CN115558285B - Polyamide composite material and preparation method thereof - Google Patents
Polyamide composite material and preparation method thereof Download PDFInfo
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- CN115558285B CN115558285B CN202211242471.4A CN202211242471A CN115558285B CN 115558285 B CN115558285 B CN 115558285B CN 202211242471 A CN202211242471 A CN 202211242471A CN 115558285 B CN115558285 B CN 115558285B
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 98
- 229920002647 polyamide Polymers 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 86
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical class [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 63
- 229920002292 Nylon 6 Polymers 0.000 claims abstract description 59
- 239000004593 Epoxy Substances 0.000 claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 52
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 52
- 229920001971 elastomer Polymers 0.000 claims abstract description 44
- 239000000806 elastomer Substances 0.000 claims abstract description 42
- 229920006345 thermoplastic polyamide Polymers 0.000 claims abstract description 42
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 239000000314 lubricant Substances 0.000 claims abstract description 33
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 33
- WBWXVCMXGYSMQA-UHFFFAOYSA-N 3,9-bis[2,4-bis(2-phenylpropan-2-yl)phenoxy]-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C=1C=C(OP2OCC3(CO2)COP(OC=2C(=CC(=CC=2)C(C)(C)C=2C=CC=CC=2)C(C)(C)C=2C=CC=CC=2)OC3)C(C(C)(C)C=2C=CC=CC=2)=CC=1C(C)(C)C1=CC=CC=C1 WBWXVCMXGYSMQA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 30
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 24
- 229920001577 copolymer Polymers 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001125 extrusion Methods 0.000 claims description 15
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 12
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 11
- -1 dimethyl siloxane Chemical class 0.000 claims description 11
- 229920000570 polyether Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 238000012653 anionic ring-opening polymerization Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 238000000707 layer-by-layer assembly Methods 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 4
- 229920003169 water-soluble polymer Polymers 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 33
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- 238000004519 manufacturing process Methods 0.000 description 8
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- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000011358 absorbing material Substances 0.000 description 4
- 230000002411 adverse Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 229920006122 polyamide resin Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229910018540 Si C Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229920002748 Basalt fiber Polymers 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZFMITUMMTDLWHR-UHFFFAOYSA-N Minoxidil Chemical compound NC1=[N+]([O-])C(N)=CC(N2CCCCC2)=N1 ZFMITUMMTDLWHR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
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- 229960003632 minoxidil Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
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- 230000007935 neutral effect Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/04—Thermoplastic elastomer
Abstract
The invention discloses a polyamide composite material and a preparation method thereof, wherein the polyamide composite material is prepared from the following raw materials: polyamide 6, modified hybrid carbon nanotubes, modified silicon carbide, thermoplastic polyamide elastomers, epoxy compatibilizers, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, and silicone lubricants. The polyamide composition has excellent wave-absorbing performance and heat conducting performance, and can be widely applied to the field of electronic components needing shielding and heat conducting functions.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a polyamide composite material and a preparation method thereof.
Background
In recent decades, with rapid progress in modern technology, various high-tech products are presented, and life style of people, such as touch screen mobile phones, notebook computers, liquid crystal televisions, smart bracelets, etc., is greatly improved. The new generation products bring convenience to people and are accompanied by potential hazard, namely electromagnetic waves can be continuously emitted to the living environment of people in the using process, and electromagnetic pollution is caused.
A wave absorbing material is a material that is capable of efficiently absorbing and attenuating electromagnetic wave energy, which can be converted into other forms of energy loss by means of internal dielectric and magnetic losses. When an incident electromagnetic wave contacts a material surface, three situations occur: (1) a part of electromagnetic waves generate electromagnetic reflection on the surface of the material and return to free space again; (2) the other part of electromagnetic waves which are not reflected enter the material and are absorbed by loss mechanisms such as dielectric loss, magnetic loss and the like in the transmission process; (3) the last small part of the electromagnetic wave is not reflected nor absorbed, and finally penetrates the other side of the material.
The polyamide is engineering plastic with excellent performance and is widely applied to the fields of automobiles, electronic appliances, military industry and the like. Silicon carbide (SiC) is formed by bonding Si and C through covalent bonds, and the basic structural unit is an S-C tetrahedron, so that the silicon carbide has good chemical stability and thermal stability, and also has good mechanical and thermal conductivity, and has wide application prospects in the fields of optoelectronics, high-temperature electronics, radiation-resistant electronics and high-frequency high-power devices.
Currently, some studies are made in the prior art on polyamides with wave-absorbing function, such as: chinese patent CN 114316577a discloses a wave-absorbing polyamide composite material synthesized from the following raw materials: caprolactam, fe 3 O 4 Graphene nano hybrid material and Fe 3 O 4 The multi-wall carbon nano tube nano composite material, a double-grafted ethylene-octene copolymer, benzoic acid, a main antioxidant and an auxiliary antioxidant; chinese patent CN 112795178A discloses a high-strength polyamide wave-absorbing material comprising the following components in parts by weight: 30-70 parts of polyamide; 5-60 parts of continuous basalt fiber; 0.1-2 parts of flow modifier; 1-30 parts of wave absorber; 0.2 to 0.8 part of antioxidant; 0.1-1 part of lubricant; chinese patent CN 107916064a discloses a wave-absorbing powder coating comprising a polyamide resin, an absorber and an antioxidant. It can be seen from the above patent that the current polyamide composite material can only realize a single wave absorbing function.
