CN104844794B - Heat-conduction nylon material based on sulfonated graphene and preparation method thereof - Google Patents

Heat-conduction nylon material based on sulfonated graphene and preparation method thereof Download PDF

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CN104844794B
CN104844794B CN201510259055.9A CN201510259055A CN104844794B CN 104844794 B CN104844794 B CN 104844794B CN 201510259055 A CN201510259055 A CN 201510259055A CN 104844794 B CN104844794 B CN 104844794B
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heat
sulfonated graphene
sulfonated
nylon material
preparation
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CN104844794A (en
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蒋永华
郝建东
栗建民
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Fuzhou Aoxi New Material Co.,Ltd.
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SUZHOU GRAPHENE NEW MATERIAL TECHNOLOGY Co Ltd
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Abstract

The invention discloses a kind of heat-conduction nylon material based on sulfonated graphene, it is included:Nylon matrix material 95wt%~99.9wt%, sulfonated graphene 0.1wt%~5wt%;The radial dimension of wherein described sulfonated graphene is 500nm~50 μm, and thickness is that the mol ratio of C and S in 1~20nm, and the sulfonated graphene is 12:1~6:1.Method present invention also offers the heat-conduction nylon material is prepared.The vertical direction thermal conductivity factor of heat-conduction nylon material of the present invention is 0.5 10W/ (m.K), and keep even optimizing nylon material mechanical property good in itself, while preparation process is simple, mild condition is controllable, sulfonated graphene addition is few, low cost, in LED lamp, switch housing, notebook computer shell, the field such as handset shell is with a wide range of applications.

