EP0892979A1 - Composition a base de polymere d'ethylene pour cables - Google Patents

Composition a base de polymere d'ethylene pour cables

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Publication number
EP0892979A1
EP0892979A1 EP97917761A EP97917761A EP0892979A1 EP 0892979 A1 EP0892979 A1 EP 0892979A1 EP 97917761 A EP97917761 A EP 97917761A EP 97917761 A EP97917761 A EP 97917761A EP 0892979 A1 EP0892979 A1 EP 0892979A1
Authority
EP
European Patent Office
Prior art keywords
cable
polymer
percent
ethylene
composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP97917761A
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German (de)
English (en)
Other versions
EP0892979B1 (fr
Inventor
Lawrence T. Kale
Trudy L. Iaccino
Kenneth E. Bow
Richard B. Mcada
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Global Technologies LLC
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Dow Chemical Co
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Publication of EP0892979A1 publication Critical patent/EP0892979A1/fr
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Publication of EP0892979B1 publication Critical patent/EP0892979B1/fr
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators 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
    • H01B3/44—Insulators 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators 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
    • H01B3/44—Insulators 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
    • H01B3/441—Insulators 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

Definitions

  • the present invention relates to cable applications, such as a coating on a fiber optical cable, coaxial cable, or telecommunications cable, comprising a layer of a specific polyethylene composition.
  • the polyethylene composition used in the cable of the present invention comprises a particular type of ethylene / ⁇ -olefin interpolymer, especially a homogeneously branched ethylene/ ⁇ olefin interpolymer, and most preferably a homogeneously branched substantially linear ethylene/ ⁇ -olefin interpolymer; and a heterogeneously branched ethylene/ ⁇ -olefin interpolymer (or linear ethylene homopolymer).
  • the cable of the present invention may have good mechanical properties such as abrasion resistance and flexibility, and good processability, moreover, may be less environmentally harmful (as compared with polyvinyl-chloride (PVC) based cables) when disposed.
  • PVC polyvinyl-chloride
  • thermoplastic polymer Various types have been used for wire and cable jacketing applications. Especially, polymer compositions based on ethylene homopolymer via high pressure polymerization processes (low density polyethylene (LDPE)), and polyvinyl-chloride (PVC) have been used conventionally.
  • LDPE low density polyethylene
  • PVC polyvinyl-chloride
  • mechanical properties are desired for the cable jacketing application, for example, mechanical properties such as abrasion resistance, flexibility and reduced notch sensitivity are highly required. Moreover, good processability is also required for production efficiency and good appearance or quality of produced cable.
  • LDPE low stiffness
  • PVC polyethylene glycol
  • PVC-based cables release environmentally harmful gas such as hydrochloride gas when combusted.
  • polymers such as PVC especially those containing lead stabilizers, tend to release environmental harmful materials (for example, lead leached into ground water) when combusted or landfilled and should be avoided for this application.
  • the plasticizers leach out of a PVC formulation, the cable becomes brittle which leads to premature failure.
  • Linear polyethylene has also been used as a layer in a cable application, but these linear polyethylene polymers do not have adequate abuse resistance in combination with the necessary flexibility; that is, to increase abuse resistance in a linear polyethylene, one merely has to increase the density of the polyethylene, however raising the density reduces the flexibility. Reduced flexibility hampers installation of the cable, especially where the cable must be routed through numerous bends and twists/turns Jacket or sheath damage resulting from poor flexibility usually results in cable failure.
  • One aspect of the present invention is a cable comp ⁇ sing a layer of a polyethylene composition characterized in that the polyethylene composition comp ⁇ ses:
  • melt index (I2) from 0.001 g/lOmin. to 10 g/10min.
  • CDBI a CDBI of greater than 50 percent
  • the cable composes a layer of a polyethylene composition characterized in that the polyethylene composition comprises about 40 percent (by weight of the total composition) of the at least one first polymer which is characte ⁇ zed as having:
  • Another aspect of the present invention is a cable jacket comp ⁇ sing the polyethylene composition of the invention which has at least 10 percent, preferably at least 20 percent, more flexibility than a cable made using conventional heterogeneous linear ethylene polymer having about the same density as the inventive polyethylene composition
  • Yet another aspect of the invention is a cable comprising a thermoplastic cable jacket having a thickness from 80 to 90 mils (2 0 to 2 3 mm) in contact with a metal shield creating a notch in said jacket, wherein a sample of said notched jacket taken in a circumferential direction, in accordance with ASTM D 638, has less than 55 percent loss of elongation than an un-notched cable jacket sample from said cable
  • Still another aspect of the invention is a cable comprising a thermoplastic ethylene polymer cable jacket composition, wherein a plaque having a single notch, a thickness from 70 to 80 mils (1 8 to 2 0 mm) made from said jacket composition has at least 100 percent, preferably at least 200 percent, more preferably at least 300 percent, especially at least 400 percent, and most especially at least 500 percent, ultimate tensile elongation, wherein the notch has a depth of at least 10 mils (0.25 mm), a radius from 0 275 mm to 0 55 mm, preferably 0 3 mm to 0525 mm, and especially from 0 38 mm to 051 mm, and wherein said ethylene polymer composition has a density of at least 0 945 g/cm 1
  • the invention is a cable comp ⁇ sing at least one layer of a thermoplastic polymer, especially a polyethylene polymer composition of the invention, wherein the thermoplastic polymer has a strain hardening modulus, Gp
  • the strain hardening modulus (Gp) is calculated from the conventional tensile stress-strain curve using the theory of rubber elasticity More specifically, the true stress, ⁇ , is calculated from the engmee ⁇ ng stress, ⁇ nn g , and draw ratio, ⁇ , as shown in Equation (I) For cable jacket resins.
