WO2002036680A1 - Crosslinkable ethylene polymer blends - Google Patents

Crosslinkable ethylene polymer blends Download PDF

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Publication number
WO2002036680A1
WO2002036680A1 PCT/IB2001/002742 IB0102742W WO0236680A1 WO 2002036680 A1 WO2002036680 A1 WO 2002036680A1 IB 0102742 W IB0102742 W IB 0102742W WO 0236680 A1 WO0236680 A1 WO 0236680A1
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Prior art keywords
weight
parts
component
hdpe
polydispersity
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PCT/IB2001/002742
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French (fr)
Inventor
Olivier Biles
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BP Köln GmbH
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Priority to AU2002216321A priority Critical patent/AU2002216321A1/en
Publication of WO2002036680A1 publication Critical patent/WO2002036680A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/04—Antistatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions 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
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking

Definitions

  • the present invention relates to novel polymer blends and in particular to blends particularly suitable for use as components of cross-linkable compositions for use as automotive cables.
  • the novel polymer blends allow such cross-linkable compositions to impart improved mechanical properties and processability in such cables.
  • automotive cables are commonly insulated with polyvinyl chloride and are designed to service temperatures of 100°C.
  • increased working temperatures and reduced space under automobile bonnets have led the industry to increase the service temperature of automotive wires.
  • automotive wires need to exhibit improved thermal resistance.
  • PNC polyvinyl chloride
  • the wires In addition to the thermal resistance requirement of the new automotive specifications, the wires must also offer high mechanical properties, high abrasion resistance, excellent resistance to oils and solvents and resistance to fire.
  • US 5439965 describes polymeric compositions useful as insulation for wire and cable products for example automotive applications.
  • crosslinkable polymeric compositions comprising copolymers of ethylene and vinyl esters are disclosed in combination with flame retardant materials. Similar materials are described in US 4477523 and US 4255303.
  • US 4035325 describes flame retardant combinations of antimony trioxide and hexabromocyclododecane improved by the addition of certain organometallic compounds.
  • novel blends comprising high density polyethylenes (HDPE) having polydispersity (Mw/Mn) of ⁇ 12 maybe suitably used as components of cross-linkable polymeric compositions for use as automotive cables.
  • HDPE high density polyethylenes
  • Mw/Mn polydispersity
  • ⁇ 12 polydispersity of ⁇ 12
  • novel polymer blends comprising such HDPE with a low density polyethylene (LDPE) and optionally an ethylene vinyl acetate (EN A) component have been developed.
  • LDPE low density polyethylene
  • EN A ethylene vinyl acetate
  • crosslinkable polymeric composition comprising a blend of: (i) 100 parts by weight LDPE component (A)
  • a preferred composition comprises a blend of: (i) 100 parts by weight LDPE component (A)
  • a highly preferred composition comprises a blend of: (i) 100 parts by weight LDPE component (A), and
  • a particularly preferred composition comprises a blend of:
  • a most preferred composition comprises a blend of:
  • the LDPE component (A) has a density in the range 0.918 - 0.940 g/cm 3 , preferably a density in the range 0.923 - 0.940 g/cm 3 , most preferably a density in the range 0.926 - 0.940 g/cm 3 , and even more preferably a density in the range 0.930 - 0.940 g/cm 3 .
  • the LDPE component (A) has a MFR in the range 0.1 - 3 g/10 minutes, more preferably a MFR in the range 0.15 - 2 g/10 minutes, and most preferably a MFR in the range 0.5 to 1.5 g/10 minutes.
  • the HDPE component (B) has a density in the range 0.940 to 0.965 g/cm 3 , preferably a density in the range 0.940 - 0.960 g/cm 3 , and most preferably a density in the range 0.950 - 0.960 g/cm 3 .
  • the HDPE component (B) has a MFR in the range 1 - 10 g/lOminutes, and preferably a MFR in the range 2 - 6 g/lOminutes,
  • the preferred HDPE component (B) has a polydispersity (Mw/Mn) ⁇ 9 and a particularly preferred polydispersity (Mw/Mn) ⁇ 7.
  • the ENA component (C) has a vinyl acetate (NA) content in the range 1 -45 % by weight and a MFR in the range 0.1 - 50 g/10 minutes.
