CN111087778A - Heat-conducting polycarbonate composition with improved flow property, preparation method and application - Google Patents
Heat-conducting polycarbonate composition with improved flow property, preparation method and application Download PDFInfo
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- CN111087778A CN111087778A CN201811234897.9A CN201811234897A CN111087778A CN 111087778 A CN111087778 A CN 111087778A CN 201811234897 A CN201811234897 A CN 201811234897A CN 111087778 A CN111087778 A CN 111087778A
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a heat-conducting polycarbonate composition with improved flow property, a preparation method and application thereof, and mainly solves the problem of poor melt flow property of a heat-conducting polycarbonate material in the prior art. The invention adopts a heat-conducting polycarbonate composition with improved flow property, which comprises the following components in parts by weight: the heat-conducting resin composition comprises, by weight, 40-99 parts of polycarbonate resin, 1-50 parts of heat-conducting filler, 1-20 parts of flow modifier and 0-10 parts of additive, wherein the flow modifier is selected from at least one of styrene polymer and phosphorus-containing organic compound.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a heat-conducting polycarbonate composition with improved flow property, and a preparation method and application thereof. The heat-conducting polycarbonate composition with improved flow property is suitable for heat dissipation parts of electronics, household appliances, automobiles, communication, lighting products and the like.
Background
The polymer material has the characteristics of chemical corrosion resistance, easiness in forming and processing, excellent fatigue resistance, good insulating property and the like, and has received wide attention of people. In recent years, the application of polymer materials in the field of electronic and electric appliances is increasing. However, most of the polymer materials are poor thermal conductors, which limits the application of the polymer materials in the aspect of heat conduction, so that the development of novel polymer materials with good heat conduction performance becomes an important development direction of the existing heat conduction materials. Particularly, with the rapid development of high-power electronic and electrical products and the development of light weight, miniaturization and high performance of electronic and electrical equipment in recent years, more and more problems of reduced product efficacy, shortened service life and the like caused by heat generation of product components inevitably occur.
The data show that the reliability of the electronic component is reduced by 10% when the temperature of the electronic component is increased by 2 ℃; the lifetime at 50 ℃ is only 1/6 at 25 ℃. The density of semiconductor integrated circuits is increasing, and more transistors are contained on the silicon chip, the power is increased, the generated heat is increased, and the requirement for the heat conductivity of the packaging material is increased. The application of the high polymer material to the high-end information product accessories develops towards high power, high integration and rapid heat dissipation, and provides a wider stage for the development of the heat-conducting high polymer material in new fields.
The polymer-based heat conduction material is a high molecular substance capable of effectively transferring heat, and has wide application in the fields of heat exchange engineering, aerospace, heating engineering, electronic and electrical engineering and the like. The polymer-based heat-conducting composite material can be divided into a single-component type and a multi-component type according to different components of the filler in the heat-conducting material. The larger the heat conductivity of the high-thermal-conductivity polymer composite material is, the better the heat conductivity is. CN102482449A, CN 105531309A, CN 104428354a, etc. disclose and report the composition, structure and performance of thermally conductive polymers in different thermally conductive composite systems. In order to improve the thermal conductivity and usability of the heat-conducting polymer material, a large amount of heat-conducting filler, reinforcing agent and additive are required to be introduced into the polymer material, so that the problem of reduction of mechanical properties is inevitably brought about. How to improve the heat-conducting property of the composite material by the heat-conducting filler with a special structural form and not to generate the reduction of the mechanical property of the high-heat-conducting polymer has become a research direction. Meanwhile, the preparation method of the polymer material with the high heat-conducting matrix and the physicochemical modification of the polymer resin matrix are researched, so that the problems of poor flowing property, poor processing property and the like of the resin caused by the addition of excessive fillers are solved, the balance and optimization of the material in the aspects of processability, heat conductivity and usability are ensured, and the important research subject is significant.
