CN101608061A - A kind of polyamide/oxidized graphite composite material and preparation method thereof with high conduction performance - Google Patents
A kind of polyamide/oxidized graphite composite material and preparation method thereof with high conduction performance Download PDFInfo
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Abstract
The invention discloses a kind of polyamide/graphite matrix material and preparation method thereof with high conduction performance.This matrix material is made up of polyamide substrate and nano-graphite, makes by in-situ polymerization.Nano-graphite of the present invention has high radius-thickness ratio, uses less nano-graphite just can form effective conductive network in polymkeric substance.And low nano-graphite conductive filler material content can make conducting polymer materials keep original excellent mechanical performances.Volume conductance with polyamide/graphite matrix material of high conduction performance of the present invention can reach 8 * 10
-3S/cm contrasts the excellent properties that traditional natural graphite, expanded graphite conducing composite material have low sizing amount high conductivity.
Description
Technical field
The invention belongs to the conductive polymer composite field, be specifically related to a kind ofly have polyamide compoiste material of high conduction performance and preparation method thereof by what polyamide/oxidized graphite was formed.
Background technology
Polymeric amide is the widely used thermoplastic engineering plastic of a kind of excellent performance.But because its specific conductivity is 10
-15Below the S/cm, the antistatic property of goods is poor, has limited its range of application.The raising of specific conductivity normally by adding a certain amount of electro-conductive material, connects into conductive path by conductive filler material, thereby makes polymer materials have certain electroconductibility.The graphite-like conductive filler material mostly is natural graphite, expanded graphite etc. in the prior art, be subjected to the influence of filler size and reunion situation, need high amount of filler could form conductive network in the system, the percolation threshold height, intensity and toughness infringement to matrix material are bigger, and have caused the decline of conducing composite material processing characteristics.Natural graphite has lamellated ordered structure, owing to have Van der Waals force between graphite flake layer, makes its interlayer be difficult for peeling off.Therefore untreated natural graphite is difficult to realize the distribution of individual layer state in polymkeric substance.
Conducing composite material preparation method based on graphite mainly contains solution method, scorification, situ aggregation method at present.
Solution method is dissolved in polymkeric substance in the solvent earlier, graphite is scattered in the polymers soln of gained again, removes solvent then and promptly gets the polymer/graphite matrix material.The shortcoming of this method is for abundant dissolve polymer and fully disperses graphite, and the consumption of solvent is often very big, simultaneously solvent thoroughly to remove difficulty bigger.The solvent of some polymkeric substance is special, and is difficult for obtaining.These have all limited the application of solution method.
The fusion rule is direct and Mixing of Polymer Melt with graphite, makes mixing of materials even by mechanical shear stress.The problem of this method is that the viscosity of polymer melt is very high, and graphite is difficult in homodisperse in the polymkeric substance, reunites easily, causes percolation threshold higher.
Graphite is dispersed in the monomer of polyamide, can prepares the polyamide/graphite conducing composite material by in-situ polymerization.If graphite disperses with the nano level graphite wafer in polyamide substrate, then the conduction percolation threshold of this polyamide/graphite conducing composite material is low, promptly under the low situation of graphite consumption, just can in the polyamide/graphite conducing composite material, form the spatial conductive network, and show excellent conductivity, form polyamide/nano graphite composite material with high conduction performance.For example; among the Chinese patent ZL99108082.3 with the mixture of expanded graphite, caprolactam monomer, initiator after proper method is handled; under nitrogen protection, carry out in-situ polymerization; when the graphite addition was 3wt%, prepared nylon 6/ graphite conductive nano composites volume conductance reached 10
-4More than the S/cm.Chen Guohuas etc. are made free Nano graphite thin slice by ultrasonic with expanded graphite, carry out in-situ polymerization with polymer monomer again, the exceeding of nylon 6/ graphite conductive nano composites of preparing oozes thresholding and can reach 0.74vol%, and when content of graphite was 1.3vol%, the resistivity of matrix material reached 10
-4S/cm (Wengui Weng, et al.Fabrication and characterization of Nylon 6/foliated graphiteelectrically conducting nanocomposite.Journal of Polymer Science:Part B:Polymer Physics, 2004,42:2844-2856).One side expanded graphite interlayer is peeled off insufficient, and profile is fluffy, and interlayer obviously has adhesion, and expanded graphite subsides under external force easily on the other hand, will be bonding mutually between the nano level graphite flake that has expanded, and specific surface area reduces greatly.Therefore limited the application of expanded graphite in the electroconductibility field of improving graphite composite material.
