CN102850652B - Ternary-dielectric-filled polymer conductive composite and preparation method - Google Patents
Ternary-dielectric-filled polymer conductive composite and preparation method Download PDFInfo
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Abstract
A ternary-dielectric-filled polymer conductive composite comprises, by weight, (3-8)% of stainless steel fibers, (2-6)% of carbon black, (1-5)% of polyaniline, (65-70)% of polypropylene, (10-22)% of polyethylene or polyolefin plastics and (2-6)% of additives for improving polypropylene forming process performance. The composite is an aggregate of a sheath-core structure, the stainless steel fibers with polyaniline films by means of surface electrochemical deposition serve as the core, the coating sheath layer is a composite obtained by milling modified carbon black pellets of three-layer structures, polypropylene and the like, and each modified carbon black pellet of the three-layer structure includes a carbon black core layer, a secondary nickel plating surface layer and an outer polyaniline film surface layer. The ternary-dielectric-filled polymer conductive composite is high in electric conductivity and mechanical property, and in order to obtain the same conductivity, the composite is lower in required conductive dielectric addition amount, high in mechanical property and lower in material cost.
Description
Technical field
The invention belongs to technical field of polymer composite materials, be specifically related to a kind of ternary Filled Dielectrics composite conducting polymer material and preparation method.
Background technology
To have fixing resistivity different from metallic conductor, conductive polymer composite can be filled phase kind, form, quantity and matrix classification etc. by adjustment and be obtained different resistivity and resistance characteristic thereof, in addition its price is lower, density is less, be easy to the advantages such as machine-shaping, become one of the fastest electro-conductive material of development in recent years, be the critical material of the field development such as electronics, information, electromagnetic shielding, application constantly expands.
The modes such as conductive polymer composite is by filled conductive medium, compound through dispersion, lamination is compound obtain the heterogeneous composite material system with conducting function.The filled media adopting at present mainly contains: electro-conductive fiber, and as carbon fiber, steel fiber, nickel plating (or silver-plated) glass fibre etc.Conductive particle, as carbon black, metal powder etc.What domestic coming into the market applied is mainly carbon black filled polymkeric substance, Stainless Steel Fibre filled polymer and filled with carbon fibers polymkeric substance.Abroad, except above-mentioned kind, carbon nano-tube filled polymkeric substance in addition in recent years grew up.The subject matter that domestic carbon black filled conductive polymer composite exists is that loading level is high, and mechanical property is not high, and electric conductivity adjustable extent is less, and material category is limited, is mainly used in anti-electrostatic field.And carbon nano-tube filled conducting polymer polymer composite mainly adopts import, cost is higher.Stainless Steel Fibre (SSF), has obtained paying close attention to widely and studying in eighties of last century because of its good electroconductibility and processing characteristics as a kind of novel steel fiber the eighties.The most outstanding performance of Stainless Steel Fibre is in high temperature process moulding process, is difficult for producing surface oxidation, is difficult for getting rusty, and this has just saved the step of carrying out numerous and diverse deoxidation layer and surfacecti proteon processing, also can keep electroconductibility and electro-magnetic screen function simultaneously.The SSF diameter of being produced by drawing technique is little, less to performance impacts such as matrix shrinking percentage, tensile strength, modulus in flexurees.Meanwhile, different from carbon black, carbon nanotube, the interpolation of SSF is less on the appearance color impact of matrix, easily obtains the conductive plastic object of different color, and adds a small amount of SSF and just can reach desirable conductivity and electromagnet shield effect.But there is following problem: the consistency of (1) Stainless Steel Fibre and matrix is lower, cause the boundary strength of fiber and matrix lower, thereby reduced the mechanical property of material; (2) in the course of processing, the length-to-diameter ratio of fiber has decline in various degree, thereby makes its capability of electromagnetic shielding produce decline in various degree; (3), when strengthening conductive filler material consumption raising conductivity, reduced process industrial art performance, the mechanical property of material; (4) dispersiveness of conductive filler material in matrix is not high, and loading level awaits further reducing, to reduce preparation and the tooling cost of conductive plastics.
Summary of the invention
for addressing the above problem, the invention provides a kind of ternary Filled Dielectrics composite conducting polymer material and preparation method, improved electric conductivity and mechanical property, effectively reduce its percolation threshold.
The technical solution used in the present invention is:
A kind of ternary Filled Dielectrics composite conducting polymer material, it forms according to weight percent meter, comprise: Stainless Steel Fibre (3-8) %, carbon black (2-6) %, polyaniline (1-5) %, polypropylene (65-70) %, polyethylene or polyolefin plastics (10-22) %, improves additive (2-6) % of polypropylene building-up properties, wherein said matrix material is the pellet of skin-core structure, core is the Stainless Steel Fibre through surface electrochemistry deposition polyaniline film, the thickness of polyaniline film is (0.1-0.25) μ m, coated cortex is the modified carbon black particle of three-decker, polypropylene, polyethylene or polyolefine and improve the mixing matrix material obtaining of additive of polypropylene building-up properties, the modified carbon black grain pattern of three-decker wherein: core layer is carbon black, inferior top layer is nickel layer, extexine is polyaniline film, wherein the thickness of nickel layer is (0.2-1) μ m, the thickness of polyaniline film is (0.1-0.25) μ m.