Disclosure of Invention
One of the technical problems to be solved by the present invention is to provide a heat conductive polycarbonate composition with improved flowability, which is a problem of poor melt flowability of a heat conductive polycarbonate material in the prior art. The heat-conducting polycarbonate composition with improved flowing property meets the requirements of the usability and the heat conductivity of a workpiece, obviously improves the melt flowing property and the processability, and is suitable for heat-radiating components of electronics, household appliances, automobiles, communication, lighting products and the like.
The second technical problem to be solved by the present invention is to provide a method for preparing a thermally conductive polycarbonate composition with improved flow properties corresponding to the first technical problem.
The present invention is also directed to a method of using a thermally conductive polycarbonate composition with improved flow properties, which method corresponds to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: a heat-conducting polycarbonate composition with improved flow property comprises the following components in parts by weight:
(A) 40-99 parts of polycarbonate resin;
(B) 1-50 parts of heat-conducting filler;
(C) 1-20 parts of a flow modifier;
(D) 0-10 parts of an additive;
wherein, the flow modifier is selected from at least one of styrene polymer and phosphorus-containing organic compound.
In the technical scheme, the polycarbonate resin has the weight average molecular weight of 5000-10000, and the melt index of 15-30 g-10 min under the conditions of 300 ℃ and 1.2kg-1The aromatic polycarbonate resin has a weight average molecular weight of 10000 to 50000, and a melt index of 1 to 15 g.10 min under the conditions of 300 ℃ and 1.2kg-1At least one of the aromatic polycarbonate resins of (1).
In the above technical solution, the heat conductive filler is selected from at least one of oxides, sulfides, and nitrides of II, III, and IV main group elements treated with a surface treatment agent, glass fibers treated with a surface treatment agent, asbestos fibers treated with a surface treatment agent, or carbon materials treated with a surface treatment agent. The carbon material is at least one selected from carbon black, carbon nano tubes, nano fibers, carbon fiber long fibers, carbon fiber short fibers, carbon fiber powder, carbon fiber felt, graphite and graphene.
In the above technical scheme, the surface treatment agent is at least one selected from silane treatment agents, titanate treatment agents and aluminate treatment agents.
In the above technical solution, the styrene polymer is selected from at least one of polystyrene, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylate copolymer, styrene-acrylonitrile-acrylate copolymer and maleic anhydride graft copolymer thereof.
In the above technical solution, the phosphorus-containing organic compound is at least one selected from phosphite ester compounds represented by formula (1) and phosphate ester compounds represented by formula (2):
in the formula (1), R1、R2Selected from the group consisting of hydrocarbyl, arylalkyl, substituted arylalkyl, R3、R4The compound is selected from hydrogen, alkyl, aryl and substituted aryl, and m is selected from 1-10;
in the formula (2), R5、R6Selected from the group consisting of hydrocarbyl, arylalkyl, substituted arylalkyl, R7、R8The aryl is selected from hydrogen, alkyl, aryl and substituted aryl, and n is selected from 1-10.
In the technical scheme, the additive is selected from flame retardants, plasticizers, heat stabilizers, lubricants, antistatic agents, antioxidants, UV absorbers and mold release agents.
In the technical scheme, the flame retardant is at least one selected from triphenyl phosphate, triisopropylphenyl phosphate, tributyl phosphate and trioctyl phosphate.
In the above technical solution, the plasticizer is at least one selected from phthalate, glyceryl tristearate and epoxidized soybean oil.
In the above technical scheme, the heat stabilizer is at least one selected from triphenyl phosphite, tris- (2, 6-dimethylphenyl) phosphite, trimethyl phosphate, dimethylphenyl phosphate and benzotriazole.
In the above technical solution, the lubricant is at least one selected from methyl stearate, polyethylene glycol and polypropylene glycol.
In the technical scheme, the antistatic agent is selected from at least one of glyceryl monostearate, sodium stearyl sulfonate, sodium dodecyl benzene sulfonate and carbon materials.
In the above technical solution, the antioxidant is at least one selected from the group consisting of tris (nonylphenyl) phosphite, tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], n-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, and 2, 6-di-tert-butyl-4-methylphenol.
