CN1100557A - preparation of conductive plastics - Google Patents

Abstract

Solvent, oxidant and dopant are compounded into reaction solution, which then constitutes ternary reaction system together with powdered thermoplastics and reactant monomar with a material proportion of 1 to 98.9 to 0.1-40 to 40 to 20. The material is stirred and reacts at -20 to 100 deg.C for 5 min to 24 hr. After being washed and desiccated, the product is processed into conductive plastics product with high conductivity and mechanical property and machinability of base plastics.

Description

preparation of conductive plastics

The invention belongs to the applied chemistry technical field, particularly intrinsic conducting polymer synthesizes and makes powdered form thermoplastics surface conductanceization, is reprocessed into the technology of Markite goods.

Up to the present, conductive plastics mainly is that matrix and a certain amount of electroconductive stuffing are composited with plastics.These electroconductive stuffings roughly can be divided into following a few class:

1, metal system: as silver powder, nickel powder, stainless steel fibre etc.;

2, carbon element system: as acetylene carbon black, carbon fiber, graphite;

3, intrinsic conducting polymer system: as polyacetylene, polypyrrole, polythiophene, polyaniline etc., this base polymer can be high conductivity after mixing.

For metal is conductive plastics, it conducts electricity very well, but the electroconductive stuffing addition is generally higher, makes that the conservation rate of the original mechanical property of plastic substrate is lower, especially proportion increases and has lost the high characteristics of specific strength that plastics have, and cost is very high.

For carbon element was conductive plastics, its conductivity was still good, and proportion is also little, but the electroconductive stuffing addition is also very high, and except increasing cost, maximum weakness is very low for the conservation rate of the original mechanical property of matrix plastic.

Intrinsic conducting polymer is the macromolecular material that a class has conjugated double bond structures, can present high conductivity after mixing.Its special electricity, electrochemistry, optical property etc. make it have a wide range of applications in many field of engineering technology.Relevant research and development work is very active.But, pure intrinsic conducting polymer, bad because of its processability, mechanical property is very poor, has almost lost the characteristic of " plastics " on the engineering significance.Therefore, from utilizing the angle of its " conductivity ", prior art is mostly compound and constitute conductive plastics as electroconductive stuffing and common plastics with it.There are some researches show, with carbon element is that electroconductive stuffing is compared, under the approaching situation of conductivity, the loading of intrinsic conducting polymer is lower, and the conservation rate of the original mechanical property of matrix plastic is higher, but advantage is still not obvious, because the intrinsic conducting polymer cost is too high, and to reach the level approaching with pure intrinsic conducting polymer conductivity, at this moment loading is processed into difficulty of Markite goods generally up to 30～50% of percentage meter by volume.So far this class conductive plastics still can't industrialization.

The objective of the invention is to avoid the weak point of above-mentioned background technology, provide a kind of intrinsic conducting polymer that utilizes synthetic and deposit to powdered form thermoplastics particle surface, make its surface conductanceization, and then adopt mold pressing, the typical plastics product processing method such as inject, extrude, directly make the technology of Markite goods.This preparation method's products obtained therefrom is because of the extremely low conductivity height of content of intrinsic conducting polymer, thus cost is descended significantly, and conservation rate such as the original mechanical property of matrix plastic, processing characteristics is high, is expected to quicken the heavy industrialization process.

The objective of the invention is to realize by following measure:

The preparation method of conductive plastics comprises following processing step:

Step 1: the preparation of reaction solution

Reaction solution is formulated by following component:

(1) refers to oxidant, dopant favorable solubility, and pending plastic powders is not had deliquescent solvent, as water or alcohols or ketone or ester class or nitrile and other mixed solvent;

(2) concentration in reaction solution is the oxidant of 0.01～3 mol, as trivalent iron salt or dichloride copper or persulfate or bichromate or ammonium ceric nitrate or potassium permanganate or potassium triiodide;

(3) concentration in reaction solution is the dopant of 0～5 mol, as p-methyl benzenesulfonic acid and sodium salt or perchlorate or Bronsted acid or frerrous chloride or borofluoride;

Step 2: powdered form thermoplastics particle surface conductionization

Form the ternary reaction system by powdered form thermoplastics, reaction solution and reaction monomers, this reaction system by volume rate of charge of percentage meter is 1: 98.9: 0.1～40: 40: 20, fully stirring of back feeds intake, under-20 ℃～100 ℃ temperature, reacted 5 minutes～24 hours, after reaction finishes, through separating drying for standby;

The powdered form thermoplastics is meant that particle diameter is 10 ^-4Polyamide, polyimides, polymethacrylates and copolymer thereof, polyvinyl chloride and copolymer thereof, polystyrene and copolymer thereof, polyethylene and copolymer thereof, polypropylene, polyacrylonitrile and copolymer thereof in～1 millimeter scope, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, poly-trifluoro-ethylene, polytrifluorochloroethylene, polyformaldehyde, polyphenylene sulfide, Merlon, polyester etc.;

Reaction monomers is meant pyrroles and derivative, thiophene and derivative thereof, aniline and derivative thereof;

Step 3: the moulding of the powdered form thermoplastics of surface conductanceization

Typical plastics processing method such as adopt mold pressing, inject, extrude is processed into required Markite goods with the powdered form thermoplastics on surface conduction.

