WO1999027015A1 - Procede de production de compositions thermoplastiques resistant au feu - Google Patents

Procede de production de compositions thermoplastiques resistant au feu Download PDF

Info

Publication number
WO1999027015A1
WO1999027015A1 PCT/IT1997/000291 IT9700291W WO9927015A1 WO 1999027015 A1 WO1999027015 A1 WO 1999027015A1 IT 9700291 W IT9700291 W IT 9700291W WO 9927015 A1 WO9927015 A1 WO 9927015A1
Authority
WO
WIPO (PCT)
Prior art keywords
inorganic filler
blend
fire resistant
composition
thermoplastic
Prior art date
Application number
PCT/IT1997/000291
Other languages
English (en)
Inventor
Francesco Mascia
Cristiano Puppi
Original Assignee
Johnson Control S.P.A.
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 Johnson Control S.P.A. filed Critical Johnson Control S.P.A.
Priority to PCT/IT1997/000291 priority Critical patent/WO1999027015A1/fr
Priority to AU51349/98A priority patent/AU5134998A/en
Priority to EP97946051A priority patent/EP1034219A1/fr
Publication of WO1999027015A1 publication Critical patent/WO1999027015A1/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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/006—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to block copolymers containing at least one sequence of polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • 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
    • H01B3/28—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances natural or synthetic rubbers
    • 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
    • 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
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers

Definitions

  • the present invention relates to a process of producing fire resistant thermoplastic based materials, to the polymer compositions thus obtained and to the products using said compositions .
  • the invention relates to halogen-free thermoplastic materials that, filled with a high level of inorganic compounds, grafted in bulk with compatibilizing substances and dinamically "cured” with free radical generator catalysts, are both fire resistant and provided with surprisingly high thermomechanical properties.
  • Halogen-free thermoplastic materials have a broad and useful range of mechanical properties.
  • polyolefins are a chemically homogeneous class of polymers with a wide spectrum of properties and a low level of environmental impact, so their use is growing with an impressive rate and new materials, obtained from new catalitic systems, came into the market offering new applications .
  • thermoset materials that contain mainly carbon and hydrogen, can burn and propagate the flame very easily and there has been a constant search for a way of removing this characteristic without compromising their mechanical properties and without transforming them in thermoset materials.
  • a first, known, solution is to use inorganic compounds, i.e. metal hydroxides (e.g. Mg and Al hydroxides), oxides and/or inorganic salts, having endothermical decomposition and releasing nonflammable gas (like water or carbon dioxide) , and/or creating a protective shield when heated, as fillers in plastics or elastomers to impart flame retarding properties to said materials.
  • inorganic compounds i.e. metal hydroxides (e.g. Mg and Al hydroxides), oxides and/or inorganic salts, having endothermical decomposition and releasing nonflammable gas (like water or carbon dioxide) , and/or creating a protective shield when heated, as fillers in plastics or elastomers to impart flame retarding properties to said materials.
  • the flame retarding action of these inorganic compounds is based on physical reasons. Their endothermic thermal decomposition process subtracts heat to the burning bulk, reducing the release of flammable pyrolytic gases, and further diluting it with non flammable gas released by the inorganic compounds. In addition some of them can create a protective layer that acts as a shield against the flame propagation.
  • the main drawback of these inorganic fillers is that their effectiveness is pretty low and a high amount of filler is required to impart the polymer effective fire retarding properties (particulary with resins, like polyolefins, that can burn completely) . In fact, the required amount of filler is so high that the mechanical properties of the final material are dramatically jeopardized.
  • the aim of the present invention is to improve the mechanical properties of halogen-free fire resistant thermoplastic materials in which the fire resistance is given by an inorganic filler, by means of a chemical modification of the polymeric matrix during the blend with the filler, and to substantially maintain the thermoplastic characteristics of the starting materials in the final composition.
  • the invention relates to a reactive process to prepare halogen- free thermoplastic compositions having fire resistance characteristics, according to claim 1.
  • the inorganic filler is selected from Al(OH) 3 , g(OH) 2 , CaC0 3 , boric acid, borates, CaO, silica and mixtures thereof;
  • the radical generating agent is a peroxide and the compatibilizing agent is selected from maleic and fumaric acids, maleic and fumaric anhydrides and mixtures thereof.
  • This invention also concerns halogen-free, fire resistant thermoplastic compositions as obtainable according to the claimed process, wherein compatibilizing agents are grafted over all the bulk of said thermoplastic material.
  • the final composition is thermoplastic and is partially crosslinked.
  • the invention also relates to electric cables provided with a layer made with a fire resistant thermoplastic material according to the invention. Preferably, such layer is a shield.
  • the invention also relates to the use of a composition as above disclosed for the production of electric appliances and their parts, such as boxes, pipes, etc.
  • the invention provides several advantageous features.
  • the invention process results in a final composition that is thermoplastic, i.e. it is further processable and recyclable. There thus is no need to give the product its final shape before curing it by heating the mixture and activating the peroxides; in fact a preferred shape for the invention composition is as pellets.
  • the invention compositions have surprisingly good properties, namely higher values of mechanical modulus, stress strain and elongation at break, impact behaviour, abrasion resistance, compression set and softening or distortion temperature, with respect to the properties of corresponding materials made according to known techniques.
  • thermoplastic material useful for carrying out the process are selected from alpha- defines homo and co-polymers such as ethylene, propylene, ethylene/propylene, propylene copolymers containing one or more alpha olefins with 2-10 carbon atoms (e.g.
  • SBR styrol/butadiene rubbers
  • the starting thermoplastic material must contain both crosslinkable and non-crosslinkable compounds.
  • the amount of thermoplastic material is usually about 5-70 wt.%, in any case it is such as to bring to 100 the composition.
  • the inorganic fillers imparting fire resistance are those inorganic fillers that endotermically decompose with release of non-flammable gas and inert ashes. Examples of these fillers are aluminiun trihydroxide, magnesium hydroxide, huntite [3MgC ⁇ 3xCaC0 3 ] or hydromagnesite [Mg 5 (C0 3 ) 4 (OH) 2 x 4H 2 0], boric acid.
  • Other suitable fillers are those that can vetrify like borate or hydrate borate, sodium bicarbonate, calcium oxide and silica.
  • the fillers can be mixed together or diluted with inert materials like silica, or materials that decompose at higher temperatures than the polymer decomposition temperature, like calcium carbonate. Their total amount is within the range of 30- 80 wt.%, typically from 40% to 75% by weight of the final blend.
