cu») United States US 2020036986081 2) Patent Application Publication co) Pub. No.: US 2020/0369860 A1 Nilsson et al. (54) FLAME RETARDANT AND POLYOLEFIN COMPOSITION (1) Applicant: Borealis AG, Vienna (AT) (72) Inventors: Susanne Nilsson, Stennngsund (SE; innéa Nilsson, Gteborg (SE) Bernt-AKe Sultan, Stemingsund (SE) (21) Appl.No: — 160767,633 (22) PCT Filed: Dee. 12, 2018 (86) PCT No, $371 (eX), (2) Date PCTEP2O18084492 May 28, 2020 G0) Foreign Application Priority Data Dee. 12, 2017 (FP) 172066789 Publication Classiieation (1) Incl. OBL 23106 CosK 3722 (2006.01) (2006.01) (43) Pub. Date: Nov. 26, 2020 cosK 4738 200501) CosL 23/08 (2006.01), (2) US. cl, cP OBL, 24/06 (2013.01); CO8K 322 (2013.01): CasK 4738 (2013.01); COSL 8:04 (013.01); COSK 2003/3217 (2013.01), COSK 2201/005 (2013.01), COSK 203/387 (2013.01); CoB 23/0869 (2013.01) on ABSTRACT The present inventions directed to a polyolefin composition whieh has fame retardant andor fie resistant properties and is suitable as ame retardant andior fire resistant layer of @ ‘wire of cable, The polyolefin composition of the present invention comprises an polyolefin homo- oF capalymer, arvund magnesium hydroxide having particle size dist tion Dy, of 1.5 © 5.0 yam in aa amount of 30 to 65 wt % ‘based on the weight of the polyolefin composition, and & silicone Mud of gum in an amount of 0.1 1 20 Wt % based fn the weight of the polyolefin composition. The present invention is further diwcted 1o a wire or cable comprising ‘one oF more layers, wherein at least one layer thetwor is joblained from the polyolefin composition of the present invention, Finally, the present invention is further directed 9 the use of a polyolefin composition ofthe present invention as aflame retardant layer of @ wire ot cable.US 2020/0369860 AI FLAME RETARDANT AND FIRE RESISTANT ‘POLYOLEFIN COMPOSITION [0001] This upplicaion is a 371 of PCTIEP2018°084492 filed Dec. 12, 2018, which claims priority to European Patent Application No. 17206678.9, fled Dee. 12,2017, the ‘contents of which are incorporated herein in their entirety. ‘TECHNICAL FIELD 10002] The present invention is directed to a polyolefin ‘composition which has flame reterdant and fire resistant properties and is suitable as flame retardant andor fire resistant layer of a wire or cable. The present inveation is further directed toa wire or eable comprising one or more layers, wherein at least one layer thereof comprises the polyolefin composition ofthe present invention, Finally, dhe present invention is further directed to the wse of polyolefin ‘composition of the present invention as a flame retardant layer of a ire of eable BACKGROUND OF THE INVENTION 10003] A typical electrical power cable or wire generally ‘comprises one or more conductors in a cable core, which is surrounded by one or more insulation layers or sheaths of polymeric material. The core is typically copper ar alv- ‘inium but it may also be non-metallic, surounded by @ ‘umber of different polymeric layers, each serving a specific funetion, eg. a semi-conducting shield layer, an insulation Iayer, a metallic tape shield layer and a polymeric jacket. Esch layer con provide more than one function. Por ‘example, low voltage wire or cable is often surrounded by f single polymeric layer that serves as both an insulating Tayer and an outer jacket, while medium to extr-high vollage wire and cable are olen surrounded by at east separate insulating and jacket layers. A power eable core ray for example be surrounded by first polymere semi ‘conducting shield layer, a polymeric insblating layer, 9 second polymeric semicondicting shield layer, 8 metalic tape shield, and @ polymeric jacket. 10004] "A wide variety of polymeric materials have been Uuilized os electrical insulating and shield materials for cables. 10005] Sch polymeric materials in addition to having suitable dielectric propertics must also be enduring and must substantially retain thei inital properties Jor elletive and fale performance over many yours of service. [0006] Sach materials have also to mest stringent safety requirements a aid dosen in intomational standaeds. Ta particular, single cable, or bundle of cables, must not burn by ‘self or transmit fire the combustion gases ofa cable must be as hamaless at possible to humans, the smoke and ‘combustion gases formed must not obscure escape routes OF be corse. [0007] Following the invention of polyethylene (PE) in 1936, the value of its excellent electrical properties was ‘quickly recognized and became the mai focus for its rapid development. 