CN104844794A - Heat conducting nylon material based on sulfonated graphene and preparation method thereof - Google Patents
Heat conducting nylon material based on sulfonated graphene and preparation method thereof Download PDFInfo
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- CN104844794A CN104844794A CN201510259055.9A CN201510259055A CN104844794A CN 104844794 A CN104844794 A CN 104844794A CN 201510259055 A CN201510259055 A CN 201510259055A CN 104844794 A CN104844794 A CN 104844794A
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Abstract
The invention discloses a heat conducting nylon material based on sulfonated graphene. The heat conducting nylon material comprises the following raw materials of 95wt percent to 99.9wt percent of nylon-based material and 0.1wt percent to 5wt percent of sulfonated graphene, wherein the radial size of the sulfonated graphene is 500nm to 50mum, the thickness of the sulfonated graphene is 1 to 20nm, and the molar ratio of C (carbon) and S (sulfur) in the sulfonated graphene is (12 to 1) to (6 to 1). The invention also provides a method for preparing the heat conducting nylon material. The heat conducting nylon material has the advantages that the heat conducting coefficient of the heat conducting nylon material along the vertical direction is 0.5 to 10W per (m.k), and the self good mechanical property of the nylon material is maintained and even optimized; the preparation technology is simple, the condition is moderate and controllable, the adding amount of sulfonated graphene is less, and the cost is low; the application prospect is broad in the fields of LED (light emitting diode) lamps, switch outer casings, notebook computer outer casings, mobile phone casings and the like.
Description
Technical field
The present invention relates to a kind of modified nylon materials, particularly a kind of heat-conduction nylon material based on sulfonated graphene and preparation method thereof.
Background technology
Nylon is a kind of thermoplastic engineering plastic of excellent performance, there is excellent mechanical property, preferably electrical property and wear-resisting, oil resistant, solvent resistant, self-lubricating, corrosion-resistant and good processing characteristics etc., be widely used in the industrial circles such as automobile, electronic apparatus, machinery, aerospace and daily life.But nylon is heat insulation body, which has limited it in some field, such as, application in thermally conductive material field.For promoting the heat conductivility of nylon, usually adopt the heat conductive filler of high addition at present, such as BN, AlN, Si
3n
4with SiC etc., modification is carried out to nylon, but this can undermine other performance reducing nylon simultaneously, such as mechanical property.
In recent years, industry attempts carbon nanotube, Graphene etc. to carry out modification as heat conductive filler to nylon, although it improves the heat conductivility of nylon to a certain extent, and less to other performance impact of nylon.But it still exists some shortcomings, such as, in nylon base, dispersion is uneven, and heat conductivility lifting is limited.
Summary of the invention
Main purpose of the present invention is to provide a kind of heat-conduction nylon material based on sulfonated graphene and preparation method thereof, to overcome deficiency of the prior art.
For realizing aforementioned invention object, the technical solution used in the present invention comprises:
Provide a kind of heat-conduction nylon material based on sulfonated graphene among an embodiment of the present invention, it comprises: nylon matrix material 95wt% ~ 99.9wt%, sulfonated graphene 0.1wt% ~ 5wt%; The radial dimension of wherein said sulfonated graphene is 500nm ~ 50 μm, and thickness is 1 ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
Further, the vertical direction thermal conductivity of described heat-conduction nylon material is 0.5 ~ 10W/ (m.K).
Additionally provide a kind of method based on the heat-conduction nylon material of sulfonated graphene described in preparation among an embodiment of the present invention, it comprises:
There is provided sulfonated graphene, its radial dimension is 500nm ~ 50 μm, and thickness is 1 ~ 20nm, and the mol ratio of contained C and S is 12:1 ~ 6:1;
Described sulfonated graphene and nylon monomer, water are added autoclave, is warming up to 100 ~ 150 DEG C and more than Keep agitation 0.5h, then continues to be warming up to temperature of reaction, more than pressurize 2h under 2 ~ 5MPa, then be evacuated to stable viscosity, discharging, obtain target product.
Among a comparatively preferred embodiment, described preparation method comprises: sulfonated graphite aqueous solution and nylon monomer, water are added autoclave by the mass ratio of 0.01 ~ 25:60 ~ 85:15 ~ 40,100 ~ 150 DEG C are warming up to by 3-10 DEG C/min, and more than Keep agitation 0.5h, continue to be warming up to temperature of reaction 250-290 DEG C, under 2 ~ 5MPa, pressurize 2-5h, is then evacuated to stable viscosity again, discharging, granulation, obtain target product.
Further, the concentration of described sulfonated graphite aqueous solution is 5-20wt%.
Further, described nylon monomer comprises hexanolactam and/or nylon salt, but is not limited thereto.
Among a comparatively preferred embodiment, the preparation method of described sulfonated graphene comprises: be 500nm ~ 50 μm by radial dimension, thickness is that to add primarily of mass ratio be in the mixed acid solution that forms of the oleum of 1 ~ 4:3 ~ 6 and chlorsulfonic acid for the Graphene of 1 ~ 20nm or graphene oxide, and 1 ~ 10h is reacted at 60 ~ 150 DEG C, then distill more than 160 DEG C, residue, after cleaning, obtains described sulfonated graphene.