In the above technical scheme, the UV absorber is selected from at least one of hydroxybenzodiazole, hydroxybenzotriazine, hydroxybenzophenone, benzoxazinone, nano-sized titanium dioxide, and zinc oxide.
In the above technical scheme, the mold release agent is at least one selected from zinc stearate, calcium stearate, barium stearate, magnesium stearate, stearyl stearate, pentaerythritol tetrastearate and paraffin.
In the technical scheme, the molded sample of the heat-conducting polycarbonate composition with improved flow property has the heat conductivity of 0.5-20W/mK.
In the above technical solution, the flow modifier is selected from styrene polymer and organic compound containing phosphorus, and the two compounds can act synergistically to improve the fluidity of the composition.
To solve the second technical problem, the invention adopts the following technical scheme: a method for preparing a thermally conductive polycarbonate composition with improved flow properties according to any of the above-mentioned embodiments for solving the above-mentioned problems, comprising the steps of:
and (2) blending required amounts of the polycarbonate, the heat-conducting filler, the flow modifier and the additive, and then carrying out melt kneading or calendaring molding on the mixed materials to obtain the heat-conducting polycarbonate composition with improved flow property.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: a method of using a thermally conductive polycarbonate composition with improved flow properties as described in any of the above solutions to one of the above problems.
In the above technical scheme, the application method is not particularly limited, and those skilled in the art can apply the composition according to the application of the composition in the prior art, for example, but not limited to, the composition is used for heat dissipation parts such as electronics, home appliances, automobiles, communication, lighting products, and the like.
According to the method disclosed by the invention, the proper flow modifier and the combination thereof are selected and introduced into the polycarbonate resin together with the heat-conducting filler, so that the prepared heat-conducting polycarbonate composition with improved flow property has the advantages that the in-plane heat conductivity, the toughness and the modulus of the material are kept, the melt index is obviously improved, and the heat-conducting polycarbonate composition has excellent processing fluidity, heat conductivity and use performance.
By adopting the technical scheme of the invention, the obtained heat-conducting polycarbonate composition with improved flow property has the advantages of obviously improved melt index, excellent processing flow property, heat conductivity and excellent service performance while keeping the in-plane heat conductivity, toughness and modulus of the material, and better technical effect is obtained.
The performance of the invention was determined as follows:
melt index (MFR) determination: measured by a LLOYD DAVENPORT melt index instrument according to ISO 1133 standard, the temperature is 300 ℃, and the load is 1.2 kg.
And (3) testing tensile property: the tensile rate was 50mm/min, determined according to ISO 527 using a material testing machine from Instron, USA.
Notched impact strength test: measured according to ASTM D256 using an impact tester from CEAST, Italy.
And (3) testing thermal conductivity: measured according to ASTM E1461 standard on a thermal conductivity meter of NETZSCH company, Germany.
Limiting oxygen index test: measured by an oxygen index meter of Shanghai Qianshi precision electro-mechanical technology company according to the GB/T2406.2-2009 standard.
The invention is further illustrated by the following specific examples.
Detailed Description
[ example 1 ]
Surface treatment of the heat-conducting filler: weighing 1 part of flake graphene YH5 (particle size 150 mu m and thickness 80nm), 5 parts of carbon fiber short fiber SCF (particle size 10 mu m and length 5mm) and 2 parts of ethanol solution of silane treating agent KH-550 with concentration of 3.0%, fully stirring and mixing for 10 minutes in a stainless steel vessel, naturally drying, and drying at 100 ℃ for 4 hours to obtain the pretreated thermal conductive filler TCF-1.
67 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 3 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then are put into a high-speed mixer to be blended with TCF-130 parts, 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil for 1.5 minutes, the mixed materials are introduced into a co-rotating twin-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading granulation at the processing temperature of 280 ℃ and the screw rotating speed of 150 rpm to obtain the heat-conductive polycarbonate composition I-1 with the improved flow property, and the processing and extrusion technological parameters are shown in Table 1.