Disclosure of Invention
Based on the above, one of the purposes of the present invention is to provide a polyamide composite material, which has excellent wave absorbing performance and heat conducting performance, and can be widely applied to the field of electronic components needing shielding and heat conducting functions.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
the polyamide composite material is prepared from the following raw materials in parts by weight:
the modified hybrid carbon nanotube is prepared by uniformly mixing gamma-aminopropyl triethoxysilane and the hybrid carbon nanotube; the hybrid carbon nano tube is prepared by preparing a modified carbon nano tube and modified graphite phase carbon nitride in an electrostatic self-assembly mode;
The modified silicon carbide is prepared by uniformly mixing gamma-aminopropyl triethoxysilane and silicon carbide;
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate;
the silicone lubricant is prepared by taking a mixed ring of dimethyl siloxane as a monomer and tetramethyl ammonium hydroxide silicon alkoxide as an initiator through anionic ring-opening polymerization.
In some embodiments, the polyamide composite material is prepared from the following raw materials in parts by weight:
in some embodiments, the polyamide composite material is prepared from the following raw materials in parts by weight:
in some of these embodiments, the polyamide 6 has a number average molecular weightThe mass is 22000-28000 g/mol; the thermoplastic polyamide elastomer is formed by alternately copolymerizing hard segment polyamide 6 and soft segment polyether, wherein the content of the soft segment polyether is 25-35 wt%; the number average molecular weight of the epoxy compatilizer is 6500-7200 g/mol, and the epoxy equivalent is 280-310 g/mol; the silicone lubricant has a number average molecular weight of (0.84-1.60) x 10 6 g/mol。
In some of these embodiments, the modified hybrid carbon nanotubes are prepared as follows:
(1) Calcining melamine at 500-600 ℃ for 2-3 h to obtain graphite-phase carbon nitride, dispersing 100g of graphite-phase carbon nitride in 200-300 mL of concentrated hydrochloric acid, stirring for 7-9 h to carry out protonizing reaction, adding 200-300 mL of deionized water, carrying out ultrasonic treatment for 1-2 h, carrying out high-speed centrifugal separation, washing with water and ethanol for multiple times to neutrality, and drying to obtain modified graphite-phase carbon nitride;
(2) Mixing 100g of carbon nano tube with 9-11 mL of concentrated sulfuric acid and 2-4 mL of hydrogen peroxide, performing ultrasonic treatment for 3-5 h, then dropwise adding 5-7 mL of concentrated nitric acid in an ice-water bath, stirring to room temperature, performing ultrasonic treatment for 2-3 h, washing with water and ethanol for many times to neutrality, and drying to obtain the modified carbon nano tube;
(3) Dispersing 90-110 g of modified graphite phase carbon nitride in ethanol by an ultrasonic method to obtain a solution A, dispersing 60-80 g of modified carbon nano tube in ethanol to obtain a solution B, mixing the solution A and the solution B, refluxing and stirring for 10-14 h at 55-65 ℃, washing with water and ethanol for multiple times to neutrality, drying, and uniformly mixing with 2-4 g of gamma-aminopropyl triethoxysilane to obtain the modified hybrid carbon nano tube.
In some of these embodiments, the modified silicon carbide is prepared as follows: and uniformly mixing 100g of silicon carbide with 1-2 g of gamma-aminopropyl triethoxysilane to obtain the modified silicon carbide.
Another object of the present invention is to provide a method for preparing the above polyamide composite material.
The specific technical scheme for realizing the aim of the invention comprises the following steps:
a method for preparing a polyamide composite material, comprising the steps of:
(1) Drying the polyamide 6 at 105-115 ℃ for 2-4 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) in the lateral direction (such as a third zone) of the parallel double-screw extruder (total eight zones), and carrying out melt extrusion and granulation, wherein the technological parameters comprise: the temperature of the first area is 210-230 ℃, the temperature of the second area is 215-235 ℃, the temperature of the third area is 220-240 ℃, the temperature of the fourth area is 220-240 ℃, the temperature of the fifth area is 225-245 ℃, the temperature of the sixth area is 225-245 ℃, the temperature of the seventh area is 225-245 ℃, the temperature of the eighth area is 220-240 ℃, the temperature of the die head is 220-240 ℃, and the screw rotating speed is 300-700 rpm.