  • Equation (II) was used to calculate the strain hardening modulus, where ⁇ note and ⁇ * represent the natural draw ratio and engmee ⁇ ng draw stress, respectively The natural draw ratio was determined by measu ⁇ ng the elongation of a grid pattern which was p ⁇ nted on the tensile dogbones
  • the strain hardening modulus is inversely related to the molecular weight between entanglements, M-, that is, the molecular weight of the tie-molecules between crystalline domains and p is the density of the resin
  • Figure 4 shows strain hardening modulus as a function of density of the ethvlene polymer composition
  • E, En, A, and An the strain hardening modulus relationship can be approximated by the following equation
  • the polyethylene composition used in the cable of the present invention is prepared by a process comp ⁇ sing the steps of
  • step (iv) removing the solvent from the polymer solution of step (in) and recovering the polyethylene composition
  • T e cables of the present invention have good flexibility, mechanical properties and good processability, furthermore, are environmentally less harmful when disposed relative to cables comp ⁇ sing conventional PVC
  • An important aspect of the present invention is the fact that cables, where the outer cable jacket comprises the compositions disclosed in this invention, have improved flexibility relative to comparative cables where the jacket is produced from conventional heterogeneous linear low density polyethylenes (LLDPE) Cable flexibility is an important performance criteria, since more flexible cables are easier to install and bend around corners Cable flexibility was measured by clamping a piece of cable ho ⁇ zontally in an Instron tensile machine and measu ⁇ ng the force required to deflect the cable in the upward direction Lower deflection forces demonstrate improved flexibility, as shown in Figure 1 Cable jackets produced from the copolymers of this invention are preferably 10 percent more flexible, and more preferably 20 percent more flexible than comparative cables made using conventional heterogeneous linear low density ethylene polymers having about the same density (that is, the density of each polymer is within 10 percent of the other)
  • FIG 1 is a plot of deflection force (kg) versus cable deflection (mm) for example A and comparative example G,
  • FIG 2 is a plot of ultimate tensile elongation (percent) versus notch number in the test sample for example B and for comparative example G,
  • FIG 3 is a plot of change in the relative tensile elongation versus temperature for example A and comparative example G,
  • FIG 4 is a plot of strain hardening modulus (MPa) versus polymer and composition density for example polymers A, An, B, Bn, E, and En, and for comparative examples D, G, I and J,
  • FIG 5 is a surface roughness scan of a cable jacket made from example B
  • FIG 6 is a surface roughness scan of a cable jacket made from comparative example G.
  • FIG 7 is a schematic representation, in perspective and party broken away, showing one cable of the present invention
  • the "substantially linear” ethylene/ ⁇ -olefm inte ⁇ olymers useful in the present invention are not “linear” polymers in the traditional sense of the term, as used to desc ⁇ be linear low density polyethylene (Ziegler polyme ⁇ zed linear low density polyethylene (LLDPE)), nor are they highly branched polymers, as used to desc ⁇ be low density polyethylene (LDPE)
  • the "substantially linear” ethylene/ ⁇ -olefin inte ⁇ olymers have long chain branching, wherein the backbone is substituted with 0 01 long chain branches/ 1000 carbons to 3 long chain branches/ 1000 carbons, more preferably from 001 long chain branches/1000 carbons to 1 long chain branches/1000 carbons, and especially from 0 05 long chain branches/1000 carbons to 1 long chain branches/1000 carbons Note that the long chain branches are not the same as the short chain branches resulting from inco ⁇ oration of the comonomer Thus, for an ethylene/ 1-octene copolymer, the
  • Both the homogeneous linear and the substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers useful for forming the compositions of the present invention are those in which the comonomer is randomly dist ⁇ ubbed within a given inte ⁇ olymer molecule and wherein substantially all of the inte ⁇ olymer molecules have the same ethylene / comonomer ratio within that inte ⁇ olymer, as desc ⁇ bed in USP 3,645,992 (Elston)
  • the homogeneity of the inte ⁇ olymers is typically desc ⁇ bed by the SCBDI (Short Chain Branching Dist ⁇ bution Index) or CDBI (Composition Dist ⁇ bution Branch/Breadth Index) and is defined as the weight percent of the polymer molecules having a comonomer content within 50 percent of the median total molar comonomer content
  • the CDBI of a polymer is readily calculated from data obtained from techniques known in the art, such as, for example, temperature nsing elution fractionation (abb
  • the SCBDI or CDBI for the homogeneous ethylene/ ⁇ -olefin inte ⁇ olymer used in the present invention is greater than 50 percent, more preferably greater than about 70 percent, and especially greater than about 90 percent
  • the homogeneous ethylene/ ⁇ -olefin inte ⁇ olymers used in the present invention essentially lack a linear polymer fraction which is measurable as "high density" fraction by the TREF technique (that is homogeneously branched ethylene/ ⁇ -olefin inte ⁇ olymers do not contain a polymer fraction with a degree of branching less than or equal to 1 methyl/1000 carbons)
