WO2010142376A1 - Composition polymère hautement fluide et procédé de production correspondant - Google Patents

Composition polymère hautement fluide et procédé de production correspondant Download PDF

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Publication number
WO2010142376A1
WO2010142376A1 PCT/EP2010/003207 EP2010003207W WO2010142376A1 WO 2010142376 A1 WO2010142376 A1 WO 2010142376A1 EP 2010003207 W EP2010003207 W EP 2010003207W WO 2010142376 A1 WO2010142376 A1 WO 2010142376A1
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polymer composition
carbon nanotubes
metal
mixed
composition according
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German (de)
English (en)
Inventor
Heiko Hocke
Michael Bierdel
Volker Michele
Sigurd Buchholz
Leslaw Mleczko
Reiner Rudolf
Aurel Wolf
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Covestro Deutschland AG
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Bayer MaterialScience AG
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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

Definitions

  • the invention relates to the process for improving the flowability of a polymer composition (hereinafter also referred to as composite for short) of thermoplastic polymers, in particular polycarbonate, and carbon nanotubes (CNT).
  • a polymer composition hereinafter also referred to as composite for short
  • thermoplastic polymers in particular polycarbonate, and carbon nanotubes (CNT).
  • the thermoplastics such as polycarbonate
  • reinforcing agents glass fibers, mineral fillers such as talc and calcium carbonate, carbon fibers and various carbon blacks.
  • one property e.g., strength
  • other properties e.g., fracture toughness
  • nanoparticulate fillers are known in which this counteracting effect is not so pronounced.
  • a special position in this group is found in carbon nanotubes (CNTs), which have an outstanding combination of mechanical and physical properties.
  • Such tubes with the perfect crystalline structure have nanoscale diameter and reach a length of 1 mm and more. They have a very high modulus of elasticity up to about 1 TPa and a strength of 50-100 GPa. In addition, they are excellent electrical and thermal conductors. It is to be expected that such nanotubes, when incorporated into thermoplastic and thermoreactive polymeric composites, not only positively affect their mechanical profile, but also make the material electrically conductive. In the case of polycarbonate, this additional option is of particular importance because these polymer composites are often used in the electrical and electronics industries.
  • thermoplastics Special importance in the injection molding of thermoplastics has a good flowability of the polymeric composites. This property is often dramatically degraded by the addition of nanoscale fillers. As a result, these composites can not be used where they actually need to be used, namely in the manufacture of thin-walled components in the electrical, electronics and automotive industries. In this case, low-viscosity composites are required, which allow a fast filling of the mold with the lowest possible filling pressures or closing forces of the corresponding injection molding machines.
  • a second or third main group metal oxide such as MgO
  • adding a second or third main group metal oxide, such as MgO, to the polymer composition of, for example, polycarbonate and carbon nanotubes results in a significant improvement in the flowability of the polymer composition equal to or even higher than that of the starting polymer (eg, PC) without additive the carbon nanotube.
  • the invention relates to a polymer composition based on thermoplastic polymers, in particular of polycarbonate (component A), polyester (component B), preferably
  • Polymer composition at least one finely divided metal oxide or mixed oxide of a metal of the second or third main group or the fourth subgroup of the Periodic Table of the Elements, preferably MgO, CaO, BaO, A12O3, hydrotalcite, TiO2, or ZrO2 particularly preferably MgO.
  • a polymer composition which is characterized in that the carbon nanotubes and / or the Leitruß and / or graphite in an amount of 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-% based on the mass of the polymer composition are included.
  • Another object of the invention is that the electrically conductive carbon particles, in particular the carbon nanotubes and the metal oxide can be added in the form of an agglomerate with each other or individually of the polymer composition.
  • Carbon nanotubes in the context of the invention are all single-walled or multi-walled carbon nanotubes of the cylinder type, scroll type or onion-like structure. Preference is given to using multi-walled carbon nanotubes of the cylinder type, scroll type or mixtures thereof.
  • the carbon nanotubes are used in particular in an amount of 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-% based on the polymer composition in the finished compound. In masterbatches, the concentration of carbon nanotubes may be greater and may be up to 80% by weight.
  • Carbon nanotubes with a ratio of length to outer diameter of greater than 5, preferably greater than 40, are particularly preferably used.
  • the carbon nanotubes are particularly preferably used in the form of agglomerates, the agglomerates in particular having an average diameter in the range of 0.01 to 5 mm, preferably 0.05 to 2 mm, particularly preferably 0.1 to 1 mm.
  • the carbon nanotubes to be used have particularly preferably essentially an average diameter of 3 to 100 nm, preferably 5 to 80 nm, particularly preferably 6 to 60 nm.
  • the novel polymer composition preferably has an electrical resistance (surface resistance) of less than 10 10 ohms, preferably less than 10 7 ohms or electrically dissipative.
