POLYOLEFINS HALOGEN-FREE FLAME RETARDANT MOULDING COMPOSITIONS COMPRISING AN INORGANIC HYPOPHOSPHOROUS ACID METAL SALT

Abstract

The present invention relates to halogen-free flame retardant compositions, comprising polyolefins polymers as active ingredient and a flame retardant system. The flame retardant system comprises at least an Hypophosphorous acid metal salt (preferred is Aluminium hypophosphite) as main flame retardant component, at least a sterically hindered N-alkoxyamine with a specific structure as first flame retardant synergic component, at least a silicon oxide or aluminium oxide or a mixture thereof with specific properties as second flame retardant synergic component.

Claims

1. A composition comprising: a) a thermoplastic polyolefin b) at least an Hypophosphorus acid metal salt wherein phosphorus valence state is equal to +1, as a main flame retardant component (FR); c) at least a sterically hindered N-alkoxyamine as a first flame retardant synergic component (FRSYN1) having the following chemical formula (I): ##STR00008## where R represent C.sub.1-C.sub.30 linear or cyclic alkyl group, and R′ is selected as C═O or C═O(CH.sub.2).sub.8C═O; and d) at least a silicon oxide or aluminium oxide or their mixtures as a second flame retardant synergic component (FRSYN2).

2. A composition according to claim 1, wherein said R is a C.sub.7-C.sub.12 linear or cyclic alkyl group.

3. A composition according to claim 1, wherein said R is a C.sub.8-C.sub.11 linear or cyclic alkyl group.

4. A composition according to claim 1, wherein said Hypophosphorus acid metal salt is Aluminium Hypophosphite or Calcium Hypophosphite.

5. A composition according to claim 1, wherein said sterically hindered N-alkoxy amine is a compound identified by CAS number: 129757-67-1.

6. A composition according to claim 1, wherein said sterically hindered N-alkoxy amine is a compound identified by CAS number: 705257-84-7.

7. A composition according to claim 1, wherein said sterically hindered N-alkoxy amine is a mixture of compounds identified by CAS number: 705257-84-7 and CAS number: 129757-67-1.

8. A composition according to claim 1, wherein said silicon oxide or aluminium oxide or their mixtures has acidic pH ranging from pH 3 to pH 6.

9. A composition comprising: a) a thermoplastic polyolefin or polar polyolefin, b) at least Aluminium Hypophosphite or Calcium Hypophosphite, c) at least a compound identified by CAS number: 129757-67-1 or CAS number: 705257-84-7 or a mixtures of both, and d) at least a silicon oxide or aluminium oxide or their mixtures with acidic pH ranging from pH 3 to pH 6.

10. A composition according to claim 9, wherein said thermoplastic polymer is high density medium density or low density polyethylene.

11. A flame retardant powder mixture useful to flame retard a polyolefin polymer for moulding different plastic articles, said powder mixture comprising: a) Aluminium Hypophosphite or Calcium Hypophosphite at a concentration from 70% to 94%, b) a compound identified by CAS number: 129757-67-1 or CAS number: 705257-84-7 or mixture of the both at a concentration from 3% to 15%, and e) a silicon oxide or aluminium oxide or their mixture with acidic pH ranging from pH 3 to pH 6 at a concentration from 3% to 15%, with respect to the total weight of the composition.

12. A composition according to claim 11, further comprising from 10% to 20% by weight respect to the total composition of a meltable solid organic phosphate flame retardant component in powder form.

13. A thermoplastic concentrate in pellet form or Masterbatch useful to flame retard a polyolefin polymer for moulding different plastic articles, said thermoplastic concentrate comprising: a) a thermoplastic polyolefin or polar polyolefin from 70% to 30%, and b) a flame retardant powder mixture according to claim 11 from 30% to 70%, c) optionally from 0% to 10% of additives with respect to the total weight of the composition.