  • TREF technique that is homogeneously branched ethylene/ ⁇ -olefin inte ⁇ olymers do not contain a polymer fraction with a degree of branching less than or equal to 1 methyl/1000 carbons
  • the homogeneous linear or substantially linear ethylene/ ⁇ -olefin inte ⁇ olymer for use in the present invention typically are inte ⁇ olymers of ethylene and at least one C3-C20 ⁇ - olefm and/or C4-C]g diolefm, preferably inte ⁇ olymers of ethylene and C3-C20 ⁇ -olefins, more preferably a copolymer of ethylene and a C4-C8 ⁇ -olefin, most preferably a copolymer of ethylene and 1-octe ⁇ e
  • inte ⁇ olymer is used herein to indicate a copolymer, or a te ⁇ olymer, or the like That is, at least one other comonomer is polyme ⁇ zed with ethylene to make the inte ⁇ olymer Ethylene polyme ⁇ zed with two or more comonomers can also be used to make the homogeneously branched substantially linear inte ⁇ olymers useful in
  • the homogeneously branched linear and substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers used in the present invention have a single melting peak, as determined using differential scanning calo ⁇ metry (DSC) using a second heat and a scanning range from -30°C to 140°C at 10°C/m ⁇ nute, as opposed to traditional heterogeneously branched Ziegler polyme ⁇ zed ethylene/ ⁇ -olefin copolymers having two or more melting peaks, as determined using DSC
  • the density of the homogeneously branched linear or substantially linear ethylene/ ⁇ - olefin inte ⁇ olymers (as measured in accordance with ASTM D-792) for use in the present invention is generally from 0 865 g/c ⁇ to 0 95 g/cm- ⁇ preferably from 0 89 g/cm ⁇ to 0 94 g/cm ⁇ , and more preferably from 0 9 g/cm ⁇ to 0935 g/cm ⁇
  • the amount of the homogeneously branched linear or substantially linear ethylene/ ⁇ - olefin inte ⁇ olymer inco ⁇ orated into the composition used in the cable of the present invention varies depending upon the heterogeneously branched ethylene polymer to which it is combined However, preferably from 5 to 95 percent, more preferably from 20 to 80 percent, most preferably from 25 to 45 percent (by weight of the total composition ) of the homogeneous linear or substantially linear ethylene/ ⁇ -olefin polymer may be inco ⁇ orated in the polyethylene composition for use in the cable of the present invention
  • the molecular weight of the homogeneously branched linear or substantially linear ethylene/ ⁇ -olefin polymer for use in the present invention is conveniently indicated usine melt index measurement according to ASTM D- 1238, condition 190°C/2 16 kg (formerly known as "condition (E)", and also known as h) Melt index is inversely proportional to the molecular weight of the polymer, although, the relationship is not linear
  • the homogeneously branched linear or substantially linear ethylene/ ⁇ -olefin inte ⁇ olymer will have a melt index of no more than lOg/10 mm , preferably less than about 1 g /10 min., and especially less than 0.5 g/10 mm.
  • melt index measurement Another measurement useful in charactenzing the molecular weight of the homogeneously branched substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers is conveniently indicated in melt index measurement according to ASTM D- 1238, condition 190°C/10 kg (formerly know as "Condition (N)" and also known as I I ).
  • the ratio of the I JQ and I2 melt index is the melt flow ratio and is designated as I10 I2
  • the I10 I2 ratio for the homogeneously branched linear ethylene/ ⁇ -olef ⁇ n inte ⁇ olymers is about 5.6.
  • the I JQ 12 ratio indicates the degree of long chain branching, that is, the higher the I10 I2 ratio, the more long chain branching in the inte ⁇ olymer.
  • the I10/I2 ratio of the homogeneously branched substantially linear ethylene/ ⁇ -olefin inte ⁇ olymers is at least 6, preferably at least 7, especially at least 8 or above, and can be as high as 20.
  • the molecular weight distnbution of the substantially linear ethylene inte ⁇ olymer in the present invention may be analyzed by gel permeation chromatography (GPC) on a Waters 150°C high temperature chromatographic unit equipped with three mixed porosity columns
  • the molecular weight determination is deducted by using narrow molecular weight dist ⁇ bution polystyrene standards (from Polymer Laborato ⁇ es) m conjunction with their elution columns
  • the equivalent polyethylene molecular weights are determined by using appropriate Mark-Houwmk coefficient for polyethylene and polystyrene ( as desc ⁇ bed by Williams and Ward in Journal of Polymer Science. Polymer Letters, Vol 6, (621) 1968, inco ⁇ orated herein by reference) to derive the following equation.
  • the molecular weight distribution (M w /Mschreib) is less than 3.5, preferably from 1.8 to 2.8, more preferably from 1.89 to 2.2 and especially about 2.
  • the ethylene polymer to be combined with the homogeneously branched linear or substantially linear ethylene/ ⁇ -olefin inte ⁇ olymer is a heterogeneously branched ethylene polymer, preferably a heterogeneously branched (for example, Ziegler polymerized) inte ⁇ olymer of ethylene with at least one C3-C20 ⁇ -olefin (for example, linear low density polyethylene (LLDPE)).
  • a heterogeneously branched ethylene polymer preferably a heterogeneously branched (for example, Ziegler polymerized) inte ⁇ olymer of ethylene with at least one C3-C20 ⁇ -olefin (for example, linear low density polyethylene (LLDPE)).
  • LLDPE linear low density polyethylene
  • Heterogeneously branched ethylene/ ⁇ -olefm inte ⁇ olymers differ from the homogeneously branched ethylene/ ⁇ -olefin inte ⁇ olymers prima ⁇ ly in their branching distribution.
