NZ525352A

NZ525352A - Halogen-free flame retardant polymeric compositions with metallocene catalysed olefin polymers

Info

Publication number: NZ525352A
Application number: NZ525352A
Authority: NZ
Inventors: Hans Anton Mayer; Barry Keith Harmsworth; Kelvin Gregory Cooper
Original assignee: Compco Pty Ltd
Priority date: 2000-09-29
Filing date: 2001-09-28
Publication date: 2004-03-26
Also published as: WO2002026879A1; AUPR043300A0

Abstract

A halogen-free flame retardant polymeric composition is disclosed wherein it comprises: (a) at least two metallocene catalysed olefin polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is a metallocene catalysed polyolefin elastomer (POE) and at least one is a metallocene catalysed polyolefin plastomer (POP); and (b) an effective amount of at least one filler which is capable of providing the polymeric composition with flame retardant properties substantially similar to that of plasticised PVC such that at least one of the layers of a cable composed of the polymeric composition passes the single vertical cable combustion propagation test of AS/NZS1660.5.6:1998. A process for preparing the halogen-free flame retardant polymeric composition and articles that are composed wholly or partly of the halogen-free polymeric composition is also disclosed.

Description

New Zealand Paient Spedficaiion for Paient Number 525352 525352 PCT/AU01 ./01226 Received 16 August 2002 HALOGEN-FREE FLAME RETARDANT POLYMERIC COMPOSITIONS The present invention relates to halogen-free flame retardant polymeric compositions that are capable of 5 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 15 cables, etc. Another intrinsic property of plasticised PVC is its ability to retard the spread of flames. 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 20 produced sometimes cause more problems than the firp' 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.

Attempts to modify the properties of polyolefins such as polyethylene have been made in order to provide a substitute for polyvinyl chloride, especially as sheathing for electrical cable. Hydrocarbon oil has been added in some cases to copolymers based on polyolefins in order to 30 improve their flexibility. However, the addition of hydrocarbon oil increases flammability and requires the addition of considerably more flame retardant in order to match the flame retardant properties of plasticised PVC. Polysiloxanes may also be added to ethylene, butyl acrylate 35 and ethylene ethyl acrylate copolymers containing low cost mineral fillers. However, the addition of a polysiloxane makes the compound more expensive than plasticised PVC.

AMENDED 8HEBT 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. Furthermore, having migrated to the surface, the polysiloxane can be removed by abrasion resulting in the reduction or loss of flame retardance.

Similarly, 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. However, aluminium hydroxide and magnesium hydroxide are intrinsically more expensive in the proportions necessary to provide appropriate flame retardance and add considerably to the cost.

A requirement accordingly exists to provide a polymeric composition with similar properties to plasticised PVC but without decomposing to produce acrid fumes when exposed to fire.

Accordingly, the present invention provides a halogen-free flame retardant polymeric composition including: (a) at least two metaliocene catalysed olefin polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is a metaliocene catalysed polyolefin elastomer (POE) and at least one is a metaliocene catalysed polyolefin plastomer (POP); and (b) an effective amount of at least one filler which is capable of providing the polymeric composition with flame retardant properties substantially similar to that of plasticised 20 PVC such that at least one of the layers of a cable composed of the polymeric composition passes the single vertical cable combustion propagation test to AS/NZS 1660.5.6:1998.

The present invention also provides a process for preparing the halogen-free flame retardant polymeric composition defined above which includes mixing (a) at least two metaliocene catalysed olefin polymers and/or copolymers wherein 25 at least one of the olefin polymers and/or copolymers is elastomer; and (b) an effective amount of at least one filler which is capable of providing the polymeric composition with flame retardant properties substantially similar to that of plasticised PVC.

InteHectual Property Office, of NZ FEB 2004 *eceivm> WO 02/26879 PCT/AU01/01226 The term "metaliocene catalysed olefin polymers and/or copolymers" is used herein in its broadest sense to refer to olefin polymers and/or copolymers produced using a metaliocene catalyst. Suitable metaliocene catalysed 5 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 10 copolymers, ethylene hexene copolymers and ethylene octene copolymers. Commercially available metaliocene 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 C3 or higher alkene such as hexene 15 or octene. Preferred metaliocene catalysed olefin polymers and/or copolymers are polyethylene, ethylene hexene copolymers and ethylene octene copolymers, more preferably ethylene octene copolymers.