Further, the pellet mean length 5mm of described ternary Filled Dielectrics composite conducting polymer material, the average 3mm of pellet diameter.
A preparation method for ternary Filled Dielectrics composite conducting polymer material, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment
Carbon blacksurface is carried out to chemical nickel plating processing, wherein thickness of coating (0.2-1) μ m;
Second step: nickel plating carbon deposition polyaniline film
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is (0.1-0.25) μ m;
The 3rd step: Stainless Steel Fibre deposition polyaniline film
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is (0.1-0.25) μ m;
The 4th step: the preparation of once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene or polyolefine and the additive that improves polypropylene building-up properties carry out mixing, obtain mixing matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyethylene or polyolefine, improve the additive of polypropylene building-up properties according to weight percent meter, carbon black nano particle (2-6.5) % of three-decker, polypropylene (67-76) %, polyethylene or polyolefine (11-24) %, improve additive (2-6.5) % of polypropylene building-up properties, melting temperature: (160-210) ℃, mixing time: (5-15) minute, then by mixing matrix material granulation, obtain once-combined material masterbatch,
The 5th step: the preparation of secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the Stainless Steel Fibre of the surface electrochemistry deposition polyaniline film that the 3rd step obtains, then granulation, obtain ternary Filled Dielectrics composite conducting polymer material, the add-on of the Stainless Steel Fibre of the surface electrochemistry deposition polyaniline film that wherein once-combined material masterbatch and the 3rd step obtain is according to weight percent meter, Stainless Steel Fibre content is (3-8) %, and surplus is once-combined material masterbatch.
Further, before the first step, carbon black Nickel Plating Treatment, carbon black is carried out to surface oxidation, sensitization and activation treatment, it comprises the following steps:
A, oil removing: by carbon black at sodium hydroxide: (50-60) g/L, sodium carbonate: (10-15) g/L, sodium phosphate: (20-25) g/L, clean-out system: (3-5) oil removing in the alkaline solution of g/L, temperature: (40-50) ℃, time: (30-50) min, then with distilled water, at room temperature clean, remove impurity;
B, alligatoring: the carbon black that oil removal treatment is crossed is at ammonium peroxydisulfate: (180-200) g/L; Sulfuric acid: (80-100) soak (10-20) min in ml/L coarsening solution, temperature is (60-70) ℃, then uses (50-100) g/L sodium hydroxide solution at room temperature to neutralize, and finally at room temperature cleans with distilled water;
C, sensitization are processed: the carbon black after roughening treatment is carried out in stannous chloride solution to sensitization processing, wherein in stannous chloride solution, tin protochloride is (15-20) g/L, hydrochloric acid is (40-50) g/L, at room temperature processes (3-10) min, then with distilled water, at room temperature cleans;
D, activation treatment: the carbon black after sensitization is processed is processed in containing the noble metal compound solution of catalytic activity again, its formula is: Palladous chloride: (0.3-0.6) g/L, hydrochloric acid: (8-12) ml/L, react at normal temperatures (1-5) min, then in (10-30) g/L sodium hypophosphite solution, at room temperature neutralize, finally with distilled water, at room temperature clean standby.
Further, in the described the first step, carbon black Nickel Plating Treatment, plating solution is: single nickel salt (15-20) g/L, sodium hypophosphite (20-30) g/L, sodium-acetate (20-30) g/L, Trisodium Citrate (20-25) g/L, thiocarbamide (1-2) g/L, pH value: 5-5.5, bath temperature (70-80) ℃, time (20-60) min.
Further, the electrolytic solution of described second step, nickel plating carbon blacksurface electrochemical deposition polyaniline film: concentration of aniline is (0.2-0.5) mol/ L, sulfuric acid concentration is (1-3) mol/ L, electrolyte ph: 2-3.
Further, the electrolytic solution of the 3rd described step, Stainless Steel Fibre surface electrochemistry deposition polyaniline film: concentration of aniline is (0.2-0.5) mol/ L, and sulfuric acid concentration is (1-3) mol/ L, electrolyte ph: 2-3.
Further, described electrochemical deposition polyaniline film is at room temperature adopting pulse potential deposition, pulse potential 1v, and the burst length is 10s, the turn-off time is 10-40s. circulating cycle issue 20-60.
Further, the described additive that improves polypropylene building-up properties is Zinic stearas, anti-oxidant DLTP or clay.
