WO2017021800A1 - Composition de gaine résistant à l'huile et à la boue - Google Patents

Composition de gaine résistant à l'huile et à la boue Download PDF

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Publication number
WO2017021800A1
WO2017021800A1 PCT/IB2016/054162 IB2016054162W WO2017021800A1 WO 2017021800 A1 WO2017021800 A1 WO 2017021800A1 IB 2016054162 W IB2016054162 W IB 2016054162W WO 2017021800 A1 WO2017021800 A1 WO 2017021800A1
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WO
WIPO (PCT)
Prior art keywords
composition
vinyl acetate
polymer
flame retardant
crosslinkable
Prior art date
Application number
PCT/IB2016/054162
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English (en)
Inventor
Mike Edward SLEVIN
David Richard Thomas ROBERTS
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Aei Compounds Ltd.
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 Aei Compounds Ltd. filed Critical Aei Compounds Ltd.
Publication of WO2017021800A1 publication Critical patent/WO2017021800A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • Cables for use in marine structures such as oil well drilling ships, oil well drilling structures or drillships are required to have more excellent oil resistances compared to cables for more general use.
  • cables for such applications often are also required to maintain their flexibility even at low temperatures, e.g. down to - 40 °C. It has generally proved to be very difficult for a cable sheath material having flexibility at a such low temperatures as well as to satisfy both the oil resistance requirement of IEC 60092-359 and the oil resistance requirement of the NEK 606.
  • halogen such as bromine or chlorine
  • halogen-containing compounds have been reported to generate environmental hormones, which can result in a toxicity to the human body and a variety of adverse human health consequences.
  • halogens can cause chemical reactions through interaction with water and heat, resulting in the generation of highly toxic products.
  • a fire breaks out in, for example, in ships provided with halogen-containing cables, the risk of human casualties can be increased due to the generation of such harmful gases.
  • the present application relates generally to the field of materials which can be used as sheathing materials in wire and cable applications.
  • the sheathing materials are desirably moisture curable, halogen-free polymer compositions, which includes a crosslinkable thermoplastic polymer and flame retardant material.
  • the flame retardant material typically includes a metal hydroxide flame retardant, such as a magnesium, calcium, zinc and/or aluminum hydroxide.
  • the crosslinkable thermoplastic polymer commonly includes a thermoplastic polyester elastomer, which may be blended with one or more other thermoplastic polymers, such as an ethylene/vinyl acetate copolymer.
  • the polymer component of the sheathing material may also include an aromatic
  • polycarbodiimide such as a polycarbodiimide based on aromatic diisocyanate chemistry, e.g., substituted phenyl diisocyanate chemistry.
  • the crosslinkable thermoplastic polymer is desirably curable by exposure to moisture, e.g., by the inclusion of moisture curable silane functionality in the thermoplastic polymer. This may be accomplished by grafting silane functional groups onto a thermoplastic polymer.
  • crosslinkable thermoplastic polymer may include thermoplastic polyester elastomer and/or ethylene/vinyl acetate copolymer, which has been grafted with silane functional groups, e.g., through free radical initiated reaction with a vinyl alkoxysilane, such as a vinyltrialkoxysilane.
  • the present application provides a moisture curable, halogen-free polymer wire sheathing composition.
  • the wire sheathing composition includes a crosslinkable thermoplastic polymer component, which includes silane-grafted polymer blend, and metal hydroxide flame retardant.
  • the silane-grafted polymer blend is typically formed by silane- grafting a polymer blend which includes thermoplastic polyester elastomer and
  • the thermoplastic polyester elastomer may be a thermoplastic elastomer ether ester, such a block copolymer, which includes a polyalkylene terephthalate segment and a long-chain polyalkylene ether segment, e.g., a polybutylene terephthalate segment, and a long-chain polyether glycol, such as a polyethyleneglycol segment.
  • a thermoplastic elastomer ether ester such a block copolymer, which includes a polyalkylene terephthalate segment and a long-chain polyalkylene ether segment, e.g., a polybutylene terephthalate segment, and a long-chain polyether glycol, such as a polyethyleneglycol segment.
  • the polymer blend may also include an aromatic polycarbodiimide, such as an aromatic polycarbodiimide based on 2,6-diisopropyl phenyl isocyanate (DIPPI) and/or 2,4,6-triisopropyl phenyl diisocyanate (TRIDI) chemistry.
  • aromatic polycarbodiimide such as an aromatic polycarbodiimide based on 2,6-diisopropyl phenyl isocyanate (DIPPI) and/or 2,4,6-triisopropyl phenyl diisocyanate (TRIDI) chemistry.
  • DIPPI 2,6-diisopropyl phenyl isocyanate
  • TIDI 2,4,6-triisopropyl phenyl diisocyanate
  • the metal hydroxide flame retardant may include magnesium, calcium, zinc or aluminum hydroxide(s) or a mixture thereof.