It will be understood that metaliocene polymers 20 and/or copolymers are also prefixed in the art by "m" e.g., metaliocene catalysed VLDPE would be referred to as mVLDPE.

The metaliocene catalysed olefin polymers and/or copolymers may be conveniently classified into polyolefin elastomers (POE) and polyolefin plastomers (POP). 25 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.

It will be appreciated that such properties will 30 vary depending on the type of metaliocene catalysed olefin polymer and/or copolymer and its method of manufacture. However, generally polyolefin elastomers (POE) are elastomeric and highly flexible and polyolefin plastomers (POP) are plastomeric or thermoplastic elastomeric and 35 flexible.

For example, polyolefin elastomers (POE) composed of ethylene octene copolymers having less than about 18% PCT/AU01 ./Ol 226 Received 16 August 2002 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 3 0 MPa. However, there is sometimes 10 confusion in the marketplace as to whether particular polyolefins are classified as elastomers or plastomers.

Such polyolefins for example, Engage 8440 as described above is classified as a POE and Affinity 1440 which is exactly the same product is classified as POP, will 15 hereinafter be referred to in this specification as wPOP/POE" or "POE/POP".

Component (a) of the composition of the present invention contains at least one metaliocene catalysed polyolefin elastomer (POE) and at least one metaliocene 20 catalysed polyolefin plastomer (POP), preferably the metaliocene catalysed polyolefin elastomer is present in a proportion of about 3 0% or more, more preferably about 50% or more based on the total amount of component (a).

Ideally, the metaliocene catalysed olefin 25 polymers and/or copolymers have a S.G. in the range of from about 0.850 to about 0.915, preferably about 0.860 to about . 0.90 and more preferably about 0.88 to about 0.90; 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 30 range of from about 66 to about 96 Shore A and preferably about 85 to about 93 Shore A; and 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 35 about 35% of a non-metallocene and/or metaliocene catalysed olefin copolymer elastomer or a rubbery flexible copolymer AMENDED SHEET IPEA/AU WO 02/26879 PCT/AU01/01226 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 5 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 10 classical rubbers made with conventional catalysts, however they can also be metaliocene 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 15 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), 20 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).

It will be understood that other polymers, 25 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 30 ester copolymers and rubbers such as silicone rubber, nitrile butadiene rubber (NBR) and butyl rubber (BR).

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 35 more than about 10 PHR so as to minimise costs.

PCT/AU01 ./01226 Received 16 August 2002 In a preferred embodiment, component (a) of the composition includes at least about 30 PHR of at least one metaliocene catalysed polyolefin elastomer (POE), for example, an ethylene Cg-Ca alphaolefin elastomer with an 5 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 metaliocene catalysed 10 polyolefin plastomer (POP) or plastomer with elastomer behaviour (with an S.G. of above about 0.885).

In another preferred embodiment which provides a more flexible composition, component (a) includes at least about 20% of an olefin copolymer elastomer and/or a 15 rubbery, flexible copolymer and even more preferably at least about 33% of a synthetic rubber with the remainder being at least one metaliocene catalysed polyolefin elastomer and at,least one metaliocene catalysed polyolefin plastomer, for example, about 40% of POE about 40% of POP 20 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 3 0 to about 35% of synthetic rubber/polyolefin 25 copolymer elastomer.

Component (b) may contain one or more fillers provided that at least one has flame retardant properties. Preferably, the flame retardant filler is capable of developing H20 and/or H20 and C02 in an endothermic process 30 in the case of a fire. Suitable fillers include inorganic and/or mineral fillers such as alkaline earth metal carbonates, 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, 35 stearates such as calcium stearate, vinyl silanes and/or titanates. While such coatings may be used to coat the fillers, it will be appreciated that they can also be AMENDED SHEET IPEA/AU added simultaneously, sequentially and/or separately with the fillers. 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.

Preferably the filler is huntite and hydromagnesite which may be in the form of a natural mineral, compound or mixture such as products marketed lander the trade names of ULTRACARB or SECUROC which costs less than the currently used aluminium or magnesium 10 hydroxide, but possesses substantially similar flame retardance.

