinforcing the waste plastics.
2. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 1, wherein the preparation method of the recycled carbon fiber in the step (1) comprises the following steps:
A. placing the recovered carbon fiber leftover materials in a muffle furnace, heating to 400-650 ℃ at a heating rate of 5-25 ℃/min, preserving heat for 30-240 min, and naturally cooling to room temperature;
B. soaking the carbon fiber obtained in the step A in an acetone solution, performing ultrasonic treatment at 50-60 ℃ for 1-4 hours, and drying to obtain recovered carbon fiber;
3. the waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 2, wherein the carbon fiber scraps taken in the step a are in the form of one or a combination of continuous fibers, long fibers, short fibers, powder fibers or fiber fabrics.
4. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 1, wherein the carrier is one or a combination of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyoxymethylene, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
5. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 1, wherein the recycled plastic particles are one or a combination of polyethylene, polypropylene, polyvinyl chloride, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, polyoxymethylene, polyphenylene sulfide, polyether sulfone and polyether ether ketone.
6. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 1, wherein the additives comprise a dispersant, an antioxidant and a coupling agent.
7. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 6, wherein the dispersant is one of polyethylene wax, polypropylene wax and EVA wax.
8. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 6, wherein the antioxidant is one or a combination of several of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant CA, antioxidant TNP and antioxidant MB.
9. The waste plastic recycling-enhanced recycled carbon fiber thermoplastic composite material as claimed in claim 6, wherein the coupling agent comprises one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.
10. A waste plastic regeneration enhanced recycled carbon fiber thermoplastic composite material is characterized by being prepared by the preparation method of any one of claims 1 to 9.
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