The present invention compares with background technology has following advantage:

1, the conductance of the Markite goods of this law preparation can be near the level of pure intrinsic conducting polymer.

2, keeping under the prerequisite of high conductance, intrinsic conducting polymer content can reduce to only account for by volume 1～2%, so cost is descended significantly.

3, the conservation rate of the original various performances of matrix plastic (as mechanical property, processing characteristics etc.) is high.

4, because the molding technological condition of the powdered form thermoplastics of surface conductanceization, identical as temperature, time, pressure etc. with original powdered form thermoplastics, therefore this preparation method synthesizes with typical plastics and processing technology has favorable compatibility and wide adaptability, helps realizing large-scale industrial production.

5, the Markite that is prepared from of this law not only can be used as the antistatic material of high-strength light, and can be used for plating of electromagnetic shielding material, microwave absorbing material, plastic products etc.

Embodiment 1:

The aqueous solution of at first preparing 1 liter of ferric trichloride concentration and be 0.01 mol, ferric fluoborate concentration and be 0.3 mol is as reaction solution.Adding acrylonitrile-butadiene-styrene copolymer again is ABS powder 500 grams.At last, under stirring, add pyrroles's 150 grams.The temperature of above-mentioned ternary reaction system is controlled at-20 ℃-5 ℃, was fully reacting 5 hours under the stirring, after reaction finishes, filter, rinse well also dry with clear water.With product in 150 ℃, pressure 500 kilograms per centimeter ², mold pressing cooling and demolding after 10 minutes.The ABS goods that make have with the same process bar under the close mechanical property of pure ABS goods that makes, conductivity is 10 Siemens/cm.

Embodiment 2:

The aqueous solution that at first to prepare 200 milliliters of ferric trichloride concentration be 0.2 mol is as reaction solution, and adding polymethyl methacrylate again is powder 50 grams of PMMA resin.At last, under stirring, add pyrroles's 1 gram.The temperature of above-mentioned ternary reaction system is controlled at 0 ℃-5 ℃, is fully stirring under the shape reaction after 2 hours, filter, wash, drying.With product in 140 ℃, pressure 300 kilograms per centimeter ², mold pressing 20 minutes, the cooling back demoulding.The PMMA goods that make have with the same process condition under the identical mechanical property of pure PMMA goods that makes, conductivity is 0.1 Siemens/cm.

Embodiment 3:

The aqueous solution of at first preparing 1 liter of concentration of hydrochloric acid and be 5 mol, filter acid ammonium concentration and be 0.5 mol is as reaction solution, and adding polyvinylidene fluoride again is PVDF toner 200 grams.At last, under stirring, add aniline 20 grams.The temperature of above-mentioned ternary reaction system is controlled at 20 ℃-30 ℃, and reaction after 30 minutes under abundant stirring is filtered, is washed, drying.With product in 180 ℃, pressure 150 kilograms per centimeter ², mold pressing 15 minutes, the cooling back demoulding.The PVDF goods that make have with the same process condition under the close mechanical property of pure PVDF goods that makes, conductivity is 5 Siemens/cm.

Embodiment 4:

Acetonitrile/water (90: the 10) solution of at first preparing 200 milliliters of ferric trichloride concentration and be 0.2 mol, p-methyl benzenesulfonic acid na concn and be 0.1 mol is as reaction solution, and adding polyvinyl chloride again is polyvinyl chloride resin powder 50 grams.At last, under stirring, add pyrroles's 0.5 gram.The temperature of above-mentioned ternary reaction system is controlled at 20 ℃-40 ℃, reacts after 4 hours, filter, wash, drying.With product in 170 ℃, pressure 500 kilograms per centimeter ², mold pressing 15 minutes, the cooling back demoulding.Prepared PVC goods have with the same process bar under the identical mechanical property of pure PVC goods that makes, conductivity is 0.01 Siemens/cm.

Embodiment 5:

The aqueous solution of at first preparing 2 liters of sulfuric acid concentrations and be 2 mol, potassium peroxydisulfate concentration and be 0.25 mol adds nylon 11 powder 600 grams again as reaction solution.At last, under stirring, add aniline 10 grams.The temperature of above-mentioned ternary reaction system is controlled at 0 ℃-20 ℃, and reaction after 1 hour under abundant stirring is filtered, is washed, drying.Is 200 kilograms per centimeter with product in 200 ℃, pressure ², mold pressing 20 minutes, the cooling back demoulding.Prepared nylon 11 goods have with the same process bar under the close mechanical property of pure nylon 11 goods that makes, conductivity is 0.5 Siemens/cm.

