EP1407459A1 - Compositions electriquement conductrices, leurs procedes de production et leur utilisation - Google Patents

Compositions electriquement conductrices, leurs procedes de production et leur utilisation

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Publication number
EP1407459A1
EP1407459A1 EP02754772A EP02754772A EP1407459A1 EP 1407459 A1 EP1407459 A1 EP 1407459A1 EP 02754772 A EP02754772 A EP 02754772A EP 02754772 A EP02754772 A EP 02754772A EP 1407459 A1 EP1407459 A1 EP 1407459A1
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EP
European Patent Office
Prior art keywords
expanded graphite
weight
composition according
copolymers
electrically conductive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP02754772A
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German (de)
English (en)
Inventor
Reinhard Wagener
Michael Haubs
Arnold Schneller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ticona GmbH
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Ticona GmbH
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Publication date
Application filed by Ticona GmbH filed Critical Ticona GmbH
Publication of EP1407459A1 publication Critical patent/EP1407459A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • H01B1/20—Conductive material dispersed in non-conductive organic material

Definitions

  • the invention relates to electrically conductive compositions containing selected thermoplastic polymers and expanded graphite.
  • the thermoplastic polymers belong to the group of polyacetals, cycloolefin copolymers or polyesters.
  • Another object of the invention is a selected process for the production of compositions containing thermoplastic polymers and expanded graphite.
  • plastics For the use of plastics in electrical or electronic devices or workshops, it is often desirable to make plastics electrically conductive.
  • thermoplastic polymers in particular polyacetals, polyamides or polyesters, which are characterized by good mechanical and thermal properties and chemical resistance, this can be achieved by adding carbon.
  • the intrinsic conductivity of carbon (as graphite, carbon black or carbon fibers) is in principle sufficient to achieve the desired electromagnetic shielding or dissipation of electrostatic charges.
  • CA 1 193 091 discloses electrically conductive compositions made of polybutylene terephthalate with finely divided carbon.
  • the desired electrical conductivity of over 10 "10 S / cm (volume resistivity ⁇ ⁇ 10 10 ohm * cm) is only achieved if the composite contains more than 10% by weight carbon.
  • US 4,351,745 discloses electrically conductive compositions made of thermoplastic polyester elastomers which contain more than 30% by weight of carbon in the form of a mixture of carbon black and graphite. Graphite alone as a conductivity additive is said to be unusable.
  • JP-A-59-155,459 discloses electrically conductive compositions made of polyethylene terephthalate with carbon black and graphite. A specific volume resistance ⁇ ⁇ 10 10 ohrrvcm is only achieved for more than 10% by weight of carbon.
  • JP-A-2000-143.956 discloses electrically conductive compositions made from fully aromatic polyesters (polyarylates) with carbon black. A specific volume resistance ⁇ ⁇ 10 10 ohm * cm is only achieved for more than 10% by weight of carbon.
  • US-A-4,772,422 discloses electrically conductive compositions of liquid crystalline polymers with carbon black, which have an extremely low electrical resistance even at 1% by weight of carbon. This surprising effect is attributed to the special, direction-dependent properties in the melt of the liquid-crystalline polymers, in contrast to the isotropic melt of conventional thermoplastics.
  • JP-A-60-192,764 discloses an electrically conductive composition made of a polyester resin - thermoset with expanded graphite. A specific volume resistance ⁇ ⁇ 10 8 ohm * cm is achieved by composites with 4% by weight carbon.
  • EP-A-557,088 discloses electrically conductive compositions of a polyarylene sulfide, an alkoxysilane and expanded graphite.
  • JP-A-07/11, 063 discloses electrically conductive masterbatches which, in addition to a polyolefin, have a special carbon black. From WO-A-01 / 36,536 conductive polyphenylene ether / polyamide mixtures are known which contain talc and carbon. Carbon black and carbon fibers are listed as examples of carbon.
