WO2002085954A2 - Blends of epdm and metallocene plastomers for wire and cable applications - Google Patents

Blends of epdm and metallocene plastomers for wire and cable applications Download PDF

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WO2002085954A2
WO2002085954A2 PCT/US2002/008739 US0208739W WO02085954A2 WO 2002085954 A2 WO2002085954 A2 WO 2002085954A2 US 0208739 W US0208739 W US 0208739W WO 02085954 A2 WO02085954 A2 WO 02085954A2
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ethylene alpha
olefin
coating compound
olefin copolymer
ethylene
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PCT/US2002/008739
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French (fr)
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WO2002085954A3 (en
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George J. Pehlert
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Exxonmobil Chemical Patents Inc.
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Priority to US10/475,594 priority Critical patent/US7750080B2/en
Priority to EP02719306A priority patent/EP1453866B1/en
Priority to DE60220709T priority patent/DE60220709D1/en
Priority to AU2002250396A priority patent/AU2002250396A1/en
Priority to JP2002583480A priority patent/JP4000062B2/en
Publication of WO2002085954A2 publication Critical patent/WO2002085954A2/en
Publication of WO2002085954A3 publication Critical patent/WO2002085954A3/en

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/44Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
    • H01B3/441Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from alkenes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/28Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • C08L2203/202Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts

Definitions

  • the present invention is directed generally to coating compounds for electrical applications, and to electrical devices including such coating compounds. More particularly, the coating compounds include an ethylene alpha- olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio ol of at least 7 and/or a Melt Index Ratio I 1 /I 2 of at least 20, and to electrical devices including extruded coating compounds, the extruded compound's having low surface roughness at high extrusion rates.
  • the coating compounds include an ethylene alpha- olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio ol of at least 7 and/or a Melt Index Ratio I 1 /I 2 of at least 20, and to electrical devices including extruded coating compounds, the extruded compound's having low surface roughness at high extrusion rates.
  • Typical insulating compounds include elastomers such as ethylene, ⁇ -olefin, non- conjugated diene terpolymers (EPDM), along with fillers and various additives.
  • EPDM polymers can provide good insulating properties, but usually require relatively slow extrusion rates, because surface characteristics of the extrudate in a compound based on these elastomeric polymers will not be as smooth as desired if the extrusion rates are higher.
  • EP(D)M- VNB ethylene propylene vinyl norbornene elastomers
  • ENB ethylidine norbornene
  • the enhanced extrusion characteristics are attributed to a high level of long chain branching. However the high level of branching also degrades the compound physical properties, notably elongation to break.
  • EP(D)M-VNB polymers can be improved by combination with metallocene-catalyzed ethylene alpha-olefin copolymers.
  • the amount of ethylene alpha-olefin copolymer that could be used is limited, however, by processability problems that occur at high ethylene alpha-olefin content.
  • power cable coating compounds can be prepared with very high levels of ethylene alpha-olefin copolymers blended with an ethylene alpha olefin diene terpolymer, while still maintaining excellent mechanical, electrical and processing characteristics. This surprising result is achieved at least in part by proper selection of the ethylene alpha-olefin copolymer.
  • the present invention is directed to a power cable coating compound, the coating compound including ' an ethylene alpha-olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio I 10 I 2 of at least 7.
  • the ethylene alpha-olefin copolymer has a Melt Index Ratio I 21 /I 2 of at least 20.
  • the ethylene alpha-olefin copolymer is present in the coating compound in an amount of from 10 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer, or in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer, or in an amount greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
  • the ethylene alpha-olefin diene elastomeric terpolymer has one or more of: a branching index less than 0.5; from 50 to 90 mol % ethylene-derived units; from 0.1 to 1.5 mol % diene-derived units; and a ratio M w /Mschreib greater than 10.
  • the present invention is directed to an electrically conductive device, the device including an electrically conductive portion, and an electrically insulating portion.
  • the electrically insulating portion includes a coating compound, which can be any of the coating compounds described herein.
  • Suitable devices include any device having electrically conductive or semi- conductive and electrically insulative portions.
  • a preferred, non-limiting example of such a device is an electrical cable.
  • Extruded compounds according to the present invention have good processability characteristics at high extrusion rate, characterized by a low surface roughness factor as defined herein.
  • the present invention provides an electrically conductive device including an extruded coating compound having an extrusion profile measured from a sample extruded at 100 rpm and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by
  • Ra Ra + 0.1Rt
  • Ra is the mean absolute vertical deviation from the mean extrudate surface line
  • Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
  • the present invention is directed to a power cable coating compound including an ethylene alpha-olefin diene elastomeric terpolymer and an ethylene alpha-olefin copolymer.
  • the ethylene alpha-olefin copolymer as described below, has a Melt Index Ratio I1 0 /I2 of at least 7.
  • power cable coating compound or simply “compound” is used to mean a polymer component or components in combination with fillers, accelerants, curatives, extenders and other components commonly used in the art to form a material having the requisite processing, heat aging, electrical and other properties suitable for use as an insulative coating layer in an electrical cable. Power cable coating compounds are described in more detail below.
  • Embodiments of the present invention include an ethylene alpha-olefin elastomer.
  • the elastomer is a terpolymer of ethylene; an alpha olefin, such as propylene; and a non-conjugated diene.
  • Non-conjugated dienes useful as co- monomers preferably are straight or branched chain hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having about 6 to about 15 carbon atoms, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene and 1,6- octadiene; (b) branched chain acyclic dienes, such as 5-methyl- 1,4-hexadiene; 3,7- dimethyl-l,6-octadiene; and 3,7-dimethyl-l,7-octadiene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,7- cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl
  • Preferred non-conjugated dienes are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2- norbornene (VNB), with VNB being most preferred. Note that throughout this application the terms “non-conjugated diene” and “diene” are used interchangeably.
  • the elastomer can contain ethylene-derived units in a range from a lower limit of 50, or 60, or 65, or 68 mole percent to an upper limit of 80 or 85 or 90 mole percent, based on the total moles of monomer-derived units in the polymer.
  • the elastomer can contain alpha-olefin-derived units in a range from a lower limit of 10 or 15 or 20 mole percent to an upper limit of 32 or 35 or 40 or 50 mole percent, based on the total moles of monomer-derived units in the polymer.
  • the elastomer can contain the non-conjugated diene-derived units in a range of from a lower limit of 0.1 or 0.16 mole percent to an upper limit of 0.4 or 1.5 or 5 mole percent, based on the total moles of monomer-derived units in the polymer.
  • the elastomeric polymer can also be characterized by a Mooney viscosity (ML [1+4] 125 °C ) of from 10 to 80, and a molecular weight distribution M w Qp ; ALLS /
  • a preferred non-conjugated diene is vinyl norbornene.
  • VNB vinyl norbornene
  • This method of branching permits the production of ethylene, alpha-olefin, vinyl norbornene elastomeric polymers substantially free of gel which would normally be associated with cationically branched ethylene, alpha-olefin, vinyl norbornene elastomeric polymers containing, for instance, a less-preferred non-conjugated diene such as 5-ethylidene-2-norbornene or 1,4-hexadiene.
  • a less-preferred non-conjugated diene such as 5-ethylidene-2-norbornene or 1,4-hexadiene.
  • a procedure suitable for preparing ethylene alpha-olefin diene terpolymers is as follows.
  • the catalysts used are VOCl 3 (vanadium oxytrichloride) or VC1 4 (vanadium tetrachloride) with the latter as the preferred catalyst.
  • the co-catalyst is chosen from (i) ethyl aluminum sesqui chloride (SESQUI), (ii) diethyl aluminum chloride (DEAC), and (iii) equivalent mixture of diethyl aluminum chloride and triethyl aluminum (TEAL).
  • SESQUI ethyl aluminum sesqui chloride
  • DEAC diethyl aluminum chloride
  • TEAL triethyl aluminum
  • An elastomer with a broader composition distribution is expected to provide better tensile strength in a cable coating compound.
  • the polymerization is carried out in a continuous stirred tank reactor at 20-65 °C at a residence time of 6-15 minutes and a pressure of 7 kg/cm 2 .
  • the concentration ratio of vanadium to alkyl is from 1 to 4 to 1 to 8.
  • About 0.3 to 1.5 kg of polymer is produced per gram of catalyst fed to the reactor.
  • the polymer concentration in the hexane solvent is in the range of 3-7% by weight.
  • the intrinsic viscosity measured in decalin at 135 °C was in the range of 1 to 2 dL/g.
  • the molecular weight distribution (M W;LALLS /M n GPC DRI ) was greater than 10.
  • the branching index was in the range of 0.1 to 0.3.
  • Metallocene catalysis to form the ethylene alpha-olefin diene terpolymer is also contemplated. Suitable metallocene compounds, activators, and processes are well known in the art and can be found in U.S. Patent No. 5,763,533 and references cited therein.
  • ethylene, alpha-olefin, diene monomer elastomeric polymers wherein the diene monomer is vinyl norbornene require lower levels of peroxide to attain the same cure state, compared to analogous polymers wherein the diene monomer is ethylidene norbornene, at the same level of incorporated diene.
  • 20 to 40 % lower peroxide consumption can be realized using ethylene, alpha-olefin, vinyl norbornene.
  • the efficiency of vinyl norbornene in providing high crosslink density with peroxide vulcanization also permits a reduction in the overall diene level to attain the same cure state as with ethylidene norbornene polymers, and results in enhanced heat aging performance.
  • the unique combinations of improved processability, lower peroxide usage and enhanced heat aging are particular advantages provided by ethylene, alpha-olefin, vinyl norbornene terpolymers over less preferred terpolymers containing non- conjugated dienes such as ethylidene norbornene or 1-4, hexadiene.
  • MWD Molecular weight distribution
  • GPC size exclusion chromatography
  • SEC size exclusion chromatography
  • Nj is the number of molecules having a molecular weight Mj.
  • M is the number average molecular weight Mn.
  • M is the weight average molecular weight Mw.
  • M is the Z-average molecular weight Mz.
  • the desired MWD function (e.g., Mw/Mn or Mz/Mw) is the ratio of the corresponding M values. Measurement of M and MWD is well known in the art and is discussed in more detail in, for example, Slade, P. E.
  • the relative degree of branching in the ethylene, alpha-olefin, diene monomer terpolymer is determined using a branching index factor.
  • Calculating the branching index factor requires a series of three laboratory measurements of polymer properties in solutions: (i) weight average molecular weight (M W LALLS) measured using a low angle laser light scattering (LALLS) technique; (ii) weight average molecular weight (M W ⁇ JRT); and (iii) viscosity average molecular weight (M v DRJ) using a differential refractive index detector
  • the branching index (BI) is defined as: p _ y ,brJylw,DRI , AL L s -v,DRI
  • the ethylene alpha-olefin diene terpolymer can have a molecular weight distribution Mw/Mn of greater than 6, or alternatively greater than 10.
  • the ethylene alpha-olefin diene terpolymer can have a branching index less than 1.0, less than 0.9, less than 0.7, 0.5, less than 0.4, or less than 0.3, and greater than 0.05, or greater than 0.1.
  • Embodiments of the present invention also include an ethylene alpha- olefin copolymer. It has been surprisingly discovered that ethylene alpha-olefin copolymers can be used with ethylene alpha-olefin diene elastomers in cable coating compounds in much higher levels than previously thought practical due to processibility (melt fracture) problems at relatively high extrusion rates. In particular, it has been surprisingly found that, by selecting a specific type of ethylene-alpha olef ⁇ n copolymer as described below, cable coating compounds can be formed having a wide range of ethylene alpha-olefin content, while still maintaining good electrical and processability properties.
  • Suitable ethylene alpha-olefins are metallocene-catalyzed copolymers of ethylene and an alpha-olefin comonomer, the alpha-olefin being a C 3 -C 2 o ⁇ -olefm and preferably a C 3 -C 12 -olefins.
  • the ⁇ -olefin comonomer can be linear or
  • alpha-olefin comonomers examples include propylene, linear C 4 -C 12 ⁇ -olefins, and ⁇ -olefins having one or more C C alkyl branches.
  • Specific examples include propylene; 3 -methyl- 1-butene; 3,3-dimethyl-l-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1-decene, or 1-dodecene.
  • Preferred comonomers include ethylene, 1-butene, 1-pentene, 3 -methyl- 1-butene, 1-hexene, 3 -methyl- 1-pentene, 4-methyl- 1-pentene, 3,3-dimethyl-l-butene, 1-heptene, 1-hexene with a methyl substituent on any of C -C 5 , 1-pentene with two methyl substituents in any stoichiometrically acceptable combination on C 3 or C , 3-ethyl-l-pentene, 1-octene, 1-pentene with a methyl substituent on any of C 3 or
  • CDBI Composition Distribution Breadth Index
  • ethylene alpha-olefms examples include several of the copolymers sold under the trademark EXACT and available from the ExxonMobil Chemical Co., Houston, Texas, as well as the ENGAGE polymers available from DuPont/Dow.
  • EXACT copolymers include EXACT 0201, EXACT 0201HS, EXACT 0203, EXACT 8201, EXACT 8203, EXACT 210, and EXACT 8210, to name but a few.