Huntite is a magnesium calcium carbonate having the formula Mg3Ca(C03)4 and hydromagnesite is a hydrated magnesium carbonate having the formula Mg4 (CO3) 3 (OH) 2.3H2O. 15 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 Mg3Ca (CO3) 4-Mg4 (CO3) 3) 0H2. 3H20. The huntite/hydromagnesite specific surface measured by 20 nitrogen absorption of preferably 4-12 m2/g, more preferably of 5-10 m2/g) and is preferably a coated grade e.g. with stearic acid or calcium stearate. The particle size preferably is about 50% below about 1 micron.

The main advantage of the huntite and 25 hydromagnesite filler is that it develops H20 and C02 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. Furthermore, the processing temperatures of 30 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 35 voids. This is a significant advantage for huntite and hydromagnesite allowing higher processing speeds.

WO 02/26879 PCT/AU01/01226 Another preferred low cost filler combination is 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 5 name OMYACARB 2 or 2T where more CO2 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 10 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) 15 them 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 20 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 25 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 30 further increasing the flame retardance properties of the composition. Surprisingly 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.

Other 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 5 15 PHR, most preferably about 5 to about 10 PHR depending on the type of additive.

It will be appreciated that one or more additives known in the art of polymer processing can also be included in the composition. Suitable additives include 10 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 15 marketed by Ciba-Geigy or aminic antioxidants such as Vulcanox HS and Flectol H which are polymerised 2,2,4-trimethyl-l,2-dihydroquinoline; metal deactivators and/or copper inhibitors, for example, hydrazides such as oxalic acid benzoyl hydrazide (OABH) or Irganox 1024 which is 20 2,3-bis-((3-(3,5-di-tert-butyl-4-hydroxyphenyl) proponyl))propiono hydrazide; UV absorbers, for example Tinuvin or HALS type UV absorbers; foaming or blowing agents which may be either endothermic or exothermic for example, p.p-oxybis benzene-sulfonyl-hydrazide, azo-iso-25 butyro-nitrile and azodicarbonamide; processing and/or thermal stabilisers, for example tris (2,4-ditert-butylphenyl) phosphite (phosphite based), pentaerythritol tetrakis (3-(3,5-di-tertbutyl-4-hydroxyphenyl)propionate), octadecyl-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 30 3,3',3',5,5',5'-hexa-tert-butyl-a,a',a'-(mesitylene-2,4,6-triyl)tri-p-cresol (phenolic based) and dioctadecyl-3,3'-thiodipropionate (thioester based); and pigments, for -example, inorganic pigments such as titanium dioxide and carbon black and organic pigments. The metal deactivators 35 and/or copper inhibitors are particularly useful when the polymeric composition is in contact with copper conductors or wire.

WO 02/26879 PCT/AUO1/01226 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 5 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. 10 The polymers used for component (a) are preferably granulated, pelletised and/or powderised. In the case of rubber, preferably cut or diced. Components (a) and (b) can then be pre-mixed or added simultaneously, sequentially and/or separately to any suitable known 15 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 20 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, 25 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 3 0 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). Catalysts for cross-linking include DBTDL (di-butyl-tin-dilaurate) or dioctyl-tin-dilaurate 35 (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 5 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 metaliocene catalysed olefin polymers and/or copolymers have melting temperatures (DCS melting peaks) of 15 about 60°C to about 98°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 20 lower than 50%. The 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 25 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 30 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 35 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 5 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 10 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 15 composition include: Electrical and optical: cables, wires and fibre such as power cables, building wires, data cables and communication cables; Floor coverings: sheets or tiles which may be 20 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; Buildings: seals, weather shields, flooring, 25 panel trims, window seals, cladding and floormats; and General: flexible tubing, hose, artificial leather, laminated films or sheets with or without textile backing.

Thus, the present invention further provides 30 articles which are composed wholly or partly of the polymeric composition defined above.

Examples of compositions according to the invention and physical properties of the compositions are set out below. These examples are not to be construed as 35 limiting the invention in any way.

Most of the 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 5 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 of sheathed cable was placed vertically to IEC 332 1:1993 or to AS 10 1660.5.6:1998 to pass the single vertical cable combustion propagation test.

The flame tests on samples of the product are more relevant to check the flame retardance than the LOI test.

In the following examples, a combination of at least two metaliocene catalysed polymers were used: a POE (Engage 8401 and/or Engage 8003) with an S.G. of 0.885 and a 15 POP/POE with an S.G. of 0.897 (Engage 8440). The amounts quoted in the examples are expressed in PHR.

