CN110684313B - ceramic/ABS super-strong and super-tough composite material and application thereof in electrical field - Google Patents
ceramic/ABS super-strong and super-tough composite material and application thereof in electrical field Download PDFInfo
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- CN110684313B CN110684313B CN201910885390.8A CN201910885390A CN110684313B CN 110684313 B CN110684313 B CN 110684313B CN 201910885390 A CN201910885390 A CN 201910885390A CN 110684313 B CN110684313 B CN 110684313B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K3/28—Nitrogen-containing compounds
- C08K2003/282—Binary compounds of nitrogen with aluminium
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention relates to the technical field of nylon, in particular to a ceramic/ABS (acrylonitrile-butadiene-styrene) super-strong super-tough composite material and application thereof in the electrical field, wherein the ceramic/ABS super-strong super-tough composite material comprises the following raw materials in parts by weight: ABS, modified ceramic, pearl powder, compatilizer, lubricant and antioxidant. The invention takes the aluminum nitride ceramic as the main heat-conducting filler and the montmorillonite as the secondary heat-conducting filler, thereby improving the heat-conducting property of the ABS. In addition, the invention also carries out montmorillonite intercalation modification on the nylon, nylon molecules are inserted between montmorillonite layers to form a composite material, and the montmorillonite builds a heat conduction passage for the aluminum nitride in the nylon, thereby avoiding the problem that the heat conductivity is reduced by nylon obstruction.
Description
Technical Field
The invention relates to the technical field of ABS, in particular to a ceramic/ABS super-strong and super-tough composite material and application thereof in the electrical field.
Background
The ABS plastic is a terpolymer of three monomers of acrylonitrile (A), butadiene (B) and styrene (S), and the relative contents of the three monomers can be changed at will to prepare various resins. ABS has the common properties of three components, A makes it resistant to chemical corrosion and heat and has a certain surface hardness, B makes it have high elasticity and toughness, and S makes it have the processing and forming characteristics of thermoplastic plastics and improves the electrical properties. Therefore, ABS plastic is a tough, hard and rigid material with easily available raw materials, good comprehensive performance, low price and wide application. ABS plastics are widely applied to the manufacturing industries of machinery, electricity, textiles, automobiles, airplanes, ships and the like and chemical engineering.
ABS is difficult to use for accessories that require heat dissipation due to its low thermal conductivity. In order to develop a thermally conductive ABS material, the existing ABS must be modified. The ABS has excellent comprehensive performance, the market competition of the general ABS is intensified in recent years, and the heat-conducting ABS material is developed, so that the application of the ABS material in the aspect of electronic and electric appliance shells can be expanded, and the additional value of products is improved.
The method for improving the thermal conductivity of the ABS generally comprises the steps of mixing the thermal conductive filler to form an effective thermal conductive path in an ABS matrix, so that the filling amount of the thermal conductive filler in the ABS is required to be large, the thermal conductivity is generally required to reach more than 50 wt% of the filling amount to be obviously improved, but the strength and the toughness of the ABS are reduced due to the problem of stress concentration, the processability is also deteriorated, and the industrial production is not facilitated.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a ceramic/ABS super-strong super-tough heat-conducting composite material and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) dissolving 15-25 parts by weight of PA6 in 100 parts by weight of formic acid to form a nylon solution;
(2) adding 30-40 parts by weight of montmorillonite into the nylon solution, and uniformly stirring to obtain a suspension;
(3) spray drying the suspension to obtain the intercalation modified nylon;
(4) adding the intercalation modified nylon, the aluminum nitride and the surfactant into deionized water, wherein the weight ratio of the intercalation modified nylon, the aluminum nitride, the surfactant to the deionized water is 10-15:30-40:1-2:100, then carrying out ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic.
The invention takes the aluminum nitride ceramic as the main heat-conducting filler and the montmorillonite as the secondary heat-conducting filler, thereby improving the heat-conducting property of the ABS. In addition, the invention also carries out montmorillonite intercalation modification on the nylon, nylon molecules are inserted between montmorillonite layers to form a composite material, and the montmorillonite builds a heat conduction path for the aluminum nitride in the nylon, thereby avoiding the problem that the heat conductivity is reduced by nylon obstruction; in addition, the compatilizer is added to effectively improve the interfacial property of the PA6 and the ABS, so that the ABS material with good mechanical property and thermal conductivity can be obtained finally.