  • the present application provides moisture curable, halogen-free polymer wire sheathing compositions, which typically exhibit excellent oil and mud resistance.
  • the moisture curable, halogen-free sheathing materials may be used in wire and cable applications.
  • the sheathing material includes a crosslinkable thermoplastic polymer and flame retardant material.
  • the flame retardant material may include a metal hydroxide flame retardant, such as a magnesium, calcium, zinc and/or aluminum hydroxide.
  • crosslinkable thermoplastic polymer includes a thermoplastic polyester elastomer, which may be blended with one or more other thermoplastic polymers.
  • the polymer component of the sheathing material may also include an aromatic polycarbodiimide.
  • the crosslinkable thermoplastic polymer is typically curable by exposure to moisture and may include moisture curable silane functionality in the thermoplastic polymer, e.g., silane functionality that has been grafted onto the thermoplastic polymer(s).
  • the halogen-free polymer wire sheathing composition typically includes about 10 to about 200 parts by weight of the metal hydroxide flame retardant per 100 parts by weight of the crosslinkable thermoplastic polymer.
  • the wire sheathing composition may include about 80 to about 150 parts by weight magnesium dihydroxide per 100 parts by weight of the crosslinkable thermoplastic polymer.
  • the crosslinkable thermoplastic polymer typically includes a silane-grafted polymer blend, which may be formed by reacting a mixture which includes the thermoplastic polyester elastomer, the ethylene/vinyl acetate copolymer, vinylalkoxysilane and a free radical initiator.
  • the mixture may also include an aromatic polycarbodiimide (PCD).
  • the thermoplastic polyester elastomer may include a thermoplastic elastomer ether ester, such as a thermoplastic polyester ether elastomer with polyalkylene terephthalate and long-chain polyether glycol segments.
  • a suitable thermoplastic polyester ether elastomer is a block copolymer, which includes a polybutylene terephthalate segment and a long-chain polyether glycol.
  • the ethylene/vinyl acetate (EVA) copolymer is typically a random ethylene /vinyl acetate copolymer.
  • the ethylene/vinyl acetate copolymer may have a vinyl acetate content of about 25-30%, more commonly about 27-29%.
  • Such ethylene/vinyl acetate copolymers may suitably have a melt flow index (MFI as determined pursuant to ISO 11357) of about 0.1 - 1 g/10 min (@ 230 C) and a density of about 0.94-0.96.
  • MFI melt flow index
  • Such EVA copolymers may suitably have a Shore A hardness (as determined pursuant to ISO 868) of about 70-80 and/or a melting temperature of about 135-145 °C (as determined pursuant to ISO 11357).
  • the aromatic polycarbodiimide may be introduced into the mixture to be silane grafted as a polymer blend with the thermoplastic polyester elastomer.
  • the aromatic polycarbodiimide may be a polycarbodiimide based on substituted phenyl diisocyanate chemistry.
  • a suitable example is an aromatic polycarbodiimide based on 2,6- diisopropyl phenyl isocyanate (DIPPI) and/or 2,4,6-triisopropyl phenyl diisocyanate (TRIDI) chemistry.
  • the polymer blend may include about 10-25 wt.% of the
  • PCD polycarbodiimide
  • the flame retardant material may be metal hydroxide flame retardant, such as a magnesium, calcium, zinc and/or aluminum hydroxide.
  • the flame retardant material typically includes magnesium hydroxide and/or aluminum hydroxide, which commonly has an average particle size no more than about 3 microns.
  • the flame retardant material may include magnesium hydroxide, such as a precipitated magnesium dihydroxide (MDH) having average particle size of no more than about 2 microns.
  • MDH precipitated magnesium dihydroxide
  • the magnesium dihydroxide may be in the form of hexagonal platelets having average particle size of about 0.8-2 microns.
  • the present crosslinkable polymer composites may suitably contain a number of optional ingredients.
  • the composites may include anti-oxidant(s), a UV protector/light stabilizer, colorant, and optional processing aids such as an UHMW silicone, which may be dispersed in a thermoplastic polyolefin, and/or chalk.
  • processing aids such as an UHMW silicone, which may be dispersed in a thermoplastic polyolefin, and/or chalk.
  • the tables below provide illustrative formulations that can be used to produce the present wire sheathing materials.
  • the silane grafted polyester blends may be formed by combining a thermoplastic polyester ether elastomer, such as a polyester ether having polybutylene terephthalate and long-chain polyether glycol segments, with a
  • polycarbodiimide available as a blend in the polyester ether
  • EVA random ethylene/vinyl acetate copolymer
  • the mixture may also include other additives, such as antioxidant, chalk (CaC0 3 ).
  • Vinyl silane e.g., vinyl trimethoxysilane, and organic peroxide (such as l, l-di(tert- butylperoxy)-3,3,5-trimethylcyclohexane) are included in the amounts shown.
  • the mixture may suitably be compounded in an extruder at a temperature of about 140 to 200°C to provide the silane grafted polymer blend.