The 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 20 compositions were made by premixing 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 25 extruder, forming a melt and then adding the filler in the second feeding port and Intellectual Property Office of NZ t3 FEB 200*1 received PCT/AU01 ./01226 Received 16 August 2002 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 5 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 missing machines with mixing parts in the 10 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 15 extruded into tapes on a laboratory extruder and/or pressed in a press and/or the granules were also injection moulded and then tested. In the case of injection moulded plaques, an average of the mechanical test results (in longitudinal and transversal direction) is shown.

AMENDED SHEET IPEA/AU PCT/AU01./01226 Received 16 August 2002 EXAMPLE 1 (Irganox 1010 antioxidant min. 0.2% added to all compounds) POE (Engage 8401) - 50 POP/POE (Engage 8440) - 50 MAH/LDPE - 10 OMYACARB 2T - 100 HYDRAL 710 - 100 LOI - 26% Shore D - 50 The Engage series of polymers are metaliocene catalysed copolymers of ethylene and 1-octene produced by 15 DuPont Dow Elastomers LLC.

Omyacarb 2T is a calcium carbonate coated with stearic acid. HYDRAL 710 is an aluminium hydroxide.

EXAMPLE 2 POE (Engage 8401) - 50 / POP/POE (Engage 8440) - 50 MAH/LDPE - 10 OMYACARB 2T - 100 ULTRACARB C5-10 - 100 Ultracarb is an intimate mixture of huntite and hydromagnesite. Huntite is a naturally occurring mixed carbonate of magnesium and calcium.

Tensile strength - 12.7 Mpa Elongation at break - 140% Shore D - 50 Hot deformation at- 80°C - 5% at -.90°C - 10% at - 100°C - 22% LOI - 25% AMENDED SHEET IPEA/AU Note: 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 5 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.

EXAMPLE 3 INSULATION POE (Engage 8401) - 50 POP/POE (Engage 8440) - 50 MAH/LDPE - 5 ULTRACARB C5-10 - 100 Tensile strength - 10.8Mpa Elongation - 320% Shore C - 75% LOI* - 24% * Note Adequate for insulation of cable cores i.e., insulation of metallic conductors as insulation in general does not 25 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.

EXAMPLE 4 INSULATION POE (Engage 8401) -50 POP/POE (Engage 8440) - 50 MAH/LDPE - 5 HYDRAL 710* * - 100 Tensile strength - 12.6Mpa Elongation at break - 520% Shore C -67 Hot deformation at 90°C - 35% LOI - 25.5% * MARTINAL OL-104LE (low electrolyte) can also be used for insulation grade EXAMPLE 5 POP/POE (Engage 8440) - 40 POE (Engage 8401) - 40 EPR (DUTRAL CO.038) - 20 FUSABOND (MAH-PE) - 5 ULTRACARB C5-10 - 100 OMYACARB 2T - 100 ANTIOXIDANT/IRGANOX 1010 MASTERBATCH - 0.2 Tensile Strength - 8.7 Mpa Elongation, Min. - 160 Shore C -78 Shore D instant - 57 Shore D instant after 15 seconds - 44 LOI - 24% EXAMPLE 6 POP/POE (Engage 8440) - 33.3 POE (Engage 8401) - 33.3 EPR (DUTRAL CO.038) - 33.3 FUSABOND (MAH-PE) - 5 ULTRACARB C5-10 - 100 OMYACARB 2T . . - 100 ANTIOXIDANT 1010 MB - 0.2 Tensile Strength - 7.7 Elongation, Min. - 220 Elongation, Max. - 265 18 - Shore C Shore D instant Shore D instant after 15 seconds Hot deformation at 90°C 76 54 44 18% 24% LOI Arch test very good (in-house test) a strip was bent, folded and placed as a V inverted, i.e. A on the table. Very good result, very flexible if it laid flat in 1 10 minute. This test was introduced to test the flexibility of the composition in plaque or strip form.

EXAMPLE 7 POP/POE (Engage 8840) - 40 POE (Engage 8401) - 40 EL VAX 4260 - 20 ULTRACARB C5-10 - 100 OMYACARB 2T - 100 ANTIOXIDANT (IRGANOX 1010 in a MB) - 0.2 Note: EVA (ELVAX 4260) included as 20 PHR into the total of 100 30 PHR of polymer, increases the LOI to 26%, vs. 24% with 20 PHR of EPR DUTRAL CO.