  • the new polymer composition has a volume resistivity of less than 10 10 ohm.cm.
  • Another object of the invention is a method for improving the flowability of a polymer composition based on polycarbonate and electrically conductive
  • Carbon particles in particular carbon nanotubes (CNT) and / or Leitruß and / or
  • Graphite in particular for the preparation of a novel polymer composition as described above, characterized in that the polymer composition at least one finely divided metal oxide or mixed oxide of a metal of the second or third main group or fourth subgroup of the Periodic Table of the Elements, preferably MgO, CaO, BaO, Al 2 O 3 .
  • Hydrotalcite, TiO 2 , or ZrO 2 particularly preferably MgO is added.
  • a particularly preferred method is characterized in that using an extruder, preferably a twin-screw extruder, the carbon nanotubes and / or Graphite and / or carbon blacks and the metal oxides are added individually and / or together to the polymer and mixed with it.
  • an extruder preferably a twin-screw extruder
  • the carbon nanotubes and / or Graphite and / or carbon blacks and the metal oxides are added individually and / or together to the polymer and mixed with it.
  • a particularly preferred method is characterized in that using an extruder, preferably a twin-screw extruder, the carbon nanotubes are first mixed with the metal oxides, this mixture is added to the polymer and mixed in this.
  • an extruder preferably a twin-screw extruder
  • CNT structures In contrast to the initially mentioned known CNTs of the scroll type with only one continuous or interrupted graphene layer CNT structures have recently been found that consist of several graphene layers, which are combined into a stack and rolled up (multiscroll type). These carbon nanotubes and carbon nanotubes agglomerates thereof are, for example, the subject of the German patent application with the official file reference 102007044031.8. Their content is hereby incorporated with respect to the CNT and its preparation to the disclosure of this application.
  • This CNT structure is similar to simple-carbon carbon nanotubes in comparison to the structure of multi-walled cylindrical monocarbon nanotubes (cylindrical MWNT) to the structure of single-walled cylindrical carbon nanotubes (cylindrical SWNT).
  • the individual graphene or graphite layers in these carbon nanotubes seen in cross-section, evidently run continuously from the center of the CNT to the outer edge without interruption. This can be z.
  • CCVD Catalytic Carbon Vapor Deposition
  • acetylene methane, ethane, ethylene, butane, butene, butadiene, benzene and other, carbon-containing starting materials called. Preference is therefore given to using CNTs obtainable from catalytic processes.
  • the catalysts usually include metals, metal oxides or decomposable or reducible
  • the metals mentioned for the catalyst are Fe, Mo, Ni, V, Mn, Sn, Co, Cu and other subgroup elements.
  • the individual metals usually have a tendency to support the formation of carbon nanotubes, according to the prior art, high yields and small proportions become more amorphous
  • Particularly advantageous catalyst systems for the production of CNTs are based on combinations of metals or metal compounds containing two or more elements from the series Fe, Co, Mn, Mo and Ni.
  • carbon nanotubes and the properties of the tubes formed are known to be complex in a manner dependent on the metal component used as a catalyst or a combination of several metal components, the catalyst support material optionally used and the interaction between the catalyst and support, the reactant gas and partial pressure, an admixture of hydrogen or other gases, the reaction temperature and the residence time or the reactor used.
  • a particularly preferred method for the production of carbon nanotubes is known from WO 2006/050903 A2.
  • carbon nanotubes of various structures are produced, which can be removed from the process predominantly as carbon nanotube powder.
  • Carbon nanotubes more suitable for the invention are obtained by methods basically described in the following references:
  • multi-walled carbon nanotubes in the form of nested seamless cylindrical nanotubes or also in the form of the described scroll or onion structures, today takes place commercially in large quantities, predominantly using catalytic processes. These processes usually show a higher yield than the abovementioned arc and other processes and are typically used today in the kilogram Scale (several hundred kilo / day worldwide) carried out.
  • the multi-walled carbon nanotubes produced in this way are generally much cheaper than the single-walled nanotubes and are therefore used, for example, as a performance-enhancing additive in other materials.
  • Inventive polycarbonates are those homopolycarbonates and copolycarbonates based on the bisphenols of the general formula (I)
  • Z is a divalent organic radical having 6 to 30 carbon atoms which contains one or more aromatic groups.
  • R 1 R 2 ( ⁇ ) (M) B is in each case C 1 -C 12 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
  • x each independently 0, 1 or 2
  • p 1 or 0
  • R 1 and R 2 for each X 1 can be selected individually, independently of one another hydrogen or C r C 6 - alkyl, preferably hydrogen, methyl or ethyl,
  • M is an integer from 4 to 7, preferably 4 or 5, with the proviso that at least one atom X 1 , R 1 and R 2 are simultaneously alkyl.
  • bisphenols according to the general formula (I) are bisphenols which belong to the following groups: dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, indanebisphenols, bis (hydroxyphenyl) sulfites, bis- (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides and ⁇ , ⁇ -bis (hydroxyphenyl) diisopropylbenzenes.
  • Also derivatives of said bisphenols, which are accessible for example by alkylation or halogenation on the aromatic rings of said bisphenols, are examples of bisphenols according to the general formula (I).
