WO2002026879A1 - Composition polymere ne contenant pas d'halogene - Google Patents

Composition polymere ne contenant pas d'halogene Download PDF

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Publication number
WO2002026879A1
WO2002026879A1 PCT/AU2001/001226 AU0101226W WO0226879A1 WO 2002026879 A1 WO2002026879 A1 WO 2002026879A1 AU 0101226 W AU0101226 W AU 0101226W WO 0226879 A1 WO0226879 A1 WO 0226879A1
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Prior art keywords
composition according
copolymer
ethylene
metallocene catalysed
copolymers
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PCT/AU2001/001226
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English (en)
Inventor
Hans Anton Mayer
Barry Keith Harmsworth
Kelvin Gregory Cooper
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Compco Pty Ltd
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Publication date
Application filed by Compco Pty Ltd filed Critical Compco Pty Ltd
Priority to NZ525352A priority Critical patent/NZ525352A/en
Priority to AU2001293499A priority patent/AU2001293499B2/en
Priority to AU9349901A priority patent/AU9349901A/xx
Publication of WO2002026879A1 publication Critical patent/WO2002026879A1/fr

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    • 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
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • 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
    • 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
    • C08L2314/00—Polymer mixtures characterised by way of preparation
    • C08L2314/06—Metallocene or single site catalysts

Definitions

  • the present invention relates to halogen-free polymeric compositions that are capable of acting as a substitute and/or enhancement to halogenated thermoplastics such as plasticised polyvinyl chloride (PVC) , especially in the production of electrical cables, power cables, building parts and wires, communication cables and automotive parts.
  • Plasticised PVC is used in a large range of applications, including cable insulation and sheathing, floor coverings, artificial leather and sound insulation.
  • PVC, and especially plasticised PVC is easily processed and readily extruded to provide, for example, sheathing for cables, etc.
  • Another intrinsic property of plasticised PVC is its ability to retard the spread of flames.
  • Plasticised PVC When exposed to fire, plasticised PVC decomposes producing hydrochloric acid, which has the effect of starving the burning material of oxygen. However, the acrid fumes produced sometimes cause more problems than the fire itself through corrosion and smoke formation. Plasticised PVC is also a good electrical insulator even when plasticised hence its suitability for use as electrical cable insulation and sheathing.
  • polysiloxanes may also be added to ethylene, butyl acrylate and ethylene ethyl acrylate copolymers containing low cost mineral fillers.
  • a polysiloxane makes the compound more expensive than plasticised PVC.
  • the polysiloxane is needed to achieve a basic flame retardance. In addition, it tends to migrate or separate to the surface and form a skin that is observable .
  • the polysiloxane can be removed by abrasion resulting in the reduction or loss of flame retardance.
  • aluminium hydroxide and/or magnesium hydroxide have been added to copolymers of ethylene and vinyl acetate to produce polymeric compositions having similar properties to plasticised PVC.
  • aluminium hydroxide and magnesium hydroxide are intrinsically more expensive in the proportions necessary to provide appropriate flame retardance and add considerably to the cost .
  • the present invention provides a halogen-free polymeric composition including: (a) at least two metallocene catalysed olefin polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is elastomeric; and
  • the present invention also provides a process for preparing the halogen-free polymeric composition defined above which includes mixing (a) at least two metallocene catalysed olefin polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is elastomeric; and
  • metallocene catalysed olefin polymers and/or copolymers is used herein in its broadest sense to refer to olefin polymers and/or copolymers produced using a metallocene catalyst.
  • Suitable metallocene catalysed olefin polymers and/or copolymers include ethylene polymers and/or copolymers such as polyethylene and ethylene based alkene or alphaolefin copolymers, for example, ultra low density polyethylene (ULDPE) , very low density polyethylene (VLDPE) , ethylene propylene copolymers, ethylene butene copolymers, ethylene hexene copolymers and ethylene octene copolymers.
  • ULDPE ultra low density polyethylene
  • VLDPE very low density polyethylene
  • ethylene propylene copolymers ethylene butene copolymers
  • ethylene hexene copolymers ethylene octene copolymers.
  • metallocene catalysed olefin polymers and/or copolymers have a minor amount preferably less than about 18%, more preferably less than about 15% by weight of a C 3 or higher alkene such as hexene or octene.
  • Preferred metallocene catalysed olefin polymers and/or copolymers are polyethylene, ethylene hexene copolymers and ethylene octene copolymers, more preferably ethylene octene copolymers .
  • metallocene polymers and/or copolymers are also prefixed in the art by "m” e.g., metallocene catalysed VLDPE would be referred to as mVLDPE .
  • the metallocene catalysed olefin polymers and/or copolymers may be conveniently classified into polyolefin elastomers (POE) and polyolefin plastomers (POP) .
  • Elastomers and plastomers can be characterised by means of specific gravity (S.G.) and other properties such as the differential scanning calorimetry (DSC) melting peak, Shore A hardness and elasticity modulus .