(Also refer to increase of LOI with EVA in Example 10 to 29% vs. 24% with 33 PHR of EPR in Example 9) Tensile strength Elongation at break Shore C Shore D instant 6.7 Mpa 310% 77 61 53 2 6% Shore D instant after 15 seconds LOI Note: MB means that 0.2 Irganox 1010 was added in form of a masterbatch.

EXAMPLE 8 POP/POE (Engage 8440) - 33.3 POE (Engage 8401) - 33.3 EVA (45% VA) e.g. (LEVAPREN 450) - 33.3 MAH-PE (FUSABOND) - 5 ULTRACARB C5-10 - 75 OMYACARB 2T - 75 ANTIOXIDANT IRGANOX '1010 MB -0.2 Tensile Strength - 7.5 MPa Elongation at break, Min. - 225% Elongation at break, Max. - 265% Shore C - 74 Shore D instant - 43 Shore D instant after 15 seconds - 34 Hot deformation at 90°C - 16% Arch Test - Very Good LOI - 26% The formation of 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.

EXAMPLE 9 POP/POE (Engage 8440) - 33.3 POE (Engage 8401) - 33.3 EPR (DUTRAL CO.034) - 33.3 MAH-PE (FUSABOND) - 5 ATH (MARTINAL 104LE) - 80 . . OMYACARB 2T - 80 ANTIOXIDANT/IRGANOX 1010MB -0.2 Tensile Strength Elongation, Min. Elongation, Max. - 7 MPa - 125% - 150% Shore C - 69 Shore D instant - 48 Shore D instant after 15 seconds - 38 Hot deformation at 90°C - 25% LOI - 24% Note: The excellently low hot deformation performeince is remarkable and unexpected in such a soft flexible and non-10 cross-linked thermoplastic compound.

EXAMPLE 10 POP/POE (Engage 8440) - 33.3 POE (Engage 8401) - 33.3 EVA (45% VA) (LEVAPREN 450) - 33.3 MAH-PE (FUSABOND) - 5 ATH (MARTINAL 104LE) - 80 OMYACARB 2T - 80 ANTIOXIDANT/IRGANOX 1010 in a MB - 0.2 Tensile Strength - 9.5 Elongation min - 200% Elongated at break max - 250% Shore D instant - 53 Shore D instant after 15 seconds - 43 LOI - 28% Note: Comparing Example 9 and Example 10 one can see: 30 - DUTRAL CO. 034 vs. .LEVAPREN 450 The compound with EPR DUTRAL is softer than with EVA (LEVAPREN) The tensile strength with EVA in Example 10 is higher than with EPR 35 - The LOI is increased from 24 to 28 (and 29 was also measured on another sample) by the EVA vs. the EPR.

PCT/AU01./01226 Received 16 August 2002 EXAMPLE 11 POE (Engage 8401) POP/POE (Engage 8440) MAH/LDPE ULTRACARB C5-10 OMYACARB 2T 50 50 150 50 Shore D instant 10 Shore D after 15 seconds LOI 56 48 27% Note: This compound has almost the same LOI as example 12 which also has additional EVA (Elvax).

EXAMPLE 12 POE (Engage 8401) POP/POE (Engage 8440) 20 ELVAX 4260 (25%VA) MAH LDPE ATH HYDRAL 710 OMYACARB 2T IRGANOX 1010 Tensile Strength Elongation at break Shore D instant Shore D after 15 seconds 30 LOI 50 50 15 15 150 50 0.3 11.7 MPa 130% 59 51 28% EXAMPLE 13 POE (Engage 8401) POP/POE (Engage 8440) MAH-LDPE ULTRACARB C5-10 OMYACARB 2T - 50 - 50 - 15 - 120 - 50 AMENDED SHEET IPEA/AU - 22 Tensile Strength Elongation at break Shore D instant 5 Shore D after 15 seconds LOI EXAMPLE 14 POE (Engage 8401) 10 POP/POE (Engage 8440) MAH-LDPE (FUSABOND) ULTRACARB C5-10 OMYACARB 2 Tensile Strength Elongation at break Min Elongation at break Max. Shore C Shore D instant 20 Shore D after 15 seconds Heat deformation at 90C LOI EXAMPLE 15 25 POP/POE (Engage 8440) POE (Engage 8401) ELVAX 42 60 ULTRACARB C5-10 OMYACARB 2 Tensile strength Elongation at break Min. Elongation at break Max. Shore C 35 LOI PCT/AU01./01226 Received 16 August 2002 11.8 MPa 125% 61 53 26.5% 50 50 5 100 100 6.7 MPa 125% 225% 74 51 41 7% 24% 33.3 33.3 33 .4 100 100 8.5 MPa 125% 145% 76 26% AMENDED SHEET IPEA/AU Note: OMYACARB 2 is untreated, improved dispersion and mechanical properties with addition of 1% stearic acid or calcium stearate.

