WO2013072070A1 - Utilisation d'une composition de polyéthylène dans le gainage et/ou l'isolation de fils et de câbles - Google Patents

Utilisation d'une composition de polyéthylène dans le gainage et/ou l'isolation de fils et de câbles Download PDF

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Publication number
WO2013072070A1
WO2013072070A1 PCT/EP2012/004796 EP2012004796W WO2013072070A1 WO 2013072070 A1 WO2013072070 A1 WO 2013072070A1 EP 2012004796 W EP2012004796 W EP 2012004796W WO 2013072070 A1 WO2013072070 A1 WO 2013072070A1
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WO
WIPO (PCT)
Prior art keywords
use according
polyethylene
salt
calcium salt
zinc salt
Prior art date
Application number
PCT/EP2012/004796
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English (en)
Inventor
De Roelof Franciscus Gerardus Maria VOS
Hao Ding
Van den Bart Albertus Hubertus ESSCHERT
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Saudi Basic Industries Corporation (Sabic)
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Publication date
Application filed by Saudi Basic Industries Corporation (Sabic) filed Critical Saudi Basic Industries Corporation (Sabic)
Publication of WO2013072070A1 publication Critical patent/WO2013072070A1/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
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/292—Protection against damage caused by extremes of temperature or by flame using material resistant to heat
    • 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 the use of a polyethylene composition in wire and cable jacketing and /or insulation.
  • Wire and cable products are critical to the modern economy. Examples of wire and cable constructions are building wire, power cable and fibre optics. Their application is increasing with the growing use of computers, the Internet, cable television, and the increase in electrical power service worldwide. Each type of cable, however, has several common elements including the core (typically copper or fiber optic), insulation, and jacketing.
  • core typically copper or fiber optic
  • insulation typically copper or fiber optic
  • jacketing One of the key components of a wire is its insulation. Its selection is determined by a number of factors such as stability and long life, dielectric properties, resistance to high temperature, resistance to moisture, mechanical strength, and flexibility. There is no single insulation that is ideal in every one of these areas. It is necessary to select a cable with the type of insulation, which fully meets the requirements of the application. Jackets cover and protect the enclosed wires or core against damage, chemical attack, fire and other harmful elements that may be present in the operating environment.
  • a wire and cable formulation may comprise for example polymers for insulation and jacketing; suitable polymers include for example polyethylene, cross linked polyethylene, chlorinated polyethylene and polyvinyl chloride; plasticizers to make the plastic flexible and easy to process; stabilizers to provide heat resistance during manufacturing as well as visible light, UV rays and heat resistance during product use; flame retardants to slow the spread of an accidental fire and reduce the amount of heat and smoke released; fillers to reduce formulation costs and improve insulation resistance; lubricants to improve the ease of processing; and colorants to give the desired colour for identification purposes.
  • suitable polymers include for example polyethylene, cross linked polyethylene, chlorinated polyethylene and polyvinyl chloride; plasticizers to make the plastic flexible and easy to process; stabilizers to provide heat resistance during manufacturing as well as visible light, UV rays and heat resistance during product use; flame retardants to slow the spread of an accidental fire and reduce the amount of heat and smoke released; fillers to reduce formulation costs and improve insulation resistance; lubricants to improve the ease of processing; and colorants to give
  • coated wire and cable is a multi-stage process.
  • Raw materials are combined in a series of manufacturing steps including resin and additive manufacturing, resin compounding, wire drawing (or fiber optic), extrusion, cabling, and jacketing.
  • Polymers and additives are combined together, directly to the reactor powder prior to pelletizing or via an extra compounding operation afterwards to produce materials formulated to meet the various insulation or jacketing performance
  • the present invention is characterised in that the polyethylene composition comprises a polyethylene and a mixture of a calcium salt of saturated monobasic straight chained fatty acid having 8 to 30 carbon atoms and a zinc salt of saturated monobasic straight chained fatty acid having 8 to 30 carbon atoms wherein the weight ratio of the calcium salt: zinc salt ranges between 5:1 and 1 :5.
  • the use of the polyethylene composition results wire and cable production without melt fracture.
  • WO94/07946A1 discloses that a process for the stabilization of recycled plastics, predominantly thermoplastics, obtained from domestic, commercial and industrial waste or from useful material collections, which comprises adding from 0.01 to 10% by weight of a mixture of a) at least one sterically hindered phenol, b) at least one organic phosphorous or phosphonous ester and c) at least one metal salt of a fatty acid to these plastics.
  • Component c may be a mixture of various metal stearates, in which the metal is an element of main or sub-group II or tin.
  • US2003/0175459A1 discloses a shaped article comprising a polymer composition, wherein the polymer composition includes: an olefinic polymer, a polar polymer; and a third polymer, wherein the third polymer is a graft or block copolymer, and wherein the third polymer comprises first and second polymer portions, the first polymer portion being compatible with the olefinic polymer and the second polymer portion being compatible wjth the polar polymer, wherein the polymer composition has a limiting oxygen index of at least about 25.