  • polyolefin elastomers POE
  • POP polyolefin plastomers
  • polyolefin elastomers composed of ethylene octene copolymers having less than about 18% octene such as Engage 8401 marketed by Dow DuPont Elastomers have a S.G. of up to about 0.885, DSC melting point up to about 80°C, Shore A hardness up to about 86 Shore A and an elasticity modulus of up to about 25 MPa.
  • Polyolefin plastomers (POP) composed of the same ethylene octene copolymers such as Engage 8440 have a S.G more than about 0.886, DSC melting peak of above about 81°C, Shore A hardness of above about 87 Shore A and an elasticity modulus of above about 30 MPa.
  • component (a) of the composition of the present invention contains at least one metallocene catalysed polyolefin elastomer (POE) and at least one metallocene catalysed polyolefin plastomer (POP) , preferably the metallocene catalysed polyolefin elastomer is present in a proportion of about 30% or more, more preferably about 50% or more based on the total amount of component (a) .
  • the metallocene catalysed olefin polymers and/or copolymers have a S.G.
  • a melt flow index in the range of from about 0.5 to about 50 and preferably about 1 to about 30
  • a Shore Hardness A in the range of from about 66 to about 96 Shore A and preferably about 85 to about 93 Shore A
  • a DSC- melting peak in the range of from about 49 to about 107°C, preferably about 65 to about 98°C and more preferably about 70 to about 92°C.
  • Component (a) may also preferably contain up to about 35% of a non-metallocene and/or metallocene catalysed olefin copolymer elastomer or a rubbery flexible copolymer which imparts even greater flexibility to the composition and in the case of some copolymers a further improved flame retardance.
  • Suitable elastomers include synthetic rubbers having at least about 25% comonomer such as ethylene propylene copolymers or terpolymers, for example, EPR, EPM, ethylene propylene diene rubber (EPDM) and/or ethylene vinyl acetate copolymer (EVA) having a vinyl acetate component of about 25 to about 70%, preferably about 30 to about 45%.
  • Such synthetic rubbers are generally known as classical rubbers made with conventional catalysts, however they can also be metallocene catalysed.
  • Component (a) may further contain from about 0.1 to about 15 PHR (parts per hundred parts of polymer) , preferably from about 2 to about 10 PHR and more preferably from about 4 to about 6 PHR of a maleic anhydride modified ethylene copolymer or graft of maleic anhydride on ethylene propylene rubber, ethylene vinyl acetate, polypropylene or polyethylene of all grades and types including high density polyethylene (HDPE) , medium density polyethylene (MDPE) , low density polyethylene (LDPE) , linear low density polyethylene (LLDPE) , ultra low density polyethylene and (ULDPE) and very low density polyethylene (VLDPE) , for example, maleic anhydride grafted polyethylene (MAH-PE) .
  • HDPE high density polyethylene
  • MDPE medium density polyethylene
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • ULDPE ultra low density polyethylene and
  • VLDPE very low density polyethylene
  • MAH-PE male
  • polymers, copolymers, elastomers and/or plastomers can be added in order to enhance the properties of the composition.
  • Such polymers, copolymers, elastomers and/or plastomers may include other ethylene, propylene or butylene polymers and copolymers, ethylene acrylic copolymers, ethylene acrylic ester copolymers and rubbers such as silicone rubber, nitrile butadiene rubber (NBR) and butyl rubber (BR) .
  • NBR nitrile butadiene rubber
  • BR butyl rubber
  • These other polymers, copolymers, elastomers and/or plastomers may be added in amounts of up to about 30 PHR, preferably no more than about 20 PHR, more preferably no more than about 10 PHR so as to minimise costs.
  • component (a) of the composition includes at least about 30 PHR of at least one metallocene catalysed polyolefin elastomer (POE) , for example, an ethylene C 6 -C 8 alphaolefin elastomer with an S.G. of up to about 0.885, preferably at least about 40 PHR, more preferably at least about 50 PHR for more flexible compositions and most preferably at least about 60 PHR for an even more flexible compositions with the remainder being at least one metallocene catalysed polyolefin plastomer (POP) or plastomer with elastomer behaviour (with an S.G. of above about 0.885).
  • POP metallocene catalysed polyolefin plastomer
  • component (a) includes at least about 20% of an olefin copolymer elastomer and/or a rubbery, flexible copolymer and even more preferably at least about 33% of a synthetic rubber with the remainder being at least one metallocene catalysed polyolefin elastomer and at least one metallocene catalysed polyolefin plastomer, for example, about 40% of POE about 40% of POP or POE and about 20% of a synthetic rubber/polyolefin copolymer elastomer or another flexible, rubbery copolymer, even more preferably about 30 to about 40% of POE, about 30 to about 35% of POP or POE (S.G. above about 0.886) and about 30 to about 35% of synthetic rubber/polyolefin copolymer elastomer.
  • component (a) includes at least about 20% of an olefin copolymer elastomer and/or a rubbery, flexible copolymer
  • Component (b) may contain one or more fillers provided that at least one has flame retardant properties .
