CN103740092A - High-thermal conductivity graphene/nylon composite material and preparation method thereof - Google Patents

High-thermal conductivity graphene/nylon composite material and preparation method thereof Download PDF

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CN103740092A
CN103740092A CN201310699879.9A CN201310699879A CN103740092A CN 103740092 A CN103740092 A CN 103740092A CN 201310699879 A CN201310699879 A CN 201310699879A CN 103740092 A CN103740092 A CN 103740092A
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nylon
parts
graphene
coupling agent
composite materials
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CN103740092B (en
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蔡铜祥
成文俊
杨玉晴
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Shanghai Yueda New Material Technology Co., Ltd.
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Jiangsu Yueda Novel Material Science And Technology Ltd
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    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract

The invention discloses a high-thermal conductivity graphene/nylon composite material and a preparation method thereof. The high-thermal conductivity graphene/nylon composite material comprises the following components in parts by weight: 30-80 parts of nylon, 4-8 parts of expandable graphite, 0.5-1.5 parts of amphipathic pyrene graft, 1-20 parts of high-oriented silicon nitride fibers, 1-15 parts of carbon fibers, 5-10 parts of boron nitride, 0.02-4 parts of high temperature resistant auxiliary, 0.02-0.8 part of antioxidant, 1-3 parts of hydrolysis resistant agent and 2-6 parts of flexibilizer. The high-thermal conductivity graphene/nylon composite material is characterized in that the novel heat-conducting auxiliary is adopted to improve the thermal conductivity of the nylon, and the heat-conducting auxiliary is graphene which is prepared from the expandable graphite and the amphipathic pyrene graft by a liquid-phase ultrasonic stripping method. In addition, the novel heat-conducting auxiliary has the advantages that the graphene is caused to be evenly dispersed in the matrix resin, and furthermore, the interface adhesive strength between the graphene and the nylon can be enhanced and the compatibility of the graphene and the nylon can be improved due to the graphene.