  • compositions with electrically conductive additives in amounts of less than 10% by weight, which have a high electrical conductivity.
  • These compositions contain polyamides which are produced by polymerizing the monomers in the presence of the electrically conductive additive.
  • Other previously known compositions contain polyphenylene sulfides and expanded graphite or polyesters or polyester amides, which are able to form a liquid-crystalline phase, and carbon black.
  • compositions containing selected polymers have now been found in which high electrical conductivity can be achieved by adding small amounts of special electrically conductive additives. These compositions can also be considered as nanocomposites. The achievable properties are to be regarded as surprising, since the
  • compositions according to the invention are distinguished by a high toughness of the material, measurable as elongation at break or stretch or impact strength according to Charpy or Izod.
  • compositions containing thermoplastic polymers and special electrically conductive additives can surprisingly be produced by simple melt extrusion, compositions comprising polyarylene sulfides also being able to be prepared without additions of alkoxysilane.
  • An object of the present invention is to provide selected electrically conductive polymer compositions which have a specific Contact resistance of ⁇ ⁇ 10 10 ohm * cm can be achieved with a carbon content of less than 10% by weight of additive.
  • Another object is to provide selected electrically conductive polymer compositions with improved mechanical properties.
  • Another object is to provide a simple manufacturing process for electrically conductive polymer compositions.
  • the present invention relates to electrically conductive compositions
  • thermoplastic polymers selected from the group consisting of polyolefins, such as polyethylene or polypropylene, polystyrene, polyalkylene halides, such as polyvinyl chloride or polyvinylidene chloride, cycloolefin copolymers, ABS and SAN copolymers, polyesters, polyimides, Polyurethanes, polycarbonates, polyarylene ethers, polyetherimides, polyacetals, polyether ketones, poly (meth) acrylic acids and their derivatives, such as esters or amides, polyarylene sulfides, polysulfones and polyether sulfones, and B) expanded graphite, the mass fraction of the expanded graphite being less than 10% by weight. % and the volume resistivity of the composition is at most 10 10 ohm * cm, with the proviso that compositions containing polyarylene sulfides have no alkoxysilane
  • a preferred embodiment of the invention are electrically conductive compositions composed of thermoplastic polymers and expanded graphite, the content of the expanded graphite being at most 6% by weight and preferably at most 4% by weight.
  • the specific volume resistance of the compositions according to the invention is preferably ⁇ ⁇ 10 8 ohm * cm.
  • thermoplastic polymers belong to the group of polyacetals, cycloolefin copolymers or polyesters.
  • the compositions according to the invention can also contain electrically conductive carbon in other forms. This can be available in different forms.
  • Examples include: carbon black, conductivity black, natural graphite, carbon fibers and carbon nanotubes.
  • the total amount of additives which increase the electrical conductivity in the composition according to the invention is preferably less than 10% by weight, in particular less than 6% by weight, based on the composition.
  • At least expanded graphite is used as the conductive carbon.
  • Expanded graphite can be produced from natural graphite according to the prior art. For example, one proceeds by producing an intercalation compound from natural graphite and a mixture of concentrated sulfuric acid and nitric acid and drying it. The dried intercalate is then quickly heated to 800-900 ° C and thus expanded into individual or largely isolated graphite flakes. The expanded graphite can then be ground to a desired particle size.
  • the average particle size D 50 of the expanded graphite used to produce the compositions according to the invention is at most 1 mm, preferably 100 to 700 ⁇ m.
  • the bulk density of the expanded graphite is usually up to 200 g / liter, preferably 80 to 200 g / liter, in particular 100 to 180 g / liter.
  • thermoplastic polymers can be used as component A) of the composition according to the invention. Mixtures or alloys of the polymers can also be used.