  • the silane-grafted polymer blend may be compounded with metal hydroxide flame retardant (e.g., magnesium hydroxide and/or aluminum hydroxide) and other conventional additives and then extruded to form a halogen free, flame-retardant, crosslinkable polymer composite.
  • metal hydroxide flame retardant e.g., magnesium hydroxide and/or aluminum hydroxide
  • This may suitably be carried out by extrusion compounding the silane-grafted polymer blend metal hydroxide flame retardant and other conventional additives in an extruder at a temperature of about 135 to 200°C.
  • the crosslinkable polymer composite is typically UV stabilized and is curable by exposure to moist conditions. In use, the crosslinkable polymer composite is typically mixed with a crosslinking catalyst
  • the moisture cured product is commonly able to satisfy the requirements of the NEK 606 and/or IEC 60092-359 standards.
  • the product typically shows good flexibility and confers tough sheathing protection. It is particular notable that the moisture cured product may exhibit oil and mud resistance, such required by specification NEK 606, in combination with one or more of the other specifications typically required for such sheathing materials.
  • the tables below provide illustrations of suitable formulations for producing the present crosslinkable halogen-free, flame retardant filled polymer composites.
  • the components for listed for Silane Grafted Polyester Blend Formulation Al can be melt processed, e.g., via extrusion, to provide Silane Grafted Polymer Blend Al . This may then be combined in the amount shown with the other ingredients listed for Flame Retardant Filled Polymer Composite Formulation HFFR-1 in a melt processing step, e.g., via extrusion, to provide a crosslinkable polymer composite.
  • the components for listed for Silane Grafted Polyester Blend Formulation A2 can be melt processed, e.g., via extrusion, to provide Silane Grafted Polymer Blend A2. This may then be combined in the amount shown with the other ingredients listed for Flame Retardant Filled Polymer Composite Formulation FIFFR-2 in a melt processing step, e.g., via extrusion, to provide a crosslinkable polymer composite.
  • Production of a halogen free flame-retardant, silane crosslinkable, UV stabilized, flexible polymer composite, curable by exposure to moist conditions can be carried out by combining the components for listed below for the 1 st Pass - Silane Grafted Polyester/EVA Blend Formula. This can be done via a melt processing operation, e.g., via extrusion compounding at about 140 to 200°C, to provide the 1 st Pass Silane Grafted Polymer Blend.
  • This may then be combined in the amount shown with the other ingredients listed for the 2 nc Pass - Flame Retardant Filled Polymer Composite in a melt processing step, e.g., via extrusion compounding at about 135 to 200° C, to provide a crosslinkable polymer composite.
  • the moisture curable, halogen-free polymer composite includes a crosslinkable thermoplastic polymer and metal hydroxide flame retardant selected from magnesium, calcium, zinc and aluminum hydroxide or mixtures thereof.
  • the crosslinkable thermoplastic polymer includes a silane-grafted polymer blend, where the polymer blend includes thermoplastic polyester elastomer and ethylene/vinyl acetate copolymer and may also include an aromatic polycarbodiimide.
  • the thermoplastic polyester elastomer typically includes a thermoplastic elastomer ether ester, such as a block copolymer, which includes a polybutylene terephthalate segment and a long-chain polyether glycol.
  • the ethylene/vinyl acetate copolymer typically has a vinyl acetate content of about 20-35% and, commonly, about 25-30%.
  • the metal hydroxide flame retardant generally includes magnesium dihydroxide (Mg(OH)2).
  • the magnesium dihydroxide may be a precipitated magnesium dihydroxide with a median particle size of about 0.1 to 3 microns (often - 0.8 - 2 microns) and may be in the form of hexagonal platelets.
  • the composition may also include one or more of chalk, antioxidant, ultrahigh molecular weight silicone processing additive and UV protector/light stabilizer additive.
  • the moisture curable, halogen-free polymer composition includes 100 parts by weight of a crosslinkable thermoplastic polymer and about 10 to about 200 parts by weight metal hydroxide selected from magnesium, calcium, zinc or aluminum hydroxides or mixtures thereof.
  • the crosslinkable thermoplastic polymer typically includes silane-grafted thermoplastic polyester elastomer and/or silane-grafted ethylene/vinyl acetate copolymer.
  • the crosslinkable thermoplastic polymer may also include an aromatic polycarbodiimide, such as an aromatic polycarbodiimide based on 2,6-diisopropyl phenyl isocyanate (DIPPI) and/or 2,4,6-triisopropyl phenyl diisocyanate (TRIDI) chemistry.
  • the composition may also include chalk and/or antioxidant.
  • the moisture curable, halogen-free polymer composition includes a crosslinkable thermoplastic polymer, which includes silane-grafted thermoplastic polyester elastomer, silane-grafted ethylene/vinyl acetate copolymer and aromatic polycarbodiimide; and metal hydroxide flame retardant, which comprises magnesium dihydroxide.
  • the magnesium dihydroxide may be precipitated magnesium dihydroxide with a median particle size of about 0.1 to 2 microns, where the precipitated magnesium dihydroxide is in the form of hexagonal platelets.