  • the flame retardant filler is capable of developing H0 and/or H0 and C0 2 in an endothermic process in the case of a fire.
  • Suitable fillers include inorganic and/or mineral fillers such as alkaline earth metal carbonates, talc, clays which may be calcined, kaolin, huntite and/or hydromagnesite.
  • the fillers may be also be used in combination with coatings, for example, stearic acid, stearates such as calcium stearate, vinyl silanes and/or titanates .
  • the fillers may be present in an amount of about 80 to about 250 PHR, preferably about 100 to about 220 PHR and more preferably about 150 to about 200 PHR.
  • the filler is huntite and hydromagnesite which may be in the form of a natural mineral, compound or mixture such as products marketed under the trade names of ULTRACARB or SECUROC which costs less than the currently used aluminium or magnesium hydroxide, but possesses substantially similar flame retardance.
  • Huntite is a magnesium calcium carbonate having the formula Mg 3 Ca(C ⁇ 3 ) and hydromagnesite is a hydrated magnesium carbonate having the formula Mg 4 (C0 3 ) 3 (OH) 2 . 3 H 2 0.
  • the huntite and hydromagnesite can also be mixed artificially in proportions of preferably about 40:60 or about 60:40.
  • the gross molecular formula of the huntite hydromagnesite is Mg 3 Ca (C0 3 ) .Mg (C0 3 ) 3 ) OH 2 .3H 2 0.
  • the huntite/hydromagnesite specific surface measured by nitrogen absorption of preferably 4-12 m2/g, more preferably of 5-10 m2/g) and is preferably a coated grade e.g.
  • the particle size preferably is about 50% below about 1 micron.
  • the main advantage of the huntite and hydromagnesite filler is that it develops H 2 0 and C0 2 in a broader temperature range of about 220 to about 600°C than aluminium and/or magnesium hydroxide and therefore gives a good protection over the range of temperatures which occurs during a fire.
  • the processing temperatures of huntite and hydromagnesite are about 30 to 40°C higher than aluminium hydroxide, ie., the former can be processed up to about 200 to about 220°C where as the latter can be processed at up to about 160 to about 180°C so as to avoid emission of water vapour that could cause porosity and voids.
  • huntite and hydromagnesite with an alkaline earth metal carbonate which may be hydrated, for example, magnesium or calcium carbonate such as products marketed under the trade name OMYACARB 2 or 2T where more C0 2 is developed in the higher temperature range in a synergistic effect.
  • alkaline earth metal carbonate which may be hydrated, for example, magnesium or calcium carbonate such as products marketed under the trade name OMYACARB 2 or 2T where more C0 2 is developed in the higher temperature range in a synergistic effect.
  • Both the huntite and hydromagnesite and the alkaline earth metal carbonate are present in an amount of about 75 to about 150 PHR, preferably about 75 to about 120 PHR and more preferably about 75 to about 100 PHR each.
  • the huntite and hydromagnesite and calcium carbonate in combination with POE/POP's result in lower heat deformation, that is, better resistance to pressure at high temperatures (higher resistance to heat compression) than that of aluminium hydroxide.
  • the fillers and compositions of the present invention including the substitutions with aluminium or magnesium hydroxide have excellent, low heat compression at about 90°C although they are thermoplastic i.e., non-cross-linked or thermoelastic and composed of POE's which melt up to below about 80°C and POP's which melt at about 95°C.
  • Such excellent, low heat compression is normally obtained only with cross-linked compositions which are of higher cost as a consequence of both the additional processing step of cross-linking and the use of cross-linking additives.
  • the huntite and hydromagnesite and/or the alkaline earth metal carbonate can be substituted as a flame retardant wholly or partly by aluminium and/or magnesium hydroxide, but with consequently higher costs further increasing the flame retardance properties of the composition.
  • amounts of, for example, 80 PHR of huntite and hydromagnesite with 80 PHR of calcium carbonate result in an LOI (limiting oxygen index) similar to that of plasticised PVC.
  • flame retardant materials and/or char forming additives may be included in the composition, for example, borates and metaborates such as zinc borate or metaborate, glass beads or particles, silica, silicon dioxide, compounds of silicon dioxide with other metal oxides in amounts of about 1 to about 30 PHR, preferably about 3 to about 20 PHR, more preferably about 5 to about 15 PHR, most preferably about 5 to about 10 PHR depending on the type of additive.
  • borates and metaborates such as zinc borate or metaborate, glass beads or particles, silica, silicon dioxide, compounds of silicon dioxide with other metal oxides in amounts of about 1 to about 30 PHR, preferably about 3 to about 20 PHR, more preferably about 5 to about 15 PHR, most preferably about 5 to about 10 PHR depending on the type of additive.
  • additives known in the art of polymer processing can also be included in the composition.