Summary of the invention
The purpose of this invention is to provide a kind of conducting polymer composite material based on graphite, this material has possessed the low and high characteristics of electroconductibility of graphite addition, and possesses good mechanical performance and processing characteristics.
Another object of the present invention provides a kind of preparation method of above-mentioned conductive polymers/oxidized graphite composite material.
Purpose of the present invention can reach by following measure:
A kind of polyamide/oxidized graphite composite material with high conduction performance, this matrix material is made up of the raw material of following weight part:
Graphite oxide 0.25～5
Monomer of polyamide composition 100
Catalyzer or initiator 0～10
Dispersion medium 0～300.
This matrix material finally is made up of polyamide substrate and nano-graphite, makes by in-situ polymerization.Wherein the raw material of graphite oxide is that particle diameter is between 10
3～10
6The purpose natural flake graphite carries out oxidation with it and peels off, resulting oxidized graphite flake thickness 1～20 nanometer, and radius-thickness ratio is 100～2000.
Wherein the monomer of polyamide composition is hexanolactam, hexosamine, nylon salt, 11-aminoundecanoic acid or omega-lauric lactam.Catalyzer or initiator are hexosamine, ten diamino acid, hexanediamine, phosphoric acid, organic phosphoric acid or organic sulfonic acid.Dispersion medium is water or ethanol.
A kind of preparation method with polyamide/oxidized graphite composite material of high conduction performance comprises the steps:
(1) preparation graphite oxide: with the natural flake graphite is raw material, is equipped with graphite oxide according to the Hummer legal system.The Hummer method is referring to J.Am.Chem.Soc.1958,80:1339.
(2) disperse graphite oxide, form pre-composition: each raw material (0.25～5 mass parts graphite oxide, 100 mass parts monomer of polyamide or raw material, 0～10 mass parts of catalyst or initiator, 0～300 mass parts dispersion medium) is mixed, and formed pre-composition in 0.5～6 hour 20 ℃～85 ℃ (preferred 70～85 ℃) ultrasonic dispersing.
Ultrasonication of the present invention can be used conventional ultrasonic device, and preferred ultrasonic frequency is 25～120kHz.
In the composition of pre-composition, the mass ratio of graphite oxide and polymer monomer composition is preferably 0.5/100～5/100.Graphite oxide directly mixes with the polymer melt monomer, again mixed solution is carried out ultrasonication, and ultrasonic treatment time is 0.5～6 hour, and the optimum handling time is 1～3 hour.
Can select dispersion medium for use in the pre-composition.Having of dispersion medium is beneficial to the full and uniform dispersion of graphite oxide in pre-composition.Wherein, dispersion medium is selected from water, ethanol.When using dispersion medium, earlier graphite oxide is scattered in the liquid medium; The graphite oxide dispersion liquid supersound process time is 0.5～6 hour, and the optimum handling time is 1～3 hour.
(3) open loop and prepolymerization form prepolymer.
(4) in-situ polymerization: in polymeric amide generation polymeric heat-processed, thermal reduction has taken place in graphite oxide, has recovered electroconductibility.In the polymerization stage of this polyamide/nano graphite composite material of preparation, need regulate polymerization time to guarantee that polymeric fully carries out according to the addition of graphite oxide.
(5) aftertreatment: in the nitrogen environment bottom discharge, through promptly getting product after granulation and the drying.
For some nylon, for example nylon 6, Ni Long11 have partial monosomy and oligopolymer and remain in the polymkeric substance after polymerization, need remove monomer by method of extraction.Concrete operations are for to boil polymeric aggregate 1～3 hour in 100 ℃ of water.
Open loop among the preparation method and prepolymerization step can for:
(1) with pre-composition through after the vacuum-drying, prepolymerization is 1～4 hour under 170 ℃～230 ℃ and nitrogen protection;
Perhaps (2) are with pre-composition prepolymerization 1.5～3 hours under 220 ℃～250 ℃ and 1.0～1.8MPa nitrogen pressure;
Perhaps (3) are with pre-composition prepolymerization 2～4 hours under 190 ℃～200 ℃ and nitrogen protection;
Perhaps (4) were warming up to 270～290 ℃ (preferred 280 ℃) with pre-composition in 1 hour, and were that 1.6～2.2MPa (preferred 1.9MPa) keeps 8～10 hours (preferred 9 hours) down at pressure.