In some of these embodiments, the method of making the polyamide composite material comprises the steps of:
(1) Drying the polyamide 6 at 108-112 ℃ for 2.6-3.4 hours, cooling, and adding the cooled polyamide 6 and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) in the lateral direction (such as a third zone) of the parallel double-screw extruder (total eight zones), and carrying out melt extrusion and granulation, wherein the technological parameters comprise: the temperature of the first area is 215-225 ℃, the temperature of the second area is 220-230 ℃, the temperature of the third area is 225-235 ℃, the temperature of the fourth area is 225-235 ℃, the temperature of the fifth area is 230-240 ℃, the temperature of the sixth area is 230-240 ℃, the temperature of the seventh area is 230-240 ℃, the temperature of the eighth area is 225-235 ℃, the temperature of the die head is 225-235 ℃, and the screw rotating speed is 450-550 rpm.
In some of these embodiments, the screw shape of the parallel twin screw extruder is single-flighted; the ratio L/D of the length L and the diameter D of the screw is 35-55; the screw is provided with more than 1 (containing 1) meshing block areas and more than 1 (containing 1) reverse thread areas.
In some of these embodiments, the ratio L/D of the screw length L to the diameter D is 40 to 50; and the screw is provided with 2 meshing block areas and 1 reverse thread area.
In some embodiments, in step (1) and/or step (2), the stirrer is a high-speed stirrer with a rotation speed of 500-1500 rpm.
The polyamide composite material of the invention has the following functions of the raw materials:
the graphite phase carbon nitride has better thermal conductivity, and can be uniformly dispersed in the polymer base material to form a heat conduction channel, so that the thermal conductivity of the polymer is improved. The hybrid carbon nanotube prepared by the modified carbon nanotube and the modified graphite phase carbon nitride in an electrostatic self-assembly mode has the synergistic heat conduction effect. Because of the electrostatic adsorption effect of the surface of the modified graphite phase carbon nitride, the modified carbon nanotubes in the hybrid carbon nanotubes are uniformly dispersed and isolated from the modified graphite phase carbon nitride, and are not easy to agglomerate, so that the interface thermal resistance is reduced, the effective dispersion of a heat conduction network is facilitated, meanwhile, the modified graphite phase carbon nitride is uniformly dispersed in polyamide 6 base material resin, the modified carbon nanotubes attached to the modified graphite phase carbon nitride act as bridges, the two cooperate to form a three-dimensional heat conduction path network, a sea-island model can be used for describing the heat conduction network, then island-shaped modified graphite phase carbon nitride is uniformly dispersed in polyamide 6 base material resin to collect heat in the base material resin, and the modified carbon nanotubes are bridged in high-speed channels of the modified graphite phase carbon nitride, so that the heat is efficiently conducted.
The silicon carbide is formed by combining Si and C through covalent bonds, the basic structural unit of the silicon carbide is a Si-C tetrahedron, and the silicon carbide has good chemical stability and thermal stability, good mechanical and thermal conductivity and good electromagnetic wave absorption performance, and is a traditional wave absorbing material. The modified silicon carbide prepared by uniformly mixing the gamma-aminopropyl triethoxy silane and the silicon carbide can be uniformly dispersed in a polyamide 6 resin substrate, so that the interfacial adhesion and the dispersibility of the modified silicon carbide and the polyamide 6 are improved, the wave absorbing performance of the composite material is improved, and the influence on the mechanical property of the composite material is reduced. And the modified silicon carbide and the modified hybrid carbon nano tube have higher electrical loss tangent angles, and can absorb electromagnetic waves by utilizing electron polarization or interface polarization attenuation of a medium in a cooperative manner.
The thermoplastic polyamide elastomer is formed by alternately copolymerizing high-crystallinity hard segment polyamide 6 and amorphous soft segment polyether, wherein the content of the soft segment polyether is 25-35 wt%. The thermodynamic incompatibility between the soft segment and the hard segment leads to microphase separation with different forms, wherein the hard segment molecular chain has amide bonds and can form hydrogen bonds, and a physical crosslinking state is formed in a natural state, so that the thermoplastic polyamide elastomer has good mechanical properties; the soft segment is polyether, so that the thermoplastic polyamide elastomer has the properties of rebound resilience, creep resistance, impact resistance and the like. The thermoplastic polyamide elastomer has the elasticity of rubber and keeps the toughness and wear resistance of polyamide resin.
The epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate, wherein the relative molecular mass of the epoxy compatilizer is 6500-7200 g/mol, and the epoxy equivalent is 280-310 g/mol. The amino end groups of the polyamide 6, the thermoplastic polyamide elastomer, the modified hybrid carbon nano tube and the modified silicon carbide can react with the epoxy functional groups of the epoxy compatilizer, so that the interfacial adhesion and the dispersibility of the modified hybrid carbon nano tube and the modified silicon carbide in the polyamide 6 base material resin are improved, and the wave absorbing performance and the heat conducting performance of the polyamide composite material are improved. Meanwhile, the epoxy compatilizer also enhances the compatibility of the thermoplastic polyamide elastomer and the polyamide 6, reduces the adverse effect on the bending strength of the polyamide composite material and improves the impact strength of the polyamide composite material.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite belongs to a solid phosphite high-temperature antioxidant, the phosphorus content is 7.3%, the molecular weight 852, the melting point is more than 225 ℃, the initial decomposition temperature is 283.8 ℃, and the introduction of the antioxidant can capture peroxy free radicals formed in the oxidation process of polyamide, limit the combination of N element and O element and inhibit oxidation chain reaction, so that the thermal oxygen stability of the polyamide composite material is effectively improved, and the oxidation resistance of the polyamide composite material is improved.
