CN112898760A - Wave-absorbing polycarbonate composition and preparation method thereof - Google Patents
Wave-absorbing polycarbonate composition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a wave-absorbing polycarbonate composition and a preparation method thereof. The wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight: 77-92 parts of polycarbonate resin, 5-15 parts of porous carbon/ferrite composite wave-absorbing material, 3-8 parts of toughening agent, 0.2-0.8 part of antioxidant and 1.2-1.8 parts of lubricant; the porous carbon/ferrite composite wave-absorbing material is prepared from a biological matrix porous carbon raw material and Fe (NO)3)3·9H2And O is obtained. The wave-absorbing polycarbonate composition has good notch impact strength and wave-absorbing rate and good comprehensive performance, and can be used in the fields of communication, automobile millimeter radar wave components and the like.
Description
Technical Field
The invention relates to the field of materials, in particular to a wave-absorbing polycarbonate composition and a preparation method thereof.
Background
The millimeter wave radar supports the application scenes of high speed, low time delay and large connection, and due to introduction of high frequency, upgrading of hardware parts and doubling of the quantity of networking equipment and antennas, electromagnetic interference between equipment and inside the equipment is ubiquitous, and the harm of the electromagnetic interference and electromagnetic radiation to electronic equipment is increasingly serious. To solve these interference problems, it is necessary to use a material having excellent wave absorption properties at ultra-high frequencies.
The traditional wave-absorbing material cannot meet the requirements of strength, width, lightness and thinness due to the defects of heavy mass, narrow effective frequency width, poor wave-absorbing performance and the like, so that the wave-absorbing composite material prepared by combining the traditional wave-absorbing material with the modern high-performance material has a modern development trend and can improve the performance of the wave-absorbing material. Carbonate is one of the most commonly used plastics in industrial production, and is widely applied to the industrial fields of electronics, electric appliances, automobiles, household appliances, toys and the like because of the advantages of excellent processability, impact resistance, heat resistance, low temperature resistance, chemical resistance, electrical properties, high gloss, excellent electroplating performance, moderate price and the like. But polycarbonate is a wave-transparent high polymer material and cannot be applied to occasions needing wave absorption. Ferrite, carbon-based wave-absorbing materials, magnetic metal micro powder, ceramics, chiral wave absorbers, conductive polymers, nano wave-absorbing materials and the like are added into the traditional resin to obtain the composite material with certain wave-absorbing performance, but the toughness of the PC material is greatly damaged by the materials.
At present, some researches on the wave-absorbing modification of polycarbonate are carried out in the prior art, such as: chinese patent application CN201810918224.9 discloses a high-strength wave-absorbing composite material, which comprises 30-50 parts of polycarbonate, 20-30 parts of polybutylene terephthalate, 0.5-2 parts of chain extender, 1-20 parts of surface-treated carbon fiber, and FeTiO2The material has the advantages of good adhesiveness with a resin matrix, absorption of electromagnetic waves in a range of 2-18GHz, general wave absorbing performance, easy transesterification of polycarbonate and polybutylene terephthalate without adding an ester exchange inhibitor, and further research on actual material toughness. Chinese patent application CN200510043010.4 discloses a nano wave-absorbing plastic material, which comprises plastic master batch and nano material with a certain contentThe electromagnetic wave absorption function of the composite material, however, the direct molding process thereof has the disadvantages that the dispersion is poor due to the easy agglomeration of the nano material, the performance stability needs to be researched, and the nano material has high cost and complex process and is not beneficial to the industrial popularization. Chinese patent application CN201710447860.3 discloses a thermoplastic resin foam pyramid high-performance wave-absorbing material which is prepared by compounding thermoplastic resin, high-structure type superconductive conductive carbon black and efficient flame retardant and can be applied to a microwave darkroom, Chinese patent application CN201210195216.9 is prepared by mixing plastic raw materials, wave-absorbing radiation-proof functional powder materials and auxiliary agents, after the raw materials are mixed, the mixed materials are extruded and molded, and then are molded by compression or injection into products. But these materials absorb electromagnetic waves at low frequencies.