  • heterogeneously branched LLDPE polymers have a dist ⁇ bution of branching, including a highly short chain branched portion (similar to a very low density polyethylene), a medium short chain branched portion (similar to linear low density polyethylene) and often a linear (that is, non-short chain branched) portion. The amount of each of these fractions vanes depending upon the whole polymer properties desired.
  • linear homopolymer polyethylene has no short chain branching.
  • a very low density heterogeneous polyethylene having a density from 0.89 g/cm 3 to 0.915 g/cm 3 such as
  • Attane copolymers sold by The Dow Chemical Company and Flexomer M sold by Union Carbide Co ⁇ oration
  • Flexomer M sold by Union Carbide Co ⁇ oration
  • the heterogeneously branched ethylene polymer is a heterogeneously branched ethylene/ ⁇ -olefin inte ⁇ olymer, most preferably Ziegler polymerized ethylene/ ⁇ - olefin copolymer.
  • the ⁇ -olefin for such ethylene inte ⁇ olymer may include ⁇ -olefin having 3 to 30 carbon atoms, more preferably an ⁇ -olefin having 4 to 8 carbon atoms, most preferably 1 -octene
  • the heterogeneously branched ethylene polymer is a copolymer of ethylene with a C -C20 ⁇ -olefin, wherein the copolymer has
  • compositions disclosed herein can be formed by any convenient method, including dry blending the individual components and subsequently melt mixing or by pre- melt mixing in a separate extruder (for example, a Banbury mixer, a Haake mixer, A Brabender intemal mixer, or a twin screw extruder)
  • 94/01052 describe, inter alia, inte ⁇ olymenzations of ethylene and C3-C20 ⁇ -olefins using a homogeneous catalyst in at least one reactor and a heterogeneous catalyst in at least one other reactor
  • the reactors can be operated in se ⁇ es or in parallel.
  • a preferred density of the polyethylene composition used for the cable of the present invention may depend upon desired stiffness of the finished cable However, typical densities will preferably be from 0.91 to 0 96 g/cm 3 , more preferably from 0 92 to 096 g/cm 3
  • a preferred melt index (that is I2) of the polyethylene composition disclosed herein may depend upon process conditions and desired physical properties
  • the melt index of the polyethylene composition disclosed herein may be from 0.1 to 50 g/10 minutes for all categones of cable, preferably not greater than 04 g/10 minute for category five (5), preferably from 04 to 1 g/10 minutes for category four (4), preferably greater than 1 to 10 g/10 minutes for category three (3), and preferably greater than 10 to 25 g/10 minutes for category two (2), and greater than 25 g/10 minutes for category one (1)
  • These general categories are found in ASTM D 1248, and are also included in the Standard Specifications for Plastic, Molding and Extrusion
  • the I2 of the polyethylene composition disclosed herein is lower than about 0 1 g/10 minutes, the polyethylene composition is often difficult to extrude and may cause melt fracture on the surface of the finished cable
  • the l of the polyethylene composition disclosed herein is higher than the above ranges, the molten polymer tends to have a low melt
  • the I i(/l2 °f tne polyethylene composition disclosed herein may be preferably from 7 to 16. more preferably from 9 to 14, most preferably from 10 to 13. If the Ii ⁇ or" tne polyethylene polymer disclosed herein is lower than the above range, surface quality of the finished cable tends to be deteriorated, and processability of the cable may become unacceptably low.
  • the resin composition of the present invention may comprise any known additives and or fillers to the extent that they do not interfere with the enhanced formulation properties discovered by Applicants.
  • Any additives commonly employed in polyolefin compositions for example, cross-linking agents, antioxidants (for example, hindered phenolics (for example,
  • phosphites for example, IrgafosTM 168 also by Ciba Geigy Co ⁇ .
  • flame retardants for example, heat stabilizers, ultra-violet absorbents, anti-static agents, slip agents, process aids, foaming agents, plasticizers, dyes, miscellaneous fillers such as clay and pigments can be included in the formulation.
  • a preferable additive of the present invention may include, for example, carbon black, and an antioxidant such as IrganoxTM 1010 and IrgafosTM 168.
  • the composition of the present invention may be further fabricated into desired cable of the present invention by using any known fabrication method.
  • the composition of the present invention may be used not only for cable jacketing, but also cable insulation or any layer of a cable.
  • the composition described herein may be heated, melted, kneaded and extruded by a mono- or bi-axial extruder through an extrusion die such as a cross-head die so as to be applied onto a core substrate, and then it may be subjected to a cooling step, or the next coating step if desired. Multiple layers of polymers may be applied onto the core substrate if desired.
  • the core substrate may comprise any known materials in the art, for example, control cables comprising any conductive material such as copper, and aluminum, insulating material such as low density polyethylene, polyvinyl-chloride, polyethylene compositions including compositions described herein, conductive or semiconductive shields such as aluminum, copper, and steel, usually in form of tape, foil, screen, net or any combinations thereof, and any reinforcement material.
  • Various cables and cable designs may include, as at least one layer, the polyethylene compositions disclosed herein.
  • USP 3,638.306 shows a communications cable which has a water proof core of conductors and a sheath including an unsoldered steel layer.