  • the co patibilizers are molecules with chemical affinity to the filler, and able to graft, with a chemical bond, the macromolecular backbone by means of a free radical catalyzed reaction.
  • these compatibilizers are unsaturated organic acids or esters, like acrylic, methacrylic, fumaric, maleic, citraconic or itaconic acid and esters, used in a concentration ranging between 0,005 and 10% by weight of the blend.
  • compatibilizers are maleic and fumaric acids, maleic anhydride and mixtures thereof.
  • Another class of useful compatibilizers are the maleinized polybutadienes or vinyl- methoxysilanes that can graft the macromolecular backbone accelerating and or promoting the crosslinking reaction, used in concentration till 15% of the total blend.
  • the preferred amount of compatibilizers is within the range of 0.01-15 wt.%.
  • the free radicals generator agentss are preferably organic peroxides like dicumil peroxide, 2, 5-di (terbutylperoxi) -2, 5- dimethylhexane, or other molecules with a strained bond that omolitically breaks upon temperature increase, like 2,3- dimethyl-2, 3-diphenyl-butane.
  • radical generator agents start radical chain reactions that both graft the compatibilizer molecule onto the macromolecules but also "cure" the polymer by crosslinking.
  • radical generating agents are provided in an amount of 0.01-2.0 wt.% of active material.
  • thermoplastic composition that is fire resistant, free from halogens and really thermoplastic (i.e.
  • a blend comprising: a halogen- free thermoplastic material containing both crosslinkable and non-crosslinkable compounds, a fire resistant inorganic filler, a compatibilizing agent for said inorganic filler, and a radical generating agent, and to dinamically cure said blend to obtain a partially crosslinked thermoplastic composition.
  • Blends "Dinamically curing" the above blend or mixture means that the blend is melted and kneaded at a temperature above the decomposition temperature of said radical generating agent in order to start and carry out the reticulation of the macromolecules, i.e. the crosslinking, or the degradation of the macromolecules, according to their nature.
  • the action of the radical generating agents occurs in the presence of the filler and of the compatibilizer to obtain the required grafting
  • the macromolecular structure of the thermoplastic material is modified in a way that depends from its initial structure and composition: with polymers having unsaturated carbon-carbon bonds like ethylene/propylene/diene rubber or styrole/butadiene rubber, or having more than 50% (moles) of ethylenic units in the backbone like polyethylene, ethylene/1-octene (or 1-hexene) copolymers, ethylene/propylene rubber, ethylene/vinylacetate, hydrogenated styrole/butadiene rubber the main result of the radical chain reactions is a macromolecular crosslinking.
  • the main radical reaction is a chain scission or degradation to give shorter chains.
  • This structural change control is a crucial point to improve the material characteristics that can be customized balancing the degradation and the crosslinking by accurate polymer and additives choice.
  • polymers like polypropylene that is degradated by radical generators, without any crosslinking reaction, are frequently employed.
  • the control of this degradation and some degree of crosslinking is possible by employing polymers rich in double bonds such as polybutadienes, polyalkenylenes, plyenes and EP(D)M rubbers that graft and join the macromolecules by free radical catalyzed reactions.
  • a curable rubber is frequently employed but the complete crosslinking that should transform the polymer in a termoset material is avoided by using some amount of polypropylene or other non-crosslinkable compound.
  • the non-crosslinkable, degradable, compound substantially acts as a continuous phase in which the cured (or crosslinked) phase is dispersed.
  • the formulation of the composition i.e. the amounts of degradable polymers, curable polymers, peroxide and polymers rich in double bonds, is balanced according to the mechanical characteristic that are required for the final product. If elastomeric properties are required, a greater amount of crosslinkable compounds will be present in the initial thermoplastic material; if a rigid final product is required, the amount of degradable, non-crosslinkable (i.e. uncurable) compound will be greater than the amount of curable (crosslinkable) compound.
  • the invention process provides to carry out the mixing, melting, kneading, compatibilizing and curing/degrading of the blend components substantially in one step.
  • the inorganic filler is usually added immediately after the reaction is started on the rest of the mixture, as disclosed by the following examples.
  • a preferred apparatus to carry out the process is an extruder, most preferably co-rotating twin screws extruders with a high dispersing and homogeneization capacity, good temperature control and high ratio L/D, where L is the barrel length and D is the barrel diameter.
  • examples 1, 5 and 6 are referring to state of the art processes.
  • no peroxide or compatibilizing agent was used; in 5 and 6 the compatibilizing agent (comp 1 ) was previously grafted on a polymer matrix (polypropylene) and subsequently added to the invention blend, the poor results are self evident, also in ex.6 where a high amount of comp 1 was added.
  • Example 2 shows a comparative example in which peroxide only was used.
  • Example 3 repeats the formulation of example 2, with the addition of maleic anhydride: the value of tension at break increased from 16 to 20 MPa.
  • comp is a compatibilizing agent "POLYBOND 3150” ® by Uniroyal Chemical
  • examples 3-10 refer to rigid compositions and show the surprising results of invention composition 11 with respect to comparative examples 9 and 10.
  • the added legenda references for table 2 are: 8) ASTM 1238 (230°C, 2.16)
  • EPDM Dutral Ter 4038 by Enichem Elastomeri