Therefore, a wave-absorbing polycarbonate composition which has strong absorption capacity on ultrahigh frequency electromagnetic waves and excellent impact performance is needed to be found.
Disclosure of Invention
The invention aims to provide a wave-absorbing polycarbonate composition which has strong absorption capacity on ultrahigh frequency electromagnetic waves and excellent impact performance and can be used in the fields of communication, automobile millimeter radar wave parts and the like.
The technical scheme for realizing the purpose is as follows:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
77-92 parts of polycarbonate resin,
5-15 parts of porous carbon/ferrite composite wave-absorbing material,
3-8 parts of a toughening agent,
the total weight of the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material and the toughening agent is 100 parts,
0.2 to 0.8 portion of antioxidant,
1.2 to 1.8 portions of lubricant,
the porous carbon/ferrite composite wave-absorbing material is prepared from a biological matrix porous carbon raw material and Fe (NO)3)3·9H2O is prepared;
the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing a biological matrix porous carbon raw material, and cooling and taking out;
(2) placing the cooled sample into Fe (NO)3)3·9H2After the O solution is soaked in vacuum, taking out a sample and freeze-drying the sample;
(3) placing the sample in N2And (3) raising the temperature to a preset temperature at a constant speed in the tube furnace under the atmosphere protection, and then preserving the temperature to obtain the composite material.
In some embodiments, the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
81-88 parts of polycarbonate resin,
7-13 parts of porous carbon/ferrite composite wave-absorbing material,
4-7 parts of a toughening agent,
the total weight of the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material and the toughening agent is 100 parts,
0.2 to 0.8 portion of antioxidant,
1.2-1.8 parts of a lubricant.
In some embodiments, the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
83-86 parts of polycarbonate resin,
9-11 parts of porous carbon/ferrite composite wave-absorbing material,
4-6 parts of a toughening agent.
In some embodiments, the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing the biological matrix porous carbon raw material for 4-10h at the temperature of 180 ℃ and 250 ℃, and taking out after cooling;
(2) putting the cooled sample into 0.05-0.15mol/L Fe (NO)3)3·9H2Carrying out vacuum infusion in the O solution for 20-30h, and taking out a sample for freeze drying;
(3) placing the sample in N2Heating to a preset temperature of 500 ℃ and 700 ℃ at a speed of 4.5-5.5 ℃/min in a tube furnace under the atmosphere protection, and preserving heat for 2-6h to obtain the catalyst.
In some embodiments, the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing the biological matrix porous carbon raw material for 4-8h at the temperature of 200-;
(2) putting the cooled sample into 0.08-0.12mol/L Fe (NO)3)3·9H2Carrying out vacuum infusion in the O solution for 22-28h, and taking out a sample for freeze drying;
(3) placing the sample in N2Heating to the preset temperature of 600-700 ℃ at the speed of 4.8-5.2 ℃/min in the tube furnace under the atmosphere protection, and preserving the heat for 2-5h to obtain the catalyst.
In some embodiments, the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing a biological matrix porous carbon raw material for 5 hours at 230 ℃, and taking out after cooling;
(2) the cooled sample is put into 0.1mol/L Fe (NO)3)3·9H2After the O solution is soaked in vacuum for 24 hours, taking out a sample and freeze-drying the sample;
(3) placing the sample in N2And (3) heating the mixture to 670 ℃ at the speed of 5 ℃/min in the tube furnace under the atmosphere protection, and preserving the heat for 3 hours to obtain the composite material.
In some of these embodiments, the weight average molecular weight of the polycarbonate is 15000-25000.
In some of these embodiments, the weight average molecular weight of the polycarbonate is 18000-20000.
In some of these embodiments, the bio-matrix porous carbon feedstock is at least one of wood species, straw species.
In some embodiments, the wood material is at least one of pine, basswood and bamboo.
In some embodiments, the straw is at least one of corn straw, wheat straw, cassava straw, reed straw, and kenaf straw.
In some of these embodiments, the bio-matrix porous carbon feedstock is corn stover.