  • the LDPE, HDPE and ENA copolymer may suitably be prepared using well known polymerisation catalysts and processes.
  • MFR melt flow rate
  • Mw Weight average molecular weight
  • Mn number average molecular weight
  • GPC Gel Permeation Chromatography
  • Sample solutions were made by dissolving the polymers in the same solvent. All solutions were tested without filtering.
  • Molecular weights were calculated as polyethylene equivalents.
  • the polydispersity is defined as the ratio of Mw to Mn.
  • novel blends of the present invention result in crosslinkable polymeric compositions having the required combination of properties suitable for use as automotive cables having a reduced halogen content compared to PNC.
  • an automotive cable comprising a crosslikable polymeric composition
  • a crosslikable polymeric composition comprising
  • a preferred crosslinkable composition comprises a blend of:
  • a highly preferred crosslinkable composition comprises a blend of:
  • a particularly preferred crosslinkable composition comprises a blend of:
  • a most preferred crosslinkable composition comprises a blend of: (i) 100 parts by weight LDPE component (A), and
  • the preferred LDPE and HDPE suitable for use in the crosslinkable compositions according to this aspect of the present invention have the densities and MFR described above.
  • the preferred HDPE have a polydispersity of ⁇ 9 and most preferably ⁇ 7.
  • the antioxidant used as component (D) may be any conventional material but is preferably a combination of well known IrganoxTM materials. A combination of IrganoxTM 1010 and IrganoxTM MD1024 has been found to be particularly useful in the present invention.
  • a preferred antioxidant for use in the present invention comprises a mixture of Irganox MD 1024TM of concentration between 0.1 - 0.9 parts per hundred by weight of polymer blend and Irganox 1010TM of content 0.2 - 0.9 parts per hundred by weight of polymer blend.
  • a particularly preferred antioxidant package comprises a mixture of Irganox MD 1024TM of concentration between 0.1 - 0.6 parts per hundred by weight of polymer blend and Irganox 1010TM of content 0.2 - 0.6 parts per hundred by weight of polymer blend.
  • the flame retardant package (E) may be comprised of any conventional halogenated materials.
  • a coagent may be used for increased efficiency of the flame retardant additive.
  • suitable brominated agents are aromatic or aliphatic compounds typically containing an amount of bromine in the range 70 -90 %. Typical examples include polybrominated diphenyl ethers, hexabromocyclododecane, ethane- l,2-bis(pentabromophenyl), tetrabromophthalate diols and polyethers, tetrabromobisphenol A and derivatives.
  • a particularly preferred flame retardant package for use in the present invention comprises a coagent of content 3 - 28 parts per hundred by weight of polymer blend and a brominated additive of content 9 - 55 parts per hundred by weight of polymer blend, most preferably with a coagent content of 6 - 20 parts per hundred by weight of polymer blend and a brominated additive of content 15 - 40 parts per hundred by weight of polymer blend.
  • the polymeric composition may be extruded and crosslinked by use of a one or two step silane crosslinking process, a peroxide crosslinking process or an irradiation crosslinking process.
  • a promoter to enhance irradiation crosslinking may be incorporated.
  • Suitable one step silane procedures include dry silane or liquid silane injection and the two step silane procedure may be the SioplasTM process described in US 3646155.
  • Crosslinking procedures are well known and may be illustrated in EP 426073.
  • Example 6 Use of Novel blends as components of silane crosslinked automotive cables

Abstract

Novel polymer blends are provided comprising crosslinkable polymeric composition comprising (a) A blend of: (i) 100 parts by weight of LDPE component (A) (ii) 1-200 parts by weight of HDPE component (B) having a polydispersity (Mw/Mn) of <12. (iii) 0-100 parts by weight of an EVA copolymer (C). Particularly preferred compositions comprise blends having HDPE components having a polydispersity of <7. The blends are particularly suitable for use in automotive cables together with flame retardants and antioxidants. The crosslinked cables show an acceptable combination of improved temperature resistance and mechanical properties, abrasion resistance, reduced halogen content, ease of use and processability.

