Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
  • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
  • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
  • H01B1/124—Intrinsically conductive polymers
  • H01B1/128—Intrinsically conductive polymers comprising six-membered aromatic rings in the main chain, e.g. polyanilines, polyphenylenes
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/02—Polyamines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
  • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
  • C09D127/04—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
  • C09D127/06—Homopolymers or copolymers of vinyl chloride
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/04—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06N3/06—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds with polyvinylchloride or its copolymerisation products
  • D06N3/065—PVC together with other resins except polyurethanes
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins

Definitions

• the present invention relates to a plasticizer composition according to the preamble of Claim 1.
• the electrical conductivity of such a composition is in general approx. 10 *2 ...10 '9 S/cm.
• the invention also relates to a process according to the preamble of Claim 9 for preparing an electrically conductive plasticizer composition and to a process according to Claim 18 for preparing an electrically conductive PVC film.
• a fabric coated with polyvinyl chloride (PVC) can be used for manufacturing, for 10 example, hoses. These are used in tunnels and mines as air-conditioning pipes. Fabric hoses are practical for this purpose, because they are easy to install in place and the support structures required by them are simple. However, particularly in the dusty conditions of a mine there tends to form in a plastic hose static electricity, which may cause sparking. This may, of course, be very dangerous. For this reason the hoses should be made electrically 15 conductive so that static electricity cannot be formed.
• the object of the present invention is to eliminate the disadvantages associated with prior known technology and to provide a clean production technology for manufacturing electrically conductive films. It is a particular object of the invention to provide an electrically conductive plasticizer composition by means of which it is possible to modify the conductivity of a polymer composition. It is also an object of the invention to provide a composition from which it is possible to manufacture an easily dyed film having very high conductivity values and high mechanical strength.
• an electrically conductive plasticizer composition having a conductivity of 10 " ...10 " S/cm is prepared by mixing a plasticizer with polyaniline in a non-conductive form in order to form a plasticizer mixture and by adding to the plasticizer mixture a counter-ion for the non-conductive polyaniline to dope the polyaniline and to form a doped plasticizer composition.
• a plasticizer composition typically comprises approx. 50 - 95 parts by weight of a plasticizer for thermoplastics and 50 - 5 parts by weight of the polyaniline and its counter-ion, which together form a doped polyaniline complex dissolved or dispersed in the plasticizer.
• plasticizer composition From the plasticizer composition it is possible to manufacture a conductive PVC film by spreading onto a substrate a fluid PVC mixture containing this composition to form a layer, whereafter the mixture is allowed to solidify so that a film is formed.
• the film may, when necessary, be detached from the substrate (e.g. transfer paper).
• plasticizer composition according to the invention is mainly characterized in what is stated in the characterizing part of Claim 1.
• the process according to the invention for producing a plasticizer composition is for its part characterized in what is stated in the characterizing part of Claim 9, and the process according to the invention for manufacturing an electrically conductive PVC film is characterized in what is stated in the characterizing part of Claim 18.
• the invention can be used advantageously for producing an electrically conductive plasticizer composition that can be mixed with many different polymers, in particular thermoplastics, whereby a migration- free polymer blend is obtained. It can be used for manufacturing films, sheets and other similar polymer products which can be joined by, for example, welding.
• the polyaniline is dissolved or dispersed in the plasticizer, in which case the processing of the composition and its mixing with polymer dispersions is easy.
• the electrical conductivity can be regulated by means of the amounts of the polyaniline and its dopant.
• the conductive component does not have a significant effect on the strength properties of the polymer product.
• a solvent of polyaniline is not used in the present invention.
• the compositions can be formulated freely when a PANT solvent setting its limitations on the plasticizers is not used.
• preferably monomeric plasticizers are used in the invention.
• an electrically conductive plasticizer composition is prepared which does not contain a thermoplastic.
• the use of the plasticizer composition is not limited by a thermoplastic polymer already present in it.