  • the composition may also include one or more of chalk, antioxidant, ultrahigh molecular weight silicone processing additive and UV protector/light stabilizer additive.
  • the moisture curable, halogen-free polymer composition includes 100 parts by weight of a crosslinkable thermoplastic polymer comprising silane- grafted polymer blend, which includes an ether ester block copolymer including a polybutylene terephthalate segment and a long-chain polyether glycol, ethylene/vinyl acetate copolymer and aromatic polycarbodiimide; and about 80 to about 150 parts by weight precipitated magnesium dihydroxide with a median particle size of about 0.1 to 2 microns.
  • the composition may also include one or more of chalk, antioxidant, ultrahigh molecular weight silicone processing additive and UV protector/light stabilizer additive.
  • a silane grafted polymer blend may be formed by combining a polyester ether having polybutylene terephthalate segment and a long-chain polyether glycol, with a polycarbodiimide (available as a blend in the polyester ether) and a random ethylene/vinyl acetate copolymer (EVA) in the amounts shown in the table above for 1 st pass ingredients.
  • the mixture also includes antioxidant, chalk (CaC03), vinyl trimethoxysilane and organic peroxide (such as l,l-di(tert-butylperoxy)-3,3,5-trimethylcyclohexane) in the amounts shown.
  • the mixture is typically passed through an extruder at a temperature of aboutl40 to 200 °C to provide the silane grafted polymer blend.
  • This silane grafted polymer blend may be compounded with metal hydroxide flame retardant and other conventional additives and then extruded to form a halogen free, flame-retardant, crosslinkable polymer composite.
  • the crosslinkable polymer composite is typically UV stabilised and is curable by exposure to moist conditions, typically at a somewhat elevated temperature.
  • the crosslinkable polymer composite is typically mixed with a crosslinking catalyst masterbatch, e.g., in a ratio of about 95:5 to 98:2.
  • the moisture cured product is commonly able to satisfy the requirements of the NEK 606 and/or IEC 60092-359 SHF2 standards.
  • the product typically shows good flexibility and confers tough sheathing protection. It is particular notable that the moisture cured product may exhibit excellent oil and mud resistance, such required by specification NEK 606, in combination with all the other specifications typically required for such sheathing materials.
  • Sheathing materials formed from curing the crosslinkable, halogen-free, flame retardant polymer composite materials described herein commonly meet one or more of the following specifications:
  • composition has a variation in tensile strength after accelerated aging in
  • IRM 903 mineral oil for 7 days at 100 °C of no more than about ⁇ 30% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a variation in elongation after accelerated aging in mineral oil (IRM 903) for 7 days at 100 °C of no more than about ⁇ 30% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a mass increase after accelerated aging in mineral oil (IRM 903) for 7 days at 100 °C of no more than about 30% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a volume swell increase after in mineral oil (IRM 903) for 7 days at 100 °C of no more than about 30% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a hot elongation after for 15 minutes at 200 °C (20N load) of no more than about 175% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a permanent elongation after treatment for 15 minutes at 200 °C and subsequent cooling of no more than about 25% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • composition has an elongation before aging at least about 120% (as
  • the composition has a tensile strength before aging at least about 9N/mm 2 (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a variation in tensile strength after accelerated aging in SHF Mud oil (EDC 95-11) for 56 days at 70 °C of no more than about ⁇ 25% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a variation in elongation after accelerated aging in SHF Mud oil (EDC 95-11) for 56 days at 70 °C of no more than about ⁇ 25% (as determined pursuant to IEC 60092-360 & NEK606:2009).
  • the composition has a mass increase after accelerated aging in SHF Mud oil (EDC 95-11) for 56 days at 70 oC of no more than about ⁇ 15% (as determined pursuant to IEC 60092-360 & EK606:2009).
  • the composition has a volume swell increase after accelerated aging in SHF Mud oil (EDC 95-11) for 56 days at 70 oC of no more than about ⁇ 20% (as determined pursuant to IEC 60092-360 & EK606:2009).
  • the composition has a variation in tensile strength after accelerated aging in air oven for 7 days at 120 °C of no more than about ⁇ 30% (as determined pursuant to IEC 60092-360 & EK606:2009).
  • the composition has a variation in elongation at break after accelerated ageing in air oven for 7 days at 120 °C of no more than about ⁇ 30% (as determined pursuant to IEC 60092-360 & EK606:2009).
  • composition exhibits no cracking after exposure to 250-300 ppm ozone at 25 °C for 24 hours as determined pursuant to to IEC 60092-360 & EK606:2009.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Insulating Materials (AREA)