Injection molding test: processing parameters are as follows: the processing temperature is 280 ℃, and the die temperature is 60 ℃. And (3) injection molding the dried I-1 into a standard sample strip by using an injection molding machine, placing the standard sample strip in a constant temperature and humidity box for 24 hours, and testing the performance of the sample.
The results of the comprehensive performance test of I-1 are shown in Table 2.
[ example 2 ]
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then are put into a high-speed mixer to be blended with TCF-130 parts, 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil for 1.5 minutes, the mixed materials are introduced into a co-rotating twin-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading granulation at the processing temperature of 280 ℃ and the screw rotating speed of 150 rpm to obtain the heat-conductive polycarbonate composition I-2 with the improved flow property, and the processing and extrusion technological parameters are shown in Table 1.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of I-2 are shown in Table 2.
[ example 3 ]
62 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 8 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25 percent) are dried for 4 hours at 120 ℃ and 70 ℃ respectively, and then are put into a high-speed mixer for blending treatment for 1.5 minutes together with TCF-130 parts, 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil, the mixed materials are introduced into a co-rotating twin-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading granulation at the processing temperature of 280 ℃ and the screw rotating speed of 150 rpm to obtain the heat-conductive polycarbonate composition I-3 with the improved flow property, and the processing and extrusion technological parameters are shown in Table 1.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of I-3 are shown in Table 2.
[ example 4 ]
58 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 12 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then are put into a high-speed mixer to be blended with TCF-130 parts, 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil for 1.5 minutes, the mixed materials are introduced into a co-rotating twin-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading granulation at the processing temperature of 280 ℃ and the screw rotating speed of 150 rpm to obtain the heat-conductive polycarbonate composition I-4 with the improved flow property, and the processing and extrusion technological parameters are shown in Table 1.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of I-4 are shown in Table 2.
Comparative example 1
The preparation of the heat-conducting polycarbonate composition is that 70 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min) are dried for 4 hours under vacuum at 120 ℃, and then put into a high-speed mixer for blending treatment with 130 parts of TCF, 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil for 1.5 minutes, the mixed materials are introduced into a co-rotating twin-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are melted, kneaded and granulated at the processing temperature of 280 ℃ and the screw rotating speed of 150 revolutions per minute to obtain the heat-conducting polycarbonate composition I-5, and the processing and extrusion technological parameters are shown in Table 1.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of I-5 are shown in Table 2.
TABLE 1
| Sample source | Melt temperature/. degree.C | Melt pressure/bar | Torque/%) |
| I-1 | 282～285 | 52～76 | 33～52 |
| I-2 | 282～284 | 52～76 | 32～53 |
| I-3 | 280～283 | 49～70 | 30～45 |
| I-4 | 280～282 | 44～67 | 28～44 |
| I-5 | 285～289 | 59～78 | 37～50 |
TABLE 2
| Performance of | Unit of | Test standard | I-1 | I-2 | I-3 | I-4 | I-5 |
| Melt index | g/10min | ISO 1133 | 3.6 | 3.9 | 4.2 | 5.5 | 2.8 |
| Tensile strength | MPa | ISO 527 | 106 | 108 | 118 | 125 | 105 |
| Tensile modulus | MPa | ISO 527 | 11437 | 11743 | 11910 | 12225 | 11517 |
| Elongation percentage | ％ | ISO 527 | 1.6 | 1.7 | 1.7 | 1.8 | 1.4 |
| Thermal conductivity | W/mK | ASTM E1461 | 3.1 | 3.0 | 3.2 | 3.2 | 3.1 |
In the group of embodiments, by introducing the flaky graphene/carbon fiber short fiber composite heat-conducting filler and the styrene-acrylonitrile copolymer flow modifier with gradually increased dosage, compared with comparative example 1, the processing and extrusion process parameters are obviously improved (the melt pressure and the screw torque are obviously reduced), which shows that the processability of the material is improved, and the prepared heat-conducting polycarbonate composition has the advantages of maintaining the good heat-conducting property of the material, obviously improving the melt index, improving the processability, increasing the tensile strength and the modulus and improving the service performance under the condition of increasing the dosage of the flow modifier.