Description

A kind of high conductive graphite alkene/nylon composite materials and preparation method thereof
Technical field
The present invention relates to a kind of high conductive graphite alkene/nylon composite materials and preparation method thereof, exactly relate to a kind of high conductive graphite alkene/nylon 6 or nylon 12 or nylon 66 composite material and preparation method thereof.
Technical background
Nylon has the good over-all propertieies such as good mechanical property, good snappiness, wear resistance, oil-proofness, self lubricity, is widely used in the fields such as automobile industry, electronic apparatus industry, mechanical means, construction industry.Because it has that the process-cycle is short, production cost is low, long service life and product design degree of freedom advantages of higher obtain applying more and more widely, application aspect heat-conductivity polymer composite is in recent years particularly outstanding, and the high-power LED radiator that for example DSM company produces has obtained the generally approval in market.
Thermally conductive material is widely used in the fields such as heat exchange engineering, Electronics and Information Engineering.For a long time, most of thermally conductive material is metallic substance, but due to factors such as the corrosion resistance of metallic substance are poor and processing characteristics is not good, product design degree of freedom is low, has limited its range of application.
In order to improve the surperficial erosion resistance of thermally conductive material, conventionally adopt the means such as metallurgy, corrosion protection coating, but this method has reduced the improvement that the heat conductivility of material and other performances of material do not obtain essence to a large extent.In recent years, along with thermally conductive material range of application is more and more extensive, to the over-all properties of material, require also more and more higher.Such as not only requiring material to there is good heat conductivility, also require material to there are good mechanical property, high temperature resistant use properties, environmental corrosion resisting performance etc.
Traditional heat-conductive composite material generally with Si3N4, SiN, AlN and BN as heat conductive filler, but because of the thermal conductivity of itself low, therefore need just can obtain higher thermal conductivity under high addition, yet this will inevitably reduce other performances of macromolecular material itself.Since Graphene is found for 2004, it,, as a kind of novel Two-dimensional Carbon nano material, has fabulous thermal conductivity, specific conductivity, is the material that known physical strength is the highest and possesses the advantages such as stable chemical performance light transmission is good.The room temperature thermal conductivity of single-layer graphene reaches 4840～5300W(mK)-1, be the highest material of current thermal conductivity.These unique character can make Graphene as a kind of novel nano heat-conductive filler, thereby the heat conductivility of polymkeric substance is greatly improved.
Summary of the invention
The present invention solves the poor technical problem of the developing heat conductivility of existing heat-conductivity polymer composite, and a kind of possess excellent heat conducting performance, good corrosion energy, high temperature resistant use properties, matrix material that comprehensive mechanical intensity is high and preparation method thereof are provided.
Technical solution of the present invention is, by making with the raw material of parts by weight proportioning below: 30～80 parts of nylon, can 4～8 parts, swollen graphite, 0.5～1.5 part of amphiphilic pyrene class grafts, high 1～20 part of silicon nitride fiber of orientation, 1～15 part, carbon fiber, 5～10 parts of boron nitride, 0.02～4 part of high temperature resistant auxiliary agent, 0.02～0.8 part, oxidation inhibitor, 1～3 part of hydrolysis-resisting agent, 2～6 parts of toughner.
Wherein said nylon is the nylon 6 of limiting viscosity between 1.6～3.8dL/g or one or several the mixture in nylon 12 or 66 3 kinds of materials of nylon;
Described can swollen graphite be granularity be 60 orders can swollen graphite or 70 orders can swollen graphite or one or several the mixture of 80 orders in can three kinds of materials of swollen graphite;
Described amphiphilic pyrene class grafts is that one or several in pyrene and dendroid polyacrylic ester-poly glycol monomethyl ether segmented copolymer or dendroid polyacrylic ester-polyoxyethylene glycol ether segmented copolymer or dendroid polyoxyethylene glycol epoxy glycerite ester block copolymer three are by the formed material of electrophilic substitution reaction;
Described high orientation silicon nitride fiber is the high orientation silicon nitride fiber after coupling agent treatment; Coupling agent used is: silane coupling agent, titante coupling agent or complex compound class coupling agent;
Described carbon fiber is the high orientation silicon nitride fiber after coupling agent treatment.Coupling agent used is: silane coupling agent, titante coupling agent or complex compound class coupling agent;
Described boron nitride is purity > 99%, and particle size range is the hexagonal boron nitride of 5～15 μ m;
Described high temperature resistant auxiliary agent is alkyl monothio cupric phosphate or alkenyl succinic acid copper or thiocarbamate copper or above several composite;
Described oxidation inhibitor is N, and N'-is two-and according to mass ratio, to be that 8:1～2:1 is composite form (3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester;
Described hydrolysis-resisting agent is that one or more in carbodiimide or poly-[nitrilo methane four nitrilos [2,4,6-tri-(1-the first and second bases)-1,3-phenylene]] or cyanacrylate are composite;
Described toughner is POE-g-GMA or EPDM-g-GMA or EPR-g-MAH or SWR-3C or above several composite use.
Concrete preparation method's step of the present invention is as follows:
1) preparation of Graphene.First can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH, carry out sonic oscillation 3～5h, then carry out centrifugal treating, centrifugal rotational speed is 1200～1500rpm, time is 15～30min, supernatant liquid is the graphene solution of dispersion, its concentration reaches 1.5～2mg/ml, supernatant liquor is placed to dry 15～20h in 70～100 ℃ of baking ovens and obtain dry powdery Graphene.