  • Figure 7 herein shows such a structure: the steel layer (1 ) is stretch- formed to attain a tightly registered longitudinal seam which eliminates the necessity of solde ⁇ ng or other means of mechanically joining the seam
  • a cable 101 includes a plurality of conductors or conductor pairs 4 within a cable core 2
  • the conductors 4 are surrounded by and the interstitial spaces therebetween are filled with a wate ⁇ roof filler material 6
  • a core wrap 8 which may be a suitable plastic or other matenal
  • a binder can be placed around core wrap 8 to hold it in position about core 2, a layer of conductive metal is placed about the core
  • a thin aluminum layer 10 having a longitudinal seam 14 therein advantageously can be used for lightning protection and shielding Longitudinal seam 14 is not required to be soldered or otherwise mechanically joined, a steel layer 20 having unsoldered overlapping edges 16 and 18 forming a longitudinal seam 17 is longitudinally wrapped about aluminum layer 10 to provide protection from mechanical forces such as abrasion
  • the use of an unsoldered seam 17 for steel layer 20 is possible, since the cable core 2 is wate ⁇ roof Steel layer 20 and aluminum layer 10 advantageously can be transversely corrugated and meshed with each other to provide
  • Corrosion protection for steel layer 20 and added protection against water penetration are provided by hot-melt flooding each side of steel layer 20 with respective coatings 12 and 22 of a corrosionproof, wate ⁇ roof matenal (such as a P ⁇ macorTM Adhesive Polymer made by The Dow Chemical Company)
  • a corrosionproof, wate ⁇ roof matenal such as a P ⁇ macorTM Adhesive Polymer made by The Dow Chemical Company
  • an exterior ethylene polymer composition jacket 24 advantageously is extruded around the exterior surface of layer 20
  • an unsoldered steel layer 20 and a thermoplastic layer or jacket 24 joined by corrosion coatings 12 and 22 provides mechanical, rodent, and wate ⁇ roof protection at a cost substantially less than the sheaths of prior art cables
  • vanous layers may comp ⁇ se the ethylene polymer compositions disclosed herein, including jacket 24, layers 22, 12 and 8, further any or all of these layers may comp ⁇ se the ethylene polymer compositions disclosed herein
  • a cable was produced by using polymer A which was an in-situ blend made according to PCT Publications WO 92/1 1269 and WO 94/01052, wherein 36 weight percent of the total composition of a homogeneously branched substantially linear ethylene/ 1-octene copolymer having a density of 0915 g/cm 3 was made in a first reactor, and 64 weight percent of the total composition of a heterogeneously branched linear ethylene/1-octene copolymer having a density of 0955 g/cm 3 was made in a second reactor Polymer A had a melt index
  • melt temperature and cable melt strength were evaluated subjectively (for example, the cable jackets did or did not have the required melt strength dunng extrusion as reported in Table 1 )
  • the surfaces of the cable jackets were evaluated visually and assigned a numencal surface rating, where the highest quality surface was given a rating of 100 The results are also reported m Table 1
  • the finished cable was subjected to physical properties test described below
  • a cable was produced by using polymer B which was an in-situ blend made according to PCT Publications WO 92/11269 and WO 94/01052, wherein 41 weight percent of the total composition of a homogeneously branched substantially linear ethylene/ 1-octene copolymer having a density of 0915 g/cm 3 was made in a first reactor, and 59 weight percent of the total composition of a heterogeneously branched linear polymer ethylene/1-octene copolymer having a density of 0 955 g/cm 3 was made in a second reactor
  • the polymer B had a melt index of 0 89 g lOminutes, 2 or" 1 1 - 3 > density of 0.957 g cm 3 (note that polymer B contained 2.6 weight percent carbon black and 400 ppm of a fluoroelastomer), 0 18 long chain branches/ 10,000 carbon atoms (1.8 long chain branches/ 1000 carbon atoms) as calculated using a kinetic model
  • An cable is produced by using polymer C which was an in-situ blend ethylene/ 1- octene copolymer produced by the same process desc ⁇ bed in Example 1 , having a melt index of 0 87 g/lOminutes, I10 I2 of 1 47 and density of 0.952 g/cm 3 (note that polymer C contained 26 weight percent carbon black and 400 ppm of a fluoroelastomer) and a M M n of 5 22
  • the polymer was extruded onto cable as desc ⁇ bed in Example I Surface rating is reported in Table 1
  • the finished cable was subjected to physical properties tests desc ⁇ bed below Comparative Cable Example 4
  • a cable was produced by using polymer D, which is a currently available polyethylene (for example UCC 8864 by Union Carbide) having melt index of 0 76 g/lOminutes, lio/Io of 12 3. density of 0 942 g/cm 1 , and M w /M n of 3 7, and no long chain branching Polymer D also contained 2.6 weight percent carbon black and about 400 ppm of a fluoroelastomer The polymer was extruded onto cable as described in Example 1 Melt tension data and cable surface rating are reported in Table 1
  • Cable Example 5 A cable was produced by using polymer E which was an in-situ blend ethylene/ 1- octene copolymer produced by the same process described in Example 1, having a melt index of 0.58 g/lOminutes, I JO/I 2 of 11.03, and density of 0.944 g/cm 3 , and M w /M n of 5.1 Polymer
  • E also contained 2.6 weight percent carbon black and 400 ppm of a fluoroelastomer.
  • the polymer was extruded onto cable as desenbed in Example 1. Melt tension and surface rating are reported in Table 1.
  • the finished cable was subjected to physical properties test desc ⁇ bed below
  • a cable was produced by using polymer F which was an in-situ blend ethylene/ 1- octene copolymer produced by the same process described in Example 1, having a melt index of 0.88 g/lOmmutes, Ijo 12 of 10 I 3 ⁇ density of 0.94 g/cm 3 , and a M w M n of about 4.6.