Wherein the melt index of the PA6 at 230 ℃/2.16kg is 17-20g/10 min.
Wherein the melt index of the ABS at the temperature of 220 ℃/10Kg is 60-65 g/min.
The ABS has better melt fluidity than PA6, so that in the blending process, the ABS is used as a continuous phase, and the modified ceramic can form a dispersion phase with stable structure in the continuous phase, thereby maintaining the integrity of a heat-conducting network and improving the heat-conducting property of the ABS. The ABS adopted by the invention is high-fluidity ABS, and can be used as a spraying-free material under the condition of being matched with the modified ceramic, and the surface of an injection molding piece is flat and has no flow mark.
Wherein the thickness of the crystal plate row of the montmorillonite is 10-20nm, the grain diameter of the aluminum nitride is 20-30nm, and the surfactant is alkylphenol polyoxyethylene.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is at least one of calcium stearate and zinc stearate.
Wherein the compatilizer is at least one of ABS-g-MAH and POE-g-MAH.
Wherein the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
The ceramic/ABS super-strong and super-tough composite material is applied to the electrical field. The ceramic/ABS super-strong and super-tough heat-conducting composite material has good insulativity and heat conductivity, is particularly suitable for the electrical field, and can be used for manufacturing products such as plugs, sockets, wiring boards, relays and the like.
The invention has the beneficial effects that: the invention takes the aluminum nitride ceramic as the main heat-conducting filler and the montmorillonite as the secondary heat-conducting filler, thereby improving the heat-conducting property of the ABS. In addition, the invention also carries out montmorillonite intercalation modification on the nylon, nylon molecules are inserted between montmorillonite layers to form a composite material, and the montmorillonite builds a heat conduction path for the aluminum nitride in the nylon, thereby avoiding the problem that the heat conductivity is reduced by nylon obstruction; in addition, the compatilizer is added to effectively improve the interfacial property of the PA6 and the ABS, so that the ABS material with good mechanical property and thermal conductivity can be obtained finally.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) dissolving 15 parts by weight of PA6 in 100 parts by weight of formic acid to form a nylon solution;
(2) adding 30 parts by weight of montmorillonite into the nylon solution, and uniformly stirring to obtain a suspension;
(3) spray drying the suspension to obtain the intercalation modified nylon;
(4) adding the intercalation modified nylon, the aluminum nitride and the surfactant into deionized water, wherein the weight ratio of the intercalation modified nylon to the aluminum nitride to the surfactant to the deionized water is 10:30:1:100, and then performing ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic.
Wherein the melt index of the PA6 at 230 ℃/2.16kg is 17g/10 min.
Wherein the melt index of the ABS at the condition of 220 ℃/10Kg is 60 g/min.
Wherein the thickness of the crystal plate row of the montmorillonite is 10nm, the grain diameter of the aluminum nitride is 20nm, and the surfactant is alkylphenol polyoxyethylene.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is calcium stearate.
Wherein the compatilizer is ABS-g-MAH.
Wherein the antioxidant is an antioxidant 1076.
The preparation method of the ceramic/ABS super-strong and super-tough composite material comprises the following steps: after being dispersed uniformly, the raw materials are added into a double-screw extruder for extrusion granulation, and the ceramic/ABS super-strong and super-tough composite material is obtained.
The working temperature of each zone of the double-screw extruder is as follows in sequence: 220 ℃, 230 ℃, 250 ℃, 240 ℃ and 230 ℃.
Example 2
A ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) dissolving 25 parts by weight of PA6 in 100 parts by weight of formic acid to form a nylon solution;
(2) adding 40 parts by weight of montmorillonite into the nylon solution, and uniformly stirring to obtain a suspension;
(3) spray drying the suspension to obtain the intercalation modified nylon;
(4) adding the intercalation modified nylon, the aluminum nitride and the surfactant into deionized water, wherein the weight ratio of the intercalation modified nylon to the aluminum nitride to the surfactant to the deionized water is 15:40:2:100, and then performing ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic.