  • Another advantage is that uniformity of the product surface is achieved.
  • a further advantage is that the melt fracture problem is solved without using a fluor polymer and consequently a halogen free product is obtained.
  • the composition does not comprise a fluoro polymer.
  • the weight ratio of the calcium salt: zinc salt ranges between 4:1 and 1 : 2.
  • the weight ratio of the calcium salt: zinc salt ranges from 5: 1 and 1 : 1 , for example 4: 1 and 1 :1 , for example between 3:1 and 1 : 1 , for example from 5:1 to 3:2.
  • the weight ratio of the calcium salt: zinc salt is around 2:1. It is advantageous that the amount of calcium is higher than the amount of zinc because the combination of these metal salts shows a synergistic effect with increasing calcium salt:zinc salt ratio.
  • the weight ratio of the calcium salt: zinc salt is about 2:1.
  • the salt mixture does not improve the surface quality compared with the use of a pure calcium or the use of a pure zinc salt.
  • the total amount of calcium salt and zinc salt in the ethylene composition is from 1500 to 4500ppm, more preferably from 2500 to 3500ppm.
  • Suitable polyethylenes include linear low density polyethylene (LLDPE), high density polyethylene (HDPE) and low density polyethylene (LDPE).
  • LLDPE linear low density polyethylene
  • HDPE high density polyethylene
  • LDPE low density polyethylene
  • the ethylene polymer composition comprises LLDPE or HDPE, whereas for wire and cable insulation, preferably the ethylene polymer composition comprises LLDPE or LDPE.
  • the polyethylene composition comprises linear low density polyethylene.
  • the polyethylene has a density in the range between 910 and 970 kg/m3 and an MFI in the range between 0.1 and 10 g/10 minutes (measured at 190°C, 2.16 kg according to ASTM-D-1238).
  • the ethylene composition may comprise other polymers than polyethylene and/or may also comprise mixtures of LLDPE, LDPE and/or HDPE.
  • LLDPE low density polyethylene
  • HDPE and/or LDPE may be present in amount from 2-30wt%, for example 5-25wt%, for example 10-20wt% based on the polyethylene.
  • LDPE low density polyethylene
  • HDPE and/or LLDPE may be present in amount from 2-30wt%, for example 5-25wt%, for example 10-20wt% based on the polyethylene.
  • LLDPE and/or LDPE may be present in amount from 2-30wt%, for example 5-25wt%, for example 10-20wt% based on the polyethylene.
  • the ethylene composition comprises one of LLDPE, LDPE or HDPE and does not comprise mixtures of polyethylenes.
  • the ethylene composition also does not comprise other polymers.
  • the ethylene composition comprises more than 80% by weight of polymer, more preferably more than 80% by weight of LLDPE, LDPE and/or HDPE.
  • the ethylene composition comprises more than 95% by weight of polyethylene, more preferably more than 95% by weight of one of LLDPE, LDPE or HDPE.
  • the ethylene composition consists essentially of polyethylene and a mixture of a calcium salt of a saturated straight chained fatty acid having 8 to 30 carbon atoms and a zinc salt of a saturated straight chained fatty acid having 8 to 30 carbon atoms, wherein the weight ratio of the calcium salt:zinc salt ranges between 5:1 and 1 :5. More preferably, the amount of polyethylene in the ethylene composition is substantially at least 90%, for example substantially at least 95%, for example substantially at least 99% by weight of the total amount of polymers in the ethylene composition.
  • the polyethylene in the ethylene composition is not recycled.
  • the mixture of calcium salt and zinc salt is added in the polyethylene production plant to the reactor polyethylene powder and extruded and pelletized to polyethylene granules.
  • the amount of salt mixture may range between for example 0.1 and 0.5 % by weight relative to the polyethylene powder.
  • the mixture of calcium salt and zinc salt is compounded with the polyethylene base resin for example LLDPE via compounding extrusion to a masterbatch.
  • the amount of salt mixture may range between for example 1 and 30 % by weight relative to the base resin.
  • the masterbatch can be added to the base polymer for example LLDPE during cable production to enhance the performance.
  • the amount of the masterbatch may range between 0.5 and 30 % by weight relative to the base resin.
  • Suitable examples of the calcium salt of a fatty acid having 8 to 30 carbon atoms include calcium laurate, calcium palmitate, calcium stearate, calcium behenate and calcium montanate.
  • fatty acid having 8 to 30 carbon atoms is meant an unsubstituted fatty acid.
  • the calcium salt of a fatty acid having 8 to 30 carbon atoms is calcium stearate.
  • Suitable examples of the zinc salt of a fatty acid having 8 to 30 carbon atoms include zinc laurate, zinc palmitate, zinc stearate, zinc behenate and zinc montanate.
  • the zinc salt of a fatty acid having 8 to 30 carbon atoms is zinc stearate.
  • the composition according to the invention may also comprise other additives for example amides, preferably fatty acid amides. These additives may be present in an amount of for example from 100 to 3000ppm, for example from 500 to 2500, for example from 1000-3000ppm, for example from 500 to 2500ppm.
  • Suitable fatty acid amides include for example amides of saturated or unsaturated monobasic or straight chained fatty acids having 8 to 30 carbon atoms, for example having 8 to 20 carbon atoms, ethylene bis-stearamide, erucamide, oleamide, ethylene bis-oleamide, stearamide, behenamide, preferably ethylene bis-stearamide. It is of course also possible to use a mixture of fatty acid amides.
  • the polyethylene composition comprises a polyethylene and a mixture of a calcium salt of saturated or unsaturated monobasic or straight chained fatty acid having 8 to 30 carbon atoms and a zinc salt of saturated or unsaturated monobasic or dibasic branched or straight chained fatty acid having 8 to 30 carbon atoms wherein the weight ratio of the calcium salt: zinc salt ranges between 5:1 and 1 :5 and a fatty acid amide is present in an amount from 100 to 3000ppm, for example from 100-1500 ppm.