EXAMPLE 16 POP/POE (Engage 8440) - 50 POE (Engage CL8003) - 50 MAH-LDPE - 5 ULTRACARB C5-10 - 100 OMYACARB 2 - 150 Tensile strength - 6 MPa Elongation at break Min. - 100% Elongation at break Max. - 135% Shore D - 51 LOI - 26% Note: Engage 8003 or CL8003 has an s.g. of 0.885 and MFI =1. (Engage 8401 has the same s.g. and MFI = 30) .

EXAMPLE 17 POP/POE (Engage 8440) - 50 POE (Engage CL8003) - 50 MAH-LDPE (XUS Dow) - 5 OMYACARB 2 - 150 ATH (5m2/g untreated) - 100 IRGANOX 1010 - 0.3 Tensile Strength - 6..9MPa . Elongation at break Min. - 120% Elongation at break Max. - 135% Shore D - 57 LOI - 27%

Claims

- 24 - EXAMPLE 18 POP/POE (Engage 8440) POE (Engage 8003) MAH-LDPE (XUS) 5 OMYACARB 2 ATH (5m2/g, untreated) IRGANOX 1010 Shore D LOI 10 - EXAMPLE 19 POP/POE (Engage 8440) POE (Engage 8401) MAH-LDPE (FUSABOND) 15 ATH (MARTINAL 104 or HYDRAL 710) IRGANOX 1010 Tensile Strength Elongation at break Min. 20 Elongation at break Max Shore C Shore D instant Shore D (15 sec.) LOI PCT/AU01./01226 Received 16 August 2002 50 50 5 100 100 0.3 50 26% 50 50 5 200 0.2 10.2/10.0 130/125% 170/150% 82/82 60/57 52/49 29% AMENDED SHEET IPEA/AU -25 CLAIMS:

1. A halogen-free flame retardant polymeric composition including: 5 (a) at least two metaliocene catalysed olefin polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is a metaliocene catalysed polyolefin elastomer (POE) and at least one is a metaliocene catalysed polyolefin plastomer (POP); and (b) an effective amount of at least one filler which is capable of 10 providing the polymeric composition with flame retardant properties substantially similar to that of plasticised PVC such that at least one of the layers of a cable composed of the polymeric composition passes the single vertical cable combustion propagation test of AS/NZS1660.5.6:1998. 15

2. A composition according to claim 1 wherein the metaliocene catalysed olefin polymer and/or copolymer is an ethylene polymer and/or copolymer.

3. A composition according to claim 1 or claim 2 wherein the metaliocene catalysed olefin polymer and/or copolymer is polyethylene or an ethylene based 20 alkene copolymer.

4. A composition according to claim 3 wherein the polyethylene is ultra low density polyethylene (ULDPE) or very low density polyethylene (VLDPE). 25

5. A composition according to claim 3 wherein the ethylene based alkene copolymer has a C3 or higher alkene.

6. A composition according to claim 3 or claim 5 wherein the ethylene based alkene copolymer is an ethylene butene copolymer, ethylene hexene copolymer or 30 ethylene octene copolymer.

7. A composition according to claim 3, claim 5 or claim 6 wherein the ethylene based alkene copolymer is an Intellectual Property Office of NZ 13 FEB 2004 RECEIVED PCT/AUO1 ./01226 Received 16 August 2002 - 26 - ethylene hexene copolymer or an ethylene octene copolymer.

8. A composition according to any one of claims 3 to 7 wherein the ethylene based alkene copolymer is an 5 ethylene octene copolymer.