  • Typical ethylene alpha-olefins will have a density of 0.86 or 0.88 to 0.91 or 0.92 g/cm 3 ; and a melt index I 2 of from a lower limit of 0.1 dg/min or 0.5 dg/min or 1.0 dg/min to an upper limit of 10 dg/min or 50 dg/min or 100 dg/min, consistent with the Melt Index Ratios described above.
  • the appropriate amount of alpha-olefin comonomer in the copolymer can be readily determined by one skilled in the art, based on the desired density of the copolymer.
  • the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount of from 10 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
  • the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer. In another embodiment, the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount of greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
  • a power cable coating compound suitable for use as an insulator in a "medium voltage” electrical cable i.e., for voltages up to about
  • TRANSLINK 37 is available from Englehard, Iselin, New Jersey.
  • DRIMIX A172 is available from Kenrich Petrochemicals, Bayonne, New Jersey.
  • ERD 90 is available from Rhein Chemie Corp, Trenton New Jersey.
  • AGERLITE MA is available from R.T. Vanderbilt Co., Norwalk, Connecticut.
  • ESCORENE LD400 is available from ExxonMobil Chemical Co., Houston, Texas.
  • Paraffin 1236 is available from C.P. Hall Co., Chicago, Illinois.
  • DICUP 40KE is available from Hercules, Inc., Wilmington Delaware.
  • the medium voltage cable compound is one which further meets the Insulated Cable Engineers Association (ICEA) specifications for medium voltage compounds. These specifications include:
  • dielectric constant of less than 4.0, and dissipation factor of less than 0.015 (ASTM Dl 50-98);
  • Heat aging properties greater than 80% tensile retention and greater than 80%) elongation retention after aging for 14 days at 121 °C (ExxonMobil Chemical Co. test procedure);
  • cable coating compounds having superior processing and other characteristics can be formed using a polymer component that includes an ethylene alpha r olefin diene terpolymer and an ethylene alpha-olefin copolymer, the ethylene alpha-olefin copolymer having a
  • Compounds can be formed using conventional mixing and extrusion techniques, as illustrated in the Examples herein.
  • the cable coating compounds can be processed using conventional mixing and extruding techniques. It is desirable to extrude the compounds at relatively high extrusion rates, while still maintaining a smooth extrusion surface. It has been surprisingly found that the compounds of the present invention maintain excellent processability, as characterized by relatively low surface roughness.
  • Surface roughness can be measured as described in the Examples below, to obtain a surface profile, i.e., a two-dimensional cross-section of the surface. Imperfections appear as ridges or "shark skin" on the extruded strands.
  • the surface profile includes a mean extrudate surface line, and positive and negative vertical deviations from the mean surface line.
  • the surface roughness is quantified using a combination of two factors: (1) Ra, the mean absolute vertical deviation from the mean extrudate surface line, in microns ( ⁇ m); and
  • Rt the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line, in microns ( ⁇ m).
  • Roughness Factor (R) is defined as:
  • R Ra + 0.1Rt and incorporates both the Ra and Rt terms.
  • Rt is given a lower weighting to adjust for its magnitude relative to Ra. R is dependent upon the extrusion rate and temperature.
  • Extruded compounds of the present invention can be characterized by the surface roughness factor R. Measured at an extrusion rate of 100 rpm and a temperature of 125 °C, extruded compounds have a surface roughness factor R ranging from an upper limit of 20 ⁇ m or 15 ⁇ m or 10 ⁇ m to a lower limit of 5 ⁇ m or 3 ⁇ m or 1 ⁇ m or 0.
  • the present invention is directed to an electrically conductive device, the device including an electrically conductive portion, and an electrically insulating portion.
  • the electrically insulating portion includes a coating compound, which can be any of the coating compounds described herein.
  • Suitable devices include any device having electrically conductive or semi- conductive and electrically insulative portions. A preferred, non-limiting example of such a device is an electrical cable.
  • EP(D)M and ethylene alpha olefin polymers used in the Examples herein are shown in Tables 2 and 3, respectively.
  • Three commercial grades of EP(D)M are shown in Table 2: VISTALONTM 1703P,
  • NORDELTM 2722 and VISTALONTM 8731 are ethylene propylene diene terpolymers made with vinyl norbornene (“VNB”), 1,4-hexadiene (“HEX”) and ethylidene norbornene (“ENB”), respectively, and are also denoted in this description as EP(D)M-VNB, EP(D)M-HEX and EP(D)M-ENB, respectively. All of these EP(D)M grades are made with conventional Ziegler- Natta catalysts and have been applied in commercial in wire and cable applications.
  • VNB vinyl norbornene
  • HEX 1,4-hexadiene
  • ENB ethylidene norbornene
  • VISTALONTM 1703P and VISTALONTM 8731 are commercially available from ExxonMobil Chemical Co., Houston, Texas; NORDELTM 2722 is commercially available from DuPont Dow Elastomers. It should be appreciated that these EPDM materials are merely exemplary, and numerous other EPDMs can be used in the embodiments described herein.
  • EXACTTM 4033 containing butene as comonomer
  • EXACTTM 8201 containing octene as comonomer
  • EO octene as comonomer
  • EXACTTM 4033 containing butene as comonomer
  • EXACTTM 8201 containing octene as comonomer
  • EXACT polymers have similar characteristics to the EP(D)M grades typically used in medium voltage insulation, low density and low MI. These attributes translate into good flexibility and sufficient melt strength to limit sagging during cable extrusion process. Both grades are made with a single- site metallocene catalyst and therefore have narrow molecular weight distribution and compositional distribution.
  • EXACT polymers are available from ExxonMobil Chemical Co., Houston, TX.
  • Polymer molecular weights are measured from gel permeation chromatography (GPC) using a differential refractive index detector (DRI) or a low angle laser light scattering (LALLS) detector. Lower moments of the molecular weight distribution, such as number average molecular weight (Mn) are obtained using a DRI. Higher moments, such as weight average molecular weight (Mw) and Z average molecular weight (Mz)are obtained from light scattering.
  • DRI differential refractive index detector
  • LALLS low angle laser light scattering
  • melt index ratio is commonly used to assess the degree of branching.
  • Melt Index Ratio is defined as the ratio of the melt flow rates measured at two different pressures, i.e., with two different load conditions.
  • the lower pressure measurement is made with a load of 2.16 kg and denoted I (sometimes referred to as "melt index")
  • the higher pressure measurement is made with a load of either 10 kg and denoted I 10 , or a load of 21.6 kg and denoted I 21 .
  • the MIR is thus expressed as either a ratio I 21 /I 2 or I 10 /I .
  • a higher MIR reflects more shear thinning and is generally indicative of enhanced processibility.
  • Cure characteristics (M L , M H , TS2, TC90, cure state (M H -M L ) and cure rate) were measured in accordance with ASTM D 2084-95, and are reported in the following units: M , dNm; M H , dNm; Ts2, min; Tc90, min; cure state, dNm; and cure rate, dNm/min.
  • Hardness was measured in accordance with ASTM D 2240-91 and is reported in units of Shore A.
  • Modulus was measured in accordance with ASTM D 412-92 and is reported in units of MPa.
  • Tensile strength was measured in accordance with ASTM D 412-92 and is reported in units of MPa.
  • Elongation was measured in accordance with ASTM D 412-92 and is reported in units of percent (%).
  • Heat aged elongation was measured after 14 days aging at 150 °C and is reported in units of percent retention.
  • Dissipation Factor was measured in accordance with ASTM D 150-98, with the samples aged in 90 °C water, and using a 600 V alternating current source at 60 s " , and is reported in units of percent (%>).
  • Dielectric constant was measured in accordance with ASTM D 150-98, with the samples aged in 90 °C water, and using a 600 V alternating current source at 60 s " , and is dimensionless.
  • Composition Distribution Breadth Index provides a measure of composition distribution.
  • the definition of Composition Distribution Breadth Index (CDBI), and the method of determining CDBI can be found in U.S. Patent No. 5,206,075 and PCT publication WO 93/03093. From the weight fraction versus composition distribution curve, the CDBI is determined by establishing the weight percentage of a sample that has a comonomer content within 50% of the median comonomer content on each side of the median.
  • the CDBI of a copolymer is readily determined utilizing well known techniques for isolating individual fractions of a sample of the copolymer. One such technique is Temperature Rising Elution Fractionation (TREF) as described in Wild, et al., J Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982).
  • TREF Temperature Rising Elution Fractionation
  • a solubility distribution curve is first generated for the copolymer. This may be accomplished using data acquired from the TREF technique described above. This solubility distribution curve is a plot of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a weight fraction versus composition distribution curve. For the purpose of simplifying the correlation of composition with elution temperature, all fractions are assumed to have a Mn > 15,000, where Mn is the number average molecular weight of the fraction. Any low weight fractions present generally represent a trivial portion of the copolymers. The remainder of this description and the appended claims maintain this convention of assuming all fractions have Mn > 15,000 in the CDBI measurement.
  • the total mixing time was seven minutes.
  • the clay was added in three stages at different time intervals for effective incorporation.
  • the dump temperature of the compounds was typically 120°C.
  • the compounds discharged from the Banbury mixer were sheeted out in a two roll mill.
  • the peroxide curatives were added on the mill and ingested into the compound.
  • the compounds were press cured for 20 minutes at 165 °C.
  • the smoothness of the extrudates was analyzed using a Mitutoyo SURFTESTM SV-500 surface characterizing instrument.
  • the instrument is equipped with a diamond stylus that moves over the surface of the extrudate under examination and records a surface profile, i.e., a two-dimensional cross-section of the surface along the path of travel of the stylus.
  • the surface profile is analyzed as described above to obtain a surface roughness factor R.
  • Table 5 shows the cure characteristics and physical properties of compounds containing combinations of EP(D)M-VNB elastomers (VISTALONTM 1709P, described above) with an ethylene alpha-olefin polymer, EXACTTM 8201.
  • Example 2 is a comparative example without the addition of an ethylene alpha- olefm polymer.
  • Example 1 is a comparative example showing a typical commercial formulation using an EP(D)M-HEX EP(D)M and no ethylene alpha- olefin; such formulations are available commercially as SUPEROHMTM 3728 type compounds.
  • Example 10 is a control having no EP(D)M polymer.
  • Each Example is a compound formulated as in Table 1, except that the EP(D)M of Table 1 has been replaced with the polymer mixture as shown in Table 5. Note that control or comparative example numbers are denoted by a "C".
  • EP(D)M-VNB 100 80 70 60 50 40 30 20 0
  • Table 6 shows the extrusion properties of the compounds in Table 5. Examples 3 through 6 are smoother or as smooth as Example 2 (comparative) at 100 rpm. Examples 7 and 8 are smoother than Example 1 (comparative). TABLE 6: Processing Characteristics
  • Table 7 shows the electrical properties, including dissipation factor, dielectric constant and breakdown strength, of the compounds in Table 5. TABLE 7: Electrical Performance
  • EP-VNB 100 80 70 60 50 40 30 20
  • Examples 11-19 are comparative examples showing the properties of cable coating compounds similar to those of discussed above, but using EXACTTM 4033 as the ethylene alpha-olefin.
  • EXACTTM 4033 is a metallocene ethylene-butene copolymer, but with a Melt Index Ratio I 10 I 2 of 5.6 (i.e., less than the minimum of 7 for copolymers of the invention) and a Melt Index Ratio I21/I2 of 17 (i.e., less than the minimum of 20 for copolymers of the invention).
  • Comparative Examples 11 and 19 are control samples, with no ethylene alpha-olefin and no ethylene alpha-olefin diene, respectively.
  • Examples 20-33 show several properties of compounds prepared and formulated as described above, except that the amount of clay in the compound is varied. Table 11 summarizes the compounds used. Note that the amounts of EP(D)M-VNB, EXACTTM 8201 and clay are in units of parts by weight, based on a total of 160 parts of these three components. The remaining components (Table 1) are unchanged in relative proportions. Note that Examples 20, 27 and 28 are controls, and are marked with a "C”. TABL E l l
  • Table 12 summarizes several properties of the compounds shown in Table 11.