Description

Heat-conduction nylon material based on sulfonated graphene and preparation method thereof
Technical field
The present invention relates to a kind of modified nylon materials, more particularly to a kind of heat-conduction nylon material based on sulfonated graphene and Its preparation method.
Background technology
Nylon is a kind of thermoplastic engineering plastic of excellent performance, with excellent mechanical property, preferable electrical property with And wear-resisting, oil resistant, solvent resistant, self-lubricating, corrosion-resistant and good processing characteristics etc., it is widely used in automobile, electronic apparatus, machine In the industrial circles such as tool, Aero-Space and daily life.But nylon is heat insulation body, which has limited it in some fields, Such as application in Heat Conduction Material field.To lift the heat conductivility of nylon, at present generally using the heat filling of addition high, Such as BN, AlN, Si3N4Nylon is modified with SiC etc., but this can undermine and reduce the other performance of nylon, such as power simultaneously Learn performance.
In recent years, industry is attempted being modified nylon CNT, Graphene etc. as heat filling, although its The heat conductivility of nylon is improve to a certain extent, and it is smaller on the other performance influence of nylon.But it is still suffered from Shortcoming, for example, disperseing uneven in nylon base, heat conductivility lifting is limited etc..
The content of the invention
It is a primary object of the present invention to provide a kind of heat-conduction nylon material based on sulfonated graphene and preparation method thereof, To overcome deficiency of the prior art.
To realize aforementioned invention purpose, the technical solution adopted by the present invention includes:
A kind of heat-conduction nylon material based on sulfonated graphene is provided among an embodiment of the invention, it is included: Nylon matrix material 95wt%~99.9wt%, sulfonated graphene 0.1wt%~5wt%;The footpath of wherein described sulfonated graphene It is 500nm~50 μm to size, thickness is that the mol ratio of C and S in 1~20nm, and the sulfonated graphene is 12:1~6: 1。
Further, the vertical direction thermal conductivity factor of the heat-conduction nylon material is 0.5~10W/ (m.K).
The heat conduction nylon material based on sulfonated graphene described in a kind of preparation is additionally provided among an embodiment of the invention The method of material, it is included:
There is provided sulfonated graphene, its radial dimension is 500nm~50 μm, thickness is 1~20nm, and contained C and S rubs You are than being 12:1~6:1;
The sulfonated graphene and nylon monomer, water are added into autoclave, 100~150 DEG C is warming up to and is persistently stirred More than 0.5h is mixed, is further continued for being warming up to reaction temperature, then more than the pressurize 2h under 2~5MPa is evacuated to viscosity stabilization, goes out Material, obtains target product.
Among one more preferred embodiment, the preparation method includes:By sulfonated graphite aqueous solution and nylon Monomer, water press 0.01~25:60~85:15~40 mass ratio adds autoclave, and 100 are warming up to by 3-10 DEG C/min ~150 DEG C, and continue to stir more than 0.5h, it is further continued for being warming up to 250-290 DEG C of reaction temperature, the pressurize 2-5h under 2~5MPa, Then viscosity stabilization is evacuated to, discharging, granulation obtain target product.
Further, the concentration of the sulfonated graphite aqueous solution is 5-20wt%.
Further, the nylon monomer includes caprolactam and/or nylon salt, but not limited to this.
Among one more preferred embodiment, the preparation method of the sulfonated graphene includes:It is by radial dimension 500nm~50 μm, thickness are that Graphene or the graphene oxide addition of 1~20nm are mainly 1~4 by mass ratio:3~6 hair In the mixed acid solution that cigarette sulfuric acid is constituted with chlorosulfonic acid, and 1~10h is reacted at 60~150 DEG C, is then distilled more than 160 DEG C, Residue is once purged, obtains the sulfonated graphene.
Compared with prior art, advantages of the present invention includes:The heat-conduction nylon material preparation process is simple of offer, condition temperature With it is controllable, sulfonated graphene addition is few, low cost, and obtained heat-conduction nylon material vertical direction thermal conductivity factor for 0.5~ 10W/ (m.K), and at least maintain and even improve the mechanical property of nylon material, in LED lamp, switch housing, notebook computer shell, The fields such as handset shell are with a wide range of applications.
Specific embodiment
Make more detailed explanation to technical scheme below in conjunction with some embodiments.
Mass ratio is 3 by embodiment 1:4 oleum adds multitube film reacter with chlorosulfonic acid, adds Graphene (radial dimension is 500nm~50 μm, and thickness is 1~20nm) uniform mixing, reaches the Graphene content in mixed reactant 2wt%, at a temperature of 60 DEG C react 10 hours, after the completion of reaction, by mixed reactant 165 DEG C distillation, residue through washing, Sulfonated graphene is obtained, then obtained sulfonated graphene is dispersed in water, form the sulfonated graphene that concentration is 5wt% water-soluble Liquid, it is standby.
The sulfonated graphite aqueous solution and nylon monomer caprolactam, water, adipic acid are pressed 10:70:20:0.35 ratio Example adds autoclave, is to slowly warm up to 150 DEG C, and stirring at low speed 0.5h, is further continued for being warming up to 260 DEG C of reaction temperature, Pressurize 2h under 5MPa, is then evacuated to viscosity stabilization, and discharging, granulation obtain target product.
Mass ratio is 1 by embodiment 2:6 oleum adds multitube film reacter with chlorosulfonic acid, adds Graphene (radial dimension is 500nm~50 μm, and thickness is 1~20nm) uniform mixing, reaches the Graphene content in mixed reactant 2wt%, at a temperature of 150 DEG C react 1 hour, after the completion of reaction, by mixed reactant 160 DEG C distillation, residue through washing, Sulfonated graphene is obtained, then obtained sulfonated graphene is dispersed in water, form the sulfonated graphene that concentration is 20wt% water-soluble Liquid, it is standby.
By obtained sulfonated graphite aqueous solution and nylon salt, water, adipic acid by 10:55:35:0.35 ratio adds high Pressure reactor, is to slowly warm up to 150 DEG C, and stirring at low speed 0.5h, is further continued for being warming up to 285 DEG C of reaction temperature, is protected under 2MPa Pressure 5h, is then evacuated to viscosity stabilization, and discharging, granulation obtain target product.
Mass ratio is 1 by embodiment 3:1 oleum adds multitube film reacter with chlorosulfonic acid, adds Graphene (radial dimension is 500nm~50 μm, and thickness is 1~20nm) uniform mixing, reaches the Graphene content in mixed reactant 2wt%, at a temperature of 100 DEG C react 2 hours, after the completion of reaction, by mixed reactant 160 DEG C distillation, residue through washing, Sulfonated graphene is obtained, then obtained sulfonated graphene is dispersed in water, form the sulfonated graphene that concentration is 10wt% water-soluble Liquid, it is standby.
By obtained sulfonated graphite aqueous solution and nylon salt, water by 10:60:30:0.35 ratio adds reaction under high pressure Kettle, is to slowly warm up to 150 DEG C, and stirring at low speed 0.5h, is further continued for being warming up to reaction temperature, and pressurize 5h, then takes out under 2MPa To viscosity stabilization, discharging, granulation obtain target product to vacuum.
Reference examples 1:With reference to the identical method of embodiment 1, and the sulfonated graphite is substituted with Graphene (with embodiment 1) Alkene, is obtained product.
Reference examples 2:With reference to the identical method of embodiment 1, and institute is substituted with graphene oxide (being prepared according to humers methods) Sulfonated graphene is stated, product is obtained.
Reference examples 3:With reference to the identical method of embodiment 1, and with sulfonated graphene (with reference to Journal of Materials Chemistry, 2011,21,11359-11364) sulfonated graphene is substituted, product is obtained.
Product is obtained with high-resolution TEM to embodiment 1-3 and reference examples 1-3 to observe, it is found that embodiment 1- In 3 products, sulfonated graphene is dispersed in nylon matrix, and Graphene (graphene oxide) is then in reference examples 1-2 products Obvious skewness, sulfonated graphene has a certain degree of reunion in the product of reference examples 3.
Mode is commonly used with industry again, for example laser thermal conductivity factor instrument (such as NETZSCH LFA447) is to embodiment 1-3 products And the heat conductivility of reference examples 1-3 products is tested respectively, it is found that the vertical direction heat conduction system of embodiment 1-3 products Number is respectively 0.65W/ (m.K), 3.46W/ (m.K), 2.13W/ (m.K), hence it is evident that higher than reference examples 1-3 product (its vertical direction Thermal conductivity factor is respectively 0.28W/ (m.K), 0.25W/ (m.K), 0.27W/ (m.K)).
Additionally, commonly use mode using industry being carried out respectively to the mechanical property of embodiment 1-3 products and reference examples 1-3 products Test, it is found that tensile strength, bending strength of embodiment 1-3 products etc. also obviously higher than reference examples 1-3 products, and It is also higher than or the correlated performance at least with pure nylon product is suitable.
It should be noted that disclosed is the various of preferred embodiment, every local change or modification and Come from technological thought of the invention and be that the people for being familiar with this technology is easy to what is deduced, patent right model of the invention is not departed from all Enclose.