Description

CROSS INKABLE ETHYLENE POLYMER BLENDS
The present invention relates to novel polymer blends and in particular to blends particularly suitable for use as components of cross-linkable compositions for use as automotive cables. The novel polymer blends allow such cross-linkable compositions to impart improved mechanical properties and processability in such cables. At present automotive cables are commonly insulated with polyvinyl chloride and are designed to service temperatures of 100°C. However, increased working temperatures and reduced space under automobile bonnets have led the industry to increase the service temperature of automotive wires. In order to meet the new criteria of higher temperatures, for example in the range 105 - 125°C, automotive wires need to exhibit improved thermal resistance. As a consequence of this increased service temperature and the drive to reduce the use of chlorinated compounds in automobile manufacturing, polyvinyl chloride (PNC) is no longer a preferred material for automotive wiring.
In addition to the thermal resistance requirement of the new automotive specifications, the wires must also offer high mechanical properties, high abrasion resistance, excellent resistance to oils and solvents and resistance to fire.
The known alternatives to PNC for the insulation of automotive wires, suffer from several drawbacks. Compounds based on halogen free retardants suffer from poor processability and inferior mechanical properties compared to PNC compounds. Sioplas compounds whether halogen-free or halogenated suffer from poor shelf life which can give rise to gel problems during extrusion.
It is one of the objects of the present invention therefore to provide a suitable resin system for automotive cables having an acceptable combination of improved temperature resistance and mechanical properties, abrasion resistance, reduced halogen content, ease of use and processability.
US 5439965 describes polymeric compositions useful as insulation for wire and cable products for example automotive applications. In particular crosslinkable polymeric compositions comprising copolymers of ethylene and vinyl esters are disclosed in combination with flame retardant materials. Similar materials are described in US 4477523 and US 4255303.
US 4035325 describes flame retardant combinations of antimony trioxide and hexabromocyclododecane improved by the addition of certain organometallic compounds.
It has now been discovered that novel blends comprising high density polyethylenes (HDPE) having polydispersity (Mw/Mn) of < 12 maybe suitably used as components of cross-linkable polymeric compositions for use as automotive cables. In particular novel polymer blends comprising such HDPE with a low density polyethylene (LDPE) and optionally an ethylene vinyl acetate (EN A) component have been developed.
Thus according to the present invention there is provided a crosslinkable polymeric composition comprising a blend of: (i) 100 parts by weight LDPE component (A)
(ii) 1 - 200 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn)1 of < 12, and
(iii) 0 - 100 parts by weight of an EN A component (C).
A preferred composition comprises a blend of: (i) 100 parts by weight LDPE component (A)
(ii) 1 - 100 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of< 12, and
(iii) 0 - 100 parts by weight of an ENA component (C).
A highly preferred composition comprises a blend of: (i) 100 parts by weight LDPE component (A), and
(ii) 1 - 60 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12. A particularly preferred composition comprises a blend of:
(i) 100 parts by weight LDPE component (A), and
(ii) 25 - 55 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12. A most preferred composition comprises a blend of:
(i) 100 parts by weight LDPE component (A), and
(ii) 35 - 55 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12.
The LDPE component (A) has a density in the range 0.918 - 0.940 g/cm3, preferably a density in the range 0.923 - 0.940 g/cm3, most preferably a density in the range 0.926 - 0.940 g/cm3, and even more preferably a density in the range 0.930 - 0.940 g/cm3.
The LDPE component (A) has a MFR in the range 0.1 - 3 g/10 minutes, more preferably a MFR in the range 0.15 - 2 g/10 minutes, and most preferably a MFR in the range 0.5 to 1.5 g/10 minutes.
The HDPE component (B) has a density in the range 0.940 to 0.965 g/cm3, preferably a density in the range 0.940 - 0.960 g/cm3, and most preferably a density in the range 0.950 - 0.960 g/cm3.