In some of the embodiments, the toughening agent is at least one of a maleic anhydride grafted polymer, a methyl methacrylate-butadiene-styrene-copolymer, a methyl methacrylate-styrene-organosilicon copolymer, an acrylate polymer, an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene-vinyl acetate copolymer, and a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, and preferably, the maleic anhydride grafted polymer is maleic anhydride grafted polyethylene.
In some embodiments, the antioxidant is a combination of n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 1:1.5 to 2.5.
In some of these embodiments, the lubricant is at least one of pentaerythritol stearate, N' -ethylene bis stearamide, oxidized polyethylene wax, polysiloxane, trimethylol propane, and montanate metal soap.
The invention also aims to provide a preparation method of the wave-absorbing polycarbonate composition.
The technical scheme for realizing the purpose is as follows:
the preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring to obtain a mixture; (2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 30-60 ℃, the temperature of the second zone is 230-280 ℃, the temperature of the third zone is 230-280 ℃, the temperature of the fourth zone is 230-280 ℃, the temperature of the fifth zone is 230-280 ℃, the temperature of the sixth zone is 220-260 ℃, the temperature of the seventh zone is 220-260 ℃, the temperature of the eighth zone is 220-260 ℃, the temperature of the die head is 210-250 ℃, and the rotating speed of the screw is 200-500 rpm;
the stirrer in the step (1) is a high-speed stirrer, and the rotating speed is 200 and 1600 revolutions per minute;
the shape of the screw of the parallel double-screw extruder in the step (2) is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35-50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
In some embodiments, the process parameters in step (2) include: the temperature of the first zone is 35-55 ℃, the temperature of the second zone is 230-260 ℃, the temperature of the third zone is 230-260 ℃, the temperature of the fourth zone is 230-260 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 220-250 ℃, the temperature of the seventh zone is 220-250 ℃, the temperature of the eighth zone is 220-250 ℃, the temperature of the die head is 210-240 ℃ and the rotating speed of the screw is 250-450 rpm.
In some embodiments, the ratio L/D between the length L and the diameter D of the screw in the step (2) is 35-45, and the screw is provided with 2 meshing block areas and 1 reverse-thread area.
The wave-absorbing polycarbonate composition disclosed by the invention has the following principle:
the inventor of the invention finds that most biomass carbon materials have a certain regular micro-pore channel structure, and electromagnetic wave energy is sufficiently attenuated in the material. The straight pore channel structure can provide a large number of natural landing sites for magnetic nanoparticles, the microstructure of natural porous and rich solid-gas heterogeneous interfaces are beneficial to enhancing the conductivity and polarization capacity of the material, the conductive loss and broadband absorption of electromagnetic waves are realized, and particularly, the carbon-based electromagnetic composite wave-absorbing material with high performance is developed by reasonably utilizing the complex and special biological structural characteristics of the porous carbon, so that the straight pore channel structure has important research significance and application value.
In the invention, when the porous carbon/ferrite composite wave-absorbing material can be completely dispersed in a polymer in a nanoscale scale, a nanoscale effect, a macroscopic quantum effect, a tunnel effect and a strong interface interaction can be generated, so that the impact property of the material is retained to the maximum extent; furthermore, the porous carbon/ferrite composite wave-absorbing material can be uniformly dispersed in the polycarbonate resin in a completely compatible state, so that the unique pore channel structure of the mesoporous material can be fully used as a framework, and the support on the strength is provided for the wave-absorbing polycarbonate composition.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the biological matrix porous carbon and the ferrite are compounded into the wave-absorbing material, the wave-absorbing material is added into the wave-absorbing polycarbonate composition, and the porous carbon/ferrite composite wave-absorbing material obtained by the specific method is combined with a proper toughening agent for use, so that the toughness of the material can be maintained on the premise of greatly improving the wave-absorbing performance of the wave-absorbing polycarbonate composition. The wave-absorbing polycarbonate composition has the advantages that under the conditions of low amount and proper addition amount of the toughening agent, the wave-absorbing rate of the wave-absorbing polycarbonate composition at the frequency of 75-110GHz is more than or equal to 90%, and the wave-absorbing polycarbonate composition has good impact strength and good comprehensive performance and can be used in the fields of communication, automobile millimeter radar wave parts and the like.