Claims (5)

1. a kind of preparation method of the heat-conduction nylon material based on sulfonated graphene, it is characterised in that including:
There is provided sulfonated graphene, its radial dimension is 500nm~50 μm, thickness is 1~20nm, and contained C and S mol ratio It is 12:1~6:1;
Sulfonated graphite aqueous solution and nylon monomer, water are pressed 0.01~25:60~85:15~40 mass ratio adds high pressure anti- Kettle is answered, 100~150 DEG C are warming up to by 3~10 DEG C/min of programming rate, and continue to stir more than 0.5h, be further continued for being warming up to Then 250-290 DEG C of reaction temperature, 2~5h of pressurize under 2~5MPa is evacuated to viscosity stabilization, and discharging, granulation obtain base In the heat-conduction nylon material of sulfonated graphene, the heat-conduction nylon material comprising 95wt%~99.9wt% nylon matrix material and 0.1wt%~5wt% sulfonated graphenes, and the vertical direction thermal conductivity factor of the heat-conduction nylon material is 0.5~10W/ (m.K)。
2. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 1, it is characterised in that:Institute The concentration for stating sulfonated graphite aqueous solution is 5~20wt%.
3. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 1, it is characterised in that institute Heat-conduction nylon material is stated to include:Nylon matrix material 95wt%~99.9wt%, sulfonated graphene 0.1wt%~5wt%.
4. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 1, it is characterised in that:Institute Stating nylon monomer includes caprolactam and/or nylon salt.
5. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 1, it is characterised in that institute The preparation method for stating sulfonated graphene includes:It is 500nm~50 μm, the Graphene or oxygen that thickness is 1~20nm by radial dimension It is 1~4 that graphite alkene is added by mass ratio:In the mixed acid solution that 3~6 oleum is constituted with chlorosulfonic acid, and 60~150 1~10h is reacted at DEG C, is then distilled more than 160 DEG C, residue is once purged, obtain the sulfonated graphene.
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CN105206802B (en) * 2015-08-24 2017-06-23 苏州高通新材料科技有限公司 Rich lithium sulfonated graphene nano silicon oxide negative material and its preparation method and application
CN106676678B (en) * 2016-12-30 2019-04-26 苏州高通新材料科技有限公司 Modified compound carbon fiber of graphene and the preparation method and application thereof
CN108727808A (en) * 2017-04-21 2018-11-02 山东圣泉新材料股份有限公司 - 6 agglomerate material of polyamide, the fiber and purposes comprising it of graphene modification
CN107641319A (en) * 2017-09-29 2018-01-30 金旸(厦门)新材料科技有限公司 Heat conductive insulating nylon 6 material that a kind of graphene is modified and preparation method thereof
CN108690350A (en) * 2017-10-19 2018-10-23 厦门稀土材料研究所 A kind of flame-retarded heat-conducting nylon plastic(s) and preparation method thereof that graphene is modified
CN110511375A (en) * 2018-05-22 2019-11-29 上海杰事杰新材料(集团)股份有限公司 A kind of static resistant polyamide composite material and preparation method
CN109593366A (en) * 2018-12-19 2019-04-09 江苏中恒电子新材料有限公司 A kind of dedicated high thermal conductivity coefficient Silica hydrogel of electronics industry and preparation method thereof
CN109608875A (en) * 2019-01-10 2019-04-12 厦门大学 A kind of thermally conductive nylon 6 resin composite material and preparation method

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CN102674337A (en) * 2012-06-06 2012-09-19 武汉理工大学 Self-extension graphene and preparation method thereof
CN103539105B (en) * 2013-10-25 2015-05-20 苏州高通新材料科技有限公司 Superhigh water-soluble functionalized graphene/oxidized graphene and preparation method thereof
CN103613097A (en) * 2013-12-04 2014-03-05 天津大学 Environment-friendly method for preparing sulfonated graphene
CN104497565B (en) * 2015-01-14 2017-04-19 苏州高通新材料科技有限公司 Nylon material having ultra-strong liquidity and preparation method thereof

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