14. A thermoplastic concentrate in pellet form or Masterbatch useful to flame retard a polyolefin polymer for moulding different plastic articles, said thermoplastic concentrate comprising: a) a thermoplastic polyolefin or polar polyolefin from 70% to 30%, and b) a flame retardant powder mixture according to claim 12 from 30% to 70%, c) optionally from 0% to 10% of additives with respect to the total weight of the composition.

15. A flame retarded polymer compound in pellet form for moulding different plastic articles containing: a) a thermoplastic polyolefin or polar polyolefin at a concentration of 99% to 85%, b) Aluminium or Calcium hypophosphite at a concentration of 1% to 12%, c) compound identified by CAS number: 129757-67-1 or CAS number: 705257-84-7 or mixture of the both at a concentration of 0.1% to 1.5%, d) silicon oxide or aluminium oxide or their mixture with acidic pH ranging from pH 3 to pH 6 at a concentration of 0.1% to 1.5%, e) optionally additives, fillers or reinforcing fibers from 0% to 40% with respect to the total weight of the composition.

16. The composition according to claim 1 as flame retarded polymer compound for molding plastic articles selected from: stadium and theatre seats, injection moulded electrical connectors and boxes, switches, appliances parts, artificial hairs, roofing covers, artificial turfs, pipes and fittings, corrugated pipes, building cables, automotive cables, telecommunication cables, air ducts profiles for ventilation systems, films and films for industrial packaging, fibres for carpets, spun bound and monofilament textiles, windows roller blinds, polyolefin foams for building insulation and industrial packaging.

Description

DESCRIPTION OF THE INVENTION

[0052] These and other objects according to the present invention are achieved by a flame-retarded composition consisting of:

[0053] a) at least an Hypophosphorus acid metal salt, also named as inorganic Phosphinate or Hypophosphite, where phosphorus valence state is equal to +1, as main flame retardant (FR) component

[0054] b) at least a sterically hindered N-alkoxyamine having the following molecular structure (I) as a first flame retardant synergic component (FRSYN1)

##STR00001##

where R represent C.sub.1-C.sub.30 linear or cyclic alkyl, preferred C.sub.7-C.sub.12, more preferred C.sub.8-C.sub.11
and R′ can be C═O or C═O(CH.sub.2).sub.8C═O

[0055] c) at least a silicon or aluminum oxide as second flame retardant synergic component (FRSYN2)

[0056] d) at least a thermoplastic polyolefin polymer or polar polyolefin polymer

[0057] e) fillers and/or reinforcing fibers other conventional additives like pigments, stabilizers, processing aids.

[0058] The total percentage of components a) to f) must be 100%.

[0059] According to the present invention, said main flame retardant component (FR) is preferably Aluminium Hypophosphite.

[0060] First flame retardant synergic component (FRSYN1) is preferably Bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) or 4-Piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy)-, 4,4′-carbonate.

[0061] Second flame retardant synergic component (FRSYN2) is preferably silicon oxide or aluminium oxide or their mixtures with a pH of 3 to 6 (measured on the powder at 4% by weight in water).

[0062] The main flame retardant (FR) agent and the first and second flame retardant synergics (FRSYN1 and FRSYN2) total content is preferably lower than 15% by weight with respect to the total composition weight, so that mechanicals and electrical properties are satisfactory with respect to most of the desired applications. Main flame retardant (FR) agent and first and second flame retardant synergics (FRSYN1 and FRSYN2) are preferably added to the polyolefin polymer in the form of a previously prepared powder mix or in the form of a concentrate (or masterbatch).

[0063] Further aspects of the present invention, are described here below in more details.

[0064] a) Hypophosphorus acid metal salt, also called inorganic Phosphinate or Hypophosphite (FR)

[0065] Hypophosphorous acid metal salts contains the higher content of phosphorus in low oxidation state compared to any other molecules, out of pure red phosphorus. Hypophorous acid metals salts during decomposition at high temperatures evolve PHs gas that is a very powerful radical scavenger in the gas phase. This make Hypophosphorus acid metal salts very active as flame retardant.