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FIG. 1 is a schematic view of a preparation method of the wave-absorbing polycarbonate composition.
Detailed Description
Unless otherwise defined, all terms used in the specification of the present invention are used only for the purpose of describing specific embodiments, and are not intended to limit the present invention.
The terms "comprises" and "comprising," and any variations thereof, of embodiments of the present invention are intended to cover non-exclusive inclusions. For example, a process, method, apparatus, product, or device that comprises a list of steps or modules is not limited to the listed steps or modules but may alternatively include other steps or modules not listed or inherent to such process, method, product, or device.
The "plurality" referred to in the present invention means two or more. "and/or" describes the association relationship of the associated objects, meaning that there may be three relationships, e.g., a and/or B, which may mean: a exists alone, A and B exist simultaneously, and B exists alone. The character "/" generally indicates that the former and latter associated objects are in an "or" relationship.
The materials used in the present invention are as follows:
polycarbonate (weight average molecular weight 18000-20000): japan Imperial corporation;
raw materials of the biological matrix: corn stover, commercially available;
Fe(NO3)3·9H2o: iron nitrate nonahydrate, available from Nanjing chemical reagents, Inc.;
a toughening agent: maleic anhydride grafted polyethylene, available from Jiangsu Co., Ltd, a good easy compatibilizer;
antioxidant: n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite, available from Ciba, Switzerland;
the antioxidant in the following examples is n-octadecyl beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) propionate and tris (2, 4-di-tert-butylphenyl) phosphite added in a mass ratio of 1: 2;
lubricant: pentaerythritol stearate, available from LONZA corporation, usa.
In order that the invention may be more readily understood, reference will now be made to the following more particular description of the invention, examples of which are set forth below. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. These embodiments are provided so that this disclosure will be thorough and complete.
Example 1:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) preparing corn straws into particles with the length of 5 mm-10 mm, placing the particles in an electric heating air blast drying oven, pre-carbonizing the particles for 5 hours at 230 ℃, cooling and taking out the particles,
(2) putting the cooled sample into 0.1mol/L of Fe (NO) prepared in advance3)3·9H2Soaking in O solution for 24h in vacuum, taking out the sample, freeze-drying,
(3) the sample is then placed in N2And (3) raising the temperature to 670 ℃ at the speed of 5 ℃/min in the tube furnace under the atmosphere protection, and preserving the temperature for 3 h.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Example 2:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw of the parallel double-screw extruder is in a single-thread shape, the ratio L/D of the length L and the diameter D of the screw is 40, and the screw is provided with 2 meshing block areas and 1 reverse-thread area.
Example 3:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Example 4:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Example 5:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Comparative example 1:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Comparative example 2:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Comparative example 3:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
Comparative example 4:
the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 250 ℃, the temperature of the third zone is 250 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 240 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
The preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
processing the purchased corn straws into particles with the length of 5 mm-10 mm, placing the particles in an electric heating blast drying oven, pre-carbonizing the particles for 12 hours at the temperature of 170 ℃, taking out the particles after cooling, and putting the pre-prepared Fe (NO) with the concentration of 0.1mol/L3)3·9H2Soaking in O solution for 18h in vacuum, taking out the sample, freeze-drying, and adding N2And (3) heating the mixture to a preset temperature of 750 ℃ at the speed of 5 ℃/min in the tube furnace under the atmosphere protection, and preserving the heat for 8 hours to obtain the composite material.
Comparative example 5
The wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
the porous carbon/ferrite composite wave-absorbing material is prepared by the preparation method of the embodiment 1.