The silicone lubricant is prepared by taking a dimethyl siloxane mixed ring as a monomer and tetramethyl ammonium hydroxide silicon alkoxide as an initiator through anionic ring-opening polymerization, and has the relative number and molecular mass of (0.84-1.60) multiplied by 10 6 g/mol, belongs to polysiloxane with ultra-high relative molecular mass, and is solid under room temperature condition. The addition of a small amount of polysiloxane with ultra-high relative molecular mass in the plastic processing and forming process can improve the processability and fluidity of the resin and also improve the wear resistance and scratch resistance of the product. Compared with low-relative molecular weight polysiloxane, the ultra-high relative molecular weight polysiloxane is more convenient to mix with plastic, does not slip when extruded in a screw rod, is safer to use, does not migrate and separate out in plastic products, and has good stability.
Compared with the prior art, the polyamide composite material and the preparation method thereof have the following steps
The beneficial effects are that:
1. the invention provides a polyamide composite material with both wave-absorbing function and heat-conducting function, aiming at the fact that the existing polyamide composite material can only realize a single wave-absorbing function. The modified hybrid carbon nano tube is used for providing a heat conduction function, the modified silicon carbide is used for providing a wave absorption function, the thermoplastic polyamide elastomer is used for improving the notch sensitivity problem of the polyamide composite material, and the epoxy compatilizer is used for improving the interfacial adhesion and the dispersibility of the modified hybrid carbon nano tube and the modified silicon carbide in the polyamide 6 base material resin and enhancing the compatibility of the thermoplastic polyamide elastomer and the polyamide 6, so that the wave absorption performance and the heat conduction performance of the polyamide composite material are improved, the adverse effect on the bending strength of the polyamide composite material is reduced, and the impact strength of the polyamide composite material is improved. The polyamide composite material has excellent wave-absorbing performance and heat conducting performance, and can be widely applied to the field of electronic components needing shielding and heat conducting functions.
2. The preparation method of the polyamide composite material has the advantages of simple process, easy control, low equipment requirement, low investment and contribution to industrial production, and the used equipment is universal polymer processing equipment.
Drawings
FIG. 1 is a flow chart of the preparation process of the polyamide composite material of the invention.
Detailed Description
In order that the invention may be understood more fully, the invention will be described with reference to the accompanying drawings. This invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The reaction mechanism in the polyamide composite material of the invention is as follows (the preparation process flow chart is shown in figure 1):
Wherein R1 is a copolymer of epoxy compatilizer styrene, methyl methacrylate and glycidyl methacrylate, and R2 is polyamide 6, or thermoplastic polyamide elastomer, or modified hybrid carbon nano tube, or modified silicon carbide.
Reaction mechanism
From the reaction formula, the amino end groups of the polyamide 6, the thermoplastic polyamide elastomer, the modified hybrid carbon nano tube and the modified silicon carbide can react with the epoxy functional groups of the epoxy compatilizer, so that the interfacial adhesion and the dispersibility of the modified hybrid carbon nano tube and the modified silicon carbide in the polyamide 6 base material resin are improved, and the wave absorbing performance and the heat conducting performance of the polyamide composite material are improved.
The raw materials used in the examples and comparative examples of the present invention are as follows:
polyamide 6, having a number average molecular weight of 26000g/mol, is available from Shen Ma Nilong chemical Co., ltd.
Melamine, available from national pharmaceutical group chemical company, inc.
Concentrated hydrochloric acid, available from national pharmaceutical groups chemical reagent company, inc.
Deionized water, available from national pharmaceutical groups chemical company, inc.
Ethanol, available from national pharmaceutical group chemical company, inc.
Concentrated sulfuric acid, available from national pharmaceutical group chemical company, inc.
Hydrogen peroxide, available from national pharmaceutical group chemical company, inc.
Concentrated nitric acid, available from national pharmaceutical group chemical company, inc.
Carbon nanotubes, available from Jiangsu Xianfeng nanomaterials technologies, inc.
Gamma-aminopropyl triethoxysilane, available from Anhui silicon Bao organosilicon New Material Co.
Silicon carbide, available from minoxidil (beijing) technologies.
Thermoplastic polyamide elastomer, soft segment polyether content of 30wt%, available from Xuang New Material technology Co., ltd;
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate, the number-average molecular weight is 6800g/mol, the epoxy equivalent is 290g/mol, and the copolymer is purchased from Shanxi province chemical engineering institute.
Bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, available from Shanghai Pu Zhu Kogyo Co.