• Doping is carried out as part of the process for preparing the plasticizer composition when the starting point is the emeraldine base of polyaniline.
• the doping can be regulated.
• the obtained plasticizer composition is acidic, i.e. the polyaniline is in a conductive form.
• the plasticization process is preferably such (cf. Example 6 below) that the composition produced by it can be used for the manufacture of a PVC film without separate roll-mill grinding and, nevertheless, a well conductive final product is obtained.
• the plasticizer composition according to the invention is electrically conductive. Its conductivity is in this case usually within the range 10 "2 ...10 '9 S/cm, typically higher than approx. 10 "6 S/cm.
• the composition contains at least two components, namely a plasticizer for thermoplastics and a doped polyaniline complex. The latter is dissolved or dispersed in the plasticizer so that the solid particles will not separate from the composition during standing.
• the particle size of the polyaniline complex in the plasticizer phase is smaller than 100 ⁇ m, usually smaller than 50 ⁇ m, preferably approx. 1 - 30 ⁇ m.
• the proportion of plasticizer of the weight of the plasticizer composition is in general over one-half, although the concentration limits may vary widely.
• the composition contains 50 - 99 parts by weight of a plasticizer andl - 50 parts by weight of a doped polyaniline complex.
• the composition may also contain other components, of which the most important are a dopant not bonded to the polyaniline complex and any possible additives and auxiliaries, such as metal compounds used for adjusting the pH value.
• the plasticiser for thermoplastics is usually selected from the group including dialkyl phthalates; dialkyl terephthalates; trialkyl and triaryl phosphates; aliphatic acid esters, such as dialkyl diapate and dialkyl sebasate; sulfonic and benzene acid esters; epoxidized oils; and mixtures thereof.
• These are typical plasticizers used as plasticizers for PVC.
• Dialkyl phthalates the alkyl groups of which are similar or different and which comprise a linear or branched carbon chain of 1 - 9 carbon atoms are considered preferred plasticizers.
• C 7 ...C 9 dialkyl phthalates i.e. mixtures of such esters, as well as dioctyl phthalate and di-iso-octyl phthalate.
• an aniline polymer the monomer is aniline or its derivative, the nitrogen atom of which is as a rule bonded to the carbon in the para position of the benzene ring of the subsequent unit.
• Unsubstituted polyaniline may appear in various forms, of which the so-called emeraldine form is in general used for conductive polymer applications.
• Polyaniline can be doped so as to become a conductive polyaniline complex in particular with protonic acids, of which some examples are HC1, H 2 SO 4 , HNO 3 , HClO 4 , HBF 4 , HPF 6 , HF, phosphoric acids, sulfonic acids, picrinic acid, n-nitrobenzene acid, dichloroacetic acid, and polymeric acids.
• a functional acid is used for the doping, for example sulfonic acid, in particular an aromatic sulfonic acid such as dodecylbenzenesulfonic acid (DBSA), camphor sulfonic acid, para-toluenesulfonic or phenolsulfonic acic.
• Acid can be used in excess for plasticizing the mixture.
• a suitable metal compound such as zinc oxide, can be used for compensating for the acidity.
• a calcium compound such as calcium carbonate.
• the pH of the mixture is, for example, 3 - 8, usually approx. 4 - 7.
• the polyaniline complex preferably contains a polyaniline, such as a polyaniline of the emeraldine form, 1 - 20 % by weight, preferably 4 - 10 % by weight, and a doping acid, such as DBSA, 50 - 90 % by weight, preferably 60 - 85 % by weight.
• a polyaniline such as a polyaniline of the emeraldine form, 1 - 20 % by weight, preferably 4 - 10 % by weight
• a doping acid such as DBSA, 50 - 90 % by weight, preferably 60 - 85 % by weight.
• An example of a preferred plasticizer composition is a composition that comprises polyaniline approx. 3 - 8 parts by weight, plasticizer approx. 70 - 90 parts by weight, and a counter-ion for the polyaniline approx. 5 - 20 parts by weight, the amount of counter-ion being in parts by weight approx. 2- to 4-fold the amount of polyaniline.
• it contains an inorganic compound approx. 1 - 10 %, calculated from the amount of the dopant, the compound at least partly neutralizing the excess of dopant and thereby raising the pH value of the composition to a suitable level.
• the composition forms a substantially non-migrating PVC blend.
• the composition described above can be prepared in a two-step process.
• the plasticizer is mixed with a polyaniline in a non-conductive form in order to form a plasticizer mixture.
• the ingredients of the plasticizer composition are usually mixed together substantially without additional heating. However, the temperature of the composition rises during the mixing and varies during the mixing operation between 25 and 50 °C.
• a counter-ion for the non- conductive polyaniline is added in order to dope the polyaniline and to form a doped plasticizer composition.
• the doped plasticizer composition is mixed for 1 - 48 hours at approx. 30 - 50 °C. However, the temperature may also be higher.
• a doping mixture is added which comprises a counter-ion for the polyaniline and an activator capable of accelerating the doping.
• the activator is preferably a volatile compound that can be removed from the plasticizer composition by vaporization.
