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WO2002036680A1 - Melanges polymeriques d'ethylene reticulable - Google Patents

Melanges polymeriques d'ethylene reticulable 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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WO
WIPO (PCT)
Prior art keywords
weight
parts
component
hdpe
polydispersity
Prior art date
Application number
PCT/IB2001/002742
Other languages
English (en)
Inventor
Olivier Biles
Original Assignee
BP Köln GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BP Köln GmbH filed Critical BP Köln GmbH
Priority to AU2002216321A priority Critical patent/AU2002216321A1/en
Publication of WO2002036680A1 publication Critical patent/WO2002036680A1/fr

Links

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
    • 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 atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • 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

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Organic Insulating Materials (AREA)
  • Insulated Conductors (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des nouveaux mélanges polymériques comprenant une composition polymérique réticulable. Cette composition comprend (a) un mélange contenant (i) 100 parties en poids d'un constituant PEBD (A), (ii) entre 1 et 200 parties en poids d'un constituant PEHD (B) présentant une polydispersité (Mw/Mn) inférieure à 12, et (iii) entre 0 et 100 parties en poids d'un copolymère EVA (C). Des compositions préférées comprennent des mélanges renfermant des constituants PEHD présentant une polydispersité inférieure à 7. Ces mélanges peuvent notamment être utilisés dans des câbles d'automobiles conjointement avec des agents ignifuges et des agents antioxydants. Les câbles réticulés permettent de combiner une résistance aux températures élevées et des propriétés mécaniques améliorées, une bonne résistance à l'abrasion, une teneur en halogène réduite, une facilité d'utilisation accrue et une aptitude au traitement améliorée.
PCT/IB2001/002742 2000-11-01 2001-10-25 Melanges polymeriques d'ethylene reticulable WO2002036680A1 (fr)

Priority Applications (1)

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

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB0026706.2 2000-11-01
GB0026706A GB0026706D0 (en) 2000-11-01 2000-11-01 Novel polymer blends

Publications (1)

Publication Number Publication Date
WO2002036680A1 true WO2002036680A1 (fr) 2002-05-10

Family

ID=9902368

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IB2001/002742 WO2002036680A1 (fr) 2000-11-01 2001-10-25 Melanges polymeriques d'ethylene reticulable

Country Status (3)

Country Link
AU (1) AU2002216321A1 (fr)
GB (1) GB0026706D0 (fr)
WO (1) WO2002036680A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041214A1 (fr) * 2003-09-30 2005-05-06 Pirelli & C. S.P.A. Cable presentant une couche de revetement constituee d'un materiau de recuperation
CN100400585C (zh) * 2006-03-10 2008-07-09 上海诚壹塑胶制品有限公司 角形注头软管材料及其软管制造方法
CN101177508B (zh) * 2006-11-09 2011-08-24 上海派瑞特塑业有限公司 改性的高密度聚乙烯材料及其制备方法
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 (zh) * 2018-08-30 2019-01-25 合肥瑞来宝电源技术有限公司 用于感应加热电源的电缆料的制备方法
CN109485989A (zh) * 2018-11-30 2019-03-19 江苏达胜高聚物股份有限公司 一种光伏电缆用电缆料及其制备方法

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 (fr) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Compositions résistantes à l'abrasion et ignifuges
WO1999065957A1 (fr) * 1998-06-19 1999-12-23 Japan Polyolefins Co., Ltd. Copolymere d'ethylene/alpha olefine, composition de ce copolymere, film forme de ce copolymere et utilisations associees

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 (fr) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Compositions résistantes à l'abrasion et ignifuges
WO1999065957A1 (fr) * 1998-06-19 1999-12-23 Japan Polyolefins Co., Ltd. Copolymere d'ethylene/alpha olefine, composition de ce copolymere, film forme de ce copolymere et utilisations associees
EP1153948A1 (fr) * 1998-06-19 2001-11-14 Japan Polyolefins Co., Ltd. Copolymere d'ethylene/alpha olefine, composition de ce copolymere, film forme de ce copolymere et utilisations associees

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005041214A1 (fr) * 2003-09-30 2005-05-06 Pirelli & C. S.P.A. Cable presentant une couche de revetement constituee d'un materiau de recuperation
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 (zh) * 2006-03-10 2008-07-09 上海诚壹塑胶制品有限公司 角形注头软管材料及其软管制造方法
CN101177508B (zh) * 2006-11-09 2011-08-24 上海派瑞特塑业有限公司 改性的高密度聚乙烯材料及其制备方法
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 (zh) * 2018-08-30 2019-01-25 合肥瑞来宝电源技术有限公司 用于感应加热电源的电缆料的制备方法
CN109485989A (zh) * 2018-11-30 2019-03-19 江苏达胜高聚物股份有限公司 一种光伏电缆用电缆料及其制备方法
CN109485989B (zh) * 2018-11-30 2021-09-14 江苏达胜高聚物股份有限公司 一种光伏电缆用电缆料及其制备方法

Also Published As

Publication number Publication date
AU2002216321A1 (en) 2002-05-15
GB0026706D0 (en) 2000-12-20

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