  • additives such as the amides can be added together with the mixture of calcium salt and zinc salt in the plant to the reactor powder and extruded and pelletized to granules.
  • the additives such as the amides can be compounded together with the mixture of calcium salt and zinc salt and the base resin carrier such as LLDPE via compounding extrusion to produce a master batch. This masterbatch can be added to the base polymer during cable production to enhance the performance.
  • polyethylenes for example LLDPE are summarised in "Handbook of Polyethylene” by Andrew Peacock (2000; Dekker; ISBN 0824795466) at pages 43-66.
  • the catalysts can be divided in three different subclasses including Ziegler Natta catalysts, Phillips catalysts and single site catalysts.
  • the wire and cable formulation obtained with the polymer composition according to the invention may be applied for example in building wire, telephone and telegraph wire, power cable coaxial and antennae cable, electronic and data wire and magnet wire.
  • the wire and cable formulations may comprise also other additives such as for example plasticizers; stabilizers; flame retardants; fillers; lubricants colorants. These additives are generally added during the production of wire and cable together with the base polymer.
  • LLDPE density 918 kg/m 3 ; MFI 3 g/10min (190°C, 2.16kg)
  • the masterbatch was obtained by mixing 10% by weight (relative to the total amount of the masterbatch) calcium stearate and 5% by weight (relative to the total amount of the masterbatch) zinc stearate with the LLDPE carrier via compounding extrusion process.
  • the temperature setting for the extruder was:
  • Figure I shows a picture of the surface of the cable as obtained. Comparative Example A
  • Example I was repeated with the only difference no mixture of calcium stearate and zinc stearate was used.
  • Figure A shows a picture of the surface of the cable as obtained without use of the mixture according to the invention.
  • Figure I shows a picture of the surface of the cable as obtained with the use of the mixture of calcium stearate and zinc stearate using the exact same processing conditions as Figure A.
  • this strand displays a rough surface. This rough surface is due to the fact that melt fracture occurred during processing.
  • the surface is uniform and smooth and there is no indication of melt fracture.
  • Example I was repeated, and line speed was increased from 20m/min to 80 m/min.
  • Figure II shows a picture of the surface of the cable as obtained at a speed of 80 m/min.
  • Example II was repeated with the only difference no mixture of calcium stearate and zinc stearate was used.
  • Figure B shows a picture of the surface of the cable as obtained without use of the mixture according to the invention. The conclusion of the comparison between figure B and figure II is that the surface quality of the cable according to Example II is improved in comparison with the surface quality of the cable according to Comparative Example B.
  • an ethylene polymer composition wherein the ethylene polymer composition comprises polyethylene and a mixture of a calcium salt of saturated straight chained fatty acid having 8 to 30 carbon atoms and a zinc salt of saturated straight chained fatty acid having 8 to 30 carbon atoms wherein the weight ratio of the calcium salt: zinc salt ranges between 5:1 and 1 :5, preferably wherein the weight ratio is from 5:1 to 3:2, for example around 2:1 , preferably wherein the total amount of calcium salt and zinc salt ranges from 1500 to 4500, for example from 2500 to 3500 can suitably be used for the production of wire and cable jacketing and /or insulation as melt fracture is reduced or may even be completely absent.
  • LLDPE low density polyethylene
  • MFI 3 g/10min 190°C, 2.16kg
  • samples were compounded on a DSM Xplore 15 cc micro compounder.
  • the melt temperature was set at 180°C.
  • the materials were premixed as a powder and compounded for 2 min at 100 rpm.
  • the powder premix of all samples also contained 2000ppm IrganoxTM B225 as a processing stabilizer.
  • IrganoxTM B225 is a mixture of IrganoxTM 1010 and IrgafosTM 168 in a ratio of 1 :1.
  • ppm indicates the amount of calcium stearate in ppm
  • - fatty acid amide indicates the amount of Crodamide EBS which is an ethylene bis- stearamide in ppm. During compounding the total sample loading was 8 grams. The force in dependence of time during compounding was recorded on the Xplore micro
  • the force during compounding is an indication for the processability of the material. The lower the force, the better the processability that is achieved.
  • the results from the different tried recipes are also displayed in Table 1.
  • the force (or processability) during the compounding for the different samples relative to one another was indicated by a figure from 1 to 8.
  • the highest force and therefore the worst processability was indicated with 1.
  • the lowest force and therefore the best processability is indicated with 8.
  • an ethylene polymer composition wherein the ethylene polymer composition comprises polyethylene and a mixture of a calcium salt of saturated straight chained fatty acid having 8 to 30 carbon atoms and a zinc salt of saturated straight chained fatty acid having 8 to 30 carbon atoms wherein the weight ratio of the calcium salt: zinc salt ranges between 5:1 and 1 :5, preferably wherein the weight ratio is from 5:1 to 3:2, for example around 2:1 , preferably wherein the total amount of calcium salt and zinc salt ranges from 1500 to 4500, for example from 2500 to 3500 can suitably be used for the production of wire and cable jacketing and /or insulation. Not only will such composition be easily processable, but this will also have a reduced melt fracture and may even show no melt fracture at all.
  • ethylene polymer composition further comprises a fatty acid amide, for example ethylene bis stearamide, in an amount from 100 to 3000ppm, for example in an amount of around 500ppm.
  • a fatty acid amide for example ethylene bis stearamide
  • III-4 2000 1000 3000 2:1 0 7