The preparation method of the wave-absorbing polycarbonate composition comprises the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring (the rotating speed is 600 revolutions per minute) to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters are as follows: the temperature of the first zone is 40 ℃, the temperature of the second zone is 290 ℃, the temperature of the third zone is 290 ℃, the temperature of the fourth zone is 290 ℃, the temperature of the fifth zone is 290 ℃, the temperature of the sixth zone is 290 ℃, the temperature of the seventh zone is 270 ℃, the temperature of the eighth zone is 270 ℃, the temperature of the die head is 260 ℃ and the rotating speed of the screw is 600 rpm;
the screw shape of the parallel double-screw extruder is a single thread; the ratio L/D of the length L of the screw to the diameter D is 40; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
The raw material compositions of examples 1-5 and comparative examples 1-5 are specifically shown in table 1 in parts by weight:
TABLE 1
The wave-absorbing polycarbonate compositions obtained in the embodiments 1 to 5 and the comparative examples 1 to 5 are baked at the temperature of 125 ℃ for 4 hours, the injection molding temperature is from the first stage to the nozzle temperature of 240 ℃, 260 ℃, the mold temperature is 100 ℃, the injection molding speed is medium speed, the following test sample strips are prepared, the state is adjusted for 24 hours under the conditions of 23 ℃ and 50% RH, and finally, the corresponding performance test is carried out:
notched impact strength: the thickness of the sample strip is 4.0mm according to the ISO 185 standard test;
wave absorption rate: the test plate size is 200mm multiplied by 2.0 mm;
the test conditions are as follows: at normal temperature, a network analyzer and a frequency expander are adopted, and 75-110GHZ is adopted;
the frequency range is as follows: 77GHz-110 GHz;
the test mode is as follows: a free space method;
the test instrument comprises: DE-science vector network analyzer n5247(0-67GHZ), U.S. VDI 75-110 GHZ;
the wave-absorbing rate calculation method comprises the following steps:
the wave absorption rate of the material is a characteristic of the material, and is related to the dielectric constant and the magnetic conductivity of the material, and in the calculation formula, the reflectivity calculation formula is as follows:
wherein Z0Is the impedance of free space, expressed as
Wherein mu0＝4π×10-7V·s/(A·m)，ε08.8541X 10-12F/m are all determined values.
ZinIs the input impedance into the material, whose calculation formula is:
wherein mur、εrIs the permeability and permittivity of the material itself, c is the speed of light in free space, f is the frequency of the electromagnetic wave, and d is the thickness of the sample.
The wave absorption rate is 1-reflectivity, and all frequencies with wave absorption rate greater than 90% are defined as effective frequencies.
The test results are shown in table 2:
TABLE 2
From the examples 1-5, it can be known that the wave-absorbing performance of the polycarbonate material is obviously improved and the polycarbonate material has good toughness under the combined action of the porous carbon/ferrite composite wave-absorbing material and the toughening agent. When a small amount of the porous carbon/ferrite composite wave-absorbing material and the toughening agent are added, the wave-absorbing performance of the PC composition is still high. The wave absorbing performance is further improved along with the increase of the addition amount of the porous carbon/ferrite composite wave absorbing material, and when the porous carbon/ferrite composite wave absorbing material reaches 10 parts and the toughening agent reaches 5 parts, the wave absorbing performance and the toughness of the material reach the optimal balance point; the contents of the porous carbon/ferrite composite wave-absorbing material and the toughening agent are continuously increased, so that the toughness of the material is slowly reduced; by comparison, the overall performance of example 3 is best.