Silicone lubricant having a number average molecular weight of 10 6 g/mol, available from Chengdu silicon technologies Co., ltd.
The modified hybrid carbon nanotubes used in the following examples and comparative examples were prepared by the following steps:
(1) Calcining melamine at 550 ℃ for 2.5 hours to obtain graphite-phase carbon nitride, dispersing 100g of graphite-phase carbon nitride in 250mL of concentrated hydrochloric acid, stirring for 8 hours to carry out protonizing reaction, adding 250mL of deionized water, carrying out ultrasonic treatment for 1.5 hours, carrying out high-speed centrifugal separation, washing with water and ethanol for multiple times to be neutral, and drying to obtain modified graphite-phase carbon nitride;
(2) Mixing 100g of carbon nano tube with 10mL of concentrated sulfuric acid and 3mL of hydrogen peroxide, performing ultrasonic treatment for 4 hours, then dropwise adding 6mL of concentrated nitric acid into an ice-water bath, stirring to room temperature, performing ultrasonic treatment for 2.5 hours, washing with water and ethanol for many times to neutrality, and drying to obtain the modified carbon nano tube;
(3) Dispersing 100g of modified graphite phase carbon nitride in ethanol by an ultrasonic method to obtain a solution A, dispersing 70g of modified carbon nano tube in ethanol to obtain a solution B, mixing the solution A and the solution B, refluxing and stirring for 12 hours at 60 ℃, washing with water and ethanol for many times to neutrality, drying, and uniformly mixing with 3g of gamma-aminopropyl triethoxysilane to obtain the modified hybrid carbon nano tube.
The modified silicon carbide used in the following examples and comparative examples was prepared by a process comprising the steps of:
and uniformly mixing 100g of silicon carbide with 1.5g of gamma-aminopropyl triethoxysilane to obtain the modified silicon carbide.
The present invention will be described in detail with reference to specific examples.
Example 1 Polyamide composite and method for producing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 115 ℃ for 2 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 230 ℃, the temperature of the second area is 235 ℃, the temperature of the third area is 240 ℃, the temperature of the fourth area is 240 ℃, the temperature of the fifth area is 245 ℃, the temperature of the sixth area is 245 ℃, the temperature of the seventh area is 245 ℃, the temperature of the eighth area is 240 ℃, the temperature of the die head is 240 ℃, and the rotating speed of the screw is 700rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 55; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1500 rpm.
Example 2 Polyamide composite and method for producing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 105 ℃ for 4 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the first zone temperature is 210 ℃, the second zone temperature is 215 ℃, the third zone temperature is 220 ℃, the fourth zone temperature is 220 ℃, the fifth zone temperature is 225 ℃, the sixth zone temperature is 225 ℃, the seventh zone temperature is 225 ℃, the eighth zone temperature is 220 ℃, the die temperature is 220 ℃, and the screw rotating speed is 300rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 35; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 500 revolutions per minute.
Example 3 Polyamide composite and method for producing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 112 ℃ for 2.6 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the first zone temperature is 225 ℃, the second zone temperature is 230 ℃, the third zone temperature is 235 ℃, the fourth zone temperature is 235 ℃, the fifth zone temperature is 240 ℃, the sixth zone temperature is 240 ℃, the seventh zone temperature is 240 ℃, the eighth zone temperature is 235 ℃, the die temperature is 235 ℃, and the screw speed is 550rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 50; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1500 rpm.
Example 4 Polyamide composite and method for producing the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 108 ℃ for 3.4 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the first zone temperature is 215 ℃, the second zone temperature is 220 ℃, the third zone temperature is 225 ℃, the fourth zone temperature is 225 ℃, the fifth zone temperature is 230 ℃, the sixth zone temperature is 230 ℃, the seventh zone temperature is 230 ℃, the eighth zone temperature is 225 ℃, the die temperature is 225 ℃, and the screw rotation speed is 450rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 40; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and/or the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 500 revolutions per minute.
Example 5 Polyamide composite and method of making the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Example 6 Polyamide composite and method of making the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Example 7 Polyamide composite and method of making the same
The polyamide composite material of the embodiment is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Comparative example 1
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Comparative example 2
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide and the thermoplastic polyamide elastomer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Comparative example 3
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6 and the silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
Comparative example 4
The polyamide composite material of the comparative example is prepared from the following raw materials in parts by weight:
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate.
The preparation method of the polyamide composite material comprises the following steps:
(1) Drying the polyamide 6 at 110 ℃ for 3 hours, cooling, and adding the cooled polyamide 6 and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, adding the mixed mixture obtained in the step (2) into the lateral direction (third zone) of the parallel double-screw extruder (total eight zones) for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 220 ℃, the temperature of the second area is 225 ℃, the temperature of the third area is 230 ℃, the temperature of the fourth area is 230 ℃, the temperature of the fifth area is 235 ℃, the temperature of the sixth area is 235 ℃, the temperature of the seventh area is 235 ℃, the temperature of the eighth area is 230 ℃, the temperature of the die head is 230 ℃, and the rotating speed of the screw is 500rpm.