  • Polymer F contained 2.6 weight percent carbon black and 400 ppm of a fluoroelastomer The polymer was extruded onto cable as desc ⁇ bed in Example 1 and subjected to physical properties tests described below Melt tension and surface rating are reported in Table 1
  • Comparative Cable Example 7 A cable was produced by using polymer G, which is a currently available polyethylene (for example UCC 3479 by Union Carbide) having melt index of 0.12 g ]0m ⁇ nutes, I10 I2 of 294, density of 0.958 g cm 3 , M w /M n of 5.6, and no long chain branching. Polymer G contained 2.6 weight percent carbon black and about 400 ppm of a fluoroelastomer. The polymer was extruded onto cable as desenbed in Example 1 and subjected to physical properties tests desc ⁇ bed below. Melt tension and surface rating are reported in Table 1 Table 1
  • Polymer G Comp. Ex 7 0.12 29.4 0.958 80 7.1
  • Example 2 and comparative Example 7 The surface roughness of Example 2 and comparative Example 7 was quantified using surface profilometry. More specifically, the average surface roughness of theses cables was measured using a Surftest 402 Surface Roughness Tester, produced by Mitutoyo. This analyzer computes various surface roughness parameters given a scan of the cable surface with a diamond tipped stylus. Surface roughness is quantified by the statistical parameter, R a , known as the average roughness. This quantity is the arithmetic mean of all departures of the roughness profile from the average mean line as in Equation (V),
  • This surface roughness data is su ⁇ rising, given the I ⁇ o/I 2 values, for example, 1 1.3 for Example 2 and 29.4 for comparative Example 7. More specifically, it is well known that processability improves and surface roughness (melt fracture) decreases as I 10 I 2 increases. In other words, the very smooth cables produced by the copolymers of this invention were su ⁇ rising, given their relatively low L0/I2 values. Circumferential and Longitudinal Tensile Tests
  • Circumferential tensile samples were cut from the finished cables pe ⁇ endicular to the cable axis with no metal seam impressions within gauge length Longitudinal tensile samples were cut parallel to the cable axis with no metal seam impressions within gauge length
  • the tensile test was earned out according to ASTM D 638, using Die V (5) (for example microtensile), with a 2 54 cm jaw separation and pulling at 1.27 cm/minutes
  • the tensile strength data are reported in Table 2
  • Circumferential tensile samples were cut pe ⁇ endicular to the cable axis from the finished cables prepared as desc ⁇ bed above, and the notch (due to the metal overlap) was centered withm the gauge length.
  • the test was earned out as desenbed in ASTM D638 using Die V (5) (for example microtensile), with a 2.54 cm jaw separation and puling at 5.08 cm/minute. The results are reported in Table 3.
  • Cable flexibility of the final cable jacket bonded to corrugated steel was determined by measuring the amount of force required to deflect the cable.
  • a cable having a length of 33 cm was cut, the cable core was discarded, and each end, approximately 3 cm in length, was flattened.
  • the cable was inserted through the upper grip assembly of the Instron tensile machine and the flattened ends were clamped to the frame of the Instron tensile machine.
  • the cable samples were deflected at a rate of 12.7 cm/minutes, and the force required to deflect the cable 5, 10, 15 and 20 mm was recorded and reported in Table 5. Lower force indicates greater flexibility This test is described in detail in "Chemical Moisture Barner Cable for Underground Systems" by K.E. Bow and Joseph H. Snow, presented at IEEE/PCIC Conference, held Sept. 1981 in Minneapolis, MN, pp. 1-20, especially pages 8-10.
  • the cables made from polymer A (density: 0.958 g/cm 3 ), polymer B (density: 0.957 g/cm 3 ) and polymer C (density: 0.952 g/cm 3 ) showed greater flexibility (that is lower force at deflection) than cable made from Polymer G (density: 0.958 g cm 1 ), where these samples are of similar density.
  • the cable made from polymer A showed supenor flexibility than the cable made from polymer G, despite the density of the both polymers being about the same.
  • the results for these two trials are also shown graphically in FIG. 1
  • the results shown in Table 5 indicate the cables of the present invention have superior flexibility than the cable made from the current polymer.
  • the data show that it takes less force to deflect a cable of the mvention for a given distance (for example, 5, 10, 15 or 20 mm as shown in the table), than for a cable made from currently commercially available polyethylene, even at similar densities.
  • the melt index of the cable jacket, after extrusion was determined according to ASTM D 1238
  • the percent dnft in melt index (MI cable -MI , t ⁇ al ) / MI ⁇ mt ⁇ al
  • MI l ⁇ ,t ⁇ a ⁇ represents a melt index of the resin pnor to extrusion
  • Mjcable represents a melt index after extrusion
  • the jacket bond test was conducted according to ASTM D 4565 for cables with a bonded steel sheath.
  • a section of the cable jackets prepared as described above was removed by slitting the jacket longitudinally along the shield overlap.
  • the cable was ringed circumferentantially with a knife, flexed at the cut point to break the steel shield at the ring.
  • the metal sheath was opened, flattened, and the cable core was discarded.
  • the specimen strip was cut in the circumferential direction. Three strips having a width of 13 mm were cut for each strip.
  • the jacket was separated from the shield or armor only of a length sufficient to permit forming a tab of each sheath component.
  • Three specimens were tested for each cable sample at a crosshead speed of 50 mm / minute. The results are reported in Table 8.