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Abstract

Power cable coating compounds are disclosed, the coating compounds including an ethylene alpha-olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio I10/I2 of at least 7 and/or a Melt Index Ratio I21/I2 of at least 20. In various embodiments, the ethylene alpha-olefin copolymer can be present in the coating compound in amounts up to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer. Also disclosed are electrical devices including extruded coating compounds, the extruded compounds having low surface roughness at high extrusion rates.

Description

BLENDS OF EPDM AND METALLOCENE PLASTOMERS FOR WIRE AND CABLE APPLICATIONS
1. FIELD OF THE INVENTION The present invention is directed generally to coating compounds for electrical applications, and to electrical devices including such coating compounds. More particularly, the coating compounds include an ethylene alpha- olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio ol of at least 7 and/or a Melt Index Ratio I 1/I2 of at least 20, and to electrical devices including extruded coating compounds, the extruded compound's having low surface roughness at high extrusion rates.
2. BACKGROUND
A wide variety of polymeric materials have been utilized as electrical insulating materials for power cables and other electrical devices. Typical insulating compounds include elastomers such as ethylene, α-olefin, non- conjugated diene terpolymers (EPDM), along with fillers and various additives. These EPDM polymers can provide good insulating properties, but usually require relatively slow extrusion rates, because surface characteristics of the extrudate in a compound based on these elastomeric polymers will not be as smooth as desired if the extrusion rates are higher. U.S. Patent No. 5,674,613 discloses that compounds containing ethylene propylene vinyl norbornene elastomers (EP(D)M- VNB) have enhanced cure characteristics, good electrical properties characterized by low power factor loss, enhanced extrusion rates and a smoother extrusion surface, compared to compounds containing commercial EPDM polymers such as those using ethylidine norbornene (ENB) or 1,4-hexadiene non-conjugated diene monomers. The enhanced extrusion characteristics are attributed to a high level of long chain branching. However the high level of branching also degrades the compound physical properties, notably elongation to break. U.S. Patent Nos. 5,763,533 and 5,952,427 disclose that the physical properties of EP(D)M-VNB polymers can be improved by combination with metallocene-catalyzed ethylene alpha-olefin copolymers. The amount of ethylene alpha-olefin copolymer that could be used is limited, however, by processability problems that occur at high ethylene alpha-olefin content.
It would be desirable to have a polymeric composition suitable for use in compounds for electrical applications, such as cable coating compounds, which exhibit good electrical and mechanical properties, while allowing higher levels of ethylene alpha-olefin incorporation, without sacrificing extrusion processability and extruded surface smoothness at relatively high (and thus economically advantageous) extrusion rates.
3. SUMMARY
It has been surprisingly found that power cable coating compounds can be prepared with very high levels of ethylene alpha-olefin copolymers blended with an ethylene alpha olefin diene terpolymer, while still maintaining excellent mechanical, electrical and processing characteristics. This surprising result is achieved at least in part by proper selection of the ethylene alpha-olefin copolymer.
In one aspect, the present invention is directed to a power cable coating compound, the coating compound including ' an ethylene alpha-olefin diene elastomeric terpolymer, and an ethylene alpha-olefin copolymer having a Melt Index Ratio I10 I2 of at least 7.
In another aspect, the ethylene alpha-olefin copolymer has a Melt Index Ratio I21/I2 of at least 20.
In various embodiments, the ethylene alpha-olefin copolymer is present in the coating compound in an amount of from 10 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer, or in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer, or in an amount greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
In various embodiments, the ethylene alpha-olefin diene elastomeric terpolymer has one or more of: a branching index less than 0.5; from 50 to 90 mol % ethylene-derived units; from 0.1 to 1.5 mol % diene-derived units; and a ratio Mw/M„ greater than 10.
In another embodiment, the present invention is directed to an electrically conductive device, the device including an electrically conductive portion, and an electrically insulating portion. The electrically insulating portion includes a coating compound, which can be any of the coating compounds described herein. Suitable devices include any device having electrically conductive or semi- conductive and electrically insulative portions. A preferred, non-limiting example of such a device is an electrical cable. Extruded compounds according to the present invention have good processability characteristics at high extrusion rate, characterized by a low surface roughness factor as defined herein. Thus, in one aspect, the present invention provides an electrically conductive device including an extruded coating compound having an extrusion profile measured from a sample extruded at 100 rpm and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by
R = Ra + 0.1Rt, Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
4. DETAILED DESCRIPTION In one embodiment, the present invention is directed to a power cable coating compound including an ethylene alpha-olefin diene elastomeric terpolymer and an ethylene alpha-olefin copolymer. The ethylene alpha-olefin copolymer, as described below, has a Melt Index Ratio I10/I2 of at least 7.
As used herein, the term "power cable coating compound" or simply "compound" is used to mean a polymer component or components in combination with fillers, accelerants, curatives, extenders and other components commonly used in the art to form a material having the requisite processing, heat aging, electrical and other properties suitable for use as an insulative coating layer in an electrical cable. Power cable coating compounds are described in more detail below.
Ethylene Alpha-Olefin Terpolymer
Embodiments of the present invention include an ethylene alpha-olefin elastomer. The elastomer is a terpolymer of ethylene; an alpha olefin, such as propylene; and a non-conjugated diene. Non-conjugated dienes useful as co- monomers preferably are straight or branched chain hydrocarbon di-olefins or cycloalkenyl-substituted alkenes, having about 6 to about 15 carbon atoms, for example: (a) straight chain acyclic dienes, such as 1,4-hexadiene and 1,6- octadiene; (b) branched chain acyclic dienes, such as 5-methyl- 1,4-hexadiene; 3,7- dimethyl-l,6-octadiene; and 3,7-dimethyl-l,7-octadiene; (c) single ring alicyclic dienes, such as 1,4-cyclohexadiene; 1,5-cyclo-octadiene and 1,7- cyclododecadiene; (d) multi-ring alicyclic fused and bridged ring dienes, such as tetrahydroindene; norbornadiene; methyl-tetrahydroindene; dicyclopentadiene (DCPD); bicyclo-(2.2.1)-hepta-2,5-diene; alkenyl, alkylidene, cycloalkenyl and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene (MNB), 5- propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-(4-cyclopentenyl)-2- norbornene, 5 -cyclohexylidene-2 -norbornene, and 5-vinyl-2-norbornene (VNB); (e) cycloalkenyl-substituted alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene, and vinyl cyclododecene. Preferred non-conjugated dienes are 5-ethylidene-2-norbornene (ENB), 1,4-hexadiene, dicyclopentadiene (DCPD), norbornadiene, and 5-vinyl-2- norbornene (VNB), with VNB being most preferred. Note that throughout this application the terms "non-conjugated diene" and "diene" are used interchangeably.
The elastomer can contain ethylene-derived units in a range from a lower limit of 50, or 60, or 65, or 68 mole percent to an upper limit of 80 or 85 or 90 mole percent, based on the total moles of monomer-derived units in the polymer. The elastomer can contain alpha-olefin-derived units in a range from a lower limit of 10 or 15 or 20 mole percent to an upper limit of 32 or 35 or 40 or 50 mole percent, based on the total moles of monomer-derived units in the polymer. The elastomer can contain the non-conjugated diene-derived units in a range of from a lower limit of 0.1 or 0.16 mole percent to an upper limit of 0.4 or 1.5 or 5 mole percent, based on the total moles of monomer-derived units in the polymer. The elastomeric polymer can also be characterized by a Mooney viscosity (ML [1+4] 125 °C ) of from 10 to 80, and a molecular weight distribution Mw Qp ; ALLS /
Mn,GPC,DRI (Mw Mn) greater than 6-
As noted above, a preferred non-conjugated diene is vinyl norbornene. Although not wishing to be bound by theory, the Ziegler polymerization of the pendent double bond in vinyl norbornene (VNB) is believed to produce a highly branched ethylene, alpha-olefin, vinyl norbornene elastomeric polymer. This method of branching permits the production of ethylene, alpha-olefin, vinyl norbornene elastomeric polymers substantially free of gel which would normally be associated with cationically branched ethylene, alpha-olefin, vinyl norbornene elastomeric polymers containing, for instance, a less-preferred non-conjugated diene such as 5-ethylidene-2-norbornene or 1,4-hexadiene. The synthesis of substantially gel-free ethylene, alpha-olefin, vinyl norbornene elastomeric polymers containing vinyl norbornene is discussed in Japanese laid open patent applications JP S61-151758 and JP S62-210169. In a particular embodiment, a procedure suitable for preparing ethylene alpha-olefin diene terpolymers is as follows. The catalysts used are VOCl3 (vanadium oxytrichloride) or VC14 (vanadium tetrachloride) with the latter as the preferred catalyst. The co-catalyst is chosen from (i) ethyl aluminum sesqui chloride (SESQUI), (ii) diethyl aluminum chloride (DEAC), and (iii) equivalent mixture of diethyl aluminum chloride and triethyl aluminum (TEAL). As shown in U.S. Patent No. 5,763,533 (Figure 8), the choice of co-catalyst influences the composition distribution in the polymer. An elastomer with a broader composition distribution is expected to provide better tensile strength in a cable coating compound. The polymerization is carried out in a continuous stirred tank reactor at 20-65 °C at a residence time of 6-15 minutes and a pressure of 7 kg/cm2. The concentration ratio of vanadium to alkyl is from 1 to 4 to 1 to 8. About 0.3 to 1.5 kg of polymer is produced per gram of catalyst fed to the reactor. The polymer concentration in the hexane solvent is in the range of 3-7% by weight. As reported in U.S. Patent No. 5,763,533, the synthesis of ethylene, alpha-olefin, vinyl norbornene polymers was conducted both in a laboratory pilot unit (output about 4 kg/day), a large scale semi works unit (output lT/day), and a commercial scale production unit (output 200,000 kg/day).