[ example 6 ]
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then mixed with TCF-130 parts, 0.5 part of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a homodromous double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and melt kneading and granulation are carried out at the processing temperature of 280 ℃ and the screw rotating speed of 150 revolutions per minute to obtain the heat-conductive polycarbonate composition with the improved flow property, and the processing and extrusion process parameters are shown in a table 3.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of II-1 are shown in Table 4.
[ example 7 ]
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then mixed with TCF-130 parts, 1.5 parts of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a homodromous double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and melt kneading and granulation are carried out at the processing temperature of 280 ℃ and the screw rotating speed of 150 revolutions per minute to obtain the heat-conductive polycarbonate composition with the improved flow property, and the processing and extrusion process parameters are shown in a table 3.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of II-2 are shown in Table 4.
[ example 8 ]
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then mixed with TCF-130 parts, 2.5 parts of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a homodromous double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and melt kneading and granulation are carried out at the processing temperature of 280 ℃ and the screw rotating speed of 150 revolutions per minute to obtain the heat-conductive polycarbonate composition with the improved flow property, and the processing and extrusion process parameters are shown in a table 3.
The injection molding test was the same as in example 1.
The results of the comprehensive performance tests of II-3 are shown in Table 4.
[ example 9 ]
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min) and 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried under vacuum at 120 ℃ and 70 ℃ for 4 hours, and then mixed with TCF-130 parts, 5 parts of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a co-rotating double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading and granulation at the processing temperature of 280 ℃ and the screw rotation speed of 150 revolutions per minute to obtain the heat-conductive polycarbonate composition II-4 with the improved flow property, and the processing and extrusion technological parameters are shown in a table 3.
The injection molding test was the same as in example 1.
The results of the comprehensive performance test of II-4 are shown in Table 4.
TABLE 3
| Sample source | Melt temperature/. degree.C | Melt pressure/bar | Torque/%) |
| I-2 | 282～284 | 52～76 | 32～53 |
| II-1 | 282～285 | 52～76 | 33～52 |
| II-2 | 280～286 | 51～70 | 30～47 |
| II-3 | 283～285 | 52～70 | 32～45 |
| II-4 | 282～283 | 47～66 | 25～40 |
TABLE 4
| Performance of | Unit of | Test standard | I-2 | II-1 | II-2 | II-3 | II-4 |
| Melt index | g/10min | ISO 1133 | 3.9 | 4.4 | 4.9 | 5.3 | 7.0 |
| Tensile strength | MPa | ISO 527 | 108 | 113 | 120 | 118 | 118 |
| Tensile modulus | MPa | ISO 527 | 11743 | 12000 | 12180 | 12298 | 12256 |
| Elongation percentage | ％ | ISO 527 | 1.7 | 1.7 | 1.7 | 1.7 | 1.7 |
| Limiting oxygen index | ％ | GB/T 2406.2-2009 | 33.1 | 32.3 | 34.9 | 37.9 | 38.5 |
In the group of embodiments, the polyaryl phosphate with increased use level is introduced into the polycarbonate/styrene-acrylonitrile copolymer/flake graphene/carbon fiber short fiber composite heat conduction system, so that the processing and extrusion process parameters are obviously improved (the melt pressure and the screw torque are obviously reduced), which shows that the processability of the material is improved.
[ example 10 ]
Surface treatment of the heat-conducting filler: weighing 1 part of flake graphene YH5 (particle size 150 mu m and thickness 80nm), 5 parts of carbon fiber short fiber SCF (particle size 10 mu m and length 5mm) and 4 parts of ethanol solution of silane treating agent KH-550 with concentration of 3.0%, fully stirring and mixing for 10 minutes in a stainless steel vessel, naturally drying, and drying at 100 ℃ for 4 hours to obtain the pretreated thermal conductive filler TCF-2.
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then mixed with TCF-230 parts, 1.5 parts of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a co-rotating double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading and granulation at the processing temperature of 280 ℃ and the screw rotation speed of 150 rpm to obtain the heat-conductive polycarbonate composition with the improved flow property, and the processing and extrusion technological parameters are shown in Table 5.