  • Suitable additives include antioxidants, for example, phenolic antioxidants such as SANTONOX R marketed by Monsanto and IRGANOX 1010 which is pentaerythritol tetrakis (3- (3 , 5-di-tert-butyl-4- hydroxyphenyl)propionate or IRGANOX 1035 which is octadecyl-3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) -propionate marketed by Ciba-Geigy or aminic antioxidants such as Vulcanox HS and Flectol H which are polymerised 2,2,4- trimethyl-1, 2-dihydroquinoline; metal deactivators and/or copper inhibitors, for example, hydrazides such as oxalic acid benzoyl hydrazide (OABH) or Irganox 1024
  • the metal deactivators and/or copper inhibitors are particularly useful when the polymeric composition is in contact with copper conductors or wire.
  • the additives may be present in amounts in the range of about 0.1 to about 4 PHR, preferably about 0.5 to about 3 PHR and more preferably about 1 to about 2 PHR for higher performance in ageing and about 0.1 to about 0.2 PHR for a good or acceptable ageing performance depending on the application or use of the intended product.
  • the metal deactivators can be added in proportions of about 0.1 to about 0.5 PHR, preferably about 0.1 to about 0.3 PHR, more preferably about 0.15 to about 0.25 PHR.
  • the polymers used for component (a) are preferably granulated, pelletised and/or powderised.
  • Components (a) and (b) can then be pre-mixed or added simultaneously, sequentially and/or separately to any suitable known apparatus, such as roll mills, internal mixers or continuous mixers for example twin screw mixers .
  • the final polymeric composition of the invention can be formed by any suitable known process including injection moulding, blow moulding, compression moulding, extrusion or calendering into articles such as tubes, pipes, cables, profiles, sheets, films and pre-forms.
  • the polymeric compositions of the invention may optionally be cross-linked by adding cross-linking catalysts such as organic peroxides, for example, dicumylperoxide, di-tert-butyl peroxide, and/or di-tert- butyl cumyl peroxide. They can also be radiation cross- linked using gamma-radiation or high energy electron beam radiation.
  • the compositions may also be cross-linked after grafting component (a) or the composition with about 1 to about 2 PHR of a vinyl-silane, for example, vinyl alkoxyl silane with the aid of about 0.1 to about 0.2 of an organic peroxide, for example dicumyl-peroxide (DICUP) or di-tert- butyl peroxide (DTBP) .
  • cross-linking catalysts such as organic peroxides, for example, dicumylperoxide, di-tert-butyl peroxide, and/or di-tert- butyl cumyl peroxide. They can also
  • Catalysts for cross-linking include DBTDL (di-butyl-tin-dilaurate) or dioctyl-tin-dilaurate (DOTDL) in an amount of about 0.1 to about 0.25 PHR, preferably about 0.1 to about 0.15 PHR.
  • the cross-linking of the peroxide cross-linkable composition or the resulting products may be conducted in steam or nitrogen under pressure at elevated temperatures, higher than the decomposition temperatures of the peroxides used to form free radicals. Radiation cross-linking is carried out at room temperatures. Silane cross-linking is carried out in the presence of water, steam or moisture at ambient or preferably at higher temperatures of up to about 90 to about 100°C.
  • the non-cross-linked polymeric compositions are thermoplastic and still pass heat compression tests at 80°C and/or 90°C and some even 100°C. This is unexpected as the preferred metallocene catalysed olefin polymers and/or copolymers have melting temperatures (DCS melting peaks) of about 60°C to about 8°C and more preferably about 75 to about 95°C, however the compositions of the present invention can pass the heat compression tests to AS (Australian Standard) 1660 which is also called pressure test at elevated temperatures and the deformation is to be lower than 50%.
  • AS Australian Standard
  • compositions to the invention contain up to about 50 to about 60 PHR of POE with lower melting temperatures below about 80 or about 90°C and they are not cross-linked, however surprisingly they pass the hard heat compressions tests to AS 1660 at about 90°C (or about 80°C or about 100°C depending on the composition requirements) .
  • the limiting oxygen index (LOI) of the polymeric compositions which is a measure of their flame retardance is typically in the range of from about 24 to about 30%.
  • the LOI ranges required to predict for various polymer systems whether they may pass real standardised flame test e.g. on single cables are quite different and indicative only for the development within the same system, depending on the polymers and/or copolymers, flame retardant filler and/or additive systems.
  • the flame test to a standard is the measure for flame retardance.
  • Regular plasticised PVC is in the range of about 26% to 28% LOI.
  • the polymeric compositions of the present invention possess advantageous properties including being low cost, anti-fogging, non-halogenated, non-corrosive and having reduced toxicity and low smoke formation as far as combustion gases are concerned compared with plasticised PVC. It will also be appreciated that the properties such as hardness, softness, flexibility , tensile strength, elongation, flame retardance and resistance to compression can be adapted depending on the desired application and without the need to include the additives contained in plasticised PVC such as phthalate plasticisers and lead thermal stabilisers which have possible physiological effects .