  • polyesters are all thermoplastic polymers and copolymers which are composed of aliphatic or cycloaliphatic diols, aromatic diphenols, aliphatic or cycloaliphatic or aromatic Dicarboxylic acids and aliphatic or cycloaliphatic or aromatic hydroxy-carboxylic acids or their derivatives, optionally with the addition of up to 20 mol% of other comonomers such as amino alcohols or diisocyanates.
  • Preferred polyesters are liquid-crystalline polyesters, polyarylates, polyester elastomers and particularly preferably the partially aromatic polyesters of the polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT) and polybutylene terephthalate (PBT) type. Mixtures or alloys or copolymers of the polyester with one another or with other polymers can also be used.
  • PET polyethylene terephthalate
  • PTT polytrimethylene terephthalate
  • PBT polybutylene terephthalate
  • Liquid crystalline polyesters melt anisotropically and form different types of liquid crystalline melts. These liquid crystalline melts are characterized by low viscosity in a preferred direction.
  • Typical representatives of the monomers used in the prior art are terephthalic acid, isophthalic acid, 4-hydroxybenzoic acid, 1, 4-dihydroxybenzene, 4,4'-and 3,4 'dihydroxy biphenyl, 6-hydroxy-2-naphthoic acid, 2,6-naphthoedicarboxylic acid or 4-aminophenol and other compounds known from the literature, the polymerization of which, under certain conditions and precisely defined conditions, gives the desired liquid-crystalline melt properties.
  • Polyarylates are isotropically melting polyesters made from aromatic dicarboxylic acids and aromatic diphenols or aromatic hydroxycarboxylic acids. Typical representatives of the monomers used in the prior art are
  • Terephthalic acid isophthalic acid, 3- and 4-hydroxybenzoic acid, 1, 3- and 1, 4-dihydroxybenzene, 4,4 ' - and 3,4 ' -dihydroxybiphenyl, 1, 4-bis (hydroxymethyl) benzene or bisphenol-A and analogues Compounds derived from aromatic bases.
  • Polyester elastomers are copolymers of aromatic dicarboxylic acids, preferably terephthalic acid or isophthalic acid, with a mixture of short-chain and long-chain diols.
  • Long chain diols are oligomeric or polymeric glycols with terminal hydroxyl groups. Typical representatives are poly ethylene glycol, poly 1, 2- or poly-1, 3-propanediol, poly-1, 4-butanediol and random or block copolymers of these glycols or alkene oxides.
  • Typical representatives of short-chain diols are ethylene glycol, 1, 2- or 1, 3-propanediol and 1,4-butanediol.
  • the particularly preferred, partially aromatic polyesters also melt isotropically. They are copolymers of aromatic dicarboxylic acids, preferably terephthalic acid or terephthalic acid / isophthalic acid mixtures with linear or branched aliphatic or cycloaliphatic diols with 2 to 8, preferably 2 to 4, carbon atoms.
  • aromatic dicarboxylic acids preferably terephthalic acid or terephthalic acid / isophthalic acid mixtures with linear or branched aliphatic or cycloaliphatic diols with 2 to 8, preferably 2 to 4, carbon atoms.
  • the most important representatives of the diols are ethylene glycol, 1,3-propanediol and 1,4-butanediol.
  • further comonomers for example cyclohexanedimethanol or 1,4-bis (hydroxymethyl) benzene, can be used in molar proportions of up to 20%.
  • polyoxymethylenes as described for example in DE-A 29 47 490, are generally unbranched linear polymers which generally contain at least 80%, preferably at least 90%, oxymethylene units (-CH 2 O -) contain.
  • POM polyoxymethylene
  • the term polyoxymethylene includes both homopolymers of formaldehyde or its cyclic oligomers such as trioxane or tetroxane and corresponding copolymers.
  • Homopolymers of formaldehyde or trioxane are those polymers whose hydroxyl end groups are chemically stabilized against degradation in a known manner, for example by esterification or etherification.
  • Copolymers are polymers of formaldehyde or its cyclic oligomers, in particular trioxane, and cyclic ethers, cyclic acetals and / or linear polyacetals.