Beneficial effect of the present invention:
Ternary Filled Dielectrics composite conducting polymer material of the present invention, takes carbon black, Stainless Steel Fibre as the main stuffing of conducting polymer medium, thereby and forms ternary filled media at its surface deposition polyaniline.Wherein, carbon black first carried out Nickel Plating Treatment before deposition polyaniline, and to form three-decker matrix material particle, its advantage has: (1) improves the electroconductibility of carbon black and the dispersiveness in matrix; (2) reduce the contact resistance between carbon black particle and Stainless Steel Fibre, improved the conductivity of material; (3) polyaniline of surface deposition between carbon black particle and carbon black work with Stainless Steel Fibre the conducting effect that is connected, the continuity of conductive network is improved, can make up the disadvantageous effect that in the course of processing, Fiber Aspect Ratio declines to conductivity, improve the electroconductibility of material, and reduce the percolation threshold of material; (4) polyaniline of surface deposition improve carbon black with the consistency of matrix, improved the mechanical property of material.
Surface modifying treatment to Stainless Steel Fibre surface deposition polyaniline, has improved the consistency of filled media and matrix effectively, and the bonding strength of fiber and matrix is increased, and has improved the mechanical property of matrix material.
With single interpolation carbon black, and the polymer composite of single interpolation Stainless Steel Fibre compares, and under identical loading level, composite material conductive rate of the present invention is high, and mechanical property is higher.Obtain identical conductivity, the required conducting medium addition of matrix material of the present invention reduces, and mechanical property is higher, and material cost decreases.
Compare with single interpolation carbon nano tube compound material, complete processing is comparatively simple and easy to do, and material cost obviously declines.
accompanying drawing explanation
Fig. 1 is the structural representation of ternary Filled Dielectrics composite conducting polymer material pellet of the present invention.
Fig. 2 is the structural representation of the carbon black nano particle of three-decker of the present invention.
Fig. 3 is the scanning electron microscope (SEM) photograph of ternary Filled Dielectrics composite conducting polymer material of the present invention.
Note: in figure, 1 is once-combined material layer, 2 is polyaniline layer, and 3 is Stainless Steel Fibre, and 4 is polyaniline layer, and 5 is nickel layer, 6 is carbon granules.
embodiment
Below in conjunction with specific embodiment, the present invention is described further.
A preparation method for ternary Filled Dielectrics composite conducting polymer material, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment:
Carbon blacksurface is carried out to chemical nickel plating processing, before carbon black Nickel Plating Treatment, carbon black is carried out to surface oxidation, sensitization and activation treatment, it comprises the following steps:
A, oil removing: by carbon black at sodium hydroxide: 60g/L, sodium carbonate: 10g/L, sodium phosphate: 25g/L, oil removing in the alkaline solution of 6501 clean-out systems: 5g/L, temperature: 40-50 ℃, time: 40min, then at room temperature cleans with distilled water, removes impurity; B, alligatoring: the carbon black that oil removal treatment is crossed is at ammonium peroxydisulfate: 200g/L; Sulfuric acid: soak 10min in 100ml/L coarsening solution, temperature is 60 ~ 70 ℃, then 60 g/L sodium hydroxide solutions at room temperature and, finally with distilled water, at room temperature clean, remove impurity;
C, sensitization are processed: the carbon black after roughening treatment is carried out in stannous chloride solution to sensitization processing, wherein in stannous chloride solution, tin protochloride is 15g/L, and hydrochloric acid is 40g/L, carries out 5min under room temperature, then with distilled water, at room temperature cleans, and removes impurity;
D, activation treatment: the carbon black after sensitization is processed is processed in containing the noble metal compound solution of catalytic activity again, its formula is: Palladous chloride: 0.5g/L, hydrochloric acid: 12ml/L, react at normal temperatures 5min, then in 30 g/L sodium hypophosphite solution, at room temperature soak 15s, neutralize cleaning, finally with distilled water, at room temperature clean, remove impurity.
Carbon black after above-mentioned processing is carried out to Nickel Plating Treatment, wherein in plating solution used, the content of single nickel salt is 20g/L, the content of sodium hypophosphite is 30g/L, the content of sodium-acetate is 20g/L, the content 25g/L of Trisodium Citrate, the content 2g/L of thiocarbamide, pH value: 5, bath temperature 70-80 ℃, time 60min, the thickness of coating 1 μ m after Nickel Plating Treatment.After nickel plating finishes, carbon black is at room temperature cleaned with distilled water, remove impurity, standby.
Second step: nickel plating carbon deposition polyaniline film:
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is (0.1-0.25) μ m.Adopt RST520 electrochemical workstation deposition polyaniline.By the carbon black after Nickel Plating Treatment and the common composition research electrode of nickel sheet, supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.3mol/L, and sulfuric acid concentration is: 3mol/L, pH value: 2.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s, circulating cycle issue 40.After deposition finishes, the carbon black pellet obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, both obtains the carbon black nano particle of three-decker, standby.