10008] Almost from the outset it was adopted as insulation ‘in communication cables. With the invention ofthe peroxide crosslinking technique in the 1950's, PF also beeame the preferred material for the insulation of medium and high Voliage ables. With the later development of silane grafting technologies and the arrival of ethylene vinyl silane copo- Jymers, competitive techniques were also developed for low Nov. 26, 2020 voltage cables, As a result ables with eosslinked polyeth- ylene (XLPE) insulation and PE jackets have gradually ‘become the material of choice for energy distribution net works, [0009] While infrastrictire cabling is predominantly based on polyolefin, eg. PE, building and equipment cables which make up the largest percentage of all wiring and cabling, were usualy polyvinyl chloride (PVC) based. Due to the lat that these systems are installed within buildings ‘and therefore close to the consumer, Name rtardaney is an important aspect. [0010] Minimizing or eliminating materials that poten- ‘ally cause fie or conteibute t ils spread isa Fundameatal nocesity to ensure the safety of people and the protection of property. Electrical wires and cables are essential t0 the functioning of vitally every aspect of moder life, in the home, transportation, communications and i the workplace, And therefore their composition is of erical importance in controling fre risks. The same counts for non-electrical, eg. optical, wires and cables in the field of communications. [O11] Flame retardant (FR) issues are complex, While PVC has relatively low calorific value and therefore low ‘burning potential, when exposed to fire it generates dense stoke, toxie gases and eorosive combustion prodcts (hy- rochloric acid), which may inhibit evacuation, damage ‘equipment and even building structures. On the other hand) polyolefin compounds have an iaherealy higher calorific value and have diliulty matching the properties of PVC ia terms of combusibility, however, in every crer respect polyolefin products have superior combustion properties to those of PVC with regard to smoke, eomosiveness and tonicity, [0012] In order wo enable cable makers to capitalise on the broader advantages offered by polyolefins, developments in the 1980's to raluce their amability esulted in compounds heavily loaded with fame retardant additives ike alumina hydroxide and magnesium hydroxide which decompose edothermicaly at temperatures borwcon 200 and 600" C., thereby Hberating inert gases. These flame retardant addi tives in polyolefins have the effect of slowing the rate of ‘combustion as wel as reducing their ealorific value [0013] The drawback of using large amounts of such fame retardant additives is the deterioration of the processability and the mechanical properties of the polymer composition. The low extrision temperature and highly viscous melt of these compounds results in a significant reduction in eable production speed compared with ordinary PVC or PE. Taese rawbacks make this technology impracticable as an alter ative to PVC for standard cables. Instead, this technology js therefore used for special cables intended for cttical installations such as public buildings, subways, ships and nuclear power stations. However, they are costly and their processing requires investment in extrsion equipment With ow compression screws and optimised crosshead. [014] The usual technique for making Dame retardant polyolefin compounds for Wire & Cable applications is by high loadings (50-65 wt %) of aluminium hydroxide, Two altemative flame retardant filers are chalk (CaCO,) and ‘magnesium hydroxide (Mg(OH),) [0015] Aluminium hydroxide stars to decompose at 200° C, which limits extrision temperature to about 160° C:, being below optimum for a high viscosity material. The altemative ame retardants donot have this limitation Accordingly, lame retardant compounds have been devel-US 2020/0369860 AI ‘oped which have a melt viscosity similar 1 unfilled PE. ‘Consequently they can be processed om standard PVC and PE exter, without any major modifeations, with 2 similar exirbionspood to that of alll PE and PVC. [0016] US. Pat. No. $034,056 discloses fre potsctants ‘contin relatively hgh loads of aluminium hydroxide and oun andor nearly ground calcium borat, their produc- tion and wse, and semifinished goods and finished prs ‘containing thom. [0017] CN 1 752 130 discloses flame retardant materials based on ehylene-vinylacetatecopolymers containing re tively high lds of nasal hydroxide (parle size 8010 150 nm) and elay, and optionally upto 3% zine boat. {W018} WO 20047115439 discloses flane-etardant poly olefin compounds and their wie in surlace coverings herein the flame-etadant polyolefin compounds contain both aanoclay and inorganic fae retardant gents amongst ‘which are metalic hydroxides and orate salts the later in ‘an amount of 29 3 wt 10019] EP 393 959 discloses a flame retardant polymer ‘composition whichis substantially fee of halogen come pounds and of organometallic sls comprising a copolymer Dfetiylene wilh one oF more eomanomers selected fom the jxoup consisting of lly acrylates, alls) metbacrylats, fcrylic avid, meaene acid and vinyl avaate, furber ‘comprising & silicone Bid or gim and an inorganic filler, preferably caleium carbonate. 