  • Such POM homopolymers or copolymers are known per se to the person skilled in the art and are described in the literature. In general, these polymers have at least 50 mol% of recurring units -CH 2 O- in the main polymer chain.
  • the homopolymers are generally prepared by polymerizing formaldehyde or trioxane, preferably in the presence of suitable catalysts.
  • POM copolymers are preferred as component (A), in particular those which, in addition to the repeating units -CH 2 O-, also up to 50, preferably from 0.1 to 20 and in particular 0.5 to 10 mol% on recurring units
  • R 1 to R 4 independently of one another are a hydrogen atom, a C 1 -C 4 -alkyl group or a halogen-substituted alkyl group having 1 to 4 C atoms and R 5 is a -CH 2 -, -O-CH 2 -, a d represent to C 4 alkyl or C to C 4 haloalkyl substituted methylene group or a corresponding oxymethylene group and n has a value in the range from 0 to 3.
  • These groups can advantageously be introduced into the copolymers by ring opening of cyclic ethers.
  • Preferred cyclic ethers are those of the formula
  • R 1 to R 5 and n have the meaning given above.
  • examples include ethylene oxide, 1,2-propylene oxide, 1,2-butylene oxide, 1,3-butylene oxide, 1,3-dioxane, 1,3-dioxolane and 1,3-dioxepane as cyclic ethers and linear oligo- or polyformals such as Polydioxolan or Polydioxepan called as comonomers.
  • Copolymers of 99.5-95 mol% of trioxane and 0.5 to 5 mol% of one of the aforementioned comonomers are particularly advantageous.
  • component (A) are oxymethylene terpolymers, for example by reacting trioxane, one of the cyclic ethers described above and with a third monomer, preferably a bifunctional compound of the formula
  • Preferred monomers of this type are ethylene diglycide, diglycidyl ether and diether from glycidylene and formaldehyde, dioxane or trioxane in a molar ratio of 2: 1 and diether from 2 mol of glycidyl compound and 1 mol of an aliphatic diol with 2 to 8 C atoms, such as, for example, the diglycidyl ether of ethylene glycol, 1 , 4-butanediol, 1, 3-butanediol, cyclobutane-1, 3-diol, 1, 2-propanediol and cyclohexane-1, 4-diol, to name just a few examples.
  • the preferred POM copolymers have melting points of at least 150 ° C. and molecular weights (weight average) M w in the range from 5,000 to 200,000, preferably from 7,000 to 150,000. End group-stabilized POM polymers which have CC bonds at the chain ends, are particularly preferred.
  • the used POM-polymers generally have a melt index (MVR value 190 / 2.16) of 2 to 50 cm 3/10 min (ISO 1133).
  • Cyclic olefin copolymers for the purposes of the invention include copolymers of ethylene or propylene on the one hand with cyclic olefins containing 0.1 to 100% by weight, preferably 0.1 to 99.9% by weight and particularly preferably 3 to 75% by weight. -%, based on the total mass of the cycloolefin polymer, polymerized units of at least one cyclic olefin of the formulas I, II, II ', III, IV, V or VI R 1
  • R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 and R 13 are the same or different and a hydrogen atom or a -C-C 2 o-hydrocarbon radical, such as a linear or branched C ⁇ -C 8 Alkyl radical, C 6 -C 8 aryl radical, C 7 -C 2 o-alkylenearyl radical, a cyclic or acyclic C 2 -C 2 o -alkenyl radical, or form a saturated, unsaturated or aromatic ring
  • the same radicals R 6 to R 13 in the different formulas I to VI can have a different meaning, in which m can assume values from 0 to 5, and 0 to 99.9%, preferably 0.1 to 99.9% by weight and particularly preferably 5 to 80% by weight, based on the total mass of the cycloolefin polymer, of polymerized units which are derived from one or more acyclic olefins of the formula VII
  • R 14 , R 15 , R 16 and R 17 are the same or different and a hydrogen atom, a linear, branched, saturated or unsaturated C1 . -C 20 - hydrocarbon radical such as a -CC 8 alkyl radical or a C 6 -C 8 aryl radical.