2) by above-mentioned steps 1) in prepared graphene powder mix with nylon particle, in three-roll grinder, grind 10～15min, standby.
3) by above-mentioned steps 2) in the particle that mixes of gained nylon/Graphene and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10～25min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
The advantage that the present invention compared with prior art possessed is:
1) adopt can swollen graphite and amphiphilic pyrene class grafts by the ultrasonic stripping method of liquid phase, prepare high concentration graphene.First pyrene can be with the Graphene of two-dirnentional structure by the good combination of aromatic ring accumulation of π-pi-conjugated pair of key, secondly on pyrene, the amphiphilic group of grafting can either make graphene uniform and is dispersed in matrix resin, can make again the interface cohesive force grow between Graphene and nylon, consistency improves;
2) three roller polishings can make Graphene be coated on well the surface of nylon particle, are easy to form good " passage of heat ";
3) filler and the height-oriented silicon nitride fiber of the different grain size size adopting are filled in matrix resin, can form maximum degree of piling up and form excellent heat conduction network chain with fiber interaction between filler.
Embodiment
Below the preferred embodiments of the present invention are described in detail, so that content characteristic of the present invention is easy to be understood by the researchist in this area, thereby protection scope of the present invention are made to more full and accurate defining.
Embodiment 1:
High conductive graphite alkene/nylon composite materials of the present invention, its component is pressed mass fraction, choose 40 parts of nylon, can swollen graphite 4 parts, 0.8 part of amphiphilic pyrene class grafts, 10 parts of high orientation silicon nitride fibers, 10 parts, carbon fiber, 7 parts of boron nitride, high temperature resistant dose 0.1 part, 0.3 part, oxidation inhibitor, 1 part of hydrolysis-resisting agent, 4 parts of toughner, first can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH=6/4, carry out sonic oscillation 3h, then carry out centrifugal treating, centrifugal rotational speed is 1200rpm, time is 16min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed to dry 15h in 70 ℃ of baking ovens and obtain dry powdery Graphene.Then prepared graphene powder is mixed with nylon particle, in three-roll grinder, grind 10min, standby.The particle finally nylon/Graphene being mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 12min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
Embodiment 2:
High conductive graphite alkene/nylon composite materials of the present invention, its component is pressed mass fraction, choose 40 parts of nylon, can swollen graphite 5 parts, 1 part of amphiphilic pyrene class grafts, 15 parts of high orientation silicon nitride fibers, 5 parts, carbon fiber, 5 parts of boron nitride, high temperature resistant dose 0.3 part, 0.2 part, oxidation inhibitor, 1 part of hydrolysis-resisting agent, 6 parts of toughner, first can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH=7/3, carry out sonic oscillation 3h, then carry out centrifugal treating, centrifugal rotational speed is 1300rpm, time is 20min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed to dry 18h in 90 ℃ of baking ovens and obtain dry powdery Graphene.Then prepared graphene powder is mixed with nylon particle, in three-roll grinder, grind 12min, standby.The particle finally nylon/Graphene being mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 15min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
Embodiment 3:
High conductive graphite alkene/nylon composite materials of the present invention, its component is pressed mass fraction, choose 50 parts of nylon, can swollen graphite 5 parts, 1.2 parts of amphiphilic pyrene class graftss, 12 parts of high orientation silicon nitride fibers, 8 parts, carbon fiber, 8 parts of boron nitride, high temperature resistant dose 0.5 part, 0.4 part, oxidation inhibitor, 1.2 parts of hydrolysis-resisting agents, 8 parts of toughner, first can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH=7/5, carry out sonic oscillation 3h, then carry out centrifugal treating, centrifugal rotational speed is 1400rpm, time is 20min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed to dry 18h in 100 ℃ of baking ovens and obtain dry powdery Graphene.Then prepared graphene powder is mixed with nylon particle, in three-roll grinder, grind 16min, standby.The particle finally nylon/Graphene being mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
Embodiment 4:
High conductive graphite alkene/nylon composite materials of the present invention, its component is pressed mass fraction, choose 60 parts of nylon, can swollen graphite 6 parts, 1.4 parts of amphiphilic pyrene class graftss, 16 parts of high orientation silicon nitride fibers, 4 parts, carbon fiber, 10 parts of boron nitride, high temperature resistant dose 1 part, 0.8 part, oxidation inhibitor, 3 parts of hydrolysis-resisting agents, 6 parts of toughner, first can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH=5/4, carry out sonic oscillation 3h, then carry out centrifugal treating, centrifugal rotational speed is 1500rpm, time is 30min, supernatant liquid is the graphene solution of dispersion, supernatant liquor is placed to dry 17h in 85 ℃ of baking ovens and obtain dry powdery Graphene.Then prepared graphene powder is mixed with nylon particle, in three-roll grinder, grind 12min, standby.The particle finally nylon/Graphene being mixed and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 17min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
According to national standard, above-mentioned high conductive graphite alkene/nylon composite materials is carried out to properties test:
The results are shown in following table:
Note: strength retention refers to that prepared matrix material soaks 24 drying treatment back draft intensity with respect to the velocity of variation of untreated matrix material in 80 ℃ of waters bath with thermostatic control.