The 3rd step, Stainless Steel Fibre deposition polyaniline film:
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is (0.1-0.25) μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Stainless Steel Fibre is wrapped in to common composition research electrode in H-wheel, to complete continuous electrochemical deposition, by H-wheel, carries out take-up.Supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.3mol/L, and sulfuric acid concentration is: 3mol/L, pH value: 2.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s. circulating cycle issue 40.After deposition finishes, the Stainless Steel Fibre obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, has both obtained modification Stainless Steel Fibre, standby.
The preparation of the 4th step, once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene or polyolefine carry out mixing with the additive that improves polypropylene building-up properties, make modified polypropene form sea-island structure, obtain matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyethylene or polyolefine, improve the additive of polypropylene building-up properties according to weight ratio meter, the carbon black nano particle 5% of three-decker, polypropylene 70%, polyethylene 23%, Zinic stearas 2%, melting temperature: 160 ℃, mixing time: 15 minutes, then by the matrix material mixing extruding pelletization on twin screw extruder, obtain once-combined material masterbatch.The extrusion neck ring mold temperature of twin screw extruder: 165 ℃.Temperature of cooling water: 25 ℃, pellet mean length: 3mm, pellet diameter is average: 1.5mm.
The preparation of the 5th step, secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the modification Stainless Steel Fibre that the 3rd step obtains, and single Stainless Steel Fibre diameter is 11 μ m, and core number is 1000.Coating mould port mould diameter 2mm.Then granulation on twin screw extruder, extrudes pellet diameter 3mm, and pelletizing length is 5mm.Obtain ternary Filled Dielectrics composite conducting polymer material, the additional proportion of the modification Stainless Steel Fibre that wherein once-combined material masterbatch and the 3rd step obtain is: Stainless Steel Fibre 6%, all the other are matrix material masterbatch.
embodiment 2
A preparation method for ternary Filled Dielectrics composite conducting polymer material, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment:
Carbon blacksurface is carried out to chemical nickel plating processing, before carbon black Nickel Plating Treatment, carbon black is carried out to surface oxidation, sensitization and activation treatment, it comprises the following steps:
A, oil removing: by carbon black at sodium hydroxide: 50g/L, sodium carbonate: 15g/L, sodium phosphate: 20g/L, oil removing in the alkaline solution of 6501 clean-out systems: 3g/L, temperature: 40-50 ℃, time: 30min, then at room temperature cleans with distilled water, removes impurity;
B, alligatoring: the carbon black that oil removal treatment is crossed is at ammonium peroxydisulfate: 180g/L; Sulfuric acid: soak 15min in 80ml/L coarsening solution, temperature is 60 ~ 70 ℃, then neutralizes at 100 g/L sodium hydroxide solutions, finally at room temperature cleans with distilled water, removes impurity;
C, sensitization are processed: the carbon black after roughening treatment is carried out in stannous chloride solution to sensitization processing, wherein in stannous chloride solution, tin protochloride is 20g/L, and hydrochloric acid is 50g/L, carries out 3min under room temperature, then with distilled water, at room temperature cleans, and removes impurity;
D, activation treatment: the carbon black after sensitization is processed is processed in containing the noble metal compound solution of catalytic activity again, its formula is: Palladous chloride: 0.3g/L, hydrochloric acid: 8ml/L, react at normal temperatures 1min, then in 10 g/L sodium hypophosphite solution, neutralize, finally with distilled water, at room temperature clean, remove impurity, standby.
Carbon black after above-mentioned processing is carried out to Nickel Plating Treatment, wherein in plating solution used, the content of single nickel salt is 15g/L, the content of sodium hypophosphite is 20g/L, the content of sodium-acetate is 25g/L, the content 20g/L of Trisodium Citrate, the content 1g/L of thiocarbamide, pH value: 5, bath temperature 70-80 ℃, time 20min, the thickness of coating 0.2 μ m after Nickel Plating Treatment.After nickel plating finishes, carbon black is at room temperature cleaned with distilled water, remove impurity, standby.
Second step, nickel plating carbon deposition polyaniline film:
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.By the carbon black after Nickel Plating Treatment and the common composition research electrode of nickel sheet, supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution: concentration of aniline is 0.2mol/L, and sulfuric acid concentration is: 1mol/L, pH value: 3.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 30s, circulating cycle issue 20.After deposition finishes, the carbon black pellet obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, both obtains the carbon black nano particle of three-decker, standby.
The 3rd step, Stainless Steel Fibre deposition polyaniline film:
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.Stainless Steel Fibre is wrapped in to common composition research electrode in H-wheel, to complete continuous electrochemical deposition, by H-wheel, carries out take-up.Supporting electrode adopts platinum electrode, and reference electrode is saturated calomel electrode.Electrolytic solution: concentration of aniline is 0.5mol/L, and sulfuric acid concentration is: 2mol/L, pH value: 3.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s, circulating cycle issue 60.After deposition finishes, the Stainless Steel Fibre obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, has both obtained modification Stainless Steel Fibre, standby.