  • the cyclic olefins also include derivatives of these cyclic olefins with polar groups such as halogen, hydroxyl, ester, alkoxy, carboxy, cyano, amido, imido or silyl groups.
  • the cycloolefin polymer used according to the invention can contain 0 to 45 mol%, based on the total composition of the cycloolefin polymer, of polymerized units which are derived from one or more monocyclic olefins of the formula VIII
  • o is a number from 2 to 10.
  • cycloolefinic materials used in the context of this invention particularly preferably contain olefins with a norbornene basic structure, very particularly preferably they contain norbornene and tetracyclododecene and optionally vinylnorbomene or norbornadiene.
  • cycloolefin polymers which contain polymerized units which are derived from acyclic olefins having terminal double bonds, such as ⁇ -olefins having 2 to 20 C atoms, particularly preferably ethylene or propylene.
  • Norbomene / ethylene and tetracyclododecene / ethylene copolymers are very particularly preferred.
  • the terpolymers are particularly preferably norbornene / vinyl norbornene / ethylene, norbornene / norbornadiene / ethylene, tetracyclododecene / vinyl norbornene / ethylene, tetracyclododecene / inyltetracyclododecene / ethylene terpolymers.
  • the proportion of the polymerized units derived from a polyene, preferably vinyl norbomene or norbornadiene, is 0.1 to 50 mol%, preferably 0.1 to 20 mol%
  • the proportion of the acyclic monoolefin of the formula VII is 0 to 99.9 mol%, preferably 5 to 80 mol%, based on the total composition of the cycloolefin polymer.
  • the proportion of the polycyclic monoolefin is 0.1 to 99.9 mol%, preferably 3 to 75 mol%, based on the total composition of the cycloolefin polymer.
  • Cycloolefin polymers based on comonomers such as ethylene and 2-norbornene are colorless, amorphous and transparent materials.
  • the glass transition temperatures of the cycloolefin polymers can be adjusted within a wide range between -50 and 220 ° C. by varying the proportions of the comonomers and the average molecular weight. Glass transition temperatures between 0 and 180 ° C. are preferred, glass transition temperatures between 10 and 120 ° C. are particularly preferred.
  • the cycloolefin polymers described here have DIN 53 728 Viscosity numbers between 5 and 5,000 ml / g. Viscosity numbers between 5 and 2000 ml / g are preferred, viscosity numbers between 5 and 1000 ml / g are particularly preferred.
  • the polymers can contain further additives for controlling the property profile of the compositions according to the invention.
  • the additives can be liquid or solid and can vary widely in processing properties. Processing properties are understood to mean, for example, the viscosity, density or surface tension in the case of liquids or the particle size, particle shape, particle size distribution, hardness, flowability, adhesion or bulk density in the case of solid additives.
  • the additives give the polymer formulation the properties required in the respective application. Examples of the large number of additives known in the prior art are, for example, fillers which can be used in spherical, fiber or plate form with dimensions from 10 nm to a few millimeters. They are mainly used to adjust the mechanical properties of the polymer formulation.
