CN111073247A - Carbon fiber reinforced polycarbonate composite material with high mechanical property, conductivity and low warpage and preparation method thereof - Google Patents
Carbon fiber reinforced polycarbonate composite material with high mechanical property, conductivity and low warpage and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2455/00—Characterised by the use of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08J2423/00 - C08J2453/00
- C08J2455/02—Acrylonitrile-Butadiene-Styrene [ABS] polymers
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Abstract
The invention discloses a carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage and a preparation method thereof; the polycarbonate composite material comprises the following components in parts by weight: 40-80 parts of polycarbonate resin, 10-50 parts of flat carbon fiber, 0-10 parts of maleic anhydride graft, 0.1-1 part of antioxidant, 0.1-2 parts of hyperbranched polymer and 0.2-2 parts of processing aid. Compared with the common carbon fiber reinforced polycarbonate composite material with a circular section in the current market, the flat carbon fiber reinforced polycarbonate composite material has the advantages of high mechanical property and conductivity, good performance of stable size and low warpage, and can be used in fields such as IC trays with high requirements on flatness.
Description
Technical Field
The invention relates to a carbon fiber reinforced polycarbonate composite material, in particular to a carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage and a preparation method thereof, which is a carbon fiber reinforced polycarbonate composite material with simple process and high requirements on mechanical property, electric conductivity and flatness.
Background
Under the promotion of high technology, engineering plastics are rapidly developed, wherein polycarbonate is increasingly popular with people due to excellent mechanical properties, impact resistance, heat resistance and cold resistance, and in order to meet the requirements of different fields, the polycarbonate is usually further modified, for example, patents CN105838052A and CN104312129A research on the improvement of mechanical properties of polycarbonate materials through carbon fiber reinforcement, and the modified polycarbonate composite material is widely applied to electronic and electrical appliances, automobiles, mechanical equipment and precision instruments. However, in recent years, in some applications such as the field of IC plastic trays, higher and higher requirements are provided for mechanical properties, electrical conductivity, dimensional accuracy and flatness of polycarbonate products, some products are made of polycarbonate filled with carbon fibers with circular cross sections, which solves the mechanical properties and electrical conductivity of polycarbonate products, but for IC tray products with higher flatness requirements, this method does not meet the relevant requirements, and some inventors select to add some anti-warping agents (such as glass beads) to improve the flatness of composite materials, but the effect is not very obvious, and the mechanical properties of composite materials and products are affected.
Therefore, in order to improve the flatness requirements of carbon fiber reinforced polycarbonate products, further intensive research work is required, and a carbon fiber reinforced polycarbonate composite material having excellent dimensional stability and flatness is developed.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage and a preparation method thereof
The technical scheme adopted by the invention for solving the technical problems is as follows:
a carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conduction and low warpage is composed of the following raw materials in percentage by weight:
polycarbonate resin: 40-80%;
flat carbon fibers: 10-50%;
maleic anhydride graft: 0 to 10 percent;
hyperbranched polymer: 0.1-1%;
lubricant: 0.2 to 1 percent
Antioxidant: 0.2 to 1 percent.
The polycarbonate resin can be one or a combination of more of melt index 10.0 to 30.0g/10 min.
The length of the flat carbon fiber is 6mm, and the length-diameter ratio of the cross section is (3-4): 1, and is treated with a silane coupling agent. The preparation method of the flat carbon fiber comprises the following steps: preparing polyacrylonitrile spinning solution, filtering and metering the demonomerized and defoamed polyacrylonitrile spinning solution, extruding the solution through a spinning nozzle to form a spinning trickle, feeding the spinning nozzle used in the production process into a coagulating bath for coagulation forming, drafting, washing, drying and densifying to obtain flat polyacrylonitrile precursor for high-performance carbon fibers, oxidizing, carbonizing at low temperature and high temperature, sizing and silanizing, then rolling to obtain flat carbon fibers, and cutting the flat carbon fibers into short flat carbon fibers with the diameter of 6 mm.
The maleic anhydride is grafted into ABS-g-MAH.
The hyperbranched polymer is provided by Wuhan hyperbranched resin science and technology company Limited and is of the trademark Hyper C100.
The lubricant is one or a combination of more of stearic acid amide, paraffin, polyethylene wax and silicone master batch.
The antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to the proportion of 1: 2.