0020} During burtng his technology allows formation ‘of a physically and thermally sable charrad ler that protects the polymer from further burning. This elfct is heved witha relatively sal mous of chalk combined withthe oxygen containing ethylene copolymer anda minor Traction of silicone elastomer. The decomposition prats ‘ofthe copolymer ffrvesc and generate a ella taste ‘The polar decomposition art ofthe copolymers tan carly stage othe burning proces reacting wit the chal, binding ‘cto the char At the same tine water and carbon dioxide se formed, citing the burnable gases. The chars stable, dve to the decomposition of the siione pu which is forming a laslke layer. The properties and cost stroeture ofthis Tecnology make it most intresting for the replacaieat of PVC in standard building cables. 10024] Nevertheless, thee is sil a need for further ‘improving flame retardant compositions for wite and cable applications based on polyolefins, eg. PE. Trying 10 improve these compositions the skied person is faced with st confict of sims. 10022} As indicate away sbov, to achieve high fame retardant propecies of halogen-tre asters Ge. PVC- fies) its nosessry to add high amounts of Rome retardant flrs ike aluminium hydroxide. Therefore its oul to moet the desired mechaical and elostical properis as wll 4s an acceptable processing performance. In addition, the novi flame retardant grades have low performance flame retardant properties and only Full eateaory E (sina wire burming tes) in the constretion product cable regulation (CPR), tn onder to fl he higher CPR classes (D to B2) it ts essential to generates stong char which snot fling off during the bunch abl fre test use for thse casitications Strong char is also essential for fie resistant cables, i ‘ables which will he i funtion also after fire Aer such ables have boen subject o fire, the chr wil in fact set ‘insulator Nov. 26, 2020 [0023] Thus, the object of the present invention is to ‘overcome the drwhacks of the stato! the art and to provide polyolefiacbased lame retardant compesition with Jimproved ame retardant properties, while maintaining or ‘oven iniproving the desired mechanical and electrical prop: ferties as Well as the processing performance, It is furher desirable to provide fie resistant properties, SUMMARY OF THE INVENTION [024] The present invention is based on the finding that the abject can he solved by provision of & polvoletia composition comprising ground magnesium hydroxide ba Jing & predefined particle size distribution in combination with silicone Haid or gum. 0025} ‘The polyolefin composition according tothe pres- ent invention has the advantage of having essentially no on of harmfal gases and combining excellent flame retardant properties with very good mechanical properties and. processability [0026] In particule, the inventive compositions have out- Standing flame retardant performance and give very ston char which mht also allow their use for extrdable fan resistant applications. [0027] Accordingly, the present invention is directed to 4 polyolefin composition comprising (A) a polyolefin homo- or copolymer, (@) ground magnesium hydroxide having particle size di {eibution Do of 1.5 t 5.0 um in an amount of 30 to 65 wt % based om the weight af the polyolefin composition, and (©) silicone Muid or gum in an amount of 0 20 wt % based on the weight of the polyolefin composition. [0028] The term “polyolelinhomo- or copolymer” as used herein denotes homopolymers or copolymers of ethylene and, alternatively, homopolymers oF copolymers of propyl- fene. Also mixtures thereof are possible. Copolymers are prefered [0029] ‘Tae term “copolymer” as used herein covers poly Imers obtained from co-polymerisation of at least to, three or more different monomers, i. the term Iymer” as used herein does include so-called terpolymers ‘oblained from co-polymersation of at least thre dilleent [0030] The content ofthe polyolefin homo. or copolymer in the polyolefin composition of the present invention may be 15 0 60 wt %, preferably 20 w0 SO wt %, more preferably 2010 40 wt %, [0031] As indicated already above, the polyolefin homo- ‘or copolymer (A) ean be a homopolymer of copolymer of tthylene or a homopolymers or copolymers of prapylene. Suitable copolymers of ethylene are thermoplastic or elas- tomerie co-polymerisation products of ethylene with ane oF mor CyC-alpha-olefins, prelerably with propylene, Tbutene, Ichexene and I-octene. Preferably, these copoly mers of eylene have a density of 860 10 930 yin [0032] Suitable copolymers of peopylene are eo-polymeri- sation products of propylene with ethylene andlor one oF pore CC,.alphiolefins, preferably with ethylene, I -butene, I-hexene and L-octene,Preferrd are block copo- Jymers with