  • a cold bend test was conducted according to ICEA specification S-84-608- 1988 which calls out ASTM 4565 for the specifics on the test procedure Samples were equilibrated in a cold room at - 30°C for 4 hours, pnor to the testing A cable sample having length of 91 4 cm was bent in a 180° arc around a mandrel having a diameter of 8 times the cable diameter, then the sample was straightened, rotated 180°, and then bent again 180° Upon completion of the second bend, the cable was straightened, rotated 90° and bent m a 180° arc Upon completion of the third bend, the cable was straightened, rotated 180° and then bent for the fourth time
  • a room temperature bend test was conducted m a manner similar to ASTM 4565 The cable samples were conditioned at 20°C for 4 hours pnor to testing A cable sample was bent in the same manner as the cold bend test as desenbed above, except the sample was bent around a mandrel having a diameter of 20 times the cable diameter
  • a hot bend test was conducted in a manner similar to ASTM 4565 The cable samples were conditioned at 60°C for 4 hours pnor to testing A cable sample was bent in the same manner as the cold bend test as desenbed above, except the sample was bent around a mandrel having a diameter of 10 times that of the cable diameter After bending each cable sample, the surface area of the samples were inspected for cracks in the bent area using normal or corrected to normal vision Results of the cold, room temperature and hot bend test are reported in Table 9 Table 9
  • Example 14 Polymer H** 0.82 1 1.45 0.952 * "n" denotes natural version of these polymers, that is, no carbon black or fluoroelastomer * *Sample contains 2.6 wt percent carbon black and 400 ppm of fluoroelastomer
  • Example 8 Polymer An 0.033
  • Plaque samples for standard microtensile test according to ASTM D-l 708, Die V (5) were prepared using a special mold containing four ridges with the dimensions desenbed in Table 14 These ridges produced well defined notches m the final plaques Microtensile dogbone samples were cut from the plaque, with the notch centered within the gauge length The tensile test was conducted according to ASTM D 638 at 25 4 cm mmutes cross-head speed (pull rate) with 2.5 cm jaw separation at three temperatures, for example -30°C, 0°C and 25°C, using each notched sample and control samples having no notch The results are reported in Table 15
  • Example 18 Polymer E / Control 624 505 472 252 1 284 9 299 9 0948 Notch 1 543 497 310 2107 281 1 2760
  • Example 19 Polymer F / Control 671 573 452 261 0 215 1 270 8 0940 Notch 1 574 524 326 2084 281 2 253 4
  • the polymers used in the cable of the present invention were less notch sensitive than the polymers currently available in the industry (for example Polymer D and G), comparing at about same density, for example.
  • Polymers B and C have the higher elongation at break than Polymer G
  • polymers E and F have the higher elongation at break than Polymer D, at almost all temperatures.
  • Reduced Notch Sensitivity Compression Molded Plaques
  • the copolymers useful in this invention also have improved low temperature tensile properties.
  • the reduction in tensile elongation for Example A was 18 percent at 0°C and 56 percent at -30°C.
  • the reduction in tensile elongation for comparative Example G was 52 percent at 0°C and 80 percent at -30°C.
  • the copolymers of this invention have improved tensile properties at low temperature.
  • the cables of this invention are easier to install at low temperatures, for example, less susceptible to failures (splitting) at low temperatures.

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)

Abstract

Cette invention a trait à un câble comportant une couche obtenue à partir d'une composition à base de polyéthylène constituée, d'une part, (A), de 5 à 95 pour cent en poids de la composition totale d'au moins un premier polymère, en l'occurrence un interpolymère d'éthylène/α-oléfine, (i) d'une densité comprise entre 0,865 et 0,95 g/cm3, (ii) d'une répartition des masses moléculaires (M¿w?/ Mn) comprise entre 1,8 et 3,5, (iii) d'un indice de fusion (I2) s'échelonnant entre 0,001 g/10 min. et 10 g/10 min. et, (iv) d'un indice de largeur de répartition de composition supérieur à 50 pour cent et, d'autre part, (B), de 5 à 95 pour cent en poids de la composition totale d'au moins un second polymère, en l'occurrence un polymère d'éthylène ramifié de façon hétérogène ou un homopolymère d'éthylène ramifié de façon homogène, d'une densité comprise entre 0,9 et 0,965 g/cm?3¿. Le câble selon l'invention possède des propriétés mécaniques ainsi qu'une aptitude au façonnage supérieures à celles des câbles classiques faisant appel à des polymères courants, du type polyéthylène basse densité (PEBD), polyéthylène basse densité à structure linéaire (PEBDL) et poly(chlorure de vinyle) (PVC).