  • bisphenols according to the general formula (I) are in particular the following compounds: hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3, 5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) -p / m-diisopropylbenzene 1,1-Bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) -3 methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) -4-
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and 1,1 - bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • the described bisphenols according to the general formula (I) can be prepared by known methods, e.g. from the corresponding phenols and ketones.
  • 1,1-Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and its preparation is e.g. described in US-A 4,982,014.
  • Polycarbonates can be prepared by known methods. Suitable processes for the preparation of polycarbonates are, for example, the preparation from bisphenols with phosgene by the interfacial process or from bisphenols with phosgene by the homogeneous-phase process, the so-called pyridine process, or from bisphenols with carbonic acid esters by the melt transesterification process. These production methods are e.g. described in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. 9, pp. 31-76, Interscience Publishers, New York, London, Sidney, 1964. The above preparation methods are also described in D. Freitag, U Grigo, PR Muller, H.
  • the polycarbonates which are particularly suitable for the inventive polymer composition preferably have a weight average molar mass (M w ), which can be determined, for example, by ultracentrifugation or scattered light measurement, of from 10,000 to 200,000 g / mol. More preferably, they have a weight average molecular weight of 12,000 to 80,000 g / mol, more preferably 15,000 to 35,000 g / mol.
  • M w weight average molar mass
  • the average molar mass of the polycarbonates which are particularly suitable for the polymer composition according to the invention can be adjusted, for example, in a known manner by a corresponding amount of chain terminators.
  • the chain terminators can be used singly or as a mixture of different chain terminators.
  • Suitable chain terminators are both monophenols and monocarboxylic acids.
  • Suitable monophenols are e.g. Phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, e.g. 4- (l, l, 3,3-tetramethylbutyl) -phenol or monoalkylphenols or dialkylphenols having a total of 8 to 20 C atoms in the alkyl substituents, e.g.
  • Suitable monocarboxylic acids are benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • Preferred chain terminators are phenol, p-tert-butylphenol, 4- (l, l, 3,3-tetramethylbutyl) phenol and cumylphenol.
  • the amount of chain terminators is preferably between 0.25 and 10 mol%, based on the sum of the bisphenols used in each case.
  • the polycarbonates which are particularly suitable for the polymer composition according to the invention can be branched in a known manner, preferably by the incorporation of trifunctional or more than trifunctional branching agents.
  • Suitable branching agents are e.g. those having three or more than three phenolic groups or those having three or more than three carboxylic acid groups, such as, for example, 1,1-tris (4-hydroxyphenyl) ethane and 3,3-bis- (3-methyl-4-) hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • the amount of optionally used branching agent is preferably from 0.05 mol% to 2 mol%, based on moles of bisphenols used
  • the polycarbonates may contain conventional additives such as e.g. Mold release agents, stabilizers and / or flow aids are mixed in the melt or applied to the surface.
  • the polycarbonates used preferably already contain mold release agents, such as, for example, pentaerythritol tetrastearate before being combined with the other components of the polymer composition according to the invention.
  • Hydrotalcite is understood to mean here all synthetic or natural hydrotalcites or other basic metal-aluminum-hydroxy compounds, in particular those of the general formula (1)
  • M ⁇ + represents magnesium or zinc, in particular magnesium
  • a n - is an anion with the valence number from the series OH ", F", Cl “, Br, CO 3 2 ' , SO 4 2' , HPO 4 2" , silicate, acetate or oxalate, in particular CO 3 2 " ,
  • Invention-relevant polyesters comprise one or more thermoplastic polyalkylene terephthalates.
  • the polyalkylene terephthalates of component B are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Preferred polyalkylene terephthalates contain at least 80 wt .-%, preferably at least 90 wt .-%, based on the dicarboxylic acid terephthalate and at least 80 wt .-%, preferably at least 90 mol%, based on the diol component of ethylene glycol and / or butanediol-1 , 4-residues.
  • the preferred polyalkylene terephthalates may contain, in addition to terephthalic acid residues, up to 20 mole%, preferably up to 10 mole%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms.
  • radicals for example radicals of 1,3-propanediol, 2-ethylpropanediol 1, 3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2, 4, 2-methylpentanediol-2,4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3,2-diethylpropanediol-1,3-hexanediol-2,5,1,4 Di ( ⁇ -hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4 - ⁇ -hydroxyethoxy-phenyl) -propane and 2,2-bis (4-hydroxy
  • the polyalkylene terephthalates can be branched by incorporation of relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900 270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Mixtures of polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, as measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C. in the Ubbelohde viscometer.
  • the polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, pp. 695 et seq., Carl-Hanser-Verlag, Kunststoff 1973).