  • Examples of applications of the polymeric composition include:
  • cables, wires and fibre such as power cables, building wires, data cables and communication cables;
  • Floor coverings sheets or tiles which may be laminated or in combination with textiles, industrial mats, carpets, used in buildings, transport, vehicles;
  • Automotive mudflaps, trays, seals, fabrics, soft feel coverings, console, sound/noise attenuation
  • the present invention further provides articles which are composed wholly or partly of the polymeric composition defined above.
  • compositions according to the invention and physical properties of the compositions are set out below. These examples are not to be construed as limiting the invention in any way.
  • compositions set out below have been tested to determine their flame retardant properties by the LOI expressed in % which gives some indication of flame retardance.
  • Some of the compositions have been used to produce cable sheathing, insulated cores and/or sheathing or jacketing. 2 or 3 core building wires to Australian
  • Standard eg. flat building wires have been produced by extrusion.
  • the metallic copper conductors of the cores were insulated with either flame retardant and/or non-flame retardant compositions from an example of this invention or just regular non-flame retardant XLPE and sheathed with compositions of the invention.
  • the sample sheathed cable was placed vertically to IEC 332 part A or to AS 1660 part 5 to pass the single bunsen burner test.
  • the flame tests on samples of the product are more relevant to check the flame retardance than the LOI test.
  • compositions of the examples were made on laboratory mills and/or continuously mixing plant machinery twin screw mixers e.g. on contra-rotating mixer with twin screws of 80mm and on co-rotating twin screw mixers of 53 and/or 83 mm diameter.
  • the compositions were made by pre- mixing the polymer granules/pellets with the filler powders in a pre-mixer and which were then fed into the hopper of the twin screw mixer (this could result in some slight separation of the components in the hopper and possibly some variation in the results) , larger factory equipment with several ports of entrance for the ingredients allows a variety of filling sequences, e.g. the pre-mixed polymers in the hopper of the twin screw extruder, forming a melt and then adding the filler in the second feeding port and possibly another part in the third feeding port and thereby more homogenous compounds with further improved results .
  • Internal mixers for example of the Banbury type may also be used alternatively in batch processing where the components are added either all together or in sequences, i.e., either the polymers first and fillers later or by the upside down method where the fillers are added first followed by the polymers.
  • Single screw extrusion mising machines with mixing parts in the cylinder of Buss-Ko-Kneader type for continuous mixing could also be used.
  • the samples made on the laboratory mills and/or continuously mixed on the twin screw mixers were then granulated or pelletised.
  • the granules were either extruded into tapes on a laboratory extruder and/or pressed in a press and/or the granules were also injection moulded and then tested.
  • injection moulded plaques an average of the mechanical test results (in longitudinal and transversal direction) is shown.
  • the Engage series of polymers are metallocene catalysed copolymers of ethylene and 1-octene produced by DuPont Dow Elastomers LLC.
  • Omyacarb 2T is a calcium carbonate coated with stearic acid.
  • HYDRAL 710 is an aluminium hydroxide.
  • Ultracarb is an intimate mixture of huntite and hydromagnesite. Huntite is a naturally occurring mixed carbonate of magnesium and calcium.
  • Melting points to DSC melting peak are 76°C for 8401 and 95°C (for 8440) - yet the composition or plaques and/or cable samples passes the toughest test to Australian Standard of pressure at high temperature or hot deformation or heat compression AS 1660 of hot deformation at 90°C for a temperature rating of 90°C (the maximum permitted is 50%) . The test was also passed at 100°C.
  • Adequate for insulation of cable cores i.e., insulation of metallic conductors as insulation in general does not require a higher flame retardance. It contributes to a higher flame retardance of- the whole cable where the core(s) is/are attached with a flame retardant sheathing or jacketing composition according to the invention.
  • ANTIOXIDANT (IRGANOX 1010 in a MB) - 0.2
  • EVA included as 20 PHR into the total of 100 PHR of polymer, increases the LOI to 26%, vs. 24% with 20 PHR of EPR DUTRAL CO.
  • Example 8 seems to be very good for flexible building wire sheath, in particular for their flexibility.
  • the highly flexible sheath also passed the bunsen burner test on a vertical building wire.
  • the excellently low hot deformation performance is remarkable and unexpected in such a soft flexible and non- cross-linked thermoplastic compound.
  • Example 9 Comparing Example 9 and Example 10 one can see: - DUTRAL CO.034 vs. .LEVAPREN 450
  • This compound has almost the same LOI as example 12 which also has additional EVA (Elvax) .
  • EXAMPLE 14 POE (Engage 8401) 50 POP/POE (Engage 8440 50 MAH-LDPE (FUSABOND) 5 ULTRACARB C5-10 100 OMYACARB 2 100
  • POP/POE (Engage 8440) 33.3 POE (Engage 8401) 33.3 ELVAX 4260 33.4 USTRACARB C5-10 100 OMYACARB 2 100
  • OMYACARB 2 is untreated, improved dispersion and mechanical properties with addition of 1% stearic acid or calcium stearate .