In-situ polymerization step among the preparation method can for:
(1) with prepolymer polymerization 4～12 hours under 240 ℃～260 ℃ and nitrogen protection condition, reducing pressure in 1～4 hour before polymerization procedure finishes removes the small molecules operation, the inner maintenance of system vacuum;
Release gradually after perhaps (2) are heated to 250～277 ℃ with prepolymer kept temperature and vacuum condition 0.5～1 hour;
Perhaps (3) after removing the small molecules product, polymerization is 14～17 hours under 140～160 ℃ of conditions with prepolymer;
Perhaps (4) prepolymer pressure in 0.5 hour is reduced to normal atmosphere gradually, and temperature is reduced to 240～260 ℃ (preferred 250 ℃), nitrogen environment, and keep 0.2～1 hour (preferred 0.5 hour).
After adopting such scheme, graphite oxide has high radius-thickness ratio in the polyamide/oxidized graphite conducing composite material of the present invention, and through the thermal reduction reaction that takes place in the polymerization process, the conjugation conductive structure of graphite is restored, therefore uses less graphite oxide just can in polymkeric substance, form effective conductive network.And low graphite oxide conductive filler material content can make conducting polymer materials keep the excellent mechanical performances of polymkeric substance self.
The present invention introduces a large amount of oxy radicals by oxidizing reaction on the natural graphite surface, forms the graphite oxide that is easy to peel off, and its carbon-to-oxygen ratio can reach 80/20～95/5.Simultaneously in preparation method of the present invention, graphite oxide carries out in polymeric amide the hot environment of in-situ polymerization thermal reduction reaction having taken place, and the carbon-to-oxygen ratio after its reduction can reach 50/50～91/9.Graphite in this polyamide/oxidized graphite composite material has recovered high conductivity by graphite oxide through reduction.When content of graphite was 1.5wt%, the specific conductivity of polyamide/oxidized graphite composite material can reach 8 * 10
-3S/cm.Contrast traditional natural graphite, expanded graphite conducing composite material, have the excellent properties of low sizing amount high conductivity.
The thickness through the oxidized graphite flake of oxide treatment that uses among the present invention is nano level, and diameter is a micron order, has high radius-thickness ratio.And oxidized reaction destructive conjugation conductive structure is reduced in high temperature polymerization process greatly, therefore can reduce the consumption of conductive filler material greatly, reduces the percolation threshold of system, and is little to the mechanical property influence of material.
And the raw material of graphite oxide, promptly natural graphite is rich in mineral resources in China, low price.In addition, graphite oxide is compared with expanded graphite and had the following advantages: graphite flake layer is peeled off more abundant, and effectively specific surface area is higher, disperses more evenly in polymeric matrix, and reaction conditions does not need High Temperature High Pressure, and conversion unit is simpler.Therefore graphite oxide will have competitive power as a kind of conductive phase raw material for preparing conducing composite material.
Embodiment
Related concrete pharmaceutical chemicals among the present invention:
Natural graphite: Shanghai one sail graphite company limited;
Potassium permanganate (analytical pure): Dihua worker company limited is won in Tianjin;
SODIUMNITRATE (analytical pure): Shanghai green grass or young crops is analysed Chemical Industry Science Co., Ltd;
Hydrogen peroxide 30% (analytical pure), the vitriol oil (analytical pure), hexanolactam (chemical pure), hexosamine (analytical pure), 11-aminoundecanoic acid (analytical pure), 12 (analytical pure), omega-lauric lactam (analytical pure), hexanediamine (analytical pure), phosphoric acid (analytical pure), ethanol (analytical pure): Chemical Reagent Co., Ltd., Sinopharm Group;
Nylon salt: China Shenma Group Co.,Ltd.
The preparation method of graphite oxide is:
98% vitriol oil of getting 400 mass parts places ice bath, adds 10 mass parts natural flake graphites, 5 mass parts SODIUMNITRATE, 30 mass parts potassium permanganate, keeps in this process constantly stirring 1 hour, and prevents that mixeding liquid temperature from surpassing 20 ℃.Remove ice bath, mixed solution was placed 35 ℃ of water-bath constant temperature 4 hours.With 500 mass parts deionized waters dilutions, make mixed solution 90 ℃ of holding temperatures 15 minutes.With the dilution of deionization 900 mass parts water, add 60 mass parts hydrogen peroxide and filtered while hot.Be washed till no SO with deionized water
4 2-Ion gets final product.