  • additives are, for example, light stabilizers, in particular stabilizers against UV and visible light, flame retardants,
  • Processing aids, pigments, lubricants and friction additives such as polyethylene waxes and oxidized polyethylene waxes, adhesion promoters, impact modifiers, flow agents, mold release agents, nucleating agents, acid and base scavengers, oxidation stabilizers, nitrogen-containing stabilizers, colorants, esters from polyhydric alcohols and fatty acids, metal salts of Fatty acids, sterically hindered amines and phenol compounds as well as benzotriazole derivatives or benzophenone derivatives, nucleating agents such as polyoxymethylene terpolymers or talc, fillers such as glass spheres, wollastonite, clay, molybdenum disulfide, inorganic or organic fibers such as glass fibers, carbon fibers or aramid fibers and thermoplastic or thermosetting plastic additives or elastomers such as polyethylene, polyurethane, polymethyl methacrylate, polybutadiene, polystyrene or graft copoly
  • Colorants for example any inorganic pigments such as titanium dioxide, ultramarine blue, cobalt blue or organic pigments and colors such as phthalocyanines, anthraquinones or carbon black, either individually or as a mixture or together with polymer-soluble dyes in amounts of generally 0.1-5.0% by weight, can be used as further additives. preferably 0.5 - 2.0% are used. Nitrogen-containing stabilizers can also be used as additives.
  • suitable nitrogen-containing stabilizers are usually heterocyclic compounds having at least one nitrogen atom as a hetero atom which is adjacent to either an amino-substituted carbon atom or a carbonyl group, such as, for example, pyridazine, pyrimidine, pyrazine, pyrrolidone, aminopyridine and compounds derived therefrom.
  • Advantageous compounds of this type are aminopyridine and compounds derived therefrom. In principle, all aminopyridines, such as melamine, 2,6-diaminopyridine, substituted and dimeric aminopyridines and mixtures prepared from these compounds, are suitable.
  • Polyamides and dicyandiamide, urea and its derivatives, and pyrrolidone and compounds derived therefrom are also advantageous.
  • suitable pyrrolidones are, for example, imidazolidinone and compounds derived therefrom, such as, for example, hydantoin, the derivatives of which are particularly advantageous, and allantoin and its derivatives are particularly advantageous of these compounds.
  • Triamino-1, 3,5-triazine (melamine) and its derivatives, such as, for example, melamine-formaldehyde condensates and methylolmelamine are also particularly advantageous. Melamine, methylolmelamine, melamine-formaldehyde condensates and allantoin are very particularly preferred.
  • the nitrogen-containing stabilizers can be used individually or in combination and are usually used in amounts of 0.01-0.5%, preferably 0.03-0.3%. It is also possible to use esters from a polyhydric alcohol and at least one fatty acid, in particular esters from higher fatty acids with 10-32 C atoms, preferably 24-32 C atoms, and polyhydric alcohols from 2-8 C atoms, preferably 2- 5 carbon atoms used.
  • the acids do not have to be completely esterified, but can also only be partially esterified or the esters can be partially saponified.
  • Particularly preferred alcohols are ethylene glycol, glycerol, butylene glycol and pentaerythritol, among the fatty acids montanic acids are particularly preferred.
  • Very particularly preferred esters are diesters of glycol or glycerol and montanic acids (Licowachs E and Licolub WE4, manufacturer Clariant AG).
  • Metal salts of a fatty acid can also be contained in the composition according to the invention.
  • the fatty acids can be both unsaturated and saturated and can also be substituted with hydroxyl or amino groups.
  • composition according to the invention can also contain one or more sterically hindered phenol compounds.
  • sterically hindered phenol compounds examples include pentaerithrityl tetrakis - [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1010, from Ciba Geigy), triethylene glycol bis [3- (3-tert .butyl-4-hydroxy-5-methylphenyl) propionate] (Irganox 245, from Ciba Geigy), 3,3'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionohydrazide] (Irganox MD 1024, from Ciba Geigy), hexamethylene glycol bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 259, from Ciba Geigy), 3,5-
  • compositions can contain one or more stabilizers from the group of benzotriazole derivatives or benzophenone derivatives or aromatic benzoate derivatives.
  • benzotriazole derivatives or benzophenone derivatives or aromatic benzoate derivatives.
  • 2- [2'-hydroxy-3 ', 5'-bis (1, 1-dimethylbenzyl) phenyl] benzotriazole which is commercially available as Tinuvin 234 (Ciba Geigy).