Landscapes

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

Abstract

L'invention concerne une composition thermoplastique exempte d'halogène et résistant au feu. On produit cette composition en préparant un mélange renfermant une matière thermoplastique exempte d'halogène renfermant des composés réticulés et non réticulés, une matière de charge inorganique résistant au feu, un agent de compatibilité pour ladite matière de charge inorganique et un agent générateur de radicaux. On mélange le mélange et on le durcit de manière dynamique à une température dépassant la température de décomposition dudit agent générateur de radicaux afin d'obtenir une composition thermoplastique partiellement réticulée et un greffage de l'agent de compatibilité sur tout le volume de la matière thermoplastique.
PCT/IT1997/000291 1997-11-21 1997-11-21 Procede de production de compositions thermoplastiques resistant au feu WO1999027015A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PCT/IT1997/000291 WO1999027015A1 (fr) 1997-11-21 1997-11-21 Procede de production de compositions thermoplastiques resistant au feu
AU51349/98A AU5134998A (en) 1997-11-21 1997-11-21 A process of producing fire resistant thermoplastic compositions and compositions thus obtained
EP97946051A EP1034219A1 (fr) 1997-11-21 1997-11-21 Procede de production de compositions thermoplastiques resistant au feu

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/IT1997/000291 WO1999027015A1 (fr) 1997-11-21 1997-11-21 Procede de production de compositions thermoplastiques resistant au feu

Publications (1)

Publication Number Publication Date
WO1999027015A1 true WO1999027015A1 (fr) 1999-06-03

Family

ID=11332737

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IT1997/000291 WO1999027015A1 (fr) 1997-11-21 1997-11-21 Procede de production de compositions thermoplastiques resistant au feu

Country Status (3)

Country Link
EP (1) EP1034219A1 (fr)
AU (1) AU5134998A (fr)
WO (1) WO1999027015A1 (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6646205B2 (en) 2000-12-12 2003-11-11 Sumitomo Wiring Systems, Ltd. Electrical wire having a resin composition covering
WO2006052138A1 (fr) * 2004-11-03 2006-05-18 Elkem Asa Plastique technique haute performance et additif pour utilisation dans des plastiques techniques
GB2433742A (en) * 2005-12-26 2007-07-04 Ind Tech Res Inst Organic-inorganic composite
FR2911148A1 (fr) * 2007-01-10 2008-07-11 Ind Tech Res Inst Materiau de revetement resistant au feu
EP1973123A1 (fr) * 2007-03-19 2008-09-24 Nexans Procédé de fabrication d'une couche reticulée pour cable d'energie et/ou de télécommunication
WO2009007118A1 (fr) * 2007-07-12 2009-01-15 Borealis Technology Oy Composition de polymère insaturé
WO2012127785A1 (fr) * 2011-03-22 2012-09-27 Yazaki Corporation Câble électrique
US8330045B2 (en) 2005-12-26 2012-12-11 Industrial Technology Research Institute Fire-resistant wire/cable
CN104194101A (zh) * 2014-09-22 2014-12-10 江阴海达橡塑股份有限公司 一种无卤阻燃橡胶的制备方法
CN104311916A (zh) * 2014-10-30 2015-01-28 安徽电信器材贸易工业有限责任公司 一种高阻燃性电缆料及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106700289B (zh) * 2017-01-09 2019-06-18 中广核三角洲（中山）高聚物有限公司 一种高耐水耐臭氧的低烟无卤阻燃聚烯烃电缆料

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0237713A2 (fr) * 1986-01-20 1987-09-23 Sumitomo Bakelite Company Limited Composition ignifugée de polyoléfine
EP0269274A2 (fr) * 1986-10-29 1988-06-01 Mitsui Petrochemical Industries, Ltd. Procédé pour la préparation de compositions élastomères thermoplastiques
EP0280761A2 (fr) * 1987-03-02 1988-09-07 Sumitomo Bakelite Company Limited Composition de résine oléfinique retardatrice de flamme
EP0370518A2 (fr) * 1988-11-25 1990-05-30 Nippon Unicar Company Limited Composition ignifugée
EP0370517A2 (fr) * 1988-11-25 1990-05-30 Nippon Unicar Company Limited Composition ignifugée
EP0462680A2 (fr) * 1985-03-19 1991-12-27 Mitsui Petrochemical Industries, Ltd. Composition à base de polyoléfines et structure laminée utilisant cette composition comme couche adhésive
EP0546841A1 (fr) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Compositions résistantes à l'abrasion et ignifuges
EP0614940A2 (fr) * 1988-04-08 1994-09-14 Mitsui Petrochemical Industries, Ltd. Composition à base de résine ou élastomère thermoplastic ayant une excellente adhésion à la peinture et multicouche comprenant une couche de cet élastomère thermoplastic et une couche de polyuréthane
EP0822223A1 (fr) * 1996-07-31 1998-02-04 COMMER S.p.A. Procédé de préparation de polyoléfines renforcées et compositions contenant des polyoléfines renforcées