Wherein as the natural flake graphite particle diameter of raw material between 103～106 orders.Resulting oxidized graphite flake thickness 1～20 nanometer after peroxidation is peeled off, radius-thickness ratio is 100～2000.
Embodiment 1
Graphite oxide 0.25～5 mass parts, hexanolactam 100 mass parts, 6-aminocaprolc acid 6 mass parts are mixed, handled 3 hours, promptly obtain pre-composition through the ultra-sonic oscillation under 80 ℃ of conditions.
With pre-composition under vacuum tightness 0.1MPa condition dry 2 hours, through 180 ℃ and nitrogen environment prepolymerization down after 2 hours, polymerization was 8 hours under 250 ℃ and nitrogen environment, in the nitrogen environment bottom discharge, promptly got product after passing through granulation, extraction and drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 1.
Table 1 does not use the matrix material specific conductivity of dispersion medium
Comparative Examples 1
Commercially available natural flake graphite (12000 order) 1.5 mass parts, hexanolactam 100 mass parts, 6-aminocaprolc acid 6 mass parts are mixed, and ultrasonication is 3 hours under 80 ℃ of conditions.Move to then in the reaction tubes,, carry out polymerization according to the identical technology of embodiment 1.The volume conductance of products therefrom is 4 * 10
-13S/cm.
Embodiment 2
Graphite oxide 1.5 mass parts, hexanolactam 100 mass parts, 6-aminocaprolc acid 6 mass parts are mixed dispersion medium 0～300 mass parts.Handled 3 hours through the ultra-sonic oscillation under 80 ℃ of conditions, promptly obtain pre-composition.
With pre-composition under vacuum tightness 0.1MPa condition dry 2 hours, through 180 ℃ and nitrogen environment prepolymerization down after 2 hours, polymerization was 8 hours under 250 ℃ and nitrogen environment, in the nitrogen environment bottom discharge, promptly got product after passing through granulation, extraction and drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 2.
Table 2 uses the matrix material specific conductivity of different dispersion
Embodiment 3
Graphite oxide 1.5 mass parts, hexanolactam 100 mass parts, 6-aminocaprolc acid 6 mass parts are mixed.Handled 3 hours through the ultra-sonic oscillation under 80 ℃ of conditions, promptly obtain pre-composition.
With pre-composition under vacuum tightness 0.1MPa condition dry 2 hours, through 210 ℃ and nitrogen environment prepolymerization down after 2 hours, 250 ℃ with nitrogen environment under polymerization 8 hours.Reduced pressure in 1～4 hour before polymerization procedure finishes and remove the small molecules operation, the inner vacuum tightness 0.1MPa that keeps of system.In the nitrogen environment bottom discharge, promptly get product through after granulation, extraction and the drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 3.
The matrix material specific conductivity of the different vacuum times of table 3
Embodiment 4
Graphite oxide 0.25～5 mass parts, nylon salt 100 mass parts, hexanediamine 3 mass parts, water 150 mass parts are mixed.Handled 3 hours through the ultra-sonic oscillation under 80 ℃ of conditions, obtain pre-composition.
Pre-composition prepolymerization 2.5 hours under 227 ℃ and 1.72MPa nitrogen pressure.Release gradually after prepolymer is heated to 271 ℃ kept 1 hour under 272 ℃ and vacuum tightness 0.1MPa condition, and removed the water vapor that forms in the reaction process and be retained in the melt.In the nitrogen environment bottom discharge, in water-bath, cool off, through promptly getting product after granulation and the drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 4.
The matrix material specific conductivity of the different content of graphite of table 4
Embodiment 5
With graphite oxide 0.5～5 mass parts, 11-aminoundecanoic acid 100 mass parts, phosphatase 11 mass parts, water 300 mass parts.Handled 3 hours through the ultra-sonic oscillation under 80 ℃ of conditions, obtain pre-composition.
Pre-composition is through prepolymerization 3 hours under 190 ℃ and nitrogen protection after the thorough drying.Prepolymer was handled 1 hour under vacuum tightness 0.1MPa condition, to remove the small molecules product, and polymerization 15 hours under 150 ℃ of conditions then.In the nitrogen environment bottom discharge, promptly get product through after granulation, extraction and the drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 5.