  • Tinuvin 234 Tinuvin 234
  • one or more sterically hindered amines for light stabilization can be contained in the composition according to the invention.
  • 2,2,6,6-tetramethyl-4-piperidyl compounds e.g. Bis- (2,2,6,6-tetramethyl-4-piperidyl) sebazate (Tinuvin 770, Ciba Geigy) or the polymer of dimethyl succinate and 1- (2-hydroxyethyl) -4-hydroxy-2,2,6 , 6-tetramethyl-4-piperidine (Tinuvin 622, from Ciba Geigy), which in amounts of generally 0.0-0.5% by weight, preferably 0.01-0.4% by weight, very particularly preferably 0.4 % By weight can be used.
  • Another object of the invention is a method for producing the electrically conductive compositions according to the invention.
  • compositions according to the invention can be prepared by mixing the components in the liquid melt phase of the polymer at temperatures from 150 ° C. to 400 ° C., preferably from 200 ° C. to 350 ° C. and particularly preferably from 220 ° C. to 270 ° C.
  • compositions containing thermoplastic polymers other than those listed above, such as e.g. Polyamides can be produced by mixing the components in the liquid melt phase of the polymer at the temperatures mentioned above.
  • the invention therefore also relates to a process for producing electrically conductive compositions comprising the mixing of A) at least one thermoplastic polymer and B) up to 10% by weight, based on the composition, of expanded graphite in the liquid or liquid-crystalline melt phase of the polymer at temperatures from 150 ° C. to 400 ° C., preferably from 200 ° C. to 350 ° C. and particularly preferably from 220 ° C. to 270 ° C., with the proviso that the use of alkoxysilanes is excluded when using polyarylene sulfides.
  • Melt extruders of various types are suitable as mixing units, for example single-screw and counter-rotating or co-rotating twin-screw extruders.
  • the powdered expanded graphite can be fed to the extruder via a metering device behind the melting zone of the polymer.
  • expanded graphite can, if appropriate, first be mixed together with further electrically conductive carbon and polymer powder or granules and then fed together to the melting zone of the extruder.
  • a composition with a higher carbon content a so-called masterbatch
  • the mass fraction of carbon in the masterbatch is 6-25% by weight, preferably 8-20% by weight.
  • the process according to the invention is then carried out with at most 6% by weight, preferably at most 4% by weight, of expanded graphite by coextruding the masterbatch with polymer.
  • compositions according to the invention are suitable for the production of moldings which are used in potentially explosive environments or where the build-up of electrostatic charges must be avoided. Examples of this include use as a fuel filler neck, as a conveyor element in potentially explosive environments, for example in mines, or in ATMs.
  • the invention also relates to the uses of the compositions for these purposes.
  • the mixtures were kneaded in the melt at 250 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90).
  • the cooled melts were ground.
  • Expanded graphite and PBT were weighed in the proportions given in Table 2 and mixed on a roller bench.
  • Example 3 and Comparative Example 1 The mixtures were kneaded in the melt at 250 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90). The cooled melts were ground.
  • Example 3 and Comparative Example 1 The mixtures were kneaded in the melt at 250 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90). The cooled melts were ground.
  • Polybutylene terephthalate was weighed with expanded graphite or the polybutylene terephthalate masterbatch in the proportions given in Table 3 and mixed on a roller bench.
  • the mixtures were kneaded in the melt at 250 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90).
  • the cooled melts were ground.
  • the polyamide masterbatch produced in was weighed in the proportions given in Table 4 with polyamide 6.6 and mixed on a roller bench.
  • the mixtures were kneaded in the melt at 280 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90).
  • the cooled melts were ground.
  • Polyamide 6.6 was weighed with expanded graphite or the polyamide masterbatch in the proportions given in Table 5 and mixed on a roller bench.
  • the mixtures were kneaded in the melt at 280 ° C. for 15 minutes in a melt kneader (Haake Rheocord System 90).