9 . A composition according to any one of claims 3 to 8 wherein the amount of alkene present in the ethylene based alkene copolymer is less than about 18%. 10

10. A composition according to any one of claims 1 to 9 wherein the metaliocene catalysed polyolefin (POE) elastomer is present in an amount of about 30% or more based on the total amount of component (a). 15

11. A composition according to any one of the preceding claims wherein the metaliocene catalysed olefin polymer and/or copolymer has an S.G. in the range of about 0.850 to about 0.915. 20

12. A composition according to claim 11 wherein the metaliocene catalysed olefin polymer and/or copolymer has an S.G. in the range of about 0.860 to about 0.90. 25

13. A composition according to claim 11 or claim 12 wherein the metaliocene catalysed olefin polymer and/or copolymer has an S.G. in the range of about 0.88 to about 0.90. 30

14. A composition according to any one of the preceding claims wherein the metaliocene catalysed olefin polymer and/or copolymer has a melt flow index in the range of about 0.5 to about 50. 35

15. A composition according to claim 14 wherein the metaliocene catalysed olefin polymer and/or copolymer has a melt flow index in the range of about 1 to about 30. AMENDED SHEET IPEA/AU PCT/AU01 ./01226 Received 16 August 2002 - 27 -

16. A composition according to any one of the preceding claims wherein the metaliocene catalysed olefin polymer and/or copolymer has a Shore Hardness A in the 5 range of about 66 to about 96 Shore A.

17. A composition according to claim 16 wherein the metaliocene catalysed olefin polymer and/or copolymer has a Shore Hardness A in the range of about 85 to about 93 or 10 Shore A.

18. A composition according to any one of the preceding claims wherein the metaliocene catalysed olefin polymer and/or copolymer has a DSC melting peak in the 15 range of about 49 to about 107°C.

19. A composition according to claim 18 wherein the metaliocene catalysed olefin polymer and/or copolymer has a DSC melting peak in the range of about 65 to about 98°C. 20

20. A composition according to claim 18 or claim 19, wherein the metaliocene catalysed olefin polymer and/or copolymer has a DSC melting peak in the range of about 70 to about 92°C. 25

21. A composition according to any one of the preceding claims wherein component (a) further contains up to about 35% of a non-metallocene and/or metaliocene catalysed olefin copolymer elastomer with at least about 30 20% comonomer.

22. A composition according to claim 21 wherein the elastomer is a synthetic rubber. 3 5

23. A composition according to claim 22 wherein the synthetic rubber is ethylene propylene rubber (EPR, EPM), ethylene propylene diene rubber (EPDM) and/or ethylene AMENDED SHEET IPEA/AU PCT/AU01./01226 Received 16 August 2002 - 28 - vinyl acetate copolymer (EVA).

24. A composition according to claim 23 wherein the ethylene vinyl acetate copolymer has a vinyl acetate 5 component of about 25 to about 70%.

25. A composition according to claim 24 wherein the ethylene vinyl acetate copolymer has a vinyl acetate component of about 3 0 to about 45%. 10

26. A composition according to any one of the preceding claims wherein component (a) further contains a maleic anhydride modified ethylene copolymer or a graft of maleic anhydride on ethylene propylene rubber or 15 polyethylene.

27. A composition according to claim 26 wherein the amount of a maleic anhydride modified ethylene copolymer or graft of maleic anhydride on ethylene propylene rubber, 20 ethylene vinyl acetate, polypropylene or polyethylene is about 0.1 to about 15 PHR.

28. A composition according to any one of the preceding claims wherein component (a) further contains 25 other polymers, copolymers, elastomers and/or plastomers.

29. A composition according to claim 28 wherein the other polymers, copolymers, elastomers and/or plastomers are other ethylene, propylene or butylene polymers and 30 copolymers, ethylene acrylic copolymers, ethylene acrylic ester copolymers and rubbers.

30. A composition according to claim 29 wherein the rubber is silicone rubber nitrile butadiene rubber (NBR) 35 or butyl rubber (BR).

31. A composition according to claim 28 to claim 30 AMENDED SHEET IPEA/AU PCT/AU01 ./01226 Received 16 August 2002 - 29 - wherein the amount of other polymers, copolymers, elastomers and/or plastomers is up to about 30 PHR.