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0462680A2 (fr) * 1985-03-19 1991-12-27 Mitsui Petrochemical Industries, Ltd. Composition à base de polyoléfines et structure laminée utilisant cette composition comme couche adhésive
EP0237713A2 (fr) * 1986-01-20 1987-09-23 Sumitomo Bakelite Company Limited Composition ignifugée de polyoléfine
EP0269274A2 (fr) * 1986-10-29 1988-06-01 Mitsui Petrochemical Industries, Ltd. Procédé pour la préparation de compositions élastomères thermoplastiques
EP0280761A2 (fr) * 1987-03-02 1988-09-07 Sumitomo Bakelite Company Limited Composition de résine oléfinique retardatrice de flamme
EP0614940A2 (fr) * 1988-04-08 1994-09-14 Mitsui Petrochemical Industries, Ltd. Composition à base de résine ou élastomère thermoplastic ayant une excellente adhésion à la peinture et multicouche comprenant une couche de cet élastomère thermoplastic et une couche de polyuréthane
EP0370518A2 (fr) * 1988-11-25 1990-05-30 Nippon Unicar Company Limited Composition ignifugée
EP0370517A2 (fr) * 1988-11-25 1990-05-30 Nippon Unicar Company Limited Composition ignifugée
EP0546841A1 (fr) * 1991-12-10 1993-06-16 Nippon Petrochemicals Company, Limited Compositions résistantes à l'abrasion et ignifuges
EP0822223A1 (fr) * 1996-07-31 1998-02-04 COMMER S.p.A. Procédé de préparation de polyoléfines renforcées et compositions contenant des polyoléfines renforcées

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KEONELLI, E. ET AL.: "Non-halogenated, flame retardant ...", KAUTSCHUK + GUMMI KUNSTSTOFFE, vol. 44, no. 10, 1991, pages 960-962, XP002072157 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6646205B2 (en) 2000-12-12 2003-11-11 Sumitomo Wiring Systems, Ltd. Electrical wire having a resin composition covering
US6756440B2 (en) 2000-12-12 2004-06-29 Sumitomo Wiring Systems, Ltd. Fire resistant resin composition and electrical wire having fire resistant covering
US6809140B2 (en) 2000-12-12 2004-10-26 Sumitomo Wiring Systems, Ltd. Fire resistant resin composition and electrical wire having fire resistant covering
US8729172B2 (en) 2004-11-03 2014-05-20 Elkem As High performance engineering plastics and additive for use in engineering plastics
WO2006052138A1 (fr) * 2004-11-03 2006-05-18 Elkem Asa Plastique technique haute performance et additif pour utilisation dans des plastiques techniques
GB2433742A (en) * 2005-12-26 2007-07-04 Ind Tech Res Inst Organic-inorganic composite
GB2433741A (en) * 2005-12-26 2007-07-04 Ind Tech Res Inst Fire-resistant coating material
JP2007191711A (ja) * 2005-12-26 2007-08-02 Ind Technol Res Inst 耐火塗料
DE102006062146B4 (de) 2005-12-26 2017-03-30 Industrial Technology Research Institute Organisch/Anorganischer Verbundstoff und eine feuerbeständige Platte und deren Verwendung
US8329820B2 (en) 2005-12-26 2012-12-11 Industrial Technology Research Institute Fire-resistant coating material
US8330045B2 (en) 2005-12-26 2012-12-11 Industrial Technology Research Institute Fire-resistant wire/cable
US8329819B2 (en) 2005-12-26 2012-12-11 Industrial Technology Research Institute Organic/inorganic composite and fire-resistant plate utilizing the same
GB2433741B (en) * 2005-12-26 2010-08-18 Ind Tech Res Inst Fire-resistant coating material
GB2433742B (en) * 2005-12-26 2010-09-08 Ind Tech Res Inst Organic-inorganic composite
GB2433831B (en) * 2005-12-26 2010-09-08 Ind Tech Res Inst Fire-resistant wire/cable
FR2911148A1 (fr) * 2007-01-10 2008-07-11 Ind Tech Res Inst Materiau de revetement resistant au feu
FR2913908A1 (fr) * 2007-03-19 2008-09-26 Nexans Sa Procede de fabrication d'une couche reticulee pour cable d'energie et/ou de telecomunication
KR101400304B1 (ko) * 2007-03-19 2014-05-28 넥쌍 전선 및/또는 텔레커뮤니케이션 케이블용 교차 결합층의가공 방법
EP1973123A1 (fr) * 2007-03-19 2008-09-24 Nexans Procédé de fabrication d'une couche reticulée pour cable d'energie et/ou de télécommunication
WO2009007117A1 (fr) 2007-07-12 2009-01-15 Borealis Technology Oy Compositions de polymères modifiés, procédé de modification et agents générant des radicaux libres
WO2009007118A1 (fr) * 2007-07-12 2009-01-15 Borealis Technology Oy Composition de polymère insaturé
EA018671B1 (ru) * 2007-07-12 2013-09-30 Бореалис Текнолоджи Ой Полимерная композиция, модифицированная полимерная композиция, сшиваемый кабель и сшитый кабель, включающие указанную полимерную композицию
EA021922B1 (ru) * 2007-07-12 2015-09-30 Бореалис Текнолоджи Ой Симметричное соединение для модификации полимерной композиции, полимерная композиция, способный к вулканизации кабель и способы вулканизации
WO2012127785A1 (fr) * 2011-03-22 2012-09-27 Yazaki Corporation Câble électrique
US9236165B2 (en) 2011-03-22 2016-01-12 Yazaki Corporation Electric cable
CN104194101A (zh) * 2014-09-22 2014-12-10 江阴海达橡塑股份有限公司 一种无卤阻燃橡胶的制备方法
CN104194101B (zh) * 2014-09-22 2016-01-06 江阴海达橡塑股份有限公司 一种无卤阻燃橡胶的制备方法
CN104311916A (zh) * 2014-10-30 2015-01-28 安徽电信器材贸易工业有限责任公司 一种高阻燃性电缆料及其制备方法