  • the cooled melts were ground.
  • compositions produced in Examples 1 to 5 and in Comparative Examples 1 and 2 were produced in a vacuum press at 250 ° C. (PBT samples from Examples 1, 2, 3 and V1) or 280 ° C. (polyamide 6.6 samples) Examples 4, 5 and V2) pressed into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity was determined on the plates over a circle diameter of 50 mm.
  • the specific volume resistance was determined in accordance with IEC 60093, in accordance with VDE 0303 Part 30.
  • compositions thus produced were pressed in a vacuum press at 210 ° C. into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity was determined on the plates over a circle diameter of 50 mm.
  • the specific volume resistance was determined in accordance with IEC 60093, in accordance with VDE 0303 Part 30. Table 7 summarizes the results. Table 7:
  • a melt kneader HaakePolylab
  • compositions thus produced were pressed in a vacuum press at 210 ° C. into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity was determined on the plates over a circle diameter of 50 mm.
  • the specific volume resistance was determined in accordance with IEC 60093, in accordance with VDE 0303 Part 30. Table 8 summarizes the results.
  • a melt kneader HaakePolylab
  • compositions thus produced were pressed in a vacuum press at 210 ° C. into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity was determined on the plates over a circle diameter of 50 mm. The determination of the specific
  • the polyphenylene sulfide masterbatches produced in this way were weighed in the proportions given in Table 11 with further Fortron 214 and mixed on a roller bench. The mixtures were kneaded in the melt at 300 ° C. for 15 minutes in a melt kneader (Haake Polylab). The cooled melts were ground.
  • a silane-based coupling agent was not used for the production of masterbatches 10a to 10e (Table 10) or for the production of compositions 10f to 10o (Table 11)
  • compositions thus produced were pressed in a vacuum press at 310 ° C. into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity of the plates was measured using a
  • Circle diameter of 50 mm determined.
  • the specific volume resistance was determined in accordance with IEC 60093, in accordance with VDE 0303 Part 30.
  • the values for volume resistance are also entered in Table 11. Table 11
  • a melt kneader HaakePolylab
  • the mixture was kneaded in the melt at 200 ° C. for 15 minutes.
  • the cooled melt was ground.
  • the compositions thus produced were pressed in a vacuum press at 210 ° C. into circular plates of 120 mm in diameter and 1 mm in thickness.
  • the volume resistivity was determined on the plates over a circle diameter of 50 mm.
  • the specific volume resistance was determined in accordance with IEC 60093, in accordance with VDE 0303 Part 30. Table 12 summarizes the results.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions électriquement conductrices constituées de polymères thermoplastiques sélectionnés et de graphite expansé, la proportion en masse de graphite expansé étant inférieure à 10 % en poids et la résistance transversale spécifique des compositions étant de 1010ohm*cm maximum. La présente invention porte également sur un procédé selon lequel au moins un polymère thermoplastique est mélangé à du graphite expansé, le polymère étant en phase de fusion liquide, à des températures allant de 150 °C à 400°C.
EP02754772A 2001-07-04 2002-06-27 Compositions electriquement conductrices, leurs procedes de production et leur utilisation Withdrawn EP1407459A1 (fr)

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DE10132456 2001-07-04
PCT/EP2002/007111 WO2003005378A1 (fr) 2001-07-04 2002-06-27 Compositions electriquement conductrices, leurs procedes de production et leur utilisation

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US9786194B2 (en) 1999-06-11 2017-10-10 Sydney Hyman Image making medium compositions and images
US20040127621A1 (en) * 2002-09-12 2004-07-01 Board Of Trustees Of Michigan State University Expanded graphite and products produced therefrom
US11355027B2 (en) 2004-04-30 2022-06-07 Sydney Hyman Image making medium compositions and images
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US20040217332A1 (en) 2004-11-04

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