The injection molding test was the same as in example 1.
The results of the overall performance test of III are shown in Table 6.
[ example 11 ]
Surface treatment of the heat-conducting filler: weighing 1 part of flake graphene YH5 (particle size 150 mu m and thickness 80nm), 5 parts of carbon fiber short fiber SCF (particle size 10 mu m and length 5mm) and 6 parts of ethanol solution of silane treating agent KH-550 with concentration of 3.0%, fully stirring and mixing for 10 minutes in a stainless steel vessel, naturally drying, and drying at 100 ℃ for 4 hours to obtain the pretreated thermal conductive filler TCF-3.
65 parts of polycarbonate particles (with the weight-average molecular weight of 17000 and the melt index of 11.7g/10min), 5 parts of styrene-acrylonitrile copolymer AS (with the weight-average molecular weight of 25 ten thousand and the acrylonitrile content of 25%) are dried at 120 ℃ and 70 ℃ for 4 hours respectively, and then mixed with TCF-330 parts, 1.5 parts of polyaryl phosphate (GD-2000 and the phosphorus content of 10.7%), 0.8 part of tetra [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, the mixed materials are introduced into a co-rotating double-screw extruder (with the screw diameter of 26 mm and the length-diameter ratio of 40), and are subjected to melt kneading and granulation at the processing temperature of 280 ℃ and the screw rotation speed of 150 rpm to obtain the heat-conductive polycarbonate composition with the improved flow property, and the processing and extrusion technological parameters are shown in Table 5.
The injection molding test was the same as in example 1.
The results of the comprehensive property test of IV are shown in Table 6.
[ example 12 ]
A heat-conductive polycarbonate composition with improved flowability was prepared by drying 45 parts of polycarbonate particles (weight-average molecular weight 17000, melt index 11.7g/10min), 20 parts of polycarbonate particles (weight-average molecular weight 9000, melt index 25.8g/10min), 5 parts of styrene-acrylonitrile copolymer AS (weight-average molecular weight 25 ten thousand, acrylonitrile content 25%) at 120 ℃ under 70 ℃ under vacuum for 4 hours, and then blending the resulting mixture with 0.8 part of TCF-330, 1.5 parts of polyaryl phosphate (GD-2000, phosphorus content 10.7%), 0.8 part of tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, introducing the blended material into a co-rotating twin-screw extruder (screw diameter 26 mm, length-diameter ratio 40), at 280 ℃ under 150 rpm, melt-granulating and kneading to obtain a polycarbonate composition with improved flowability, and extrusion process parameters are shown in Table 5.
The injection molding test was the same as in example 1.
The results of the overall performance test of V are shown in Table 6.
TABLE 5
| Sample source | Melt temperature/. degree.C | Melt pressure/bar | Torque/%) |
| II-2 | 280～286 | 51～70 | 30～47 |
| III | 280～284 | 48～66 | 28～44 |
| IV | 280～282 | 43～60 | 25～35 |
| V | 281～283 | 40～58 | 20～30 |
TABLE 6
| Performance of | Unit of | Test standard | II-2 | III | IV | V |
| Melt index | g/10min | ISO 1133 | 4.9 | 5.1 | 5.7 | 6.6 |
| Tensile strength | MPa | ISO 527 | 120 | 118 | 119 | 117 |
| Tensile modulus | MPa | ISO 527 | 12180 | 12056 | 12212 | 12095 |
| Elongation percentage | ％ | ISO 527 | 1.7 | 1.8 | 1.8 | 2.0 |
| Notched impact strength | J/m | ASTM D256 | 38.8 | 39.1 | 42.0 | 41.5 |
| Thermal conductivity | W/mK | ASTM E1461 | 3.2 | 3.3 | 3.2 | 3.2 |
| Limiting oxygen index | ％ | GB/T 2406.2-2009 | 34.9 | 32.6 | 33.5 | 34.5 |
In the group of embodiments, the silane treatment agent with an increased amount and the polycarbonate resin composition with different molecular weight levels are introduced into the polycarbonate/styrene-acrylonitrile copolymer/flake graphene/carbon fiber short fiber/polyaryl phosphate composite heat conduction system, so that the processing and extrusion technological parameters are obviously improved (the melt pressure and the screw torque are obviously reduced), which indicates that the processability of the material is further improved.