Also Published As

Publication number Publication date
EP1034219A1 (fr) 2000-09-13
AU5134998A (en) 1999-06-15

Similar Documents

Publication Publication Date Title
US10559407B2 (en) Process for producing electrical wire molded body
CA2712555C (fr) Formulations thermoplastiques ignifugeantes exemptes d'halogene
AU1013201A (en) Crosslinked compositions containing silane-modified polyolefins and polypropylenes
JP6452611B2 (ja) 耐熱性シラン架橋樹脂成形体及びその製造方法、耐熱性シラン架橋性樹脂組成物及びその製造方法、シランマスターバッチ、並びに耐熱性シラン架橋樹脂成形体を用いた耐熱性製品
HUT61796A (en) Graft copolymer compositions
JP6265876B2 (ja) 耐熱性シラン架橋樹脂成形体及びその製造方法、耐熱性シラン架橋性樹脂組成物及びその製造方法、シランマスターバッチ、並びに耐熱性シラン架橋樹脂成形体を用いた耐熱性製品
US5221781A (en) Filler-incorporated thermoplastic resin composition
JP7060581B2 (ja) 難燃性架橋樹脂成形体及びその製造方法、シランマスターバッチ、マスターバッチ混合物及びその成形体、並びに、難燃性製品
CN112210160B (zh) 一种激光打标无卤标识热缩管及其制造方法
WO1999027015A1 (fr) Procede de production de compositions thermoplastiques resistant au feu
JP7050678B2 (ja) ハロゲン不含耐火性ゴム組成物及びホース
JP2007277530A (ja) 難燃性樹脂組成物及び当該樹脂組成物を被覆した絶縁電線
Azizi et al. Silane crosslinking of polyethylene: The effects of EVA, ATH and Sb2O3 on properties of the production in continuous grafting of LDPE
JP2022113710A (ja) 耐熱性シラン架橋樹脂成形体及びその製造方法、並びに、耐熱性シラン架橋樹脂成形体を用いた耐熱性製品
JP2007246578A (ja) 発泡剤
JPH03269028A (ja) 難燃性発泡組成物
CA2346225C (fr) Une composition aux proprietes thermomecaniques ameliorees et une methode pour sa reticulation
JP6462606B2 (ja) 耐熱性シラン架橋樹脂成形体及び耐熱性シラン架橋性樹脂組成物とそれらの製造方法、シランマスターバッチ、並びに、耐熱性製品
JP4955964B2 (ja) 熱可塑性部分架橋樹脂成形体の製造方法
JPH03269029A (ja) 難燃性発泡組成物、難燃性発泡体およびその製造法
Beltrán-Ramírez et al. Study of the Addition of a thermoplastic vulcanizate to a HDPE composite highly filled with magnesium hydroxide and its effect on the tensile and flame retardant properties
JPS5817137A (ja) 熱可塑性エラストマ−組成物
EP0405982A1 (fr) Composition de résine thermoplastique contenant une charge
JPH08199010A (ja) オレフィン系熱可塑性樹脂エラストマー
JPH0564662B2 (fr)

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
NENP Non-entry into the national phase

Ref country code: KR

WWE Wipo information: entry into national phase

Ref document number: 1997946051

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1997946051

Country of ref document: EP

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

WWW Wipo information: withdrawn in national office

Ref document number: 1997946051

Country of ref document: EP