The preparation of the 4th step, once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene or polyolefine carry out mixing with the additive that improves polypropylene building-up properties, make modified polypropene form sea-island structure, obtain matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyethylene, improve the additive of polypropylene building-up properties according to weight ratio meter, the carbon black nano particle 2% of three-decker, polypropylene 76%, polyethylene 18%, Zinic stearas 4%, melting temperature: 200 ℃, mixing time: 5 minutes, then by the matrix material mixing extruding pelletization on twin screw extruder, obtain once-combined material masterbatch.The extrusion neck ring mold temperature of twin screw extruder: 165 ℃.Temperature of cooling water: 25 ℃, pellet mean length: 3mm, pellet diameter is average: 1.5mm.
The preparation of the 5th step, secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the Stainless Steel Fibre that the 3rd step obtains, and single Stainless Steel Fibre diameter is 11 μ m, and core number is 1000.Coating mould port mould diameter 2mm.Then granulation on twin screw extruder, extrudes pellet diameter 3mm, and pelletizing length is 5mm.Obtain ternary Filled Dielectrics composite conducting polymer material, the additional proportion of the Stainless Steel Fibre that wherein once-combined material masterbatch and the 3rd step obtain is: Stainless Steel Fibre 8%, all the other are matrix material masterbatch.
embodiment 3
A preparation method for ternary Filled Dielectrics composite conducting polymer material, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment:
Carbon blacksurface is carried out to chemical nickel plating processing, before carbon black Nickel Plating Treatment, carbon black is carried out to surface oxidation, sensitization and activation treatment, it comprises the following steps:
A, oil removing: by carbon black at sodium hydroxide: 55g/L, sodium carbonate: 15g/L, sodium phosphate: 20g/L, oil removing in the alkaline solution of 6501 clean-out systems: 4g/L, temperature: 40-50 ℃, time: 50min, then at room temperature cleans with distilled water, removes impurity;
B, alligatoring: the carbon black that oil removal treatment is crossed is at ammonium peroxydisulfate: 190g/L; Sulfuric acid: soak 20min in 90ml/L coarsening solution, temperature is 60 ~ 70 ℃, then carries out neutralization reaction at 50 g/L sodium hydroxide solutions, finally at room temperature cleans with distilled water, removes impurity;
C, sensitization are processed: the carbon black after roughening treatment is carried out in stannous chloride solution to sensitization processing, wherein in stannous chloride solution, tin protochloride is 18g/L, and hydrochloric acid is 45g/L, carries out 10min under room temperature, then with distilled water, at room temperature cleans, and removes impurity;
D, activation treatment: the carbon black after sensitization is processed is processed in containing the noble metal compound solution of catalytic activity again, its formula is: Palladous chloride: 0.6g/L, hydrochloric acid: 10ml/L, react at normal temperatures 3min, then in 20 g/L sodium hypophosphite solution, at room temperature neutralize cleaning, finally with distilled water, at room temperature clean, remove impurity, standby.
Carbon black after above-mentioned processing is carried out to Nickel Plating Treatment, wherein in plating solution used, the content of single nickel salt is 18g/L, the content of sodium hypophosphite is 25g/L, the content of sodium-acetate is 30g/L, the content 23g/L of Trisodium Citrate, the content 1.5g/L of thiocarbamide, pH value: 5, bath temperature 70-80 ℃, time 40min, the thickness of coating 0.8 μ m after Nickel Plating Treatment.After nickel plating finishes, carbon black is at room temperature cleaned with distilled water, remove impurity, standby.
Second step, nickel plating carbon deposition polyaniline film:
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.By the carbon black after Nickel Plating Treatment and the common composition research electrode of nickel sheet, supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.5mol/L, and sulfuric acid concentration is: 2mol/L, pH value: 3.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s. circulating cycle issue 60.After deposition finishes, the carbon black pellet obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, both obtains the carbon black nano particle of three-decker, standby.
The 3rd step, Stainless Steel Fibre deposition polyaniline film:
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.Stainless Steel Fibre is wrapped in to common composition research electrode in H-wheel, to complete continuous electrochemical deposition, by H-wheel, carries out take-up.Supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.2mol/L, and sulfuric acid concentration is: 1mol/L, pH value: 3.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 30s. circulating cycle issue 20.After deposition finishes, the Stainless Steel Fibre obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, has both obtained modification Stainless Steel Fibre, standby.
The preparation of the 4th step, once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene or polyolefine carry out mixing with the additive that improves polypropylene building-up properties, make modified polypropene form sea-island structure, obtain matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyethylene, improve the additive of polypropylene building-up properties according to weight ratio meter, the carbon black nano particle 6.5% of three-decker, polypropylene 67%, polyethylene 24%, Zinic stearas 2.5%, melting temperature: 180 ℃, mixing time: 10 minutes, then by the matrix material mixing extruding pelletization on twin screw extruder, obtain once-combined material masterbatch.The extrusion neck ring mold temperature of twin screw extruder: 165 ℃.Temperature of cooling water: 25 ℃, pellet mean length: 3mm, pellet diameter is average: 1.5mm.