  • POP/POE (Engage 8440) - 50 POE (Engage CL8003) - 50 MAH-LDPE - 5 ULTRACARB C5-10 - 100 OMYACARB 2 - 150
  • POP/POE (Engage 8440) 50 POE (Engage 8401) 50 MAH-LDPE (FUSABOND) 5 ATH (MARTINAL 104 or HYLRAL 710) 200 IRGANOX 1010 0.2

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

La présente invention se rapporte à une composition polymère sans halogène qui contient: (a) au moins deux polymères et/ou copolymères oléfiniques catalysés par un métallocène, l'un au moins de ces polymères et/ou copolymères oléfiniques étant élastomère; et (b) une quantité efficace d'au moins une charge susceptible de conférer à la composition polymère des caractéristiques d'ininflammabilité sensiblement similaires à celle du PVC plastifié. L'invention se rapporte également à un procédé de préparation de ladite composition polymère sans halogène et à des articles qui sont composés, en totalité ou en partie, de ladite composition polymère sans halogène.
PCT/AU2001/001226 2000-09-29 2001-09-28 Composition polymere ne contenant pas d'halogene WO2002026879A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
NZ525352A NZ525352A (en) 2000-09-29 2001-09-28 Halogen-free flame retardant polymeric compositions with metallocene catalysed olefin polymers
AU2001293499A AU2001293499B2 (en) 2000-09-29 2001-09-28 Halogen-free flame retardant polymeric compositions
AU9349901A AU9349901A (en) 2000-09-29 2001-09-28 Halogen-free polymeric compositions

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AUPR0433 2000-09-29
AUPR0433A AUPR043300A0 (en) 2000-09-29 2000-09-29 Halogen-free polymeric compositions

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WO2002026879A1 true WO2002026879A1 (fr) 2002-04-04

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Cited By (37)

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JP2003160735A (ja) * 2001-09-14 2003-06-06 Showa Denko Kk 樹脂組成物
US7094715B2 (en) * 2003-10-29 2006-08-22 Suminoe Textile Co., Ltd Non-halogen series floor material
EP1695997A1 (fr) * 2005-02-23 2006-08-30 Borealis Technology Oy Câble d'alimentation ou de communication avec une couche de résine ignifuge
WO2007070091A1 (fr) * 2005-12-15 2007-06-21 Kimberly-Clark Worldwide, Inc. Adhesif de fixation elastique resistant a l'huile et stratifies contenant cet adhesif
WO2011063849A1 (fr) * 2009-11-27 2011-06-03 Tarkett Gdl S.A. Revêtement de sol ou de mur
EP2532707A1 (fr) * 2011-06-08 2012-12-12 Borealis AG Composition de polymère ignifuge
CN102955212A (zh) * 2011-08-30 2013-03-06 苏州亨利通信材料有限公司 接入网用蝶形引入光缆专用低烟无卤阻燃包覆层材料
CN103146057A (zh) * 2013-03-06 2013-06-12 苏州旭光聚合物有限公司 一种增韧增强的pp及其制备方法
CN103275385A (zh) * 2013-05-23 2013-09-04 宝胜科技创新股份有限公司 核电用无卤低烟阻燃高伸长率、长寿命电缆护套料及其制备方法
US20140083738A1 (en) * 2012-09-27 2014-03-27 Hitachi Metals, Ltd. Non-halogen flame-retardant insulated wire
US20140221559A1 (en) * 2011-09-23 2014-08-07 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
CN104140586A (zh) * 2014-08-11 2014-11-12 江苏理工学院 无卤阻燃poe材料及其制备方法
CN104231420A (zh) * 2014-10-17 2014-12-24 上海至正道化高分子材料股份有限公司 105℃耐温等级辐照交联低烟无卤阻燃绝缘料及其制备方法
CN104795146A (zh) * 2015-04-22 2015-07-22 深圳宝兴电线电缆制造有限公司 一种太阳能光伏电缆
CN105367888A (zh) * 2015-12-11 2016-03-02 无锡市华美电缆有限公司 一种无卤低烟电缆料
CN105859970A (zh) * 2016-03-28 2016-08-17 山东省科学院能源研究所 一种提高聚烯烃接枝效率的方法
JP2016528325A (ja) * 2013-06-27 2016-09-15 ブルースター・シリコーンズ・フランス・エスアエス 電気ワイヤ又は電気ケーブルの製造に特に利用し得る熱加硫性ポリオルガノシロキサン組成物
JP2017530226A (ja) * 2014-10-02 2017-10-12 ダウ グローバル テクノロジーズ エルエルシー 良好な難燃性を有する高周波溶接性エチレン系ポリマー組成物
EP3246359A1 (fr) * 2016-05-19 2017-11-22 Nanosync Sp Z O O Procédé de production de composites de polymère ignifuge exempt d'halogène