The carbon fiber polycarbonate composite material with high mechanical property, conductivity and low warpage and the preparation method thereof are as follows:
1) weighing the raw materials according to the weight ratio;
2) putting the raw materials except the carbon fiber into a high-speed mixer for dry mixing for 3-5 min;
3) feeding the substance obtained in the step 2) into a double-screw extruder through a main feeder, and adding carbon fibers into a side feeding port of the double-screw extruder;
4) extruding, cooling, granulating and drying the substance obtained in the step 3), wherein the rotating speed of a double-screw extruder is 300-400 r.p.m; the temperature of each section of the double-screw extruder is 220-260 ℃.
The invention has the advantages that:
1. the carbon fiber with the flat section is used for the modified composite material, and compared with the carbon fiber modified polycarbonate composite material with the round section, the carbon fiber modified polycarbonate composite material has the advantages of better dimensional stability, lower warping degree and more excellent flatness.
Detailed Description
The technical features of the present invention will be further described with reference to the following embodiments.
In the examples of the present invention, polycarbonate was supplied by LG corporation of Korea, model number PC-201-22, melt index 22g/10 min; the flat carbon fiber has a length of 6mm, a tensile strength of 4.0GPa, and a tensile modulus of 230GPa, the bulk density of 350g/l, which is provided by a high-performance laboratory of the university of east China; the chopped carbon fiber (abbreviated as round carbon fiber) having a round carbon fiber shape was a 6 mm-long chopped round rod-shaped carbon fiber supplied by Korea TYM, and had a tensile strength of 4.0GPa, a tensile modulus of 230GPa, and a density of 1.78g/cm3(ii) a The bulk density was 350 g/l. The maleic anhydride graft is formed by grafting maleic anhydride into ABS-g-MAH; the lubricant is silicone master batch provided by German Wake; the antioxidant is 1010 and the antioxidant 168 according to the weight ratio of 1:2, compounding in proportion; the hyperbranched polymer is provided by Wuhan hyperbranched resin science and technology company Limited and has the trademark of Hyper C100.
Example 1:
(1) weighing 85.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) Adding 10% by weight of flat carbon fibers from a double-screw side feeding port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Example 2:
(1) weighing 80.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) 15% by weight of flat carbon fibers were added from a feed inlet on the side of the twin screw.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Example 3:
(1) weighing 75.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) 20% by weight of flat carbon fibers were fed through a twin-screw side feed port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Example 4:
(1) weighing 70.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) Adding 25% by weight of flat carbon fibers from a double-screw side feeding port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Example 5:
(1) weighing 65.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) 30% by weight of flat carbon fibers were fed through a double-screw side feed port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparative example 1:
(1) weighing 85.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) Adding 10% of round carbon fiber by weight into the double-screw side feeding port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparative example 2:
(1) weighing 80.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) Adding 15% by weight of round carbon fiber from a feeding port at the side of the double screw.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparative example 3:
(1) weighing 75.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) 20 percent of round carbon fiber by weight is added from a feeding port at the side of the double screw.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparative example 4:
(1) weighing 70.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) Adding 25% round carbon fiber by weight into the double-screw side feeding port.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparative example 5:
(1) weighing 65.9% of polycarbonate, 3% of ABS-g-MAH, 0.3% of antioxidant, 0.3% of lubricant and 0.5% of hyperbranched polymer according to the weight ratio.
(2) The raw materials are put into a high-speed mixer to be blended for 5 minutes and then are added from the main feeding port of a double-screw extruder.
(3) 30 percent of circular carbon fiber by weight is added from a feeding port at the side of the double screw.
(4) The materials are extruded and granulated by a double-screw extruder, the temperature from a temperature port to a machine head is 230 ℃, 230 ℃, 245 ℃, 255 ℃, 255 ℃, 260 ℃, 260 ℃ and the rotating speed is 380r.p.m, and the mixture is subjected to composite treatment such as shearing, melting and the like in the double-screw extruder.
(5) And (4) extruding, cooling, granulating and drying the substance obtained in the step (4).