The HDPE component (B) has a MFR in the range 1 - 10 g/lOminutes, and preferably a MFR in the range 2 - 6 g/lOminutes,
The preferred HDPE component (B) has a polydispersity (Mw/Mn) <9 and a particularly preferred polydispersity (Mw/Mn) <7.
The ENA component (C) has a vinyl acetate (NA) content in the range 1 -45 % by weight and a MFR in the range 0.1 - 50 g/10 minutes. The LDPE, HDPE and ENA copolymer may suitably be prepared using well known polymerisation catalysts and processes.
The melt flow rate (MFR) measurements are made according to ISO 1133 condition D and density measurements are made according to ISO 1183 method D. Weight average molecular weight (Mw) and number average molecular weight (Mn) were measured by Gel Permeation Chromatography (GPC) using a Waters 150C instrument using a mobile phase of 1,2,4-trichlorobenzene at 140°C. Sample solutions were made by dissolving the polymers in the same solvent. All solutions were tested without filtering. Molecular weights were calculated as polyethylene equivalents. The polydispersity is defined as the ratio of Mw to Mn.
When used in combination with an antioxidant system (D) and a flame retardant package (E) the novel blends of the present invention result in crosslinkable polymeric compositions having the required combination of properties suitable for use as automotive cables having a reduced halogen content compared to PNC.
Thus according to another aspect of the present invention there is provided an automotive cable comprising a crosslikable polymeric composition comprising
(a) a blend of (i) 100 parts by weight LDPE component (A)
(ii) 1 - 200 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12, and
(iii) 0 - 100 parts by weight of an ENA copolymer (C).
(b) an antioxidant system (D), and (c) a flame retardant material (E).
A preferred crosslinkable composition comprises a blend of:
(i) 100 parts by weight LDPE component (A)
(ii) 1 - 100 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12, and (iii) 0 - 100 parts by weight of an ENA copolymer (C).
A highly preferred crosslinkable composition comprises a blend of:
(i) 100 parts by weight LDPE component (A), and
(ii) 1 - 60 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12. A particularly preferred crosslinkable composition comprises a blend of:
(i) 100 parts by weight LDPE component (A), and
(ii) 35 - 55 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12.
A most preferred crosslinkable composition comprises a blend of: (i) 100 parts by weight LDPE component (A), and
(ii) 25 - 55 parts by weight HDPE component (B) having a polydispersity
(Mw/Mn) of < 12. The preferred LDPE and HDPE suitable for use in the crosslinkable compositions according to this aspect of the present invention have the densities and MFR described above.
The preferred HDPE have a polydispersity of < 9 and most preferably < 7. The antioxidant used as component (D) may be any conventional material but is preferably a combination of well known Irganox™ materials. A combination of Irganox™ 1010 and Irganox™ MD1024 has been found to be particularly useful in the present invention.
A preferred antioxidant for use in the present invention comprises a mixture of Irganox MD 1024™ of concentration between 0.1 - 0.9 parts per hundred by weight of polymer blend and Irganox 1010™ of content 0.2 - 0.9 parts per hundred by weight of polymer blend. A particularly preferred antioxidant package comprises a mixture of Irganox MD 1024™ of concentration between 0.1 - 0.6 parts per hundred by weight of polymer blend and Irganox 1010™ of content 0.2 - 0.6 parts per hundred by weight of polymer blend.
The flame retardant package (E) may be comprised of any conventional halogenated materials. As part of the flame retardant package (E) optionally a coagent may be used for increased efficiency of the flame retardant additive. Examples of suitable brominated agents are aromatic or aliphatic compounds typically containing an amount of bromine in the range 70 -90 %. Typical examples include polybrominated diphenyl ethers, hexabromocyclododecane, ethane- l,2-bis(pentabromophenyl), tetrabromophthalate diols and polyethers, tetrabromobisphenol A and derivatives. Typical examples of coagents include antimony trioxide, Zinc sulphide, Zinc oxide, Zinc borate and boric acid. A particularly preferred flame retardant package for use in the present invention comprises a coagent of content 3 - 28 parts per hundred by weight of polymer blend and a brominated additive of content 9 - 55 parts per hundred by weight of polymer blend, most preferably with a coagent content of 6 - 20 parts per hundred by weight of polymer blend and a brominated additive of content 15 - 40 parts per hundred by weight of polymer blend.