Compared with prior art, advantage of the present invention comprises: the heat-conduction nylon material preparation technology provided is simple, mild condition is controlled, sulfonated graphene addition is few, and cost is low, and obtain heat-conduction nylon material vertical direction thermal conductivity be 0.5 ~ 10W/ (m.K), and at least maintain and even improve the mechanical property of nylon material, at LED lamp, switch housing, notebook computer shell, the fields such as handset shell are with a wide range of applications.
Embodiment
Below in conjunction with some embodiments to technical scheme do of the present invention explanation explanation specifically.
Mass ratio is that the oleum of 3:4 and chlorsulfonic acid add multitube film reacter by embodiment 1, (radial dimension is 500nm ~ 50 μm to add Graphene again, thickness is 1 ~ 20nm) Homogeneous phase mixing, the Graphene content in mixed reactant is made to reach 2wt%, react 10 hours at 60 DEG C of temperature, after having reacted, by mixed reactant 165 DEG C of distillations, residue is through washing, obtain sulfonated graphene, again obtained sulfonated graphene is scattered in water, forms the sulfonated graphite aqueous solution that concentration is 5wt%, for subsequent use.
Described sulfonated graphite aqueous solution and nylon monomer hexanolactam, water, hexanodioic acid are added autoclave in the ratio of 10:70:20:0.35, slowly be warming up to 150 DEG C, and stirring at low speed 0.5h, continue again to be warming up to temperature of reaction 260 DEG C, pressurize 2h under 5MPa, then be evacuated to stable viscosity, discharging, granulation, obtain target product.
Mass ratio is that the oleum of 1:6 and chlorsulfonic acid add multitube film reacter by embodiment 2, (radial dimension is 500nm ~ 50 μm to add Graphene again, thickness is 1 ~ 20nm) Homogeneous phase mixing, the Graphene content in mixed reactant is made to reach 2wt%, react 1 hour at 150 DEG C of temperature, after having reacted, by mixed reactant 160 DEG C of distillations, residue is through washing, obtain sulfonated graphene, again obtained sulfonated graphene is scattered in water, forms the sulfonated graphite aqueous solution that concentration is 20wt%, for subsequent use.
Obtained sulfonated graphite aqueous solution and nylon salt, water, hexanodioic acid are added autoclave in the ratio of 10:55:35:0.35, slowly be warming up to 150 DEG C, and stirring at low speed 0.5h, continue again to be warming up to temperature of reaction 285 DEG C, pressurize 5h under 2MPa, then be evacuated to stable viscosity, discharging, granulation, obtain target product.
Mass ratio is that the oleum of 1:1 and chlorsulfonic acid add multitube film reacter by embodiment 3, (radial dimension is 500nm ~ 50 μm to add Graphene again, thickness is 1 ~ 20nm) Homogeneous phase mixing, the Graphene content in mixed reactant is made to reach 2wt%, react 2 hours at 100 DEG C of temperature, after having reacted, by mixed reactant 160 DEG C of distillations, residue is through washing, obtain sulfonated graphene, again obtained sulfonated graphene is scattered in water, forms the sulfonated graphite aqueous solution that concentration is 10wt%, for subsequent use.
Obtained sulfonated graphite aqueous solution and nylon salt, water are added autoclave in the ratio of 10:60:30:0.35, slowly be warming up to 150 DEG C, and stirring at low speed 0.5h, continue again to be warming up to temperature of reaction, pressurize 5h under 2MPa, then be evacuated to stable viscosity, discharging, granulation, obtain target product.
Reference examples 1: with reference to the method that embodiment 1 is identical, and substitute described sulfonated graphene with Graphene (with embodiment 1), obtained product.
Reference examples 2: with reference to the method that embodiment 1 is identical, and substitute described sulfonated graphene with graphene oxide (standby according to humers legal system), obtained product.
Reference examples 3: with reference to the method that embodiment 1 is identical, and substitute described sulfonated graphene with sulfonated graphene (with reference to Journal of Materials Chemistry, 2011,21,11359-11364), obtained product.
With high resolving power TEM, embodiment 1-3 and product that reference examples 1-3 obtains are observed, can find, in embodiment 1-3 product, sulfonated graphene is dispersed in nylon matrix, Graphene (graphene oxide) then obvious skewness in reference examples 1-2 product, in reference examples 3 product, sulfonated graphene has reunion to a certain degree.
Mode is commonly used again with industry, such as laser thermal conductivity instrument (as the NETZSCH LFA447) heat conductivility to embodiment 1-3 product and reference examples 1-3 product is tested respectively, can find, the vertical direction thermal conductivity of embodiment 1-3 product is respectively 0.65W/ (m.K), 3.46W/ (m.K), 2.13W/ (m.K), apparently higher than reference examples 1-3 product (its vertical direction thermal conductivity is respectively 0.28W/ (m.K), 0.25W/ (m.K), 0.27W/ (m.K)).