• Such activators include alkanic acids, in particular formic acid and acetic acid, formic acid being especially advantageous.
• the activator is removed by means of vacuum and by raising the temperature of the composition to approx. 35 - 150 °C.
• 3 - 8 parts by weight of a polyaniline and approx. 70 - 90 parts by weight of a plasticizer are mixed to form a plasticizer mixture, and to this mixture is added a dopant mixture that contains approx. 5 - 20 parts by weight of a counter-ion for the polyaniline and 1 - 10 parts by weight of activator.
• the plasticizer composition described above can be used for manufacturing desired electrically conductive polymer films by surfacing or coating a suitable substrate with a mixture of the plasticizer composition and a polymer dispersion.
• the coating can be carried out by the spread-coating blade technique or the roller coating technique.
• swipe coating technique is meant here generally coating methods in which a fluid polyaniline complex mixture is first spread onto a backing or a corresponding substrate by means of spread coating blades or rollers, whereafter the mixture is cured or solidified to form a film.
• the application mixtures most preferably contain a fluidizer, for example a plasticizer or solvent by means of which the desired fluidity is obtained for the mixture.
• the mixture can in general be cured (i.e. hardened) by heating. In the heating, volatiles, such as solvent, are also removed.
• the coating is preferably carried out by the spread-coating blade technique, wherein the plastic blend is spread onto a web of fabric into a uniform layer by means of a spread-coating blade. After the spread coating, the web is preferably directed to a curing kiln, where the mixture forms a continuous film on the fabric. After the curing, any post-treatment possibly needed, such as smoothing or patterning and cooling, is carried out.
• the obtained surface resistance of the product varies according to the amount of polyaniline complex and the thickness of the coating.
• the surface resistance is, for example, approx. 10 4 - 10 9 , preferably 10 5 - 10 8 ⁇ /sq.
• a strong and flexible fabric can be manufactured by the process according to the invention.
• a lacquer-like coating can be produced on the fabric.
• the fabric can be used for manufacturing a hose by joining the edges of the web together. The joining can be carried out by high-frequency welding.
• the hose can be used in particular as ventilation tube for mines and tunnels.
• the fabric can also be used in other applications requiring protection against static electricity or electromagnetic radiation.
• the uses may include, for example, protective covers, storage containers (e.g. biogas collection bags) and conveyor belts, used in industry in situations in which there is a fire or explosion hazard. Potential uses also include protection for electronic equipment or military hardware.
• the fabric is best applicable to uses where it is not greatly exposed to UV radiation.
• a solid polyaniline complex can be mixed with a suitable fluidizer, such as a plasticizer or a solvent.
• a suitable fluidizer such as a plasticizer or a solvent.
• a suitable particle size is, for example, 1 - 200 ⁇ m, in particular 5 - 100 ⁇ m, preferably 10 - 50 ⁇ m.
• plastics include polyacrylates, polyurethanes, polyethylene vinyl acetate, polyvinylidene chloride, polyvinyl acetate, polyvinyl alcohol, synthetic latexes, silicones, epoxy resins, and suitable blends thereof (e.g. ethylvinyl acetate and PVC).
• PVC is preferably of an emulsion type having a particle size below 60 ⁇ m.
• the mixture may contain sulfonamide as an antistatic additive.
• the proportion of the polyaniline complex in the plastic blend of the final coating may be, for example, 0.1 - 30 % by weight, preferably 1 - 20 % by weight, most preferably 5 - 15 % by weight.
• suitable additives such as plasticizers, stabilizers, fire retardants, colorants, slip agents, and modifiers can be used in the mixture.
• the plasticizers most commonly used in PVC products are dialkyl phthalates, dialkyl terephthalates, trialkyl or triaryl phosphates, aliphatic acid esters such as dialkyl diapate and dialkyl sebasate, sulfonic or benzene acid esters, epoxidized oils, and mixtures thereof.
• the stabilizers most commonly used are metal soaps, inorganic salts (e.g. barium salts and lead salts), organo-tin compounds, and epoxy compounds. Both organic and inorganic suitable agents can be used as colorants.
• the slip agents may be, for example, long-chain alcohols or various waxy substances.
• the application substrate used may be, for example, fabric, paper, cardboard or similar film-like and/or sheet-like substrates.
• Various woven and non-woven fabrics can be mentioned as backings.
• the woven material may be, for example, polyester or polyamide.
• the backing is usually coated on both sides with, for example, PVC or a halogen-free plastic, such as a blend of polyethylene methacrylic acid and polyethylene.
• An additive enhancing the adhesion of the coating may be added to the backing.
• a suitable backing is obtained, for example, by coating a net fabric with a PVC blend first by spread coating and then by calendering. If the thread count of the fabric is greater than approx. 6.5 threads/cm, mere spread coating will suffice.