The use of such a flame retardant package provides limited interference with the crosslinking and extrusion properties of the novel polymer blend and allows the mechanical properties and abrasion requirements of automotive cables to be achieved.
The polymeric composition may be extruded and crosslinked by use of a one or two step silane crosslinking process, a peroxide crosslinking process or an irradiation crosslinking process. Optionally a promoter to enhance irradiation crosslinking may be incorporated.
Suitable one step silane procedures include dry silane or liquid silane injection and the two step silane procedure may be the Sioplas™ process described in US 3646155. Crosslinking procedures are well known and may be illustrated in EP 426073.
The present invention will now be further illustrated by reference to the following examples:
Example 1 : Novel Blend Formulation
Figure imgf000007_0001
Example 2: Novel Blend Formulation
Figure imgf000007_0002
Example 3: Novel Blend Formulation
Figure imgf000007_0003
Example 4: Novel Blend Formulation
Figure imgf000008_0001
Example 5: Novel Blend Formulation
Figure imgf000008_0002
Example 6: Use of Novel blends as components of silane crosslinked automotive cables The novel polymer blends above when compounded with an antioxidant system and flame retardant package indicated below:
Figure imgf000008_0003
using a twin screw extruder (40 mm, 21 L/D, counter-rotating) with the following compounding settings:
Figure imgf000009_0001
give formulations suitable for use as a crosslinkable automotive formulation.
These formulations when extruded on a 45 mm 24 L/D extruder with addition of 2 % of Dry Silane masterbatch 7030 DS 80 from PolyOne (one step silane crosslinking) give wires suitable for use in automotive cables. - Extruder temperatures (°C):
Figure imgf000009_0002
- screw design : Elise
- extrusion tools : 3 angle die and wire guide
- speed of the line : 50 m / min
- thickness of the insulating layer : 0.3 mm
- diameter of the copper core : 0.8 mm
- temperature of the compound at the entrance of the feed zone : cold (23 °C)
- temperature of the cooling trough : 60 °C 3 - Cable properties: Crosslinking performance in air (according to IEC 811-2-D:
After 4 hours in water at 80°C :
Hot set test at 200 °C, 20 N/cm2 (%): <150% Mechanical properties before ageing (according to EEC 811-1-1):
Figure imgf000010_0001
Winding test after ageing 10 days ( ), 150°C on copper (according to IEC 811-1-2 : No cracks
Flame test (according to ISO 6722):
Pass Scrape abrasion resistance (according to ISO 6722):
Number of cycles before failure : > 300 Example 7: Use of Novel blends as components of irradiation crosslinked automotive cables
The novel polymer blends above when compounded with an antioxidant system and flame retardant package indicated below:
Figure imgf000010_0002
using a twin screw extruder (40 mm, 21 L/D, counter-rotating) using the following compounding settings:
Figure imgf000011_0001
give formulations suitable for use as an irradiation crosslinkable automotive formulation.
These formulations when extruded on a 45 mm 24 L/D extruder under the following conditions and crosslinked by irradiation under the following conditions give wires suitable for use in automotive cables.
- Extruder temperatures (°C):
Figure imgf000011_0002
- Screw design : Elise
- Extrusion tools : 3 angle die and wire guide
- Speed of the line : 50 m / min - Thickness of the insulating layer : 0.3 mm
- Diameter of the copper core : 0.8 mm
- Temperature of the compound at the entrance of the feed zone : cold (23 °C)
- Temperature of the cooling trough : 60 °C
- Irradiation energy: 20 Megarads 4 - Cable properties:
Crosslinking performance (according to IEC 811-2-1): Hot set test at 200 °C, 20 N/cm2 (%): <150% Mechanical properties before ageing (according to IEC 811-1-1):
Figure imgf000012_0001
Winding test after ageing 10 days ( ), 150°C on copper (according to IEC 811-1-2): No cracks Flame test (according to ISO 6722):
Pass Scrape abrasion resistance (according to ISO 6722): Number of cycles before failure : > 300