EP97917761A 1996-04-10 1997-04-01 Composition a base de polymere d'ethylene pour cables Expired - Lifetime EP0892979B1 (fr)

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US63132096A 1996-04-10 1996-04-10
US631320 1996-04-10
PCT/US1997/005297 WO1997038424A1 (fr) 1996-04-10 1997-04-01 Composition a base de polymere d'ethylene pour cables

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JP (1) JP2000508466A (fr)
KR (1) KR20000005334A (fr)
CN (1) CN1097825C (fr)
AR (1) AR006572A1 (fr)
AT (1) ATE241203T1 (fr)
AU (1) AU2600797A (fr)
BR (1) BR9709117A (fr)
CA (1) CA2248654C (fr)
DE (1) DE69722197T2 (fr)
ES (1) ES2200173T3 (fr)
ID (1) ID18484A (fr)
NO (1) NO984715D0 (fr)
TR (1) TR199802018T2 (fr)
TW (1) TW374934B (fr)
WO (1) WO1997038424A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7005465B2 (en) 2002-08-07 2006-02-28 General Electric Resin composition for wire and cable coverings
US7517927B2 (en) 2004-01-07 2009-04-14 Sabic Innovative Plastics Ip B.V. Flexible poly(arylene ether)composition and articles thereof
US7524894B2 (en) 2002-11-14 2009-04-28 Sabic Innovative Plastics Ip B.V. Resin composition for wire and cable covering material
US11015003B2 (en) 2016-05-31 2021-05-25 Borealis Ag Jacket with improved properties

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6103658A (en) * 1997-03-10 2000-08-15 Eastman Chemical Company Olefin polymerization catalysts containing group 8-10 transition metals, processes employing such catalysts and polymers obtained therefrom
US6822062B2 (en) 1997-03-10 2004-11-23 Eastman Chemical Company Supported group 8-10 transition metal olefin polymerization catalysts
EP1159320B1 (fr) * 1998-11-02 2011-01-12 Dow Global Technologies Inc. Interpolymeres ethylene/alpha-olefine/diene a fluidisation par cisaillement et leur preparation
ATE373252T1 (de) * 1999-08-23 2007-09-15 Prysmian Cavi Sistemi Energia Faseroptische kabelkomponenten mit verbesserter kompatibilität gegenüber wasserblockierenden substanzen
US6658185B2 (en) 1999-08-23 2003-12-02 Pirelli Cavi E Sistemi S.P.A. Optical fiber cable with components having improved compatibility with waterblocking filling compositions
IL180507A (en) 2007-01-02 2011-04-28 Teldor Wires And Cables Ltd Flexible and water and rodent cable that is especially suitable for use as an optical communication cable
KR101959473B1 (ko) 2010-03-17 2019-03-18 보레알리스 아게 유리한 전기적 특성을 갖는 와이어 및 케이블 용도의 중합체 조성물
EP2548208A1 (fr) * 2010-03-17 2013-01-23 Borealis AG Composition polymère pour application w&c à propriétés électriques avantageuses
EP3485189A1 (fr) * 2016-07-14 2019-05-22 SABIC Global Technologies B.V. Procédé permettant de déterminer le temps de rupture fragile d'un tuyau en polypropylène
JP6942245B2 (ja) 2017-09-29 2021-09-29 エルジー・ケム・リミテッド 配管用樹脂組成物の長期耐久性予測方法及び配管用樹脂に用いられるオレフィン系高分子
KR102184390B1 (ko) * 2017-09-29 2020-11-30 주식회사 엘지화학 배관용 수지 조성물의 장기 내구성 예측 방법
KR102486846B1 (ko) * 2018-02-06 2023-01-10 주식회사 엘지화학 올레핀계 고분자
BR112021000818A2 (pt) * 2018-07-25 2021-04-13 Dow Global Technologies Llc Condutor revestido
MX2023008699A (es) * 2021-02-24 2023-08-01 Dow Global Technologies Llc Composiciones polimericas coloreables que exhiben propiedades de envejecimiento mejoradas.

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3674915A (en) * 1971-06-01 1972-07-04 Phillips Petroleum Co Electrical cable having an ethylene-1-olefin copolymer as the dielectric material
KR100253826B1 (ko) * 1991-12-30 2000-04-15 그레이스 스티븐 에스. 에틸렌 공중합체의 중합방법
EP0572034A2 (fr) * 1992-05-29 1993-12-01 Idemitsu Kosan Company Limited Copolymère éthylénique et composition de copolymères éthyléniques
ES2126002T3 (es) * 1992-09-15 1999-03-16 Dow Chemical Co Modificacion de la resistencia al choque de termoplasticos.
US5414040A (en) * 1992-09-15 1995-05-09 The Dow Chemical Company Formulated ethylene/α-olefin elastomeric compounds
WO1994017112A2 (fr) * 1993-01-29 1994-08-04 The Dow Chemical Company Interpolymerisations d'ethylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9738424A1 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7005465B2 (en) 2002-08-07 2006-02-28 General Electric Resin composition for wire and cable coverings
US7524894B2 (en) 2002-11-14 2009-04-28 Sabic Innovative Plastics Ip B.V. Resin composition for wire and cable covering material
US7517927B2 (en) 2004-01-07 2009-04-14 Sabic Innovative Plastics Ip B.V. Flexible poly(arylene ether)composition and articles thereof
US11015003B2 (en) 2016-05-31 2021-05-25 Borealis Ag Jacket with improved properties
US11618795B2 (en) 2016-05-31 2023-04-04 Borealis Ag Jacket with improved properties

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TR199802018T2 (xx) 1999-01-18
BR9709117A (pt) 1999-08-03
CA2248654C (fr) 2004-05-25
AR006572A1 (es) 1999-09-08
CA2248654A1 (fr) 1997-10-16
ATE241203T1 (de) 2003-06-15
JP2000508466A (ja) 2000-07-04
NO984715L (no) 1998-10-09
WO1997038424A1 (fr) 1997-10-16
ID18484A (id) 1998-04-09
EP0892979B1 (fr) 2003-05-21
CN1097825C (zh) 2003-01-01
ES2200173T3 (es) 2004-03-01
NO984715D0 (no) 1998-10-09
DE69722197T2 (de) 2003-12-04
DE69722197D1 (de) 2003-06-26
CN1215497A (zh) 1999-04-28
AU2600797A (en) 1997-10-29
TW374934B (en) 1999-11-21
KR20000005334A (ko) 2000-01-25

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