• the materials were mixed together carefully. After the mixing, the mixture was comminuted further in a paste mill. The paste-mill treatment rendered the mixture more homogeneous and minimized its granularity.
• Example 1A An experiment according to Example 1A was carried out by merely replacing the dodecylbenzenesulfonic acid type Ufacid TPB with Ufacid K.
• the conductive complex had a lower viscosity and was easier to process in the tests than the complex of Example 1A.
• the surface resistance of the end product was 1.0...1.2 + E5 ⁇ /sq.
• Example 1A An experiment according to Example 1A was carried out by merely replacing the dodecylbenzenesulfonic acid type Ufacid TPB with Ufacid KW.
• the conductive complex had a lower viscosity and was easier to process than the complex of Example 1A.
• the surface resistance of the end product was higher than in Examples 1A and IB, being approx. 1.5 + E6 ⁇ /sq.
• the formic acid was evaporated out from the product under vacuum in the course of approx. 5 h. At the same time the temperature of the product was gradually raised to 95 °C. After the distillation of the formic acid ended, the product was cooled and was packed in transport containers.
• the materials were mixed together carefully. After the mixing, the mixture was comminuted further in a 3-roll mill in which the gap between the rollers had been adjusted to 40...50 ⁇ m. The roll-mill treatment rendered the mixture more homogeneous and minimized its granularity.
• Example 3 After the further process described in Example 3, the conductivity level was lower than in Example 3.
• dodecylbenzenesulfonic acid has a significant effect on the preparation time of the composition, but the continuing of the reaction enhances the conductivity value significantly.
• Example 5 Effects of mixing and the type of polyaniline on the quality of the end product
• Example 3 Three batches (5a, 5b and 5c) of composition were prepared using the formula of Example 3.
• the polyaniline used was polyaniline EBR1 Lot 28, and in the subsequent experiment (5c) it was EBR Lot 29.
• the reaction was carried out as described in Example 3, except that in Experiment 5a a homogenizer was used for promoting mixing throughout the reaction at 1500 m and in Experiment 5b at 3000 ⁇ m.
• Experiment 5c the processing was carried out as in Experiment 5b.
• the conductivity levels of the products were measured as resistance measurements, as described in Example 1.
• the resistance values of the experiment products were 5a: 6.02E+04 ⁇ /sq, 5b: 2.35E+04 and 5c: 1.86E+06, estimated in the manner according to Example 3. It can be concluded from the results that accelerating the stirring slightly lowered the resistance level. It was observed that the type of polyaniline also had an effect on the conductivity level of the end product.
• the temperature of the reaction mixture was raised to 50 °C, at which temperature the reaction was continued for a total of 10 h.
• the formic acid was distilled out from the product under vacuum in the course of approx. 5 h.
• the temperature of the product was gradually raised to 95 °C. After the distillation of the formic acid ended, the product was cooled and was packed in transport containers.
• a conductive PVC film was prepared in the manner described in Example 3, without a roll-mill treatment.
• the conductivity level of the end product was determined as a surface resistance measurement, and it was 1.25E+04 ⁇ /sq. The result indicates that the quality of the conductive complex was clearly better, since roll-mill treatment is not necessary. At the same time the result indicates the favorable effect of the raising of the processing temperature and the pre-mixing time on the quality of the product.
• the materials were mixed together carefully. After the mixing, the mixture was comminuted further in a paste mill. The paste-mill treatment rendered the mixture more homogeneous and minimized its granularity.
• Example 7A An experiment according to Example 7A was performed by merely replacing the dodecylbenzenesulfonic acid type Ufacid TPB with Ufacid K.
• the conductive complex had a lower viscosity and was easier to process than the complex according to Example X A.
• the surface resistance of the end product was 1.5+E5 ⁇ /sq.
• Example 7C
• Example 7A An experiment according to Example 7A was performed by merely replacing the dodecylbenzenesulfonic acid type Ufacid TPB with Ufacid KW.
• the conductive complex had a lower viscosity and was easier to process than the complex according to Example 7A.
• the surface resistance of the end product was inferior to that in Examples 7A and 7B, being approx. 2.0+E6 ⁇ /sq.

Landscapes

• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Organic Chemistry (AREA)
• Medicinal Chemistry (AREA)
• Textile Engineering (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Physics & Mathematics (AREA)
• Dispersion Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Conductive Materials (AREA)

Applications Claiming Priority (2)

Publications (2)

Family

ID=8560101

Family Applications (1)

Country Status (2)

Cited By (3)

Citations (9)

• 2001
  • 2001-01-23 FI FI20010137A patent/FI119247B/fi active IP Right Grant
• 2002
  • 2002-01-23 WO PCT/FI2002/000053 patent/WO2002059907A1/en not_active Application Discontinuation

Patent Citations (9)

Non-Patent Citations (7)

Also Published As

Similar Documents

Legal Events