Claims

Claims
1. A crosslinkable polymeric composition comprising (a) a blend of:
(i) 100 parts by weight of LDPE component (A)
(ii) 1 -200 parts by weight of HDPE component (B) having a polydispersity (Mw/Mn) of < 12.
(iii) 0 - 100 parts by weight of an ENA copolymer (C).
2. A composition according to claim 1 wherein the blend comprises (i) 100 parts by weight of LDPE component (A)
(ii) 1 - 100 parts by weight of HDPE component (B) having a polydispersity (Mw/Mn) of < 12, and
(iii) 0 - 100 parts by weight of an ENA copolymer (C).
3. A composition according to either of the preceding claims wherein the blend comprises
(i) 100 parts by weight of LDPE component (A) and (ii) 1 - 60 parts by weight of HDPE component (B) having a polydispersity
(Mw/Mn) of < 12.
4. A composition according to any of the preceding claims wherein the blend comprises
(i) 100 parts by weight of LDPE component (A) and (ii) 25 - 55 parts by weight of HDPE component (B) having a polydispersity
(Mw/Mn) of < 12.
5. A composition according to any of the preceding claims wherein the blend comprises
(i) 100 parts by weight of LDPE component (A) and
(ii) 35 - 55 parts by weight of HDPE component (B) having a polydispersity
(Mw/Mn) of < 12.
6. A composition according to any of the preceding, claims wherein the HDPE has a polydispersity of < 9.
7. A composition according to any of the preceding claims wherein the HDPE has a polydispersity of < 7.
8. A composition according to any of the preceding claims wherein the HDPE has a density in the range 0.940 - 0.960 g/cm3.
9. A composition according to any of the preceding claims wherein the HDPE has a density in the range 0.950 - 0.960 g/cm3.
10. A composition according to any of the preceding claims wherein the HDPE has ■ a MFR in the range 2 -6 g/ 10 minutes.
11. A composition according to any of the preceding claims wherein the LDPE has a density in the range 0.926 - 0.940 g.cm .
12. A composition according to any of the preceding claims wherein the LDPE has a density in the range 0.930 - 0.940 g.cm2.
13. A composition according to any of the preceding claims wherein the LDPE has a MFR in the range 0.15 - 2 g/10 minutes.
14. A composition according to any of the preceding claims wherein the ENA component (C) has a vinyl acetate (NA) content in the range 1 -45 % by weight and a MFR in the range 0.1 - 50 g/10 minutes.
15. An automotive cable comprising a crosslinkable polymeric composition comprising
(a) A blend of:
(i) 100 parts by weight of LDPE component (A)
(ii) 1 -200 parts by weight of HDPE component (B) having a polydispersity (Mw/Mn) of < 12. (iii) 0 - 100 parts by weight of an ENA copolymer (C),
(b) An antioxidant system (D) and
(c) A flame retardant material (E).
16. An automotive cable according to claim 14 comprising a crosslinkable polymeric composition as claimed in any of claims 2 to 14.
17. A cable according to claims 15 or 16 wherein the flame retardant material (E) comprises a halogenated material.
18. A cable according to any of claim 17 wherein the halogenated material is present in amount of 15 - 40 parts per hundred of the polymer blend.
19. A cable according to any of claims 15 - 18 wherein the flame retardant material (E) includes a coagent.
20. A cable according to claim 19 wherein the coagent is present in amount of 6 - 20 parts per hundred of the polymer blend.
21. A cable according to claim 19 wherein the coagent is antimony trioxide.
22. A cable according to claims 15 -21 wherein the antioxidant system (D) is present in amount of 0.2 - 0.9 parts per hundred of the polymer blend.
23. A polymeric composition according to any of the preceding claims crosslinkable by use of a silane, a peroxide or an irradiation crosslinking process.
PCT/IB2001/002742 2000-11-01 2001-10-25 Crosslinkable ethylene polymer blends WO2002036680A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002216321A AU2002216321A1 (en) 2000-11-01 2001-10-25 Crosslinkable ethylene polymer blends