Abstract

Cette invention concerne des matériaux de gaine sans halogènes, durcissables à l'humidité destinés à être utilisés dans des applications de fils et de câbles. La gaine comprend un polymère thermoplastique réticulable et un matériau ignifugeant. Le matériau ignifugeant peut comprendre un agent ignifugeant de type hydroxyde métallique, tel qu'un hydroxyde de magnésium, de calcium, de zinc et/ou d'aluminium. Le polymère thermoplastique réticulable comprend un élastomère de type polyester thermoplastique, qui peut être mélangé à un ou plusieurs autres polymères thermoplastiques. Le composant polymère du matériau de gaine peut également comprendre un polycarbodiimide aromatique. Le polymère thermoplastique réticulable est durcissable par exposition à l'humidité et peut comprendre une fonctionnalité silane durcissable à l'humidité dans le polymère thermoplastique.
PCT/IB2016/054162 2015-08-04 2016-07-12 Composition de gaine résistant à l'huile et à la boue WO2017021800A1 (fr)

Applications Claiming Priority (2)

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US201562200932P 2015-08-04 2015-08-04
US62/200,932 2015-08-04

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WO2017021800A1 true WO2017021800A1 (fr) 2017-02-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111410786A (zh) * 2020-03-25 2020-07-14 深圳市沃尔核材股份有限公司 一种无卤高阻燃耐油热缩标识管及其生产方法
CN112759823A (zh) * 2020-12-29 2021-05-07 金发科技股份有限公司 一种辐照交联低烟无卤聚烯烃电缆料及其制备方法和应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894101B2 (en) * 2000-07-20 2005-05-17 Martinswerk Gmbh Cross-linkable, halogen-free flame-resistant plastic mixture, especially for cables
US7943694B2 (en) * 2008-03-04 2011-05-17 Lanxess Deutschland Gmbh Crosslinkable compositions, thermoplastic elastomers obtainable therefrom and their use
US20130059943A1 (en) * 2010-05-24 2013-03-07 Wilson Xiao Wei Yan Halogen-Free, Flame Retardant Composition Comprising Crosslinked Silane-g-EVA

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894101B2 (en) * 2000-07-20 2005-05-17 Martinswerk Gmbh Cross-linkable, halogen-free flame-resistant plastic mixture, especially for cables
US7943694B2 (en) * 2008-03-04 2011-05-17 Lanxess Deutschland Gmbh Crosslinkable compositions, thermoplastic elastomers obtainable therefrom and their use
US20130059943A1 (en) * 2010-05-24 2013-03-07 Wilson Xiao Wei Yan Halogen-Free, Flame Retardant Composition Comprising Crosslinked Silane-g-EVA

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111410786A (zh) * 2020-03-25 2020-07-14 深圳市沃尔核材股份有限公司 一种无卤高阻燃耐油热缩标识管及其生产方法
CN111410786B (zh) * 2020-03-25 2023-07-07 深圳市沃尔核材股份有限公司 一种无卤高阻燃耐油热缩标识管及其生产方法
CN112759823A (zh) * 2020-12-29 2021-05-07 金发科技股份有限公司 一种辐照交联低烟无卤聚烯烃电缆料及其制备方法和应用

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