Compared with the comparative example 1, the wave-absorbing polycarbonate composition without maleic anhydride grafted polyethylene has very low impact strength, which shows that a certain amount of toughening agent needs to be added into a polycarbonate and porous carbon/ferrite composite wave-absorbing material system to keep the toughness of the polycarbonate material; compared with the comparative example 2, the excessive addition of the porous carbon/ferrite composite wave-absorbing material has obvious side effect on the toughness of the material, and the toughness of the material is still lower even if a large amount of the toughening agent is added; however, in the embodiment 3, compared with the comparative example 3, the porous carbon/ferrite composite wave-absorbing material is added in a small amount, so that the wave-absorbing polycarbonate has extremely high toughness, but the wave-absorbing performance is not high; compared with the comparative example 4, the inventor finds that the inappropriate low-temperature pretreatment, vacuum impregnation and high-temperature in-situ growth process also has a remarkable influence on the wave absorbing performance of the synthesized porous carbon/ferrite composite wave absorbing material, because the straw material is graphitized under the inappropriate synthesis process, and the graphitized carbon/ferrite load material has strong conductivity, so that the impedance matching is poor and the electromagnetic wave is not beneficial to absorption. Compared with the comparative example 5, the inventor finds that the toughness and the wave-absorbing performance of the load-bearing material are seriously influenced by the improper extrusion process, because the porous carbon/ferrite composite wave-absorbing material is damaged as a result of excessively high extrusion temperature, polycarbonate is decomposed, and the performance of the load-bearing material is finally influenced. Through comparison, the notch impact strength and wave absorption rate of the wave-absorbing polycarbonate composition material prepared from the raw materials are greatly improved, the comprehensive performance is good, and the wave-absorbing polycarbonate composition material can be used in the fields of communication, automobile millimeter radar wave parts and the like.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (10)
1. The wave-absorbing polycarbonate composition is characterized by being prepared from the following raw materials in parts by weight:
77-92 parts of polycarbonate resin,
5-15 parts of porous carbon/ferrite composite wave-absorbing material,
3-8 parts of a toughening agent,
the total weight of the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material and the toughening agent is 100 parts,
0.2 to 0.8 portion of antioxidant,
1.2 to 1.8 portions of lubricant,
the porous carbon/ferrite composite wave-absorbing material is prepared from a biological matrix porous carbon raw material and Fe (NO)3)3·9H2O is prepared;
the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps: (1) precarbonization of a porous carbon feedstock of a biological matrixCooling and taking out; (2) placing the cooled sample into Fe (NO)3)3·9H2After the O solution is soaked in vacuum, taking out a sample and freeze-drying the sample; (3) placing the sample in N2And (3) raising the temperature to a preset temperature at a constant speed in the tube furnace under the atmosphere protection, and then preserving the temperature to obtain the composite material.
2. The wave-absorbing polycarbonate composition of claim 1, which is prepared from the following raw materials in parts by weight:
81-88 parts of polycarbonate resin,
7-13 parts of porous carbon/ferrite composite wave-absorbing material,
4-7 parts of a toughening agent,
the total weight of the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material and the toughening agent is 100 parts,
0.2 to 0.8 portion of antioxidant,
1.2-1.8 parts of a lubricant;
preferably, the wave-absorbing polycarbonate composition is prepared from the following raw materials in parts by weight:
83-86 parts of polycarbonate resin,
9-11 parts of porous carbon/ferrite composite wave-absorbing material,
4-6 parts of a toughening agent.
3. The wave-absorbing polycarbonate composition of claim 1, wherein the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing the biological matrix porous carbon raw material for 4-10h at the temperature of 180 ℃ and 250 ℃, and taking out after cooling;
(2) putting the cooled sample into 0.05-0.15mol/L Fe (NO)3)3·9H2Carrying out vacuum infusion in the O solution for 20-30h, and taking out a sample for freeze drying;
(3) placing the sample in N2Heating to a preset temperature of 500 ℃ and 700 ℃ at a speed of 4.5-5.5 ℃/min in a tube furnace under the atmosphere protection, and preserving heat for 2-6h to obtain the catalyst.
4. The wave-absorbing polycarbonate composition of claim 3, wherein the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing the biological matrix porous carbon raw material for 4-8h at the temperature of 200-;
(2) putting the cooled sample into 0.08-0.12mol/L Fe (NO)3)3·9H2Carrying out vacuum infusion in the O solution for 22-28h, and taking out a sample for freeze drying;
(3) placing the sample in N2Heating to the preset temperature of 600-700 ℃ at the speed of 4.8-5.2 ℃/min in the tube furnace under the atmosphere protection, and preserving the heat for 2-5h to obtain the catalyst.