Embodiment 6:

Ethanol/water (20: the 80) solution that at first to prepare 500 milliliters of potassium triiodide concentration be 0.1 mol adds polyvinyl chloride resin powder end 100 grams again as reaction solution.Stir and to add pyrroles's 5 grams down, the temperature of above-mentioned ternary reaction system is controlled at 0 ℃-20 ℃.React after 6 minutes, filter, wash, drying.With product in 160 ℃, pressure 500 kilograms per centimeter ², mold pressing 15 minutes, the cooling back demoulding.Prepared polrvinyl chloride product have with the same process bar under the identical mechanical property of pure polrvinyl chloride product that makes, conductivity is 0.01 Siemens/cm.

Embodiment 7:

The aqueous solution of at first preparing 5 liters of ferric trichloride concentration and be 0.1 mol, frerrous chloride concentration and be 0.05 mol adds 2 kilograms in polycarbonate resin powder again as reaction solution.At last, under stirring, add pyrroles's 40 grams.The temperature of above-mentioned ternary reaction system is controlled at 20 ℃-40 ℃, and reaction after 20 hours under abundant stirring is filtered, is washed, drying.With product in 200 ℃, pressure 1000 kilograms per centimeter ², mold pressing 20 minutes, the cooling back demoulding.The polycarbonate article that makes have with the same process bar under the identical mechanical property of pure polycarbonate article that makes, conductivity is 0.05 Siemens/cm.

Embodiment 8:

The aqueous solution of at first preparing 200 milliliters of sulfuric acid concentrations and be 2 mol, ammonium persulfate concentration and be 0.4 mol adds polystyrene resin powder 60 grams again as reaction solution.At last, under stirring, add aniline 3 grams.The temperature of above-mentioned ternary reaction system is controlled at 30 ℃-40 ℃, reacted 1.5 hours, filter, wash, drying.With product in 160 ℃, pressure 200 kilograms per centimeter ², mold pressing 30 minutes, the cooling back demoulding.The modified styrene polymer that makes have with the same process bar under the close mechanical property of pure modified styrene polymer that makes, conductivity is 0.01 Siemens/cm.

Embodiment 9:

The aqueous solution that at first to prepare 2 liters of ferric trichloride concentration be 0.3 mol is as reaction solution, and adding ethene-amyl acetate ethylene copolymer again is EVA toner 500 grams.At last, add pyrroles's 15 grams under stirring, the temperature of above-mentioned ternary reaction system is controlled at 40 ℃-80 ℃, reaction after 5 hours under abundant stirring is filtered, is washed, drying.With product in 130 ℃, pressure 150 kilograms per centimeter ², mold pressing 10 minutes, the cooling back demoulding.The EVA goods that make have with the same process bar under the identical mechanical property of pure EVA goods that makes, conductivity is 5 Siemens/cm.

Claims (1)

1, a kind of preparation method of conductive plastics is characterized in that it comprises following processing step and condition thereof:

Reaction solution is formulated by following component:

(1) refers to oxidant, dopant favorable solubility, and pending plastic powders is not had deliquescent solvent, as water or alcohols or ketone or ester class or eyeball class and other mixed solvent;

(2) concentration in reaction solution is the oxidant of 0.01～3 mol, as trivalent iron salt or dichloride copper or persulfate or bichromate or ammonium ceric nitrate or potassium permanganate or potassium triiodide;

(3) concentration in reaction solution is the dopant of 0～5 mol, as p-methyl benzenesulfonic acid and sodium salt or perchlorate or Bronsted acid or frerrous chloride or borofluoride;

Step 2: powdered form thermoplastics particle surface conductionization

Form the ternary reaction system by powder thermoplastics, reaction solution and reaction monomers, this reaction system by volume rate of charge of percentage meter is 1: 98.9: 0.1～40: 40: 20, fully stirring of back feeds intake, under-20 ℃～100 ℃ temperature, reacted 5 minutes～24 hours, after reaction finishes, through separating drying for standby;

The powdered form thermoplastics is meant that particle diameter is 10 ^-4Polyamide, polyimides, polymethacrylates and copolymer thereof, polyvinyl chloride and copolymer thereof, polystyrene and copolymer thereof, polyethylene and copolymer thereof, polypropylene, polyacrylonitrile and copolymer thereof in～1 millimeter scope, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, poly-trifluoro-ethylene, polytrifluorochloroethylene, polyformaldehyde, polyphenylene sulfide, Merlon, polyester etc.;

Reaction monomers is meant pyrroles and derivative, thiophene and derivative thereof, aniline and derivative thereof;

Step 3: the moulding of the powdered form thermoplastics of surface conductanceization

Typical plastics processing method such as adopt mold pressing, inject, extrude is processed into required Markite goods with the powdered form thermoplastics on surface conduction.