WO2018046096A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Dispositif de conjonction de type câble et sa composition polymère de préparation
WO2018046097A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Composition polymère à souplesse et propriété ignifuge élevées
WO2018046098A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Article allongé présentant une bonne souplesse et une ininflammabilité élevée
CN109135038A (zh) * 2018-08-09 2019-01-04 苏州亨利通信材料有限公司 一种耐寒低烟无卤阻燃材料及其制备方法和应用
CN109503931A (zh) * 2018-11-13 2019-03-22 苏州亨利通信材料有限公司 陶瓷化无卤低烟耐火聚烯烃电缆料及其制备方法
CN109517258A (zh) * 2018-11-19 2019-03-26 苏州亨利通信材料有限公司 隔热型陶瓷化低烟阻燃电缆料
CN109593259A (zh) * 2018-11-19 2019-04-09 苏州亨利通信材料有限公司 快速陶瓷化聚烯烃电缆料的制备方法
CN109689768A (zh) * 2016-09-09 2019-04-26 莱尼电缆有限公司 条形元件和用于制备其的聚合物组合物
CN110734605A (zh) * 2019-10-17 2020-01-31 温州鑫泰新材料股份有限公司 一种高抗冲聚丙烯阻燃绝缘片
WO2020215700A1 (fr) * 2019-04-23 2020-10-29 台州市黄岩广环工贸有限公司 Matériau de polypropylène ignifuge sans halogène pour parties de contact électrique de véhicules électriques conformément à gb17761-2018 et son procédé de moulage par injection
CN112126155A (zh) * 2020-09-24 2020-12-25 宜兴市泰宇汽车零部件有限公司 一种轻质epp成型发泡双密度板材的制备方法
CN113045245A (zh) * 2019-12-27 2021-06-29 江苏中鑫家居新材料股份有限公司 一种spc地板及其制备方法
US11248111B2 (en) 2016-09-09 2022-02-15 Leoni Kabel Gmbh Conjunction device such as a cable and polymer composition for preparing same
WO2022135516A1 (fr) * 2020-12-25 2022-06-30 广东美的白色家电技术创新中心有限公司 Matériau d'étanchéité et son procédé de préparation, et bande d'étanchéité
US11661488B2 (en) 2012-06-27 2023-05-30 Dow Global Technologies Llc Article comprising a flame retardant polymeric foam
CN116462902A (zh) * 2023-04-03 2023-07-21 江苏益帆高分子材料有限公司 一种基于lldpe/poe/br的微交联改性低烟无卤阻燃聚烯烃电缆料及其制备方法
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WO2003025056A1 (fr) * 2001-09-14 2003-03-27 Showa Denko K. K. Composition a base de resine
JP2003160735A (ja) * 2001-09-14 2003-06-06 Showa Denko Kk 樹脂組成物
US7094715B2 (en) * 2003-10-29 2006-08-22 Suminoe Textile Co., Ltd Non-halogen series floor material
EA014257B1 (ru) * 2005-02-23 2010-10-29 Бореалис Текнолоджи Ой Силовой или коммуникационный кабель с огнезащитным полимерным слоем
WO2006089735A1 (fr) * 2005-02-23 2006-08-31 Borealis Technology Oy Câble de puissance ou de communication avec couche polymère retardatrice de flamme
US7893132B2 (en) 2005-02-23 2011-02-22 Borealis Technology Oy Power or communications cable with flame retardant polymer layer
EP1695997A1 (fr) * 2005-02-23 2006-08-30 Borealis Technology Oy Câble d'alimentation ou de communication avec une couche de résine ignifuge
WO2007070091A1 (fr) * 2005-12-15 2007-06-21 Kimberly-Clark Worldwide, Inc. Adhesif de fixation elastique resistant a l'huile et stratifies contenant cet adhesif
CN102712791B (zh) * 2009-11-27 2014-10-15 塔克特Gdl股份有限公司 地板或墙壁覆盖物
WO2011063849A1 (fr) * 2009-11-27 2011-06-03 Tarkett Gdl S.A. Revêtement de sol ou de mur
US20120309876A1 (en) * 2009-11-27 2012-12-06 Tarkett Gdl S.A. Floor or Wall Covering
EP2504389B2 (fr) † 2009-11-27 2017-01-11 Tarkett G.D.L. S.a. Revêtement de sol ou de mur
EP2532707A1 (fr) * 2011-06-08 2012-12-12 Borealis AG Composition de polymère ignifuge
WO2012167926A1 (fr) * 2011-06-08 2012-12-13 Borealis Ag Composition de polymère ignifuge
CN102955212A (zh) * 2011-08-30 2013-03-06 苏州亨利通信材料有限公司 接入网用蝶形引入光缆专用低烟无卤阻燃包覆层材料
US20140221559A1 (en) * 2011-09-23 2014-08-07 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
US9365711B2 (en) * 2011-09-23 2016-06-14 Dow Global Technologies Llc Olefin-based polymer compositions and articles prepared therefrom