5. The wave-absorbing polycarbonate composition of claim 4, wherein the preparation method of the porous carbon/ferrite composite wave-absorbing material comprises the following steps:
(1) pre-carbonizing a biological matrix porous carbon raw material for 5 hours at 230 ℃, and taking out after cooling;
(2) the cooled sample is put into 0.1mol/L Fe (NO)3)3·9H2After the O solution is soaked in vacuum for 24 hours, taking out a sample and freeze-drying the sample;
(3) placing the sample in N2And (3) heating the mixture to 670 ℃ at the speed of 5 ℃/min in the tube furnace under the atmosphere protection, and preserving the heat for 3 hours to obtain the composite material.
6. The wave absorbing polycarbonate composition of claim 1, characterized in that the weight average molecular weight of the polycarbonate is 15000-25000, preferably the weight average molecular weight of the polycarbonate is 18000-20000.
7. The wave-absorbing polycarbonate composition according to claim 1, wherein the biological matrix porous carbon raw material is at least one of wood and straw, the wood is at least one of pine, basswood and bamboo, the straw is at least one of corn straw, wheat straw, cassava straw, reed straw and kenaf straw; preferably, the biological matrix porous carbon raw material is corn stalks.
8. The wave absorbing polycarbonate composition of claim 1, wherein the toughening agent is at least one of a maleic anhydride grafted polymer, a methyl methacrylate-butadiene-styrene-copolymer, a methyl methacrylate-styrene-silicone copolymer, an acrylate polymer, an ethylene-butyl acrylate-glycidyl methacrylate copolymer, an ethylene-vinyl acetate copolymer, a styrene-acrylonitrile-glycidyl methacrylate ternary random copolymer, preferably the maleic anhydride grafted polymer is maleic anhydride grafted polyethylene;
the antioxidant is a composition of beta- (4-hydroxyphenyl-3, 5-di-tert-butyl) n-octadecyl propionate and tris (2, 4-di-tert-butylphenyl) phosphite in a mass ratio of 1: 1.5-2.5;
the lubricant is at least one of pentaerythritol stearate, N' -ethylene bis stearamide, oxidized polyethylene wax, polysiloxane, trihydroxy methyl propane and montanate metal soap.
9. A method for preparing the wave absorbing polycarbonate composition of any one of claims 1 to 8, which is characterized by comprising the following steps:
(1) adding the polycarbonate resin, the porous carbon/ferrite composite wave-absorbing material, the toughening agent, the antioxidant and the lubricant into a stirrer, and mixing and stirring to obtain a mixture;
(2) adding the obtained mixture into a parallel double-screw extruder through a feeder for melt extrusion and granulation, wherein the process parameters comprise: the temperature of the first zone is 30-60 ℃, the temperature of the second zone is 230-280 ℃, the temperature of the third zone is 230-280 ℃, the temperature of the fourth zone is 230-280 ℃, the temperature of the fifth zone is 230-280 ℃, the temperature of the sixth zone is 220-260 ℃, the temperature of the seventh zone is 220-260 ℃, the temperature of the eighth zone is 220-260 ℃, the temperature of the die head is 210-250 ℃, and the rotating speed of the screw is 200-500 rpm;
the stirrer in the step (1) is a high-speed stirrer, and the rotating speed is 200 and 1600 revolutions per minute;
the shape of the screw of the parallel double-screw extruder in the step (2) is a single thread; the ratio L/D of the length L of the screw to the diameter D of the screw is 35-50; the screw is provided with more than 1 meshing block area and more than 1 reverse thread area.
10. The method for preparing the wave-absorbing polycarbonate composition according to claim 9, wherein the process parameters in the step (2) comprise: the temperature of the first zone is 35-55 ℃, the temperature of the second zone is 230-260 ℃, the temperature of the third zone is 230-260 ℃, the temperature of the fourth zone is 230-260 ℃, the temperature of the fifth zone is 230-260 ℃, the temperature of the sixth zone is 220-250 ℃, the temperature of the seventh zone is 220-250 ℃, the temperature of the eighth zone is 220-250 ℃, the temperature of the die head is 210-240 ℃, and the rotating speed of the screw is 250-450 rpm;
the ratio L/D of the length L to the diameter D of the screw in the step (2) is 35-45; and 2 meshing block areas and 1 reverse thread area are arranged on the screw rod.
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