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition polymère à base de polymère thermoplastique et de particules de carbone électroconductrices, en particulier de nanotubes de carbone (CNT), et/ou de noir de carbone conducteur et/ou de graphite. Selon l'invention, cette composition polymère renferme au moins des fines particules d'un oxyde métallique, ou d'un mélange d'oxydes métalliques d'un métal appartenant aux deuxième ou troisième groupes principaux ou au quatrième sous-groupe dans le tableau périodique des éléments.
PCT/EP2010/003207 2009-06-09 2010-05-26 Composition polymère hautement fluide et procédé de production correspondant Ceased WO2010142376A1 (fr)

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DE200910024340 DE102009024340A1 (de) 2009-06-09 2009-06-09 Hochfließfähige Polymerzusammensetzung und Verfahren zu ihrer Herstellung
DE102009024340.2 2009-06-09

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017145371A (ja) * 2016-02-19 2017-08-24 積水化学工業株式会社 樹脂成形体

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106380797A (zh) * 2016-08-31 2017-02-08 广东顺德顺炎新材料股份有限公司 一种发热阻燃增强pbt材料及其制备方法

Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900270A1 (de) 1968-01-04 1969-11-06 Rhodiaceta Neue thermoplastische Formmassen
DE2507776A1 (de) 1975-02-22 1976-09-02 Bayer Ag Schnellkristallisierende poly (aethylen/alkylen)-terephthalate
DE2507674A1 (de) 1975-02-22 1976-09-09 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
DE2715932A1 (de) 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
WO1986003455A1 (fr) 1984-12-06 1986-06-19 Hyperion Catalysis International, Inc. Fibrilles de carbone, methode de production et compositions en contenant
US4982014A (en) 1988-08-12 1991-01-01 Bayer Aktiengesellschaft Dihydroxydiphenyl cycloalkanes, their production and their use for the production of high molecular weight polycarbonates
JPH04306256A (ja) * 1991-04-03 1992-10-29 Teijin Chem Ltd 樹脂組成物
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
DE10259498A1 (de) * 2002-12-19 2004-07-01 Bayer Ag Leitfähige Thermoplaste mit Ruß und Kohlenstoff-Nanofibrillen
US20040232389A1 (en) * 2003-05-22 2004-11-25 Elkovitch Mark D. Electrically conductive compositions and method of manufacture thereof
JP2005320515A (ja) * 2004-04-06 2005-11-17 Mitsubishi Engineering Plastics Corp 熱伝導性ポリカーボネート系樹脂組成物および成形体
WO2006050903A2 (fr) 2004-11-13 2006-05-18 Bayer Materialscience Ag Catalyseur pour produire des nanotubes de carbone par decomposition de composes de carbone gazeux sur un catalyseur heterogene
JP2007099798A (ja) * 2005-09-30 2007-04-19 Mitsubishi Engineering Plastics Corp 熱伝導性ポリカーボネート系樹脂組成物および成形体
WO2007093337A2 (fr) 2006-02-16 2007-08-23 Bayer Materialscience Ag Procédé de production continue de catalyseurs
US20070224488A1 (en) * 2006-03-22 2007-09-27 Industrial Technology Research Institute Electrically conductive composite
WO2008078849A1 (fr) * 2006-12-22 2008-07-03 Cheil Industries Inc. Composition de résine thermoplastique électroconductrice et article en plastique
DE102007044031A1 (de) * 2007-09-14 2009-03-19 Bayer Materialscience Ag Kohlenstoffnanoröhrchenpulver, Kohlenstoffnanoröhrchen und Verfahren zu ihrer Herstellung