A discussion of catalysts suitable for polymerizing the elastomeric polymer or other catalysts and co-catalysts contemplated can be found in Japanese laid open patent applications JP S61-151758 and JP S62-210169. The resulting polymers had the following molecular characteristics:
The intrinsic viscosity measured in decalin at 135 °C was in the range of 1 to 2 dL/g. The molecular weight distribution (MW;LALLS/Mn GPC DRI) was greater than 10. The branching index was in the range of 0.1 to 0.3.
Metallocene catalysis to form the ethylene alpha-olefin diene terpolymer is also contemplated. Suitable metallocene compounds, activators, and processes are well known in the art and can be found in U.S. Patent No. 5,763,533 and references cited therein.
For peroxide cure applications, ethylene, alpha-olefin, diene monomer elastomeric polymers wherein the diene monomer is vinyl norbornene require lower levels of peroxide to attain the same cure state, compared to analogous polymers wherein the diene monomer is ethylidene norbornene, at the same level of incorporated diene. Typically, 20 to 40 % lower peroxide consumption can be realized using ethylene, alpha-olefin, vinyl norbornene. The efficiency of vinyl norbornene in providing high crosslink density with peroxide vulcanization also permits a reduction in the overall diene level to attain the same cure state as with ethylidene norbornene polymers, and results in enhanced heat aging performance. The unique combinations of improved processability, lower peroxide usage and enhanced heat aging are particular advantages provided by ethylene, alpha-olefin, vinyl norbornene terpolymers over less preferred terpolymers containing non- conjugated dienes such as ethylidene norbornene or 1-4, hexadiene.
Molecular weight distribution (MWD) is a measure of the range of molecular weights within a given polymer sample. It is well known that the breadth of the MWD can be characterized by the ratios of various molecular weight averages, such as the ratio of the weight average molecular weight to the number average molecular weight, Mw/Mn, or the ratio of the Z-average molecular weight to the weight average molecular weight, Mz/Mw. Mz, Mw and Mn can be measured using gel permeation chromatography
(GPC), also known as size exclusion chromatography (SEC). This technique utilizes an instrument containing columns packed with porous beads, an elution solvent, and detector in order to separate polymer molecules of different sizes. In a typical measurement, the GPC instrument used is a Waters chromatograph equipped with ultrastyro gel columns operated at 145 °C. The elution solvent used is trichlorobenzene. The columns are calibrated using sixteen polystyrene standards of precisely known molecular weights. A correlation of polystyrene retention volume obtained from the standards, to the retention volume of the polymer tested yields the polymer molecular weight. Average molecular weights M can be computed from the expression:
M = -
∑X,M" i where Nj is the number of molecules having a molecular weight Mj. When n = 0, M is the number average molecular weight Mn. When n = 1, M is the weight average molecular weight Mw. When n = 2, M is the Z-average molecular weight Mz. The desired MWD function (e.g., Mw/Mn or Mz/Mw) is the ratio of the corresponding M values. Measurement of M and MWD is well known in the art and is discussed in more detail in, for example, Slade, P. E. Ed., Polymer Molecular Weights Part II, Marcel Dekker, Inc., NY, (1975) 287-368; Rodriguez, F., Principles of Polymer Systems 3rd ed., Hemisphere Pub. Corp., NY, (1989) 155-160; U.S. Patent No. 4,540,753; Nerstrate et al., Macromolecules, vol. 21, (1988) 3360; and references cited therein
The relative degree of branching in the ethylene, alpha-olefin, diene monomer terpolymer is determined using a branching index factor. Calculating the branching index factor requires a series of three laboratory measurements of polymer properties in solutions: (i) weight average molecular weight (MW LALLS) measured using a low angle laser light scattering (LALLS) technique; (ii) weight average molecular weight (MW ΓJRT); and (iii) viscosity average molecular weight (Mv DRJ) using a differential refractive index detector
(DRI); and (iv) intrinsic viscosity (IV) measured in decalin at 135° C. The branching index (BI) is defined as: p _ y,brJylw,DRI , ALLs -v,DRI
where Mv br = k(IV)1/a, and 'a' is the Mark-Houwink constant (= 0.759 for ethylene, alpha-olefin, diene monomer in decalin at 135° C). From equation (1), it follows that the branching index for a linear polymer is 1.0, and for branched polymers the extent of branching is defined relative to the linear polymer. Since at a constant Mn, (Mw)branch > (Mw)linear, BI for a branched polymers is less than 1.0, and a smaller BI value denotes a higher level of branching. It should be noted that this method indicates only the relative degree of branching and not a quantified amount of branching as would be determined using a direct measurement, such as by nuclear magnetic resonance (NMR). A detailed description of these measurements and calculations can be found in VerStrate, "Ethylene-Propylene Elastomers", Encyclopedia of Polymer Science and Engineering, 6, 2nd edition, (1986). The ethylene alpha-olefin diene terpolymer can have a molecular weight distribution Mw/Mn of greater than 6, or alternatively greater than 10.
The ethylene alpha-olefin diene terpolymer can have a branching index less than 1.0, less than 0.9, less than 0.7, 0.5, less than 0.4, or less than 0.3, and greater than 0.05, or greater than 0.1.
Ethylene Alpha-Olefin Copolymer
Embodiments of the present invention also include an ethylene alpha- olefin copolymer. It has been surprisingly discovered that ethylene alpha-olefin copolymers can be used with ethylene alpha-olefin diene elastomers in cable coating compounds in much higher levels than previously thought practical due to processibility (melt fracture) problems at relatively high extrusion rates. In particular, it has been surprisingly found that, by selecting a specific type of ethylene-alpha olefϊn copolymer as described below, cable coating compounds can be formed having a wide range of ethylene alpha-olefin content, while still maintaining good electrical and processability properties.
Suitable ethylene alpha-olefins are metallocene-catalyzed copolymers of ethylene and an alpha-olefin comonomer, the alpha-olefin being a C3-C2o α-olefm and preferably a C3-C12 -olefins. The α-olefin comonomer can be linear or
-branched, and two or more comonomers can be used, if desired. Examples of suitable alpha-olefin comonomers include propylene, linear C4-C12 α-olefins, and α-olefins having one or more C C alkyl branches. Specific examples include propylene; 3 -methyl- 1-butene; 3,3-dimethyl-l-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; ethyl, methyl or dimethyl-substituted 1-decene, or 1-dodecene. Preferred comonomers include ethylene, 1-butene, 1-pentene, 3 -methyl- 1-butene, 1-hexene, 3 -methyl- 1-pentene, 4-methyl- 1-pentene, 3,3-dimethyl-l-butene, 1-heptene, 1-hexene with a methyl substituent on any of C -C5, 1-pentene with two methyl substituents in any stoichiometrically acceptable combination on C3 or C , 3-ethyl-l-pentene, 1-octene, 1-pentene with a methyl substituent on any of C3 or
' C , 1-hexene with two methyl substituents in any stoichiometrically acceptable combination on C3-C5, 1-pentene with three methyl substituents in any stoichiometrically acceptable combination on C3 or C , 1-hexene with an ethyl substituent on C3 or C4, 1-pentene with an ethyl substituent on C3 and a methyl substituent in a stoichiometrically acceptable position on C3 or C4, 1-decene, 1-nonene, 1-nonene with a methyl substituent on any of C3-C , 1-octene with two methyl substituents in any stoichiometrically acceptable combination on C3-C , 1-heptene with three methyl substituents in any stoichiometrically acceptable combination on C3-C6, 1-octene with an ethyl substituent on any of C -C7, 1-hexene with two ethyl substituents in any stoichiometrically acceptable combination on C3 or C4, and 1-dodecene. It should be appreciated that the list of comonomers above is merely exemplary, and is not intended to be limiting. A particularly preferred comonomer is octene.
The ethylene alpha-olefin copolymer has the following characteristics:
(i) a molecular weight distribution Mw/Mn ranging from a lower limit of 1.5 or 1.8 to an upper limit of 40 or 20 or 10 or 5 or 3;
(ii) a Composition Distribution Breadth Index (CDBI) greater than 50% or greater than 60% or greater than 65%;
(iii) a Melt Index Ratio I10/l2 ranging from a lower limit of 7 or 8 to an upper limit of 9 or 10; and (iv) a Melt Index Ratio I21/I2 ranging from a lower limit of 20 or 25 or 30 to an upper limit of 40 or 45 or 50.
Examples of suitable ethylene alpha-olefms include several of the copolymers sold under the trademark EXACT and available from the ExxonMobil Chemical Co., Houston, Texas, as well as the ENGAGE polymers available from DuPont/Dow. Particular EXACT copolymers include EXACT 0201, EXACT 0201HS, EXACT 0203, EXACT 8201, EXACT 8203, EXACT 210, and EXACT 8210, to name but a few. Typical ethylene alpha-olefins will have a density of 0.86 or 0.88 to 0.91 or 0.92 g/cm3; and a melt index I2 of from a lower limit of 0.1 dg/min or 0.5 dg/min or 1.0 dg/min to an upper limit of 10 dg/min or 50 dg/min or 100 dg/min, consistent with the Melt Index Ratios described above.
The appropriate amount of alpha-olefin comonomer in the copolymer can be readily determined by one skilled in the art, based on the desired density of the copolymer.
In one embodiment, the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount of from 10 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
In another embodiment, the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer. In another embodiment, the ethylene alpha-olefin copolymer is present in the cable coating compound in an amount of greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
Cable Coating Compounds
As a specific example, a power cable coating compound suitable for use as an insulator in a "medium voltage" electrical cable, i.e., for voltages up to about