The preparation of the 5th step, secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the Stainless Steel Fibre that the 3rd step obtains, and single Stainless Steel Fibre diameter is 11 μ m, and core number is 1000.Coating mould port mould diameter 2mm.Then granulation on twin screw extruder, extrudes pellet diameter 3mm, and pelletizing length is 5mm.Obtain ternary Filled Dielectrics composite conducting polymer material, the additional proportion of the Stainless Steel Fibre that wherein once-combined material masterbatch and the 3rd step obtain is: Stainless Steel Fibre 3%, all the other are matrix material masterbatch.
embodiment 4
A preparation method for ternary Filled Dielectrics composite conducting polymer material, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment:
Carbon blacksurface is carried out to chemical nickel plating processing, wherein in plating solution used, the content of single nickel salt is 20g/L, the content of sodium hypophosphite is 30g/L, the content of sodium-acetate is 20g/L, the content 25g/L of Trisodium Citrate, the content 2g/L of thiocarbamide, pH value: 5, bath temperature 70-80 ℃, time 60min, the thickness of coating 1 μ m after Nickel Plating Treatment.After nickel plating finishes, carbon black is at room temperature cleaned with distilled water, remove impurity, standby.
Second step, nickel plating carbon deposition polyaniline film:
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.By the carbon black after Nickel Plating Treatment and the common composition research electrode of nickel sheet, supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.3mol/L, and sulfuric acid concentration is: 3mol/L, pH value: 2.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s. circulating cycle issue 40.After deposition finishes, the carbon black pellet obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, both obtains the carbon black nano particle of three-decker, standby.
The 3rd step, Stainless Steel Fibre deposition polyaniline film:
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is 0.1-0.25 μ m.Adopt RST520 electrochemical workstation deposition polyaniline.Employing pulse potentiostatic method deposition.Stainless Steel Fibre is wrapped in to common composition research electrode in H-wheel, to complete continuous electrochemical deposition, by H-wheel, carries out take-up.Supporting electrode adopts ruthenium titanium electrode, and reference electrode is saturated calomel electrode.Electrolytic solution concentration of aniline is 0.3mol/L, and sulfuric acid concentration is: 3mol/L, pH value: 2.5.Be electrochemically-deposited under room temperature and adopt pulse potential deposition, pulse potential 1v, burst length and turn-off time are respectively 10s and 40s. circulating cycle issue 40.After deposition finishes, the Stainless Steel Fibre obtaining is at room temperature cleaned with distilled water, remove impurity, then, under the condition of 60 ~ 80 ℃ of temperature, vacuum-drying, removes moisture, has both obtained modification Stainless Steel Fibre, standby.
The preparation of the 4th step, once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene or polyolefine carry out mixing with the additive that improves polypropylene building-up properties, make modified polypropene form sea-island structure, obtain matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyolefine, improve the additive of polypropylene building-up properties according to weight ratio meter, the carbon black nano particle 6.5% of three-decker, polypropylene 76%, polyolefine 11%, (anti-oxidant DLTP+Zinic stearas) 6.5%, melting temperature: 160 ℃, mixing time: 15 minutes, then by the matrix material mixing extruding pelletization on twin screw extruder, obtain once-combined material masterbatch.The extrusion neck ring mold temperature of twin screw extruder: 165 ℃.Temperature of cooling water: 25 ℃, pellet mean length: 3mm, pellet diameter is average: 1.5mm.
The preparation of the 5th step, secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the Stainless Steel Fibre that the 3rd step obtains, and single Stainless Steel Fibre diameter is 11 μ m, and core number is 1000.Coating mould port mould diameter 2mm.Then granulation on twin screw extruder, extrudes pellet diameter 3mm, and pelletizing length is 5mm.Obtain ternary Filled Dielectrics composite conducting polymer material, the additional proportion of the Stainless Steel Fibre that wherein once-combined material masterbatch and the 3rd step obtain is: Stainless Steel Fibre 6%, all the other are matrix material masterbatch.
Note: the preparation of the sulphuric acid soln in the present invention be take the vitriol oil as raw material, wherein H in the vitriol oil
2sO
4massfraction be 98.3%, its density is 1.84gcm
-3, its amount of substance concentration is 18.4molL
-1.Sulfuric acid: (80-100) preparation of ml/L: get the 80-100 milliliter vitriol oil, constant volume is in 1L distilled water, and sulfuric acid concentration is the preparation of (0.2-0.7) mol/ L: get the 0.2-0.7mol vitriol oil, constant volume is in 1L distilled water.