The screw shape of the parallel double-screw extruder is single-thread; the ratio L/D of the length L and the diameter D of the screw is 45; the screw is provided with 2 meshing block areas and 1 reverse thread area; in the step (1) and the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 1000 rpm.
The following is a list of the raw material compositions of examples 1-7 and comparative examples 1-6.
Table 1 list of raw material compositions of examples 1 to 7 and comparative examples 1 to 6
Wherein a is an unmodified carbon nanotube and b is an unmodified silicon carbide.
Examples 1 to 7 are polyamide composites prepared by adjusting the addition amounts of polyamide 6, modified hybrid carbon nanotubes, modified silicon carbide, thermoplastic polyamide elastomer, epoxy compatibilizer, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, silicone lubricant, comparative example 1 is polyamide composites prepared without adding thermoplastic polyamide elastomer, comparative example 2 is polyamide composites prepared without adding epoxy compatibilizer, comparative example 3 is polyamide composites prepared without adding bis (2, 4-dicumylphenyl) pentaerythritol diphosphite, comparative example 4 is polyamide composites prepared without adding silicone lubricant, comparative example 5 is unmodified carbon nanotubes, and comparative example 6 is unmodified silicon carbide.
The polyamide composite materials prepared in the above examples and comparative examples were subjected to the following performance tests:
flexural strength: the bending rate was 2mm/min according to GB/T9341-2008 standard.
Notched impact strength: tested according to GB/T1843-2008 standard.
Wave absorbing performance: cutting a sheet made of a polyamide composite material into samples with the size of 23X 10X 0.5mm, and testing the wave absorption performance of the material by using a vector network analyzer (model AGILENT N5244A PNA-X), wherein the testing method is a waveguide method, and the testing wave band is 8-12 GHz of an X wave band; the larger the test value, the better the wave absorbing performance.
Thermal conductivity: cutting a sheet made of a polyamide composite material into samples with the size of 20-0.5 mm, and testing the heat conduction performance of the material by using a heat conductivity tester (model NETZSCH LFA 457); the larger the test value, the better the thermal conductivity.
The results of the performance test are shown in Table 2.
Table 2 Table of Properties of Polyamide composites of examples 1-7 and comparative examples 1-6
As can be seen from table 2:
the modified hybrid carbon nano tube and the modified silicon carbide can play a role in reinforcing the polyamide base material, and the bending strength of the polyamide composite material is reduced along with the reduction of the addition amount of the modified hybrid carbon nano tube and the modified silicon carbide.
The thermoplastic polyamide elastomer is formed by alternately copolymerizing high-crystallinity hard segment polyamide 6 and amorphous soft segment polyether, wherein the content of the soft segment polyether is 25-35 wt%. The thermodynamic incompatibility between the soft segment and the hard segment leads to microphase separation with different forms, wherein the hard segment molecular chain has amide bonds and can form hydrogen bonds, and a physical crosslinking state is formed in a natural state, so that the thermoplastic polyamide elastomer has good mechanical properties; the soft segment is polyether, so that the thermoplastic polyamide elastomer has the properties of rebound resilience, creep resistance, impact resistance and the like. Therefore, as the amount of thermoplastic polyamide elastomer added decreases, the notched impact strength of the polyamide composite material decreases.
The silicon carbide is formed by combining Si and C through covalent bonds, the basic structural unit of the silicon carbide is a Si-C tetrahedron, and the silicon carbide has good chemical stability and thermal stability, good mechanical and thermal conductivity and good electromagnetic wave absorption performance, and is a traditional wave absorbing material. Therefore, as the amount of modified silicon carbide added decreases, the maximum value of the wave absorbing properties of the polyamide composite material decreases.
Island-shaped modified graphite phase carbon nitride is uniformly dispersed in polyamide 6 base material resin to collect heat in the base material resin, and modified carbon nano tubes are high-speed channels bridged on the modified graphite phase carbon nitride, so that heat is efficiently conducted. Therefore, as the addition amount of the modified hybrid carbon nanotubes decreases, the heat conductive property of the polyamide composite material decreases.
In summary, the polyamide composite material with excellent wave absorbing performance and heat conducting performance can be obtained by adjusting the addition amount of polyamide 6, modified hybrid carbon nano tube, modified silicon carbide, thermoplastic polyamide elastomer, epoxy compatilizer, bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and silicone lubricant under the synergistic cooperation of the auxiliary agents.
In comparison with example 5, comparative example 1 was a polyamide composite material prepared without adding a thermoplastic polyamide elastomer, and since the thermoplastic polyamide elastomer has both the elasticity of rubber and the toughness and abrasion resistance of the polyamide resin are maintained, the notched impact strength of comparative example 1 is lower than that of example 5.