US11661488B2 (en) 2012-06-27 2023-05-30 Dow Global Technologies Llc Article comprising a flame retardant polymeric foam
US20140083738A1 (en) * 2012-09-27 2014-03-27 Hitachi Metals, Ltd. Non-halogen flame-retardant insulated wire
US9251929B2 (en) * 2012-09-27 2016-02-02 Hitachi Metals, Ltd. Non-halogen flame-retardant insulated wire
CN103146057A (zh) * 2013-03-06 2013-06-12 苏州旭光聚合物有限公司 一种增韧增强的pp及其制备方法
CN103275385A (zh) * 2013-05-23 2013-09-04 宝胜科技创新股份有限公司 核电用无卤低烟阻燃高伸长率、长寿命电缆护套料及其制备方法
JP2016528325A (ja) * 2013-06-27 2016-09-15 ブルースター・シリコーンズ・フランス・エスアエス 電気ワイヤ又は電気ケーブルの製造に特に利用し得る熱加硫性ポリオルガノシロキサン組成物
CN104140586A (zh) * 2014-08-11 2014-11-12 江苏理工学院 无卤阻燃poe材料及其制备方法
KR20220147711A (ko) * 2014-10-02 2022-11-03 다우 글로벌 테크놀로지스 엘엘씨 양호한 난연성을 갖는 고주파 용접가능한 에틸렌계 폴리머 조성물
KR102520483B1 (ko) 2014-10-02 2023-04-12 다우 글로벌 테크놀로지스 엘엘씨 양호한 난연성을 갖는 고주파 용접가능한 에틸렌계 폴리머 조성물
JP7007907B2 (ja) 2014-10-02 2022-01-25 ダウ グローバル テクノロジーズ エルエルシー 良好な難燃性を有する高周波溶接性エチレン系ポリマー組成物
JP2017530226A (ja) * 2014-10-02 2017-10-12 ダウ グローバル テクノロジーズ エルエルシー 良好な難燃性を有する高周波溶接性エチレン系ポリマー組成物
CN104231420A (zh) * 2014-10-17 2014-12-24 上海至正道化高分子材料股份有限公司 105℃耐温等级辐照交联低烟无卤阻燃绝缘料及其制备方法
CN104795146A (zh) * 2015-04-22 2015-07-22 深圳宝兴电线电缆制造有限公司 一种太阳能光伏电缆
CN105367888A (zh) * 2015-12-11 2016-03-02 无锡市华美电缆有限公司 一种无卤低烟电缆料
CN105859970A (zh) * 2016-03-28 2016-08-17 山东省科学院能源研究所 一种提高聚烯烃接枝效率的方法
EP3246359A1 (fr) * 2016-05-19 2017-11-22 Nanosync Sp Z O O Procédé de production de composites de polymère ignifuge exempt d'halogène
WO2018046097A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Composition polymère à souplesse et propriété ignifuge élevées
US10669412B2 (en) 2016-09-09 2020-06-02 Leoni Kabel Gmbh Elongated article with good flexibility and high flame retardancy
US11248111B2 (en) 2016-09-09 2022-02-15 Leoni Kabel Gmbh Conjunction device such as a cable and polymer composition for preparing same
CN109690699A (zh) * 2016-09-09 2019-04-26 莱尼电缆有限公司 诸如电缆的连接装置和用于制备其的聚合物组合物
CN109689772A (zh) * 2016-09-09 2019-04-26 莱尼电缆有限公司 具有高柔韧性和阻燃性的聚合物组合物
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CN109689769A (zh) * 2016-09-09 2019-04-26 莱尼电缆有限公司 具有良好柔韧性和高阻燃性的细长制品
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US11453764B2 (en) 2016-09-09 2022-09-27 Leoni Kabel Gmbh Strand-shaped elements and polymer composition for preparing same
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WO2018046096A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Dispositif de conjonction de type câble et sa composition polymère de préparation
US10920049B2 (en) 2016-09-09 2021-02-16 Leoni Kabel Gmbh Polymer composition with high flexibility and flame retardancy
WO2018046098A1 (fr) 2016-09-09 2018-03-15 Leoni Kabel Gmbh Article allongé présentant une bonne souplesse et une ininflammabilité élevée
US11976186B2 (en) 2018-06-15 2024-05-07 Borealis Ag Flame retardant polyolefin composition
CN109135038A (zh) * 2018-08-09 2019-01-04 苏州亨利通信材料有限公司 一种耐寒低烟无卤阻燃材料及其制备方法和应用
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WO2020215700A1 (fr) * 2019-04-23 2020-10-29 台州市黄岩广环工贸有限公司 Matériau de polypropylène ignifuge sans halogène pour parties de contact électrique de véhicules électriques conformément à gb17761-2018 et son procédé de moulage par injection
CN110734605B (zh) * 2019-10-17 2022-04-01 温州鑫泰新材料股份有限公司 一种高抗冲聚丙烯阻燃绝缘片
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WO2022135516A1 (fr) * 2020-12-25 2022-06-30 广东美的白色家电技术创新中心有限公司 Matériau d'étanchéité et son procédé de préparation, et bande d'étanchéité
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