The preparation of hydrochloric acid soln is that concentrated hydrochloric acid is raw material, wherein the concentration of concentrated hydrochloric acid is 37.5%, density 1.179g/cm3, the preparation that hydrochloric acid is (40-50) g/L: take 40-50g concentrated hydrochloric acid, constant volume is in 1L distilled water, hydrochloric acid: (8-12) preparation of ml/L: measure the concentrated hydrochloric acid of 8-12mL, constant volume is in 1L distilled water.
comparative example 1
Carbon black nano particle and polypropylene carry out mixing, add as required polyethylene or polyolefine to carry out blending and modifying to polypropylene, make modified polypropene form sea-island structure, obtain matrix material, then by the matrix material mixing extruding pelletization on twin screw extruder, obtain composite conducting material, wherein the weight ratio of carbon black nano particle and modified polypropene is 1:9, and in modified polypropene, polyethylene and polypropylene weight percent are 25% and 75%.The extrusion neck ring mold temperature of twin screw extruder: 165 ℃.Temperature of cooling water: 25 ℃, extrude pellet diameter 3mm, pelletizing length is 5mm.
comparative example 2
Utilize coating mould to be coated on Stainless Steel Fibre the polypropylene after blending and modifying (polyethylene and polypropylene weight percent are 25% and 75%), single Stainless Steel Fibre diameter is 11 μ m, and core number is 1000.Coating mould port mould diameter 2mm, then granulation on twin screw extruder, extrudes pellet diameter 3mm, and pelletizing length is 5mm.Wherein the weight ratio of modified polypropene and Stainless Steel Fibre is 9:1.
performance measurement
Utilize the prepared pellet of embodiment 1 ~ 4 and comparative example 1 ~ 2 to carry out Shooting Technique test, injection moulding melt temperature: one section of temperature: 180 ℃, two sections of temperature: 210 ℃, three sections of temperature: 210 ℃, nozzle temperature: 200 ℃, injection pressure: 40MPa, dwell pressure: 30MPa.After injection moulding, measure resistivity and the mechanical property of sample, specifically in Table 1.
Measure the resistivity of the prepared pellet of embodiment 1 ~ 4 and comparative example 1 ~ 2, specifically in Table 1.
As shown in Table 1, the carbon black-filled polypropylene comparison of ternary Filled Dielectrics composite conducting polymer material of the present invention and single interpolation equal in quality mark, 2 orders of magnitude of its resistivity decreased.Under identical fabrication process condition, carbon black filled polypropylene resistivity average out to 380 Ω .cm, the resistivity of ternary Filled Dielectrics composite conducting polymer material of the present invention is 1 Ω .cm.Compare with the Stainless Steel Fibre filled polypropylene of equal in quality mark, the two resistivity is comparatively approaching, but its mechanical property, more than tensile strength has been brought up to 60MPa by 31MPa.This be mainly carbon black existence made up the imperfection of Stainless Steel Fibre overlap joint.Simultaneously, because fiber filled amount declines, the bonding interface quantity making reduces, thereby and after surface treatment Stainless Steel Fibre with the bonding force increase of matrix, the mechanical property of material is obviously improved.
The customization that the parameter of the Stainless Steel Fibre in the present invention can be selected according to the performance requriements of product, does not have large impact to effect of the present invention.Above embodiment is only for illustrating the present invention, rather than protection scope of the present invention is limited.Those skilled in the art can change and revise it after understanding spirit of the present invention and principle, thereby reaches equivalent object, and these changes all should be covered by the present invention with modification.
Claims (10)
1. a ternary Filled Dielectrics composite conducting polymer material, it is characterized in that: it forms according to weight percent meter, comprise: Stainless Steel Fibre 3%-8%, carbon black 2%-6%, polyaniline 1%-5%, polypropylene 65%-70%, polyethylene 10%-22%, improves the additive 2%-6% of polypropylene building-up properties, wherein said matrix material is the pellet of skin-core structure, core is the Stainless Steel Fibre through surface electrochemistry deposition polyaniline film, the thickness of polyaniline film is 0.1-0.25 μ m, coated cortex is the modified carbon black particle of three-decker, polypropylene, polyethylene and the mixing matrix material obtaining of additive that improves polypropylene building-up properties, the modified carbon black grain pattern of three-decker wherein: core layer is carbon black, inferior top layer is nickel layer, extexine is polyaniline film, wherein the thickness of nickel layer is 0.2-1 μ m, the thickness of polyaniline film is 0.1-0.25 μ m.
2. a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 1, is characterized in that: the pellet mean length 5mm of described ternary Filled Dielectrics composite conducting polymer material, the average 3mm of pellet diameter.
3. a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 1 and 2, is characterized in that: the described additive that improves polypropylene building-up properties is Zinic stearas, anti-oxidant DLTP or clay.