[ example 13 ]
A thermally conductive polycarbonate composition having improved flowability was prepared by drying 45 parts of polycarbonate particles (weight-average molecular weight 17000, melt index 11.7g/10min), 20 parts of polycarbonate particles (weight-average molecular weight 9000, melt index 25.8g/10min), 6.5 parts of styrene-acrylonitrile copolymer AS (weight-average molecular weight 25 ten thousand, acrylonitrile content 25%) at 120 ℃ and 70 ℃ under vacuum for 4 hours, and then blending the resulting mixture with TCF-330 parts, 0.8 part of tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, and subjecting the resulting mixture to melt kneading granulation at a processing temperature of 280 ℃ and a screw rotation speed of 150 rpm to obtain a thermally conductive polycarbonate composition having improved flowability, and having an injection molding test of the same AS in example 1 and VI, the results of the comprehensive performance test are shown in Table 7.
[ example 14 ]
A thermally conductive polycarbonate composition having improved flowability was prepared by drying 45 parts of polycarbonate particles (weight-average molecular weight 17000, melt index 11.7g/10min) and 20 parts of polycarbonate particles (weight-average molecular weight 9000, melt index 25.8g/10min) at 120 ℃ under vacuum for 4 hours, and then blending the resulting mixture with 330 parts of TCF, 6.5 parts of polyarylate (GD-2000, phosphorus content 10.7%), 0.8 part of tetrakis [ β - (3, 5-di-t-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester and 1.6 parts of white oil in a high-speed mixer for 1.5 minutes, introducing the mixed materials into a co-rotating twin-screw extruder (screw diameter 26 mm, aspect ratio 40), and melt-kneading and granulating at a processing temperature 280 ℃ and a screw rotation speed of 150 rpm to obtain a thermally conductive polycarbonate composition having improved flowability, and the results of the comprehensive properties in the injection molding test of EXAMPLE 1 and EXAMPLE VII are shown in Table 7.
TABLE 7
| Performance of | Unit of | Test standard | V | VI | VII |
| Melt index | g/10min | ISO 1133 | 6.6 | 6.0 | 6.4 |
| Tensile strength | MPa | ISO 527 | 117 | 116 | 112 |
| Tensile modulus | MPa | ISO 527 | 12095 | 12005 | 11881 |
| Elongation percentage | ％ | ISO 527 | 2.0 | 1.9 | 1.9 |
| Notched impact strength | J/m | ASTM D256 | 41.5 | 39.9 | 40.1 |
| Thermal conductivity | W/mK | ASTM E1461 | 3.2 | 3.0 | 3.0 |
| Limiting oxygen index | ％ | GB/T 2406.2-2009 | 34.5 | 32.7 | 34.0 |
In the group of embodiments, the styrene-acrylonitrile copolymer and the polyaryl phosphate are simultaneously introduced into the polycarbonate/flake graphene/carbon fiber short fiber system, so that the melt flow property, the strength, the modulus, the heat conduction property and the flame retardant property of the prepared heat-conducting polycarbonate composition are superior to those of the composition adopting a single flow modifier, and at the moment, a synergistic effect is generated between the two compounds, the fluidity and the mechanical property of the heat-conducting polycarbonate composition are improved, and a better technical effect is achieved.
Claims (10)
1. A heat-conducting polycarbonate composition with improved flow property comprises the following components in parts by weight:
(A) 40-99 parts of polycarbonate resin;
(B) 1-50 parts of heat-conducting filler;
(C) 1-20 parts of a flow modifier;
(D) 0-10 parts of an additive;
wherein the flow modifier is selected from at least one of styrene polymer and phosphorus-containing organic compound.