The matrix material specific conductivity of the different content of graphite of table 5
Embodiment 6
Graphite oxide 0.5～5 mass parts, omega-lauric lactam 100 mass parts, ethanol 300 mass parts are mixed.Handled 3 hours through the ultra-sonic oscillation under 80 ℃ of conditions, obtain pre-composition.
Pre-composition adds hexanodioic acid 0.2 mass parts through after fully sloughing solvent, is warming up to 280 ℃ in 1 hour, and pressure is 1.9MPa, keeps 9 hours.Prepolymer pressure in 0.5 hour is reduced to normal atmosphere gradually, and temperature is reduced to 250 ℃, nitrogen environment, and kept 0.5 hour.In the nitrogen environment bottom discharge, through promptly getting product after granulation and the drying.
With the conductivity of megger or four electrode method mensuration product, the volume conductance of products therefrom is listed in the table 5.
The matrix material specific conductivity of the different content of graphite of table 6
Claims (10)
1, a kind of polyamide/oxidized graphite composite material with high conduction performance is characterized in that this matrix material is made up of the raw material of following weight part:
Graphite oxide 0.25～5
Monomer of polyamide composition 100
Catalyzer or initiator 0～10
Dispersion medium 0～300.
2, matrix material according to claim 1, the radius-thickness ratio that it is characterized in that described graphite oxide is 100～2000.
3, matrix material according to claim 1 and 2 is characterized in that described graphite oxide is obtained after oxidation is peeled off by natural flake graphite.
4, matrix material according to claim 3, the particle diameter that it is characterized in that described natural flake graphite is 10
3～10
6Order.
5, matrix material according to claim 1 is characterized in that described monomer of polyamide composition is hexanolactam, hexosamine, nylon salt, 11-aminoundecanoic acid or omega-lauric lactam.
6, matrix material according to claim 1 is characterized in that described catalyzer or initiator are hexosamine, ten diamino acid, hexanediamine or phosphoric acid.
7, matrix material according to claim 1 is characterized in that described dispersion medium is water or ethanol.
8, a kind of preparation method with polyamide/oxidized graphite composite material of high conduction performance is characterized in that comprising the steps:
(1) preparation graphite oxide
With the natural flake graphite is raw material, the preparation graphite oxide;
(2) disperse graphite oxide, form pre-composition
Each raw material is mixed, and formed pre-composition in 0.5～6 hour 20 ℃～85 ℃ following ultrasonic dispersing;
(3) open loop and prepolymerization form prepolymer
(4) in-situ polymerization
In polymeric amide generation polymeric heat-processed, graphite oxide generation thermal reduction, and recover electroconductibility;
(5) aftertreatment
In the nitrogen environment bottom discharge, promptly get product through after granulation, extraction and the drying.
9, preparation method according to claim 8 is characterized in that described open loop and prepolymerization step are:
(1) with pre-composition through after the vacuum-drying, prepolymerization is 1～4 hour under 170 ℃～230 ℃ and nitrogen protection;
Or (2) are with pre-composition prepolymerization 1.5～3 hours under 220 ℃～250 ℃ and 1.0～1.8MPa nitrogen pressure;
Or (3) are with pre-composition prepolymerization 2～4 hours under 190 ℃～200 ℃ and nitrogen protection;
Or (4) be warming up to 270～290 ℃ with pre-composition in 1 hour, and be to keep under 1.6～2.2MPa 8～10 hours at pressure.
10, preparation method according to claim 8 is characterized in that described in-situ polymerization step is:
(1) with prepolymer polymerization 4～12 hours under 240 ℃～260 ℃ and nitrogen protection condition, and reduce pressure and remove the small molecules operation, the inner maintenance of system vacuum in before polymerization procedure finishes 1～4 hour;
Or (2) prepolymer is heated to 250～277 ℃ after release gradually, kept temperature and vacuum condition 0.5～1 hour;
Or after (3) removed the small molecules product with prepolymer, polymerization was 14～17 hours under 140～160 ℃ of conditions;
Or (4) reduce to normal atmosphere with prepolymer gradually 0.5 hour internal pressure, and temperature is reduced to 240～260 ℃, keeps under nitrogen environment 0.2～1 hour.
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| CN101608061B (en) | 2012-06-13 |
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