4. a preparation method for ternary Filled Dielectrics composite conducting polymer material, is characterized in that, it comprises the following steps:
The first step: carbon black Nickel Plating Treatment
Carbon blacksurface is carried out to chemical nickel plating processing, wherein thickness of coating 0.2-1 μ m;
Second step: nickel plating carbon deposition polyaniline film
By the carbon blacksurface electrochemical deposition polyaniline film after Nickel Plating Treatment in the first step, form the carbon black nano particle of three-decker, wherein polyaniline film thickness is 0.1-0.25 μ m;
The 3rd step: Stainless Steel Fibre deposition polyaniline film
Stainless Steel Fibre surface electrochemistry deposition polyaniline film, wherein polyaniline film thickness is 0.1-0.25 μ m;
The 4th step: the preparation of once-combined material master batch
By carbon black nano particle and the polypropylene of the three-decker obtaining in second step, polyethylene carries out mixing with the additive that improves polypropylene building-up properties, obtain mixing matrix material, the carbon black nano particle of three-decker wherein, polypropylene, polyethylene, improve the additive of polypropylene building-up properties according to weight percent meter, the carbon black nano particle 2%-6.5% of three-decker, polypropylene 67%-76%, polyethylene 11%-24%, improve the additive 2%-6.5% of polypropylene building-up properties, melting temperature: 160-210 ℃, mixing time: 5-15 minute, then by mixing matrix material granulation, obtain once-combined material masterbatch,
The 5th step: the preparation of secondary matrix material master batch
The once-combined material masterbatch that the 4th step is obtained utilizes coating mould to be coated on the Stainless Steel Fibre of the surface electrochemistry deposition polyaniline film that the 3rd step obtains, then granulation, obtain ternary Filled Dielectrics composite conducting polymer material, the add-on of the Stainless Steel Fibre of the surface electrochemistry deposition polyaniline film that wherein once-combined material masterbatch and the 3rd step obtain is according to weight percent meter, the Stainless Steel Fibre of surface electrochemistry deposition polyaniline film is 3%-8%, and surplus is once-combined material masterbatch.
5. the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 4, is characterized in that: before the first step, carbon black Nickel Plating Treatment, carbon black is carried out to surface oxidation, sensitization and activation treatment, it comprises the following steps:
A, oil removing: by carbon black at sodium hydroxide: 50-60g/L, sodium carbonate: 10-15g/L, sodium phosphate: 20-25g/L, oil removing in the alkaline solution of clean-out system: 3-5g/L, temperature: 40-50 ℃, time: 30-50min, then with distilled water, at room temperature clean, remove impurity;
B, alligatoring: the carbon black that oil removal treatment is crossed is at ammonium peroxydisulfate: 180-200g/L; Sulfuric acid: soak 10-20min in 80-100ml/L coarsening solution, temperature is 60-70 ℃, then at room temperature neutralizes with 50-100 g/L sodium hydroxide solution, finally at room temperature cleans with distilled water;
C, sensitization are processed: the carbon black after roughening treatment is carried out in stannous chloride solution to sensitization processing, wherein in stannous chloride solution, tin protochloride is 15-20g/L, and hydrochloric acid is 40-50g/L, at room temperature processes 3-10min, then with distilled water, at room temperature cleans;
D, activation treatment: the carbon black after sensitization is processed is processed in containing the noble metal compound solution of catalytic activity again, its formula is: Palladous chloride: 0.3-0.6g/L, hydrochloric acid: 8-12ml/L, react at normal temperatures 1-5min, then in 10-30g/L sodium hypophosphite solution, at room temperature neutralize, finally with distilled water, at room temperature clean standby.
6. the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 4, it is characterized in that: in the described the first step, carbon black Nickel Plating Treatment, plating solution is: single nickel salt 15-20g/L, sodium hypophosphite 20-30g/L, sodium-acetate 20-30g/L, Trisodium Citrate 20-25g/L, thiocarbamide 1-2g/L, pH value: 5-5.5, bath temperature 70-80 ℃, time 20-60min.
7. the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 4, it is characterized in that: the electrolytic solution of described second step, nickel plating carbon blacksurface electrochemical deposition polyaniline film: concentration of aniline is 0.2-0.5 mol/ L, sulfuric acid concentration is 1-3 mol/ L, electrolyte ph: 2-3.
8. the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 4, it is characterized in that: the electrolytic solution of the 3rd described step, Stainless Steel Fibre surface electrochemistry deposition polyaniline film: concentration of aniline is 0.2-0.5mol/ L, sulfuric acid concentration is 1-3mol/ L, electrolyte ph: 2-3.
9. the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material according to claim 4, it is characterized in that: the electrochemical deposition polyaniline film in described second step and the 3rd step is at room temperature adopting pulse potential deposition, pulse potential 1v, burst length is 10s, turn-off time is 10-40s, circulating cycle issue 20-60.
10. according to the preparation method of a kind of ternary Filled Dielectrics composite conducting polymer material described in claim 4 ~ 9 any one, it is characterized in that: the described additive that improves polypropylene building-up properties is Zinic stearas, anti-oxidant DLTP or clay.
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