Comparison of the performance tests was carried out on the samples prepared according to the examples and comparative examples, the tensile performance test being carried out according to ISO527-2, the test specimen size being 150 x 10 x 4mm, the tensile speed being 50 mm/min; bending performance testing was performed according to ISO 178, with a sample size of 80 x 10 x 4mm and a bending speed of 2 mm/min; impact strength of the simply supported beam was according to ISO 179, sample size 55 × 6 × 4; the melt flow index is tested according to ISO 1183 by adopting an ISO test standard, the surface resistance is tested by a quick 4990 surface resistance meter, the warpage is evaluated by a feeler gauge test, the test method comprises the steps of firstly beating a plate by a mould, wherein the size of the mould is 150mm x 100mm x 2mm, and the warpage is compared by a test plate at the same position. The test properties are shown in table 1 below.
Table 1 shows the test data of examples 1 to 3 and comparative examples 1 to 3
As can be seen from the table, the mechanical properties and electrical conductivity of the polycarbonate reinforced with flat carbon fibers are substantially the same as those of the polycarbonate reinforced with round carbon fibers, but the warpage of the polycarbonate reinforced with flat carbon fibers is significantly smaller than that of the polycarbonate reinforced with round carbon fibers, i.e., the flatness of the polycarbonate plate reinforced with flat carbon fibers is significantly better than that of the polycarbonate reinforced with round carbon fibers.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and is not intended to limit the invention. Several equivalent variations, which can be made by a person skilled in the art without departing from the inventive concept, are to be considered within the scope of the invention.
Claims (9)
1. A carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conduction and low warpage is characterized in that: the composite material consists of the following raw materials in percentage by weight:
polycarbonate resin: 40-80%;
flat carbon fibers: 10-50%;
maleic anhydride graft: 0 to 10 percent;
hyperbranched polymer: 0.1-1%;
lubricant: 0.2 to 1 percent
Antioxidant: 0.2 to 1 percent.
2. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the polycarbonate resin is one or a combination of more of melt index 10.0-30.0g/10 min.
3. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the length of the flat carbon fiber is 6mm, and the length-diameter ratio of the cross section is (3-4): 1, and is treated with a silane coupling agent.
4. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 3, wherein: the preparation method of the flat carbon fiber comprises the following steps: preparing polyacrylonitrile spinning solution, filtering and metering the demonomerized and defoamed polyacrylonitrile spinning solution, extruding the solution through a spinning nozzle to form a spinning trickle, feeding the spinning nozzle used in the production process into a coagulating bath for coagulation forming, drafting, washing, drying and densifying to obtain flat polyacrylonitrile precursor for high-performance carbon fibers, oxidizing, carbonizing at low temperature and high temperature, sizing and silanizing, then rolling to obtain flat carbon fibers, and cutting the flat carbon fibers into short flat carbon fibers with the diameter of 6 mm.
5. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the maleic anhydride is grafted into ABS-g-MAH.
6. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the hyperbranched polymer is provided by Wuhan hyperbranched resin science and technology company Limited and is of the trademark Hyper C100.
7. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the lubricant is one or a combination of more of stearic acid amide, paraffin, polyethylene wax and silicone master batch.
8. The carbon fiber reinforced polycarbonate composite material with high mechanical property, electric conductivity and low warpage as claimed in claim 1, wherein: the antioxidant is prepared by compounding an antioxidant 1010 and an antioxidant 168 according to the proportion of 1: 2.
9. The preparation method of the carbon fiber polycarbonate composite material with high mechanical property, electric conduction and low warpage as claimed in any one of claims 1-8, which comprises the following steps:
1) weighing the raw materials according to the weight ratio;
2) putting the raw materials except the carbon fiber into a high-speed mixer for dry mixing for 3-5 min;
3) feeding the substance obtained in the step 2) into a double-screw extruder through a main feeder, and adding carbon fibers into a side feeding port of the double-screw extruder;
4) extruding, cooling, granulating and drying the substance obtained in the step 3), wherein the rotating speed of a double-screw extruder is 300-400 r.p.m; the temperature of each section of the double-screw extruder is 220-260 ℃.
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| CN116063824A (en) * | 2021-11-02 | 2023-05-05 | 粟品(厦门)新材料科技有限公司 | High-strength carbon fiber modified polyester thermoplastic elastomer and preparation method thereof |
| CN115850938A (en) * | 2022-11-29 | 2023-03-28 | 上海日之升科技有限公司 | Hydrophobic scratch-resistant PC composite material and preparation method thereof |
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Application publication date: 20200428 |