2. The thermally conductive polycarbonate composition with improved flowability as claimed in claim 1, wherein the polycarbonate resin has a weight average molecular weight of 5000-10000, a melt index of 15-30 g-10 min at 300 ℃ under 1.2kg-1The aromatic polycarbonate resin has a weight average molecular weight of 10000 to 50000, and a melt index of 1 to 15 g.10 min under the conditions of 300 ℃ and 1.2kg-1At least one of the aromatic polycarbonate resins of (1).
3. The thermally conductive polycarbonate composition with improved flow properties of claim 1, wherein the thermally conductive filler is at least one selected from the group consisting of oxides, sulfides, nitrides of group II, III, IV elements treated with a surface treatment agent, glass fibers treated with a surface treatment agent, asbestos fibers treated with a surface treatment agent, and carbon materials treated with a surface treatment agent.
4. The thermally conductive polycarbonate composition of claim 3, having improved flow properties, wherein the surface treatment agent is selected from at least one of silane treatment agents, titanate treatment agents, aluminate treatment agents.
5. The thermally conductive polycarbonate composition with improved flow properties of claim 1, wherein the styrene polymer is at least one selected from the group consisting of polystyrene, styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-acrylate copolymer, styrene-acrylonitrile-acrylate copolymer, and maleic anhydride graft copolymer thereof.
6. The thermally conductive polycarbonate composition with improved flow properties of claim 1, wherein the phosphorus-containing organic compound is at least one selected from the group consisting of a phosphite compound represented by formula (1) and a phosphate compound represented by formula (2):
in the formula (1), R1、R2Selected from the group consisting of hydrocarbyl, arylalkyl, substituted arylalkyl, R3、R4The compound is selected from hydrogen, alkyl, aryl and substituted aryl, and m is selected from 1-10;
in the formula (2), R5、R6Selected from the group consisting of hydrocarbyl, arylalkyl, substituted arylalkyl, R7、R8The aryl is selected from hydrogen, alkyl, aryl and substituted aryl, and n is selected from 1-10.
7. The thermally conductive polycarbonate composition with improved flow properties of claim 1, wherein the additives are optionally selected from the group consisting of flame retardants, plasticizers, heat stabilizers, lubricants, antistatic agents, antioxidants, UV absorbers, mold release agents.
8. The thermally conductive polycarbonate composition with improved flow properties of claim 1, wherein the molded sample of the thermally conductive polycarbonate composition with improved flow properties has a thermal conductivity of 0.5 to 20W/mK.
9. A method of preparing a thermally conductive polycarbonate composition having improved flow properties, comprising the steps of:
blending required amounts of the polycarbonate of any one of claims 1 to 8, a heat conductive filler, a flow modifier and an additive, and then melt kneading or calendaring the mixed materials to obtain the heat conductive polycarbonate composition with improved flow property.
10. The method of using the thermally conductive polycarbonate composition with improved flow properties of any of claims 1-8.
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| CN102702715A (en) * | 2012-06-29 | 2012-10-03 | 东莞市松燊塑料科技有限公司 | High-fluidity glass fiber reinforced halogen-free flame retardant poly carbonate (PC) resin and preparation method thereof |
| CN107383825A (en) * | 2017-07-19 | 2017-11-24 | 上海仕天工程塑料有限公司 | High glaze, exempt from spraying, thin-walled property Polycarbonate flame retardant reinforcing material and application |
| CN107915973A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Thermoplasticity heat-conductive resin composition and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102702715A (en) * | 2012-06-29 | 2012-10-03 | 东莞市松燊塑料科技有限公司 | High-fluidity glass fiber reinforced halogen-free flame retardant poly carbonate (PC) resin and preparation method thereof |
| CN107915973A (en) * | 2016-10-08 | 2018-04-17 | 中国石油化工股份有限公司 | Thermoplasticity heat-conductive resin composition and preparation method thereof |
| CN107383825A (en) * | 2017-07-19 | 2017-11-24 | 上海仕天工程塑料有限公司 | High glaze, exempt from spraying, thin-walled property Polycarbonate flame retardant reinforcing material and application |
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