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5039599B2 (fr) 1973-03-30 1975-12-18
DE2407776A1 (de) 1974-02-19 1975-09-04 Licentia Gmbh Schaltung zur regelung der betriebsspannung fuer die transistor-zeilenendstufe eines fernsehempfaengers

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1900270A1 (de) 1968-01-04 1969-11-06 Rhodiaceta Neue thermoplastische Formmassen
US3692744A (en) 1968-01-04 1972-09-19 Rhodiaceta Injection molded branched polyesters
DE2507776A1 (de) 1975-02-22 1976-09-02 Bayer Ag Schnellkristallisierende poly (aethylen/alkylen)-terephthalate
DE2507674A1 (de) 1975-02-22 1976-09-09 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
DE2715932A1 (de) 1977-04-09 1978-10-19 Bayer Ag Schnellkristallisierende poly(aethylen/alkylen)-terephthalate
EP0205556B1 (fr) 1984-12-06 1995-05-10 Hyperion Catalysis International, Inc. Fibrilles de carbone, methode de production et compositions en contenant
WO1986003455A1 (fr) 1984-12-06 1986-06-19 Hyperion Catalysis International, Inc. Fibrilles de carbone, methode de production et compositions en contenant
US4982014A (en) 1988-08-12 1991-01-01 Bayer Aktiengesellschaft Dihydroxydiphenyl cycloalkanes, their production and their use for the production of high molecular weight polycarbonates
JPH04306256A (ja) * 1991-04-03 1992-10-29 Teijin Chem Ltd 樹脂組成物
US6001919A (en) * 1998-04-06 1999-12-14 The Budd Company Conductive sheet molding compound
DE10259498A1 (de) * 2002-12-19 2004-07-01 Bayer Ag Leitfähige Thermoplaste mit Ruß und Kohlenstoff-Nanofibrillen
US20040232389A1 (en) * 2003-05-22 2004-11-25 Elkovitch Mark D. Electrically conductive compositions and method of manufacture thereof
JP2005320515A (ja) * 2004-04-06 2005-11-17 Mitsubishi Engineering Plastics Corp 熱伝導性ポリカーボネート系樹脂組成物および成形体
WO2006050903A2 (fr) 2004-11-13 2006-05-18 Bayer Materialscience Ag Catalyseur pour produire des nanotubes de carbone par decomposition de composes de carbone gazeux sur un catalyseur heterogene
JP2007099798A (ja) * 2005-09-30 2007-04-19 Mitsubishi Engineering Plastics Corp 熱伝導性ポリカーボネート系樹脂組成物および成形体
WO2007093337A2 (fr) 2006-02-16 2007-08-23 Bayer Materialscience Ag Procédé de production continue de catalyseurs
US20070224488A1 (en) * 2006-03-22 2007-09-27 Industrial Technology Research Institute Electrically conductive composite
WO2008078849A1 (fr) * 2006-12-22 2008-07-03 Cheil Industries Inc. Composition de résine thermoplastique électroconductrice et article en plastique
DE102007044031A1 (de) * 2007-09-14 2009-03-19 Bayer Materialscience Ag Kohlenstoffnanoröhrchenpulver, Kohlenstoffnanoröhrchen und Verfahren zu ihrer Herstellung

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
"Synthesis of Poly(ester-carbonate) Copolymers", JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION, vol. 19, 1980, pages 75 - 90
CARBON, vol. 14, 1976, pages 133
CARBON, vol. 34, 1996, pages 1301 - 3
D.C. PREVORSEK; B.T. DEBONA; Y. KESTEN, CORPORATE RESEARCH CENTER, ALLIED CHEMICAL CORPORATION, pages 07960
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; 18 November 2005 (2005-11-18), NAGASHIMA, HIROMITSU ET AL: "Thermally conductive polycarbonate-based compositions with good flowability, and warp-resistant moldings therefrom", XP002597760, retrieved from STN Database accession no. 2005:1220300 *
DATABASE WPI Week 199250, Derwent World Patents Index; AN 1992-410443, XP002597722 *
DATABASE WPI Week 200749, Derwent World Patents Index; AN 2007-501158, XP002597708 *
KUNSTSTOFFE, vol. 9, 2000, pages 116 - 118
SCIENCE, vol. 263, 1994, pages 1744 - 7

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JP2017145371A (ja) * 2016-02-19 2017-08-24 積水化学工業株式会社 樹脂成形体

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