Wherein the melt index of the PA6 at 230 ℃/2.16kg is 20g/10 min.
Wherein the melt index of the ABS at the condition of 220 ℃/10Kg is 65 g/min.
Wherein the thickness of the crystal plate row of the montmorillonite is 20nm, the grain diameter of the aluminum nitride is 30nm, and the surfactant is alkylphenol polyoxyethylene.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is zinc stearate.
Wherein, the compatilizer is POE-g-MAH.
Wherein the antioxidant is antioxidant 168.
The preparation method of the ceramic/ABS super-strong and super-tough composite material comprises the following steps: after being dispersed uniformly, the raw materials are added into a double-screw extruder for extrusion granulation, and the ceramic/ABS super-strong and super-tough composite material is obtained.
The working temperature of each zone of the double-screw extruder is as follows in sequence: 230 ℃, 240 ℃, 250 ℃, 240 ℃ and 230 ℃.
Example 3
A ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) dissolving 20 parts by weight of PA6 in 100 parts by weight of formic acid to form a nylon solution;
(2) adding 35 parts by weight of montmorillonite into the nylon solution, and uniformly stirring to obtain a suspension;
(3) spray drying the suspension to obtain the intercalation modified nylon;
(4) adding the intercalation modified nylon, the aluminum nitride and the surfactant into deionized water, wherein the weight ratio of the intercalation modified nylon to the aluminum nitride to the surfactant to the deionized water is 12:35:1.5:100, and then carrying out ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic.
Wherein the melt index of the PA6 at 230 ℃/2.16kg is 18g/10 min.
Wherein the melt index of the ABS at the condition of 220 ℃/10Kg is 63 g/min.
The thickness of the crystal plate row of the montmorillonite is 15nm, the grain size of the aluminum nitride is 25nm, and the surfactant is alkylphenol polyoxyethylene.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is a mixture of calcium stearate and zinc stearate in a weight ratio of 1: 2.
Wherein the compatilizer is a mixture of ABS-g-MAH and POE-g-MAH according to the weight ratio of 2: 1.
Wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1076 in a weight ratio of 1: 2.
The preparation method of the ceramic/ABS super-strong and super-tough composite material comprises the following steps: after being dispersed uniformly, the raw materials are added into a double-screw extruder for extrusion granulation, and the ceramic/ABS super-strong and super-tough composite material is obtained.
The working temperature of each zone of the double-screw extruder is as follows in sequence: 225 ℃, 235 ℃, 250 ℃, 245 ℃ and 230 ℃.
Comparative example 1
A ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
wherein the melt index of the PA6 at 230 ℃/2.16kg is 18g/10 min.
Wherein the melt index of the ABS at the condition of 220 ℃/10Kg is 63 g/min.
The thickness of the wafer row of the montmorillonite is 15nm, the particle size of the aluminum nitride is 25nm, the surfactant is alkylphenol ethoxylates, and the aluminum nitride and the montmorillonite are both modified by a silane coupling agent.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is a mixture of calcium stearate and zinc stearate in a weight ratio of 1: 2.
Wherein the compatilizer is a mixture of ABS-g-MAH and POE-g-MAH according to the weight ratio of 2: 1.
Wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1076 in a weight ratio of 1: 2.
The preparation method of the ceramic/ABS super-strong and super-tough composite material comprises the following steps: after being dispersed uniformly, the raw materials are added into a double-screw extruder for extrusion granulation, and the ceramic/ABS super-strong and super-tough composite material is obtained.
The working temperature of each zone of the double-screw extruder is as follows in sequence: 225 ℃, 235 ℃, 250 ℃, 245 ℃ and 230 ℃.
Comparative example 2
A ceramic/ABS super-strong and super-tough composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) spray drying the suspension to obtain the intercalation modified nylon;
(2) adding PA6, aluminum nitride and a surfactant into deionized water, wherein the weight ratio of PA6 to aluminum nitride to the surfactant to the deionized water is 12:35:1.5:100, and then carrying out ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic.
Wherein the melt index of the PA6 at 230 ℃/2.16kg is 18g/10 min.
Wherein the melt index of the ABS at the condition of 220 ℃/10Kg is 63 g/min.