Compared with example 5, in comparative example 2, the polyamide composite material is prepared without adding the epoxy compatilizer, and as the polyamide 6, the thermoplastic polyamide elastomer, the modified hybrid carbon nano tube and the terminal amino group of the modified silicon carbide can react with the epoxy functional group of the epoxy compatilizer, the interfacial adhesion and the dispersibility of the modified hybrid carbon nano tube and the modified silicon carbide in the polyamide 6 substrate resin are improved, and the wave absorption performance and the heat conduction performance of the polyamide composite material are improved. Meanwhile, the epoxy compatilizer also enhances the compatibility of the thermoplastic polyamide elastomer and the polyamide 6, reduces the adverse effect on the bending strength of the polyamide composite material and improves the impact strength of the polyamide composite material. Thus, the flexural strength, notched impact strength, maximum value of the wave absorbing property and heat conducting property of comparative example 2 were lower than those of example 5.
Compared with example 5, in comparative example 3, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite is not added to prepare the polyamide composite material, and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite can capture peroxy radicals formed in the oxidation process of the polyamide, limit the combination of N element and O element and inhibit oxidation chain reaction, so that the thermal oxygen stability and the oxygen resistance of the polyamide composite material are effectively improved. Thus, the flexural strength, notched impact strength, maximum value of the wave absorbing property and heat conducting property of comparative example 3 were slightly inferior to those of example 5.
In comparison with example 5, comparative example 4 was a polyamide composite material prepared without adding a silicone lubricant, and since the ultra-high relative molecular weight polysiloxane can not only improve the processability and flowability of the resin, but also improve the abrasion resistance and scratch resistance of the product. Thus, the flexural strength, notched impact strength, maximum value of the wave absorbing property and heat conducting property of comparative example 4 were slightly inferior to those of example 5.
In comparison with example 5, comparative example 5 is to add unmodified carbon nanotubes, and its heat conductive properties are affected because the unmodified carbon nanotubes are easily agglomerated and lack the synergistic effect of graphite phase carbon nitride. Thus, the flexural strength, notched impact strength and heat conducting properties of comparative example 5 were inferior to those of example 5.
In comparison with example 5, comparative example 6 was an unmodified silicon carbide added, and the absorption effect was affected because the unmodified silicon carbide was easily agglomerated in the polymer base material. Thus, the maximum values of flexural strength, notched impact strength and wave absorbing properties of comparative example 6 were inferior to those of example 5.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (9)
1. The polyamide composite material is characterized by being prepared from the following raw materials in parts by weight:
Polyamide 6: 61-77 parts of a lubricant,
modified hybrid carbon nanotubes: 15 to 25 parts of the components,
modified silicon carbide: 8 to 14 parts of a mixture of components,
thermoplastic polyamide elastomer: 3 to 6 parts of the components in parts by weight,
epoxy compatilizer: 0.3 to 0.6 part of a compound,
bis (2, 4-dicumylphenyl) pentaerythritol diphosphite: 0.2 to 0.6 part of the total weight of the composition,
silicone lubricant: 0.2 to 0.6 part;
the modified hybrid carbon nanotube is prepared by uniformly mixing gamma-aminopropyl triethoxysilane and the hybrid carbon nanotube; the hybrid carbon nano tube is prepared by preparing a modified carbon nano tube and modified graphite phase carbon nitride in an electrostatic self-assembly mode;
the modified silicon carbide is prepared by uniformly mixing gamma-aminopropyl triethoxysilane and silicon carbide;
the epoxy compatilizer is a copolymer of styrene, methyl methacrylate and glycidyl methacrylate;
the silicone lubricant is prepared by taking a mixed ring of dimethyl siloxane as a monomer and tetramethyl ammonium hydroxide silicon alkoxide as an initiator through anionic ring-opening polymerization;
the preparation method of the modified hybridized carbon nano tube comprises the following steps:
(1) Calcining melamine at 500-600 ℃ for 2-3 h to obtain graphite-phase carbon nitride, dispersing 100-g graphite-phase carbon nitride in 200-300 mL concentrated hydrochloric acid, stirring for 7-9 h to carry out protonizing reaction, adding 200-300 mL deionized water for ultrasonic treatment for 1-2 h, carrying out high-speed centrifugal separation, washing with water and ethanol for multiple times to neutrality, and drying to obtain modified graphite-phase carbon nitride;
(2) Mixing 100 g carbon nanotubes with 9-11 mL concentrated sulfuric acid and 2-4 mL hydrogen peroxide, performing ultrasonic treatment for 3-5 h, then dropwise adding 5-7 mL concentrated nitric acid in an ice-water bath, stirring to room temperature, performing ultrasonic treatment for 2-3 h, washing with water and ethanol for multiple times to neutrality, and drying to obtain modified carbon nanotubes;
(3) Dispersing 90-110 g modified graphite phase carbon nitride in ethanol by an ultrasonic method to obtain a solution A, dispersing 60-80 g modified carbon nanotubes in ethanol to obtain a solution B, mixing the solution A and the solution B, refluxing and stirring at 55-65 ℃ for 10-14 h, washing with water and ethanol for multiple times to neutrality, drying, and uniformly mixing with 2-4 g gamma-aminopropyl triethoxysilane to obtain the modified hybrid carbon nanotubes.