In addition, adopt industry to commonly use the mechanical property of mode to embodiment 1-3 product and reference examples 1-3 product to test respectively, can find, the tensile strength, flexural strength etc. of embodiment 1-3 product also all apparently higher than reference examples 1-3 product, and also higher than or at least suitable with the correlated performance of pure nylon product.
It should be noted that, disclosed is the multiple of preferred embodiment, the change of every local or modification and come from technological thought of the present invention and be easy to by the people that has the knack of this technology to know by inference, all do not depart from patent right scope of the present invention.
Claims (9)
1. based on a heat-conduction nylon material for sulfonated graphene, it is characterized in that comprising: nylon matrix material 95wt% ~ 99.9wt%, sulfonated graphene 0.1wt% ~ 5wt%; The radial dimension of wherein said sulfonated graphene is 500nm ~ 50 μm, and thickness is 1 ~ 20nm, and in described sulfonated graphene, the mol ratio of C and S is 12:1 ~ 6:1.
2. the heat-conduction nylon material based on sulfonated graphene according to claim 1, is characterized in that the vertical direction thermal conductivity of described heat-conduction nylon material is 0.5 ~ 10W/ (m.K).
3., based on a preparation method for the heat-conduction nylon material of sulfonated graphene, it is characterized in that comprising:
There is provided sulfonated graphene, its radial dimension is 500nm ~ 50 μm, and thickness is 1 ~ 20nm, and the mol ratio of contained C and S is 12:1 ~ 6:1;
Described sulfonated graphene and nylon monomer, water are added autoclave, is warming up to 100 ~ 150 DEG C and more than Keep agitation 0.5h, then continues to be warming up to temperature of reaction, more than pressurize 2h under 2 ~ 5MPa, then be evacuated to stable viscosity, discharging, obtain target product.
4. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 3, it is characterized in that comprising: sulfonated graphite aqueous solution and nylon monomer, water are added autoclave by the mass ratio of 0.01 ~ 25:60 ~ 85:15 ~ 40,100 ~ 150 DEG C are warming up to by 3-10 DEG C/min, and more than Keep agitation 0.5h, continue again to be warming up to temperature of reaction 250-290 DEG C, pressurize 2-5h under 2 ~ 5MPa, then stable viscosity is evacuated to, discharging, granulation, obtain target product.
5. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 4, is characterized in that the concentration of described sulfonated graphite aqueous solution is 5-20wt%.
6. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to any one of claim 3-5, is characterized in that described heat-conduction nylon material comprises: nylon matrix material 95wt% ~ 99.9wt%, sulfonated graphene 0.1wt% ~ 5wt%.
7. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to any one of claim 3-4, is characterized in that described nylon monomer comprises hexanolactam and/or nylon salt.
8. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to any one of claim 3-5, it is characterized in that the preparation method of described sulfonated graphene comprises: be 500nm ~ 50 μm by radial dimension, thickness is that to add primarily of mass ratio be in the mixed acid solution that forms of the oleum of 1 ~ 4:3 ~ 6 and chlorsulfonic acid for the Graphene of 1 ~ 20nm or graphene oxide, and 1 ~ 10h is reacted at 60 ~ 150 DEG C, then distill more than 160 DEG C, residue, after cleaning, obtains described sulfonated graphene.
9. the preparation method of the heat-conduction nylon material based on sulfonated graphene according to claim 8, is characterized in that the vertical direction thermal conductivity of described heat-conduction nylon material is 0.5 ~ 10W/ (m.K).
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| CN105206802A (en) * | 2015-08-24 | 2015-12-30 | 苏州高通新材料科技有限公司 | Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof |
| CN106676678A (en) * | 2016-12-30 | 2017-05-17 | 苏州高通新材料科技有限公司 | Graphene modified composite carbon fibers as well as preparation method and application thereof |
| 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 |
| 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 |
| CN109354868A (en) * | 2017-10-19 | 2019-02-19 | 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 |
| 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 |
| 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 |
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| CN105206802A (en) * | 2015-08-24 | 2015-12-30 | 苏州高通新材料科技有限公司 | Lithium-rich sulfonated graphene-nanometer SiOx negative electrode material and preparation method and application thereof |
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| CN109354868B (en) * | 2017-10-19 | 2021-03-19 | 厦门稀土材料研究所 | Graphene-modified flame-retardant heat-conducting nylon plastic and preparation method thereof |
| 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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Effective date of registration: 20211027 Address after: 344000 houfa Industrial Zone, industrial park, Le'an County, Fuzhou City, Jiangxi Province Patentee after: Fuzhou Aoxi New Material Co.,Ltd. Address before: Room 112, A4 / F, bio nano Park, 218 Xinghu street, Suzhou Industrial Park, 215000, Jiangsu Province Patentee before: SUZHOU GRAPHENE-TECH Co.,Ltd. |
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