Wherein the particle size of the aluminum nitride is 25nm, and the surfactant is alkylphenol ethoxylates.
Wherein, the pearl powder is a mica sheet.
Wherein the lubricant is a mixture of calcium stearate and zinc stearate in a weight ratio of 1: 2.
Wherein the compatilizer is a mixture of ABS-g-MAH and POE-g-MAH according to the weight ratio of 2: 1.
Wherein the antioxidant is a mixture of antioxidant 168 and antioxidant 1076 in a weight ratio of 1: 2.
The preparation method of the ceramic/ABS super-strong and super-tough composite material comprises the following steps: after being dispersed uniformly, the raw materials are added into a double-screw extruder for extrusion granulation, and the ceramic/ABS super-strong and super-tough composite material is obtained.
The working temperature of each zone of the double-screw extruder is as follows in sequence: 225 ℃, 235 ℃, 250 ℃, 245 ℃ and 230 ℃.
The plastics of example 3 and comparative examples 1-2 were fabricated into test specimens and the test specimens were tested for tensile strength, flexural strength, impact strength and thermal conductivity, respectively, according to ASTM D-638, ASTM D-790, ASTM D-256, ASTM D5470, and the results are given in the following table:
compared with the silane coupling agent modification treatment of the comparative example 1, the ABS material of the embodiment 3 of the invention has better mechanical property, but the heat conduction performance is poorer, which shows that the filling amount of the heat conduction filler in the comparative example 1 is larger, and even though the silane coupling agent treatment is carried out, the better dispersion can not be realized in the matrix, so the mechanical property is poorer, but the fillers in the comparative example 1 are easy to agglomerate and contact with each other to form a heat conduction path, so the heat conduction performance is better; compared with the comparative example 2, the invention can better solve the problem of agglomeration of aluminum nitride through the ultrasonic dispersion of nylon and aluminum nitride, has better mechanical property, but the nylon can not form a better heat conduction path because of forming intervals between the aluminum nitride, so that the finally prepared ABS material has poorer heat conduction performance.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (7)
1. A ceramic/ABS super strong super tough composite material is characterized in that: the composite material comprises the following raw materials in parts by weight:
the preparation method of the modified ceramic comprises the following steps:
(1) dissolving 15-25 parts by weight of PA6 in 100 parts by weight of formic acid to form a nylon solution;
(2) adding 30-40 parts by weight of montmorillonite into the nylon solution, and uniformly stirring to obtain a suspension;
(3) spray drying the suspension to obtain the intercalation modified nylon;
(4) adding intercalation modified nylon, aluminum nitride and a surfactant into deionized water, wherein the weight ratio of the intercalation modified nylon to the aluminum nitride to the surfactant to the deionized water is 10-15:30-40:1-2:100, then performing ultrasonic dispersion, filtering, washing and drying to obtain the modified ceramic;
the melt index of the PA6 under the condition of 230 ℃/2.16kg is 17-20g/10 min;
the thickness of the crystal plate line of the montmorillonite is 10-20nm, the grain size of the aluminum nitride is 20-30nm, and the surfactant is alkylphenol polyoxyethylene.
2. The ceramic/ABS ultra-strong and ultra-tough composite material as claimed in claim 1, wherein: the melt index of the ABS under the condition of 220 ℃/10Kg is 60-65 g/min.
3. The ceramic/ABS ultra-strong and ultra-tough composite material as claimed in claim 1, wherein: the pearl powder is a mica sheet.
4. The ceramic/ABS ultra-strong and ultra-tough composite material as claimed in claim 1, wherein: the lubricant is at least one of calcium stearate and zinc stearate.
5. The ceramic/ABS ultra-strong and ultra-tough composite material as claimed in claim 1, wherein: the compatilizer is at least one of ABS-g-MAH and POE-g-MAH.
6. The ceramic/ABS ultra-strong and ultra-tough composite material as claimed in claim 1, wherein: the antioxidant is at least one of antioxidant 1010, antioxidant 168 and antioxidant 1076.
7. The use of a ceramic/ABS ultra-strong and ultra-tough composite material according to any of claims 1 to 6, wherein: application in the electrical field.
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