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation d'une composition polymère d'éthylène pour la production de gainage et/ou d'isolation de fils et de câbles caractérisée en ce que la composition polymère d'éthylène comprend du polyéthylène et un mélange de sel de calcium d'acide gras à chaîne droite saturé ayant 8 à 30 atomes de carbone et de sel de zinc d'acide gras à chaîne droite saturé ayant 8 à 30 atomes de carbone. Le ratio en poids sel de calcium:sel de zinc est compris entre 5:1 et 1:5.
PCT/EP2012/004796 2011-11-18 2012-11-19 Utilisation d'une composition de polyéthylène dans le gainage et/ou l'isolation de fils et de câbles WO2013072070A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP11075254 2011-11-18
EP11075254.0 2011-11-18

Publications (1)

Publication Number Publication Date
WO2013072070A1 true WO2013072070A1 (fr) 2013-05-23

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0297414A2 (fr) * 1987-06-24 1989-01-04 Hitachi Cable, Ltd. Composition d'isolation électrique résistant à l'arborescence
WO1994007946A1 (fr) 1992-09-25 1994-04-14 Ciba-Geigy Ag Procede de stabilisation et melanges stabilisants pour les melanges plastiques recycles
EP0656634A2 (fr) * 1993-12-03 1995-06-07 The Geon Company Revêtement de conducteurs électrique, sans plomb
US20030175459A1 (en) 2001-01-16 2003-09-18 Raman Patel Flame retardant shaped articles

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0297414A2 (fr) * 1987-06-24 1989-01-04 Hitachi Cable, Ltd. Composition d'isolation électrique résistant à l'arborescence
WO1994007946A1 (fr) 1992-09-25 1994-04-14 Ciba-Geigy Ag Procede de stabilisation et melanges stabilisants pour les melanges plastiques recycles
EP0656634A2 (fr) * 1993-12-03 1995-06-07 The Geon Company Revêtement de conducteurs électrique, sans plomb
US20030175459A1 (en) 2001-01-16 2003-09-18 Raman Patel Flame retardant shaped articles

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"Plastics Additives Handbook", November 2008, pages: 588
ANDREW PEACOCK: "Handbook of Polyethylene", 2000, DEKKER, pages: 43 - 66

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