32. A composition according to any one of the 5 preceding claims wherein component (a) includes at least about 30 PHR of at least one metaliocene catalysed polyolefin elastomer (POE) with an S.G. of less than about 0.885 with the remainder being at least one metaliocene catalysed polyolefin plastomer (POP). 10

33. A composition according to any one of the preceding claims wherein component (a) includes at least about 20% of an olefin copolymer elastomer and/or rubbery, flexible copolymer with the remainder being at least one 15 metaliocene catalysed polyolefin elastomer (POE) and at least one metaliocene catalysed polyolefin plastomer (POP).

34. A composition according to claim 33 wherein 20 component (a) includes about 40% of POE about 40%. of- POP or POE and about 20% of a synthetic rubber/polyolefin copolymer elastomer.

35. „ A composition according to any one of the 25 preceding claims wherein the filler is an inorganic and/or mineral filler.

36. A composition according to claim 35 wherein the filler is an alkaline earth metal carbonate, clays which 30 are optionally calcined, kaolin, huntite and/or hydromagnesite.

37. A composition according to claim 35 or claim 36, wherein the filler is used in combination with and/or 35 coated with stearic acid, stearate, vinyl silanes and/or titanates. AMENDED SHEET IPEA/AU PCT/AU01./01226 Received 16 August 2002 - 30 -

38. A composition according to claim 37 wherein the stearate is calcium stearate.

39. A composition according to any one of claims 35 5 to 38, wherein the filler is huntite and hydromagnesite.

40. A composition according to any one of claims 35 to 39, wherein the filler is a combination of huntite and hydromagnesite with an alkaline earth metal carbonate. 10

41. A composition according to claim 40 wherein the alkaline earth metal carbonate is magnesium carbonate and/or calcium carbonate. 15

42. A composition according*to any one of claims 35 to 41 wherein at least one of the filler is substituted wholly or partly by aluminium hydroxide and/or magnesium hydroxide. - 20

43. A composition according to any one of claims 3 5 to 42, wherein the filler is present in an amount of about 80 to about 250 PHR.

44. A composition according to any one of the 25 preceding claims which includes other flame retardant materials and/or char forming additives.

45. A composition according to claim 44, wherein the other flame retardant materials and/or char forming 30 additives are borates, metaborates, glass beads or particles, silica, silicon dioxide and/or compounds of silicon dioxide with other metal oxides.

46. A composition according to claim 44 or claim 45, 35 wherein the amount of other flame retardant materials and/or char forming additives is about 1 to about 3 0 PHR. AMENDED SHEET IPEA/AU PCT/AU01 ./01226 Received 16 August 2002 - 31 -

47. A composition according to any one of the preceding claims which further includes other additives.

48. A composition according to claim 47 wherein the 5 other additives are antioxidants, metal deactivators and/or copper inhibitors, UV absorbers, foaming or blowing agents, and/or pigments.

49. A composition according to claim 47 or claim 48 10 wherein the amount of other additives is about 0.1 to about 4 PHR each.

50. A composition according to any one of the preceding claims which is cross-linked. 15

51. A process for preparing the halogen-free flame retardant polymeric composition defined in any one of claims 1 to 50 which includes mixing (a) at least two metaliocene catalysed olefin 20 polymers and/or copolymers wherein at least one of the olefin polymers and/or copolymers is elastomeric; and (b) an effective amount of at least one filler which is capable of providing the polymeric composition with flame retardant properties substantially similar to 25 that of plasticised PVC.

52. A process according to claim 51 wherein components (a) and (b) are pre-mixed or mixed simultaneously, sequentially and/or separately. 30

53. A process according to claim 51 or claim 52 wherein the polymeric composition is cross-linked.

54. An article which is composed wholly or partly of 35 the polymeric composition defined in any one of claims 1 to 50. AMENDED SHEET IPEA/AU . 32

55. An article according to claim 54 which is an electrical or optical part, cable, or wire; floor covering; automotive part; building part; tubing; hose; or artificial leather.

56. A halogen-free flame retardant polymeric composition as claimed in any one of 5 claims 1 to 50 and substantially as hereinbefore described with reference to any one of the accompanying examples.

57. A process for preparing a halogen-free flame retardant polymeric composition as claimed in any one of claims 51 to 53 and substantially as hereinbefore described with 10 reference to any one of the accompanying examples. 15 20

58. An article comprised wholly or partly of a polymeric composition as claimed in either 54 or 55 and substantially as hereinbefore described with reference to any one of the accompanying examples. COMPCO PTY LIMITED by their authorised agents JAMES &WF.T.T.S per: ;ND OF CLAIMS