Claims (8)

1. high conductive graphite alkene/nylon composite materials, is characterized in that: by making with the raw material of parts by weight proportioning below: 30～80 parts of nylon, can 4～8 parts, swollen graphite, 0.5～1.5 part of amphiphilic pyrene class grafts, high 1～20 part of silicon nitride fiber of orientation, 1～15 part, carbon fiber, 5～10 parts of boron nitride, 0.02～4 part of high temperature resistant auxiliary agent, 0.02～0.8 part, oxidation inhibitor, 1～3 part of hydrolysis-resisting agent, 2～6 parts of toughner; Described can swollen graphite be granularity be 60 orders can swollen graphite or 70 orders can swollen graphite or one or several the mixture of 80 orders in can three kinds of materials of swollen graphite.
2. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, is characterized in that: described nylon is the nylon 6 of limiting viscosity between 1.6～3.8dL/g or one or several the mixture in nylon 12 or 66 3 kinds of materials of nylon.
3. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, is characterized in that: described amphiphilic pyrene class grafts is that one or several in pyrene and dendroid polyacrylic ester-poly glycol monomethyl ether segmented copolymer or dendroid polyacrylic ester-polyoxyethylene glycol ether segmented copolymer or dendroid polyoxyethylene glycol epoxy glycerite ester block copolymer three are by the formed material of electrophilic substitution reaction.
4. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, is characterized in that: described high orientation silicon nitride fiber is the high orientation silicon nitride fiber after coupling agent treatment; Coupling agent used is silane coupling agent, titante coupling agent or complex compound class coupling agent; Described carbon fiber is the high orientation silicon nitride fiber after coupling agent treatment; Coupling agent used is silane coupling agent, titante coupling agent or complex compound class coupling agent.
5. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, is characterized in that: described boron nitride is purity > 99%, and particle size range is the hexagonal boron nitride of 5～15 μ m.
6. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, is characterized in that: described high temperature resistant auxiliary agent is alkyl monothio cupric phosphate or alkenyl succinic acid copper or thiocarbamate copper or above several composite.
7. a kind of high conductive graphite alkene/nylon composite materials as claimed in claim 1, it is characterized in that: described oxidation inhibitor is N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) according to mass ratio, to be that 8:1～2:1 is composite form hexanediamine and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester; Described hydrolysis-resisting agent is that one or more in carbodiimide or poly-[nitrilo methane four nitrilos [2,4,6-tri-(1-the first and second bases)-1,3-phenylene]] or cyanacrylate are composite; Described toughner is POE-g-GMA or EPDM-g-GMA or EPR-g-MAH or SWR-3C or above several composite use.
8. a preparation method for high conductive graphite alkene/nylon composite materials, is characterized in that: concrete preparation method's step is as follows:
1) preparation of Graphene
First can swollen graphite and amphiphilic pyrene class grafts be together placed on and in the mixed solvent with certain proportion H2O/MeOH, carry out sonic oscillation 3～5h, then carry out centrifugal treating, centrifugal rotational speed is 1200～1500rpm, time is 15～30min, supernatant liquid is the graphene solution of dispersion, its concentration reaches 1.5～2mg/ml, supernatant liquor is placed to dry 15～20h in 70～100 ℃ of baking ovens and obtain dry powdery Graphene;
2) prepared graphene powder in step 1) is mixed with nylon particle, in three-roll grinder, grind 10～15min, standby;
3) by step 2) in the particle that mixes of gained nylon/Graphene and boron nitride, oxidation inhibitor, hydrolysis-resisting agent, high temperature resistant dose, toughner by formula rate at high-speed mixer and mixing 10～25min, after mixing, add in the hopper of twin screw extruder, high orientation silicon nitride fiber and carbon fiber add by a certain percentage from adding of screw rod fine mouth, temperature is 230～260, ℃ main frame frequency is 15～25Hz, through melt blending, extrude, extruded material dries up pelletizing after cold going, and makes high heat conduction nylon/graphene composite material.
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CN106478939A (en) * 2015-08-27 2017-03-08 合肥杰事杰新材料股份有限公司 A kind of nano composite material of Graphene/nylon/elastomer and preparation method thereof
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CN107857992A (en) * 2017-11-21 2018-03-30 四川长虹电器股份有限公司 Daiamid-6 fiber composite that graphene is modified and preparation method thereof
CN110698849A (en) * 2019-11-01 2020-01-17 嘉兴烯成新材料有限公司 Preparation method of hydroxylated graphene reinforced nylon fiber heat conduction
CN112080137A (en) * 2020-08-27 2020-12-15 浙江工业大学 Heat-conducting, electromagnetic-shielding and high-strength nylon 6 composite material and preparation method thereof
CN112080137B (en) * 2020-08-27 2023-01-31 浙江工业大学 Heat-conducting, electromagnetic-shielding and high-strength nylon 6 composite material and preparation method thereof
CN113354943A (en) * 2021-05-14 2021-09-07 金旸（厦门）新材料科技有限公司 Wear-resistant high-temperature nylon material for electronic connector
CN113354943B (en) * 2021-05-14 2023-05-12 金旸（厦门）新材料科技有限公司 Wear-resistant high-temperature nylon material for electronic connector
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