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GB0026706.2 2000-11-01
GB0026706A GB0026706D0 (en) 2000-11-01 2000-11-01 Novel polymer blends

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WO2002036680A1 true WO2002036680A1 (en) 2002-05-10

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041214A1 (en) * 2003-09-30 2005-05-06 Pirelli & C. S.P.A. Cable with a coating layer made from a waste material
CN100400585C (en) * 2006-03-10 2008-07-09 上海诚壹塑胶制品有限公司 Angular jetor flexible-piping materials and production thereof
CN101177508B (en) * 2006-11-09 2011-08-24 上海派瑞特塑业有限公司 Modified high-density polyethylene material and method for making same
US20140018481A1 (en) * 2012-07-12 2014-01-16 King Abdulaziz City for Science and Technology (KACST) Advanced halogen free flame retardant composition for heat shrinkable material and method of making the same
US9530537B2 (en) 2011-09-30 2016-12-27 Dow Global Technologies Llc Halogen-free propylene-based insulation and conductor coated with same
CN109265797A (en) * 2018-08-30 2019-01-25 合肥瑞来宝电源技术有限公司 The preparation method of CABLE MATERIALS for induction heating power
CN109485989A (en) * 2018-11-30 2019-03-19 江苏达胜高聚物股份有限公司 A kind of photovoltaic cable CABLE MATERIALS and preparation method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956567A (en) * 1973-03-05 1976-05-11 National Distillers And Chemical Corporation Insulated high voltage wire coated with a flame retardant composition and process of preparing the same
EP0546841A1 (en) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Abrasion-resistant flame-retardant composition
WO1999065957A1 (en) * 1998-06-19 1999-12-23 Japan Polyolefins Co., Ltd. ETHYLENE/α-OLEFIN COPOLYMER, COMPOSITION THEREOF, FILM THEREOF, AND USES OF THESE

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3956567A (en) * 1973-03-05 1976-05-11 National Distillers And Chemical Corporation Insulated high voltage wire coated with a flame retardant composition and process of preparing the same
EP0546841A1 (en) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Abrasion-resistant flame-retardant composition
WO1999065957A1 (en) * 1998-06-19 1999-12-23 Japan Polyolefins Co., Ltd. ETHYLENE/α-OLEFIN COPOLYMER, COMPOSITION THEREOF, FILM THEREOF, AND USES OF THESE
EP1153948A1 (en) * 1998-06-19 2001-11-14 Japan Polyolefins Co., Ltd. Ethylene/alpha-olefin copolymer, composition thereof, film thereof, and uses of these

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041214A1 (en) * 2003-09-30 2005-05-06 Pirelli & C. S.P.A. Cable with a coating layer made from a waste material
US7672555B2 (en) 2003-09-30 2010-03-02 Prysmian Cavi E Sistemi Energia S.R.L. Cable with a coating layer made from a waste material
CN100400585C (en) * 2006-03-10 2008-07-09 上海诚壹塑胶制品有限公司 Angular jetor flexible-piping materials and production thereof
CN101177508B (en) * 2006-11-09 2011-08-24 上海派瑞特塑业有限公司 Modified high-density polyethylene material and method for making same
US9530537B2 (en) 2011-09-30 2016-12-27 Dow Global Technologies Llc Halogen-free propylene-based insulation and conductor coated with same
US20140018481A1 (en) * 2012-07-12 2014-01-16 King Abdulaziz City for Science and Technology (KACST) Advanced halogen free flame retardant composition for heat shrinkable material and method of making the same
CN109265797A (en) * 2018-08-30 2019-01-25 合肥瑞来宝电源技术有限公司 The preparation method of CABLE MATERIALS for induction heating power
CN109485989A (en) * 2018-11-30 2019-03-19 江苏达胜高聚物股份有限公司 A kind of photovoltaic cable CABLE MATERIALS and preparation method thereof
CN109485989B (en) * 2018-11-30 2021-09-14 江苏达胜高聚物股份有限公司 Cable material for photovoltaic cable and preparation method thereof

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GB0026706D0 (en) 2000-12-20

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