ethylene and heerophasic propylene eopoly- ‘mers with, more preferably, ethylene as comonomer (i the ‘mateix phase andor ia the dispersed phase), [033] The polyolefin homo- oF copolymer (A) may be an cthylene copolymer comprising ethylene monomer units and comonomer units comprising a polar group.US 2020/0369860 AI 10034] Preferably, the comonomer units comprising polar group are selected from the group consisting of lefnically unsaturated carboxylic acids, sue as acrylic id, methaerylic acid, maleic atid, and famarc oid, vcry- Tate, methaeryltes, vinyl esters, soch as vinyl carboxylate ‘esters, such as ving] acetate and vinyl pivalate, derivatives of ‘aerylic acid or methaerylie aed, such as (meth)erylonitie tnd (methaerylic amide, vinyl ethers, such as ving! methyl ‘ether and vinyl phenyl eter, and mixtores threo [0035] The term “(methjeery” is intended herein to ‘embrace both ery] and methaery 10036] Suitable (methjacryats are methymeth)aerlate ‘ethyl(metijucryat, butytmeth)acrylate and hydroxyethyl {inethserylte 10037] Amongst these comonomer units, vinyl esters of monocarboxvlic acids having | to 4 carbon atoms, such as Vinyl acetate, and (methjacryates of alcohols having 1 to 4 ‘earbon atoms, seh as methyeth)veryate, ae particularly prefered 10038] Especially prefered comonomer units are butyl serylate, ethyl acrylate and methyl acrylate. Two oF more such olefinically unsaturated compounds may be used i combination, 10039] The content ofthe comonomer units comprising & polar zoup may be 2 to 35 w %, preferably § to 30 Wt % more preferably 15 and 25 wi % based on the weight ofthe ‘ethylene eopolyme. 10040] Farther, the ethylene copolymer may comprise ‘comonomer units comprising a ervaslinkabl silane Broup. ‘wherein the comonomer units comprising a polar group are position, aad (C)a silicone fuid or gum in an amount of 0.41 10 20 wt 2% based on the weight of the polyolefin composition, 2. The polyolelin composition acconting to claim 1, said polyoletia composition further comprising: (D)a borate in an amount of 5 wo 25 wt % based on the ‘Weight of the polyolefin composition. 3. The polyolefin composition according claim 2, wherein said borate (D) is selected from the group consisting of a borate of an alkali metal, a borate of an alkaline earth meta, borate ofa metal of groups 3t0 12 ofthe periodic table of ‘elements, a borate of aluminium, borie acid, boron phos= phate, and mixtures thereof, 4. The polyoletin composition according to claim 3, wherein sid borate (Ds selected fom the group consisting ‘of sodium borate, ealeium bora, zine borate, and mixtures thereof, 'S. The polyolefin composition according to claim 4, wherein said Borate (D) comprises caleium borate 6. The polyolefin composition according to claim 1, wherein said siicone fiid or gum (C) is selected from the group consisting of a polyiloxane, preferably a polydin- ‘thyhiloxane, a siloxane containing alkoxy and alky| functional groups and mixtures thereot 7. The polyolefin composition according to claim 6, ‘wherein sad silicone fluid or gum (C) isan organomoditied siloxane. 8. The polyolefin composition according to claim 1, wherein ssid polyolefin homo- or copolymer (A) is an ‘ethylene copolymer comprising ethylene monomer units and ‘comonomer unils comprising polar group. Nov. 26, 2020 9. The polyolefin composition according to claim 8, wherein said’ ethylene copolymer further comprises ‘comonomer units comprising a crosslinkable silane group, ‘wherein said comonomer units comprising a polar group fare different fom said comonomer wits comprising 2 crosslinkable silane group. 10, The polyolefin composition according to elaim 9, wherein the content of said comonomer tits comprising a polar ‘group is 210 38 wt %, oF the content of ssid comonomer units comprising a cross linkable silane group is 0.2 10 4 wt % oF the content of said comonomer units comprising a polar ‘group is 2(o 38 wt % and the content of suid comono- ner units comprising a crosslinkable silane group is 0.2 to 4 wt %, based on the weight of said ethylene copolymer, 11, The polyolefin composition avcording 1 claim 8, wherein said ‘comonomer units comprising « polar group are selected fiom the group consisting of aerylic acid, methaeryl acid, acrylates, methacrylates, vinyl esters, and mix- ures thereof 12, The polyolefin composition according to elaim 1, ‘wherein said ground magnesium hydroxide (3) has particle Sze distribution DSO of 25 to 3.5 pm. 18, The polyolefin composition according to elaim 1, ‘wherein said ground magnesium hydroxide (B) has BET seface area of 1-20 m1, 14, A wire or cable comprising one of more layers, ‘wherein at Teast one layer thereof is obtained from a poly- olefin composition aecording to claim 1 18, Use of a polyolefin composition aevording 10 1, optionally after cross-linking thereof, as a flame retardant layer of a wire or cable