35 kV, can be formulated as shown in Table 1.
TABLE 1 : CONVENTIONAL MEDIUM VOLTAGE CABLE COMPOUND
Figure imgf000012_0001
* parts by weight, based on 100 parts by weight polymer
All of the components listed in Table 1 are readily available from various commercial sources. The leftmost column of Table 1 indicates tradenames and/or typical suppliers of these components. TRANSLINK 37 is available from Englehard, Iselin, New Jersey. DRIMIX A172 is available from Kenrich Petrochemicals, Bayonne, New Jersey. ERD 90 is available from Rhein Chemie Corp, Trenton New Jersey. AGERLITE MA is available from R.T. Vanderbilt Co., Norwalk, Connecticut. ESCORENE LD400 is available from ExxonMobil Chemical Co., Houston, Texas. Paraffin 1236 is available from C.P. Hall Co., Chicago, Illinois. DICUP 40KE is available from Hercules, Inc., Wilmington Delaware. Preferably, the medium voltage cable compound is one which further meets the Insulated Cable Engineers Association (ICEA) specifications for medium voltage compounds. These specifications include:
Electrical properties: dielectric constant of less than 4.0, and dissipation factor of less than 0.015 (ASTM Dl 50-98);
Physical properties: tensile strength greater than 8.2 MPa, and elongation to break greater than 250% (ASTM D412-92);
Heat aging properties: greater than 80% tensile retention and greater than 80%) elongation retention after aging for 14 days at 121 °C (ExxonMobil Chemical Co. test procedure); and
No gels:_ an absence of gelation regions in excess of 0.254 mm (ExxonMobil Chemical Co. test procedure).
It has been surprisingly found that cable coating compounds having superior processing and other characteristics can be formed using a polymer component that includes an ethylene alpharolefin diene terpolymer and an ethylene alpha-olefin copolymer, the ethylene alpha-olefin copolymer having a
Melt Index Ratio I10/I2 of at least 7.
Compounds can be formed using conventional mixing and extrusion techniques, as illustrated in the Examples herein.
Extruded Compounds
The cable coating compounds can be processed using conventional mixing and extruding techniques. It is desirable to extrude the compounds at relatively high extrusion rates, while still maintaining a smooth extrusion surface. It has been surprisingly found that the compounds of the present invention maintain excellent processability, as characterized by relatively low surface roughness.
Surface roughness can be measured as described in the Examples below, to obtain a surface profile, i.e., a two-dimensional cross-section of the surface. Imperfections appear as ridges or "shark skin" on the extruded strands. The surface profile includes a mean extrudate surface line, and positive and negative vertical deviations from the mean surface line. The surface roughness is quantified using a combination of two factors: (1) Ra, the mean absolute vertical deviation from the mean extrudate surface line, in microns (μm); and
(2) Rt, the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line, in microns (μm). The Roughness Factor (R) is defined as:
R = Ra + 0.1Rt and incorporates both the Ra and Rt terms. Rt is given a lower weighting to adjust for its magnitude relative to Ra. R is dependent upon the extrusion rate and temperature.
Extruded compounds of the present invention can be characterized by the surface roughness factor R. Measured at an extrusion rate of 100 rpm and a temperature of 125 °C, extruded compounds have a surface roughness factor R ranging from an upper limit of 20 μm or 15 μm or 10 μm to a lower limit of 5 μm or 3 μm or 1 μm or 0.
In another embodiment, the present invention is directed to an electrically conductive device, the device including an electrically conductive portion, and an electrically insulating portion. The electrically insulating portion includes a coating compound, which can be any of the coating compounds described herein. Suitable devices include any device having electrically conductive or semi- conductive and electrically insulative portions. A preferred, non-limiting example of such a device is an electrical cable.
Certain features and advantages of embodiments of the invention are illustrated by the following, non-limiting examples.
6. EXAMPLES
Materials
Certain characteristics of the EP(D)M and ethylene alpha olefin polymers used in the Examples herein are shown in Tables 2 and 3, respectively. Three commercial grades of EP(D)M are shown in Table 2: VISTALON™ 1703P,
NORDEL™ 2722 and VISTALON™ 8731. These products are ethylene propylene diene terpolymers made with vinyl norbornene ("VNB"), 1,4-hexadiene ("HEX") and ethylidene norbornene ("ENB"), respectively, and are also denoted in this description as EP(D)M-VNB, EP(D)M-HEX and EP(D)M-ENB, respectively. All of these EP(D)M grades are made with conventional Ziegler- Natta catalysts and have been applied in commercial in wire and cable applications. VISTALON™ 1703P and VISTALON™ 8731 are commercially available from ExxonMobil Chemical Co., Houston, Texas; NORDEL™ 2722 is commercially available from DuPont Dow Elastomers. It should be appreciated that these EPDM materials are merely exemplary, and numerous other EPDMs can be used in the embodiments described herein.
Two commercial ethylene alpha olefin copolymers having similar melt index (MI) and density are used in the Examples herein: EXACT™ 4033, containing butene as comonomer ("EB") and EXACT™ 8201, containing octene as comonomer ("EO"). These polymers have similar characteristics to the EP(D)M grades typically used in medium voltage insulation, low density and low MI. These attributes translate into good flexibility and sufficient melt strength to limit sagging during cable extrusion process. Both grades are made with a single- site metallocene catalyst and therefore have narrow molecular weight distribution and compositional distribution. EXACT polymers are available from ExxonMobil Chemical Co., Houston, TX.
Figure imgf000016_0001
Figure imgf000016_0002
Polymer Characterization
Polymer molecular weights are measured from gel permeation chromatography (GPC) using a differential refractive index detector (DRI) or a low angle laser light scattering (LALLS) detector. Lower moments of the molecular weight distribution, such as number average molecular weight (Mn) are obtained using a DRI. Higher moments, such as weight average molecular weight (Mw) and Z average molecular weight (Mz)are obtained from light scattering.
For plastomers, the melt index ratio (MIR) is commonly used to assess the degree of branching. Melt Index Ratio is defined as the ratio of the melt flow rates measured at two different pressures, i.e., with two different load conditions. Conventionally, the lower pressure measurement is made with a load of 2.16 kg and denoted I (sometimes referred to as "melt index"), and the higher pressure measurement is made with a load of either 10 kg and denoted I10, or a load of 21.6 kg and denoted I21. The MIR is thus expressed as either a ratio I21/I2 or I10/I . A higher MIR reflects more shear thinning and is generally indicative of enhanced processibility. MIR values reported herein are nominal values reported by the manufacturer. Methods of determining I2, 110 and I21 are generally known and can be found in ASTM 1238. Polymer viscoelastic properties were obtained using a Rubber Process
Analyzer (RPA) 2000 instrument from Alpha Technologies. The measurements were made at 125 °C, a constant strain of 14% (1 degree arc), and an oscillating shear rate range from 0.21 to 209 s"1. The elastic modulus (G'), the loss modulus (G") and the complex viscosity (η*) were measured at varying shear rates. Mooney viscosity was measured in accordance with ASTM Dl 646-99, and is reported in Mooney units.
Cure characteristics (ML, MH, TS2, TC90, cure state (MH-ML) and cure rate) were measured in accordance with ASTM D 2084-95, and are reported in the following units: M , dNm; MH, dNm; Ts2, min; Tc90, min; cure state, dNm; and cure rate, dNm/min.
Hardness was measured in accordance with ASTM D 2240-91 and is reported in units of Shore A.
100%) Modulus was measured in accordance with ASTM D 412-92 and is reported in units of MPa. Tensile strength was measured in accordance with ASTM D 412-92 and is reported in units of MPa. Elongation was measured in accordance with ASTM D 412-92 and is reported in units of percent (%).
Heat aged elongation was measured after 14 days aging at 150 °C and is reported in units of percent retention. Dissipation Factor was measured in accordance with ASTM D 150-98, with the samples aged in 90 °C water, and using a 600 V alternating current source at 60 s" , and is reported in units of percent (%>).
Dielectric constant was measured in accordance with ASTM D 150-98, with the samples aged in 90 °C water, and using a 600 V alternating current source at 60 s" , and is dimensionless.
Composition Distribution Breadth Index (CDBI) provides a measure of composition distribution. The definition of Composition Distribution Breadth Index (CDBI), and the method of determining CDBI, can be found in U.S. Patent No. 5,206,075 and PCT publication WO 93/03093. From the weight fraction versus composition distribution curve, the CDBI is determined by establishing the weight percentage of a sample that has a comonomer content within 50% of the median comonomer content on each side of the median. The CDBI of a copolymer is readily determined utilizing well known techniques for isolating individual fractions of a sample of the copolymer. One such technique is Temperature Rising Elution Fractionation (TREF) as described in Wild, et al., J Poly. Sci., Poly. Phys. Ed., vol. 20, p. 441 (1982).
To determine CDBI, a solubility distribution curve is first generated for the copolymer. This may be accomplished using data acquired from the TREF technique described above. This solubility distribution curve is a plot of the weight fraction of the copolymer that is solubilized as a function of temperature. This is converted to a weight fraction versus composition distribution curve. For the purpose of simplifying the correlation of composition with elution temperature, all fractions are assumed to have a Mn > 15,000, where Mn is the number average molecular weight of the fraction. Any low weight fractions present generally represent a trivial portion of the copolymers. The remainder of this description and the appended claims maintain this convention of assuming all fractions have Mn > 15,000 in the CDBI measurement. Compounds as described below were mixed in a 1600 cm Banbury mixer using a volumetric fill factor of 15%. The density of the compounds ranged from 1.04 to 1.23 g/cm3 depending on the proportion of EP(D)M, plastomer and filler in the formulation. A conventional mixing procedure (polymer first followed by clay and additive ingredients) was used as follows shown in Table 4.