2. The polyamide composite material according to claim 1, which is characterized by being prepared from the following raw materials in parts by weight:
polyamide 6: 64-74 parts of a lubricant,
modified hybrid carbon nanotubes: 17-23 parts of a compound containing,
modified silicon carbide: 9 to 13 parts of a mixture of components,
thermoplastic polyamide elastomer: 3.5 to 5.5 parts of a compound,
epoxy compatilizer: 0.35 to 0.55 part of the total weight of the composition,
bis (2, 4-dicumylphenyl) pentaerythritol diphosphite: 0.3 to 0.5 part of a compound,
silicone lubricant: 0.3 to 0.5 part.
3. The polyamide composite material according to claim 2, which is characterized by being prepared from the following raw materials in parts by weight:
polyamide 6: 66-72 parts of a lubricant, wherein the lubricant comprises,
modified hybrid carbon nanotubes: 18 to 22 parts of a mixture of components,
modified silicon carbide: 10 to 12 parts of the components in parts by weight,
thermoplastic polyamide elastomer: 4-5 parts of a water-soluble polymer,
epoxy compatilizer: 0.4 to 0.5 part of the total weight of the composition,
bis (2, 4-dicumylphenyl) pentaerythritol diphosphite: 0.35 to 0.45 part of the total weight of the mixture,
silicone lubricant: 0.35 to 0.45 portion.
4. The polyamide composite material according to claim 1, characterized in that the polyamide 6 has a number average molecular mass of 22000-28000 g/mol; the thermoplastic polyamide elastomer is formed by alternately copolymerizing hard segment polyamide 6 and soft segment polyether, wherein the content of the soft segment polyether is 25-35 wt%; the number average molecular weight of the epoxy compatilizer is 6500-7200 g/mol, and the epoxy equivalent is 280-310 g/mol; the silicone lubricant has a number average molecular weight of (0.84-1.60) x 10 6 g/mol。
5. The polyamide composite material according to claim 1, wherein the modified silicon carbide is prepared by the following method: and uniformly mixing 100 g silicon carbide and 1-2 g gamma-aminopropyl triethoxysilane to obtain the modified silicon carbide.
6. A process for the preparation of a polyamide composite material according to any one of claims 1 to 5, comprising the steps of:
(1) Drying the polyamide 6 at 105-115 ℃ for 2-4 hours, cooling, and adding the cooled polyamide 6, the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, and adding the mixed mixture obtained in the step (2) in the lateral direction of the parallel double-screw extruder for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 210-230 ℃, the temperature of the second area is 215-235 ℃, the temperature of the third area is 220-240 ℃, the temperature of the fourth area is 220-240 ℃, the temperature of the fifth area is 225-245 ℃, the temperature of the sixth area is 225-245 ℃, the temperature of the seventh area is 225-245 ℃, the temperature of the eighth area is 220-240 ℃, the temperature of the die head is 220-240 ℃, and the screw rotating speed is 300-700 rpm.
7. The method of producing the polyamide composite material according to claim 6, comprising the steps of:
(1) Drying the polyamide 6 at 108-112 ℃ for 2.6-3.4 hours, cooling, and adding the cooled polyamide 6 and the bis (2, 4-dicumylphenyl) pentaerythritol diphosphite and a silicone lubricant into a stirrer for mixing;
(2) Adding the modified hybrid carbon nano tube, the modified silicon carbide, the thermoplastic polyamide elastomer and the epoxy compatilizer into another stirrer for mixing;
(3) Adding the mixed mixture obtained in the step (1) into a parallel double-screw extruder through a feeder, and adding the mixed mixture obtained in the step (2) in the lateral direction of the parallel double-screw extruder for melt extrusion, and granulating, wherein the technological parameters comprise: the temperature of the first area is 215-225 ℃, the temperature of the second area is 220-230 ℃, the temperature of the third area is 225-235 ℃, the temperature of the fourth area is 225-235 ℃, the temperature of the fifth area is 230-240 ℃, the temperature of the sixth area is 230-240 ℃, the temperature of the seventh area is 230-240 ℃, the temperature of the eighth area is 225-235 ℃, the temperature of the die head is 225-235 ℃, and the screw rotating speed is 450-550 rpm.
8. The method of any one of claims 6 to 7, wherein the parallel twin-screw extruder has a screw shape of a single-thread; and/or the ratio L/D of the screw length L and the diameter D of the parallel double screw extruder is 35-55; and/or more than 1 meshing block area and more than 1 reverse thread area are arranged on the screw of the parallel double-screw extruder; in the step (1) and/or the step (2), the stirrer is a high-speed stirrer, and the rotating speed is 500-1500 rpm.
9. The process according to claim 8, wherein the ratio L/D of the screw length L to the diameter D of the parallel twin-screw extruder is 40 to 50; and/or, the screw of the parallel double-screw extruder is provided with 2 meshing block areas and 1 reverse thread area.
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