TABLE 4: MIXING PROCEDURE
Figure imgf000019_0001
The total mixing time was seven minutes. The clay was added in three stages at different time intervals for effective incorporation. The dump temperature of the compounds was typically 120°C. The compounds discharged from the Banbury mixer were sheeted out in a two roll mill. The peroxide curatives were added on the mill and ingested into the compound. The compounds were press cured for 20 minutes at 165 °C.
Compound processability assessments were conducted on a Haake RHEOCORD™ 90 extruder. The length to diameter (L/D) of the extruder screw for this extruder is 20/1, the compression ratio of the extruder screw is 2/1. A constricted die with a land length of 0.059" (1.5 mm) and diameter of 0.069" (1.75 mm) was selected for extrudate analysis. The extrusion temperature is maintained in the range of 110 to 125 °C. Extrusion was performed over a range of screw speeds, varying from 25 to 100 rpm. Samples are obtained after the torque and the pressure drop equilibrated to a steady value at a constant screw speed.
The smoothness of the extrudates was analyzed using a Mitutoyo SURFTES™ SV-500 surface characterizing instrument. The instrument is equipped with a diamond stylus that moves over the surface of the extrudate under examination and records a surface profile, i.e., a two-dimensional cross-section of the surface along the path of travel of the stylus. The surface profile is analyzed as described above to obtain a surface roughness factor R.
Examples 1-10
Table 5 shows the cure characteristics and physical properties of compounds containing combinations of EP(D)M-VNB elastomers (VISTALON™ 1709P, described above) with an ethylene alpha-olefin polymer, EXACT™ 8201. Example 2 is a comparative example without the addition of an ethylene alpha- olefm polymer. Example 1 is a comparative example showing a typical commercial formulation using an EP(D)M-HEX EP(D)M and no ethylene alpha- olefin; such formulations are available commercially as SUPEROHM™ 3728 type compounds. Example 10 is a control having no EP(D)M polymer. Each Example is a compound formulated as in Table 1, except that the EP(D)M of Table 1 has been replaced with the polymer mixture as shown in Table 5. Note that control or comparative example numbers are denoted by a "C".
From the data in the Tables, it is evident that the addition of EXACT™ 8201 polymer to the ethylene alpha-olefin diene terpolymer improves the compound tensile strength. The tensile strength is enhanced from 11.9 MPa to 14.8 MPa with the addition of 20 to 80 parts per hundred (phr) of EXACT™ 8201. Similarly, the elongation to break is improved 270% to 440% with the addition of 20 to 80 phr of EXACT™ 8201. TABLE 5: Cure and Physical Properties
EXAMPLE 1C 2C 3 4 5 6 7 8 9 10C
EP(D)M-VNB (phr) 100 80 70 60 50 40 30 20 0
EXACT™ 8201 (phr) 20 30 40 50 60 70 80 100
EP(D)M-HEX (phr) 100
Cure Characteristics
Mooney Scorch
Ms (t3) 132°C (min) 24 18 22 23 21 20 20 20 22 23
Minimum Viscosity 15 10 13 13 13 12 13 13 13 11
ODR - 200°C, 3° Arc
ML (dN-m) 8 6 7 7 8 8 8 8 8 7
MH (dN-m) 98 89 84 81 80 79 78 77 76 66 ts2 (min) 0.7 0.6 0.6 0.7 0.7 0.6 0.6 0.6 0.7 0.6 t90 (min) 2.0 1.7 1.8 1.9 1.9 1.9 1.9 1.9 2.0 2.0
Cure Rate (dN-m/min) 96 110 85 79 73 70 68 64 60 48
MH-ML (dN-m) 90 85 77 75 72 71 71 70 68 59
Physical Properties cured 20 min, 165°C
Hardness (Shore A) 84 89 90 91 92 91 92 92 93 92
100% Modulus (MPa) 6.1 6.5 7.1 7.5 7.5 7.7 8.1 8.4 8.6 8.6
200% Modulus (MPa) 10.1 10.4 10.8 11.3 11.0 11.2 11.5 11.9 12.0 11.9
300% Modulus (MPa) . 11.9 - 12.5 13.1 12.6 13.0 13.0 13.5 13.7 13.5
Tensile Strength (MPa) 11.9 11.9 12.5 13.4 13.5 13.7 13.8 14.4 14.8 15.2
Elongation (%) 310 270 320 320 370 390 400 400 440 520
Table 6 shows the extrusion properties of the compounds in Table 5. Examples 3 through 6 are smoother or as smooth as Example 2 (comparative) at 100 rpm. Examples 7 and 8 are smoother than Example 1 (comparative). TABLE 6: Processing Characteristics
EXAMPLE 1C 2C 3 4 5 6 7 8 9 10C
EP(D)M-VNB (phr) 100 80 70 60 50 40 30 20
EXACT™ 8201 (phr) 20 30 40 50 60 70 80 100
EP(D)M-HEX (phr) 100
Processing Attributes
Surface Roughness (Ra) (μm at rpm)
25 rpm 9 3 4 4 4 5 - 5 6 29
50 rpm 7 5 3 3 3 5 4 5 6 12
75 rpm 7 4 3 3 3 4 4 5 5 11
100 rpm 7 4 2 3 3 4 5 5 8 26
Surface Roughness (Rt) (μm at rpm)
25 rpm - 24 33 31 33 40 - 44 44 142
50 rpm 55 22 26 27 41 35 39 53 105
75 rpm 52 27 30 26 29 34 32 53 56 116
100 rpm 60 33 23 20 28 33 43 43 66 167
Roughness Factor (R) (μm at rpm)
100 rpm 13 7 4 5 6 7 9 9 15 20
Extrusion Mass Rate (g/min at rpm)
25 rpm 49 46 43 38 50 47 47 49 44 41
50 rpm 107 102 104 105 105 103 99 104 89 87
75 rpm 153 160 157 156 155 144 150 153 141 101
100 rpm 196 203 198 207 203 185 184 200 175 87
Table 7 shows the electrical properties, including dissipation factor, dielectric constant and breakdown strength, of the compounds in Table 5. TABLE 7: Electrical Performance
EXAMPLE 1C 2C 3 4 5 6 7 8 9 10C
EP-VNB (phr) 100 80 70 60 50 40 30 20
EXACT™ 8201 (phr) 20 30 40 50 " 60 70 80 100
EP-HEX (phr) 100
Dielectric Strength (V/mil) 944 923 932 933 926
(V/μm) 37.2 36.3 36.7 36.7 36.5
Dissipation Factor (600V, 60Hz) (days in 90°C water)
0 days (dry) 0.0025 0.0021 0.0022 0.0022 0.0023 0.0022 0.0024 0.0023 0.0025 0.0027
1 day 0.0059 0.0042 0.0041 0.0041 0.0044 0.0040 0.0043 0.0042 0.0042 0.0045
7 days 0.0048 0.0038 0.0036 0.0036 0.0042 0.0034 0.0037 0.0042 0.0042 0.0046
14 days 0.0048 0.0042 0.0036 0.0039 0.0043 0.0037 0.0041 0.0042 0.0043 0.0049
21 days 0.0048 0.0043 0.0037 0.0041 0.0044 0.0040 0.0042 0.0044 0.0045 0.0053
28 days 0.0051 0.0044 0.0040 0.0045 0.0045 0.0040 0.0043 0.0044 0.0046 0.0055
Dielectric Constant
0 days (dry)
2.64 2.57 2.59 2.59 2.60 2.48 2.62 2.57 2.56 2.52
1 day
2.36 2.34 2.35 2.31 2.33 2.27 2.34 2.30 2.32 2.29 7 days
2.39 2.35 2.36 2.32 2.33 2.27 2.34 2.30 2.32 2.30 14 days
2.39 2.35 2.37 2.32 2.33 2.27 2.34 2.29 2.32 2.30 21 days
2.40 2.35 2.37 2.33 2.34 2.28 2.35 2.30 2.33 2.30 28 days
2.41 2.36 2.37 2.33 2.34 2.27 2.35 2.30 2.32 2.31
Examples 11-19 (Comparative)
Examples 11-19 are comparative examples showing the properties of cable coating compounds similar to those of discussed above, but using EXACT™ 4033 as the ethylene alpha-olefin. As shown above, EXACT™ 4033 is a metallocene ethylene-butene copolymer, but with a Melt Index Ratio I10 I2 of 5.6 (i.e., less than the minimum of 7 for copolymers of the invention) and a Melt Index Ratio I21/I2 of 17 (i.e., less than the minimum of 20 for copolymers of the invention).
Compounds were prepared and tested as described for Examples 1-10. The data are summarized in Tables 8, 9 and 10. Comparative Examples 11 and 19 are control samples, with no ethylene alpha-olefin and no ethylene alpha-olefin diene, respectively.
TABLE 8: COMPARATIVE EXAMPLES, CURE AND PHYSICAL PROPERTIES
EXAMPLE 11 12 13 14 15 16 17 18 19
EP(D)M-VNB (phr) 100 80 70 60 50 40 30 20
EXACT™ 4033 (phr) 20 30 40 50 60 70 80 100
Cure Characteristics
Mooney Scorch
Ms (t3) 132°C (min) 17.3 16.8 17.9 15.5 17.7 10.8 10.0 10.2 9.7
Minimum Viscosity 12.3 17.5 20.2 21.4 23.1 21.6 21.1 20.5 15.5
ODR- 200°C, 3° arc
ML (dN-m) 6 10 11 12 13 13 12 12 10
MH (dN-m) 95 94 90 101 94 100 98 101 95 ts2 (min) 0.6 0.6 0.6 0.6 0.6 0.6 0.6 0.5 0.6 t90 (min) 1.7 1.8 1.8 1.8 1.8 1.9 1.8 1.7 1.9 t98 2.2 2.3 2.3 2.3 2.3 2.3 2.3 2.2 2.4
Cure Rate (dN-m/min) 118 99 82 97 83 91 88 90 73
MH-ML (dN-m) 88 84 79 89 81 88 85 89 85
Physical Properties cured 20 min, 165°C
Hardness (Shore A) 90 91 91 91 92 93 92 94 94
100 % Modulus (MPa) 6.3 6.7 5.6 7.9 6.6 6.7 8.0 8.1 7.8
200 % Modulus (MPa) 9.5 10.0 8.4 11.4 9.9 10.1 11.6 11.8 11.3
300 % Modulus (MPa) - - 10.5 - 11.7 12.2 13.2 13.8 13.1
Tensile Strength (MPa) 9.5 11.2 11.9 12.7 12.5 11.8 13.9 14.5 14.7
Elongation (%) 226 277 382 272 363 331 366 378 471
TABLE 9: COMPARATIVE EXAMPLES, PROCESSING CHARACTERISTICS
EXAMPLE 11 12 13 14 IS 16 17 18 19
EP(D)M-VNE i (phr) 100 80 70 60 50 40 30 20
EXACT™ 4033 (phr) 20 30 40 50 60 70 80 100
Processing Attributes
Surface Rous ;hness (Ra) (μm at rpm)
25 rpm 2 6 - - 21 26 - - -
50 rpm 2.5 5.4 - - 22.4 19.3 - - -
75 rpm - 7.4 - - 19.9 28.5 - - -
100 rpm 2.9 6.8 - - 18.8 37.4 - - -
Surface Roughness (Rt) (μm at rpm)
25 rpm 14 44 - - 155 180 - - -
50 rpm 23 38 - - 140 157 - - -
75 rpm - 62 - - 135 258 - - -
100 rpm 22 48 - - 138 248 - - -
Roughness Factor (R) (μm at rpm)
100 rpm 5.1 12 33 62
TABLE 10: COMPARATIVE EXAMPLES, ELECTRICAL PERFORMANCE
EXAMPLE 11 12 13 14 15 16 17 18 19
EP(D)M-VNB (phr) 100 80 70 60 50 40 30 20
EXACT™ 4033 (phr) 20 30 40 50 60 70 80 100
Electrical Properties
Dissipation Factor (600V, 60Hz) (days in 90°C water)
0 days (dry) 0.0044 0.0036 0.0027 0.0037 0.0037 0.0034 0.0034 0.0038 0.0037
1 day 0.0063 0.0065 0.0061 0.0079 0.0079 0.0070 0.0072 0.0075 0.0077
7 days 0.0062 0.0064 0.0058 0.0076 0.0072 0.0062 0.0067 0.0071 0.0072
14 days 0.0059 0.0059 0.0059 0.0073 0.0070 0.0060 0.0066 0.0069 0.0070
Dielectric Constant
0 days (dry) 2.48 2.60 2.51 2.62 2.63 2.62 2.59 2.64 2.57
1 day 2.34 2.38 2.31 2.44 2.46 2.41 2.33 2.42 2.40
7 days 2.34 2.38 2.32 2.46 2.48 2.41 2.34 2.40 2.38
14 days 2.35 2.38 2.31 2.45 2.48 2.42 2.35 2.41 2.40
Examples 20-33
Examples 20-33 show several properties of compounds prepared and formulated as described above, except that the amount of clay in the compound is varied. Table 11 summarizes the compounds used. Note that the amounts of EP(D)M-VNB, EXACT™ 8201 and clay are in units of parts by weight, based on a total of 160 parts of these three components. The remaining components (Table 1) are unchanged in relative proportions. Note that Examples 20, 27 and 28 are controls, and are marked with a "C". TABL E l l
Example # EP(D)M-VNB EXACT™8201 Calcined Treated Clay
20C 0 95 65
21 30 100 30
22 45 45 70
23 30 100 30
24 65 65 30
25 0 95 65
26 77 27 57
27C 100 0 60
28C 100 0 60
29 45 45 70
30 27 77 57
31 53 53 53
32 100 15 45
33 100 30 30
Table 12 summarizes several properties of the compounds shown in Table 11.
TABLE 12
t
Figure imgf000028_0001
Certain features of the present invention are described in terms of a set of numerical upper limits and a set of numerical lower limits. It should be appreciated that ranges from any lower limit to any upper limit are within the scope of the invention unless otherwise indicated.
All patents, test procedures, and other documents cited in this application are fully incorporated by reference to the extent such disclosure is not inconsistent with this application and for all jurisdictions in which such incorporation is permitted.
What is claimed is:

Claims

1. A power cable coating compound comprising:
(a) an ethylene alpha-olefin diene elastomeric terpolymer; and (b) an ethylene alpha-olefin copolymer having a Melt Index Ratio
I10/I2 of at least 7, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
2. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I10/I of from 7 to 10.
3. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I10/l2 of from 8 to 10.
4. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio L of at least 20.
5. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio i/ of from 25 to 50.
6. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I2ι/I2 of from 30-40.
7. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
8. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of from 30 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
9. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 10.
10. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 5.
11. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 3.
12. The coating compound of claim 1, wherein the ethylene alpha-olefin copolymer is a copolymer of ethylene and 1-octene.
13. The coating compound of claim 1, wherein the diene of the ethylene alpha- olefin elastomeric terpolymer is vinyl norbornene.
14. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a branching index of less than 1.0.
15. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a branching index of less than 0.7.
16. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a branching index of less than 0.5.
17. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a molecular weight distribution Mw/Mn greater than 3.
18. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a molecular weight distribution Mw/Mn greater than 10.
19. The coating compound of claim 1, wherein the ethylene alpha-olefin diene elastomeric terpolymer has from 50 to 90 mol % ethylene-derived units and from 0.1 to 1.5 mol % diene-derived units.
20. A power cable coating compound comprising:
(a) an ethylene alpha-olefin diene elastomeric terpolymer having a branching index less than 1.0 and a molecular weight distribution Mw/Mn greater than 3; and
(b) an ethylene alpha-olefin copolymer having a Melt Index Ratio I10/I2 of at least 7 and a Melt Index Ratio I21/I2 of at least 20, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
21. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio Iι0/I2 of from 7 to 10.
22. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I10/I2 of from 8 to 10.
23. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I21/I2 of from 25 to 50.
24. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I21/I2 of from 30-40.
25. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of greater than 50 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
26. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of from 30 to 90 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
27. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 10.
28. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 5.
29. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 3.
30. The coating compound of claim 21, wherein the ethylene alpha-olefin copolymer is a copolymer of ethylene and 1-octene.
31. The coating compound of claim 21, wherein the diene of the ethylene alpha-olefin elastomeric terpolymer is vinyl norbornene.
32. The coating compound of claim 21, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a branching index of less than 0.7.
33. The coating compound of claim 21, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a branching index of less than 0.5.
34. The coating compound of claim 21, wherein the ethylene alpha-olefin diene elastomeric terpolymer has a molecular weight distribution Mw/Mn greater than 10.
35. The coating compound of claim 21, wherein the ethylene alpha-olefin diene elastomeric terpolymer has from 50 to 90 mol % ethylene-derived units and from 0.1 to 1.5 mol % diene-derived units.
36. A power cable coating compound comprising: (a) an ethylene alpha-olefin vinyl norbornene elastomeric terpolymer; and (b) an ethylene alpha-olefin copolymer having a Melt Index Ratio
L0/I2 of at least 7, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin vinyl norbornene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
37. A power cable coating compound comprising: (a) an ethylene alpha-olefin vinyl norbornene elastomeric terpolymer having a branching index less than 1.0 and a molecular weight distribution Mw/Mn greater than 3; and (b) an ethylene alpha-olefin copolymer having a Melt Index Ratio I10/I2 of at least 7 and a Melt Index Ratio I21/I2 of at least 20, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount of greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin vinyl norbornene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
38. An electrically conductive device comprising:
(a) an electrically conductive portion; and
(b) an electrically insulating portion comprising:
(i) an ethylene alpha-olefin diene elastomeric terpolymer; and (ii) an ethylene alpha-olefin copolymer having a Melt Index
Ratio Iιo/I2 of at least 7, wherein the ethylene alpha-olefin copolymer is present in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
39. The electrically conductive device of claim 39, wherein the coating compound is an extruded compound having an extrusion profile measured from a sample extruded at 100 m and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by
R = Ra + 0.1Rt,
Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
40. The electrically conductive device of claim 40, wherein the surface roughness factor R is less than 15.
41. The electrically conductive device of claim 40, wherein the surface roughness factor R is less than 10.
42. The electrically conductive device of claim 39, wherein the device is a medium voltage power cable.
43. An electrically conductive device comprising:
(a) an electrically conductive portion; and
(b) an electrically insulating portion comprising:
(i) an ethylene alpha-olefin diene elastomeric terpolymer having a branching index less than 1.0 and a molecular weight distribution Mw/Mn greater than 3; and (ii) an ethylene alpha-olefin copolymer having a Melt Index
Ratio I10/I2 of at least 7 and a Melt Index Ratio I21/I2 of at least 20, wherein the ethylene alpha-olefin copolymer is present in an amount of greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric terpolymer and the ethylene alpha-olefin copolymer.
44. The electrically conductive device of claim 44, wherein the coating compound is an extruded compound having an extrusion profile measured from a sample extruded at 100 m and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by
R = Ra + 0.1Rt, Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
45. The electrically conductive device of claim 45, wherein the surface roughness factor R is less than 15.
46. The electrically conductive device of claim 45, wherein the surface roughness factor R is less than 10.
47. The electrically conductive device of claim 44, wherein the device is a medium voltage power cable.
48. An electrically conductive device comprising: (a) an electrically conductive portion; and
(b) an electrically insulating portion comprising:
(i) an ethylene alpha-olefin vinyl norbornene elastomeric teφolymer; and (ii) an ethylene alpha-olefin copolymer having a Melt Index Ratio 110/I2 of at least 7, wherein the ethylene alpha-olefin copolymer is present in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin vinyl norbornene elastomeric teφolymer and the ethylene alpha-olefin copolymer.
49. The electrically conductive device of claim 49, wherein the coating compound is an extruded compound having an extrusion profile measured from a sample extruded at 100 φm and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by
R = Ra + 0.1Rt,
Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
50. The electrically conductive device of claim 50, wherein the surface roughness factor R is less than 15.
51. The electrically conductive device of claim 50, wherein the surface roughness factor R is less than 10.
52. The electrically conductive device of claim 49, wherein the device is a medium voltage power cable.
53. An electrically conductive device comprising:
(a) an electrically conductive portion; and
(b) an electrically insulating portion comprising:
(i) an ethylene alpha-olefin vinyl norbornene elastomeric teφolymer having a branching index less than 1.0 and a molecular weight distribution Mw/Mn greater than 3 ; and
(ii) an ethylene alpha-olefin copolymer having a Melt Index Ratio I10/I2 of at least 7 and a Melt Index Ratio I21/I2 of at least 20, wherein the ethylene alpha-olefin copolymer is present in an amount of greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin vinyl norbornene elastomeric teφolymer and the ethylene alpha-olefin copolymer.
54. The electrically conductive device of claim 54, wherein the coating compound is an extruded compound having an extrusion profile measured from a sample extruded at 100 φm and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by R = Ra + 0.1Rt,
Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
55. The electrically conductive device of claim 55, wherein the surface roughness factor R is less than 15.
56. The electrically conductive device of claim 55, wherein the surface roughness factor R is less than 10.
57. The electrically conductive device of claim 54, wherein the device is a medium voltage power cable.
(EP CLAIMS)
58. A power cable coating compound comprising: (a) an ethylene alpha-olefin diene elastomeric teφolymer; and
(b) an ethylene alpha-olefin copolymer having a Melt Index Ratio
I10/I2 of at least 7, wherein the ethylene alpha-olefin copolymer is present in the coating compound in an amount greater than 30 percent by weight, based on the weight of the ethylene alpha-olefin diene elastomeric teφolymer and the ethylene alpha-olefin copolymer.
59. Coating compound according to claim 58, wherein the ethylene alpha- olefin copolymer has a Melt Index Ratio Iι0/I2 of from 7 to 10.
60. Coating compound of claim 59, wherein the ethylene alpha-olefin copolymer has a Melt Index Ratio I2 of at least 20.
61. Coating compound of according to any of claims 58-60 in which the ethylene alpha-olefin copolymer is present in the coating compound in an amount of from 30 to 90 percent by weight, based on the weight of the ethylene alpha- olefin diene elastomeric teφolymer and the ethylene alpha-olefin copolymer.
62. Coating compound according to any of claims 58-61 in which the ethylene alpha-olefin copolymer has a molecular weight distribution Mw/Mn less than 5.
63. Coating compound according to any of claims 58-62 in which the ethylene alpha-olefin copolymer is a copolymer of ethylene and 1-octene.
64. Coating compound according to any of claims 58-63 in which the diene of the ethylene alpha-olefin elastomeric teφolymer is vinyl norbornene.
65. Coating compound of according to any of claims 58-64 in which the ethylene alpha-olefin diene elastomeric teφolymer has a branching index of less than 1.0.
66. Coating compound according to any of the preceding claims 58-59 in which the ethylene alpha-olefin diene elastomeric teφolymer has a molecular weight distribution Mw/Mn greater than 10.
67. Coating compound according to any of claims 58-66 in which the ethylene alpha-olefin diene elastomeric teφolymer has from 50 to 90 mol % ethylene- derived units and from 0.1 to 1.5 mol % diene-derived units.
68. An electrically conductive device comprising: (a) an electrically conductive portion; and
(b) an electrically insulating portion comprising a compound according to any of claims 58-67:
69. Electrically conductive device according to claim 68 in which the coating compound is an extruded compound having an extrusion profile measured from a sample extruded at 100 φm and 125 °C, the extrusion profile having a plurality of positive and negative vertical deviations from a mean extrudate surface line, wherein the extruded compound has a surface roughness factor R of less than 20, where R is defined by R = Ra + 0.1Rt,
Ra is the mean absolute vertical deviation from the mean extrudate surface line, and Rt is the absolute vertical difference between the maximum positive vertical deviation from the mean extrudate surface line and the maximum negative vertical deviation from the mean extrudate surface line.
70. Electrically conductive device according to claim 69 in which the surface roughness factor R is less than 15.
71. Electrically conductive device according to any of claims 68 to 70 in which the device is a medium voltage power cable.
PCT/US2002/008739 2001-04-23 2002-03-20 Blends of epdm and metallocene plastomers for wire and cable applications WO2002085954A2 (en)

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US10/475,594 US7750080B2 (en) 2001-04-23 2002-03-20 Blends of EPDM and metallocene plastomers for wire and cable applications
EP02719306A EP1453866B1 (en) 2001-04-23 2002-03-20 Blends of epdm and metallocene plastomers for wire and cable applications
DE60220709T DE60220709D1 (en) 2001-04-23 2002-03-20 MIXTURES OF EPDM AND METALOCENE PLASTOMERS FOR WIRE AND CABLE APPLICATIONS
AU2002250396A AU2002250396A1 (en) 2001-04-23 2002-03-20 Blends of epdm and metallocene plastomers for wire and cable applications
JP2002583480A JP4000062B2 (en) 2001-04-23 2002-03-20 EPDM and metallocene plastomer blends for use in wires and cables

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US28606001P 2001-04-23 2001-04-23
US60/286,060 2001-04-23

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JP2004535478A (en) 2004-11-25
US20040118592A1 (en) 2004-06-24
EP1453866A2 (en) 2004-09-08
JP4000062B2 (en) 2007-10-31
DE60220709D1 (en) 2007-07-26
AU2002250396A1 (en) 2002-11-05
EP1453866B1 (en) 2007-06-13
US7750080B2 (en) 2010-07-06
AU2002250396A8 (en) 2002-11-05
WO2002085954A3 (en) 2004-06-17

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