[0066] The selection of the most appropriate Hypophosphite is subjected to a number of critical factors. Particularly, suitable hypophosphites must have sufficient thermal stability to overcome melt processing at temperature higher than around 200° C. If they do form hydrates, they must be used in the corresponding anhydrous form and they must not be hygroscopic when successively exposed to ambient humidity. Examples of such Hypophosphites are Aluminium hypophosphite (CAS 7784-22-7), Calcium hypophosphite (CAS 7789-79-9), Manganese hypophosphite (10043-84-2), Magnesium hypophosphite (CAS 10377-57-8), Zinc hypophosphite (CAS 15060-64-7), Barium hypophosphite (CAS 171258-64-3). Most preferred according to the present invention are Aluminium and Calcium Hypophosphites.

[0067] Aluminium hypophosphite, corresponding to chemical formula Al(H.sub.2PO.sub.2).sub.3, is currently produced by Italmatch Chemicals Spa (under commercial name “Phoslite IP-A”) in a white powder form with a low humidity level, high purity and different PSD suitable for thermoplastic processing.

[0068] Calcium hypophosphite, corresponding to chemical formula Ca(H.sub.2PO.sub.2).sub.2, is also currently produced by Italmatch Chemicals Spa (under commercial name “Phoslite IP-C”) This compound shows in most cases similar or lower flame retardant performances when compared to Aluminium hypophosphite.

[0069] However, it can be advantageously used in those applications where thermal resistance of Aluminium hypophosphite would be critical. Aluminium and Calcium hypophosphites, being flammable powders as most of anhydrous hypophosphites, are often commercialized as a dry blend powder with other solid flame retardant agents or even in masterbatch form for easier transport and manipulation.

[0070] b) Sterically Hindered N-Alkoxyamine as First Flame Retardant Synergic Component (FRSYN1)

[0071] Sterically hindered N-alkoxyamine according to present invention are organic compounds characterized by the following chemical formula (I):

##STR00002##

where R represent C.sub.1-C.sub.30 linear or cyclic alkyl, preferred C.sub.7-C.sub.12, more preferred C.sub.8-C.sub.11
and R′ can be C═O or C═O(CH.sub.2).sub.8C═O

[0072] These products are currently commercially available and know to be effective as UV stabilizers in polymers, particularly in presence of acidic species like brominated flame retardant agents. Sterically hindered N-alkoxyamine are also known to act as flame retardant synergic components, according to some specific combinations, in different polymers, especially in polypropylene films and fibers.

[0073] c) Silicon Oxide or Aluminium Oxide as a Second Flame Retardant Synergic Component (FRSYN2)

[0074] Fumed silica, also known as silica or pyrogenic silica because it is produced in a flame, consists of microscopic droplets of amorphous silica fused into branched, chainlike, three-dimensional secondary particles, which then agglomerate into tertiary particles. Fumed silica serves as a universal thickening agent and an anticaking agent (free-flow agent) in powders, having an high surface area. Like silica gel, it serves as a desiccant.

[0075] It is used in cosmetics for its light-diffusing properties. It is used as a light abrasive, in products like toothpaste. It is also used in the production of cat litter box filler and as a core material in the production of vacuum insulated panels. It is also used in polymers as filler in silicone elastomer and viscosity adjustment in paints, coatings, printing inks, adhesives and unsaturated polyester resins, as processing aid, anti-blocking and surface modification in thermoplastic polymer, as nucleating agent in foam. Other uses in plastic compounds include controlled migration of additives. A further application of silica and fumed silica is as carrier for liquid additives in masterbatch or compounds production.

[0076] Activated alumina is manufactured from aluminium hydroxide by dehydroxylating it in a way that produces a highly porous material. The compound is used as a desiccant (to keep things dry by absorbing water from the air) and as a filter of fluoride, arsenic and selenium in drinking water. It is made of aluminium oxide (alumina; Al.sub.2O.sub.3). It has a very high surface-area-to-weight ratio, due to the many “tunnel like” pores that it has. Activated alumina in its phase composition can be represented only by metastable forms (gamma-Al.sub.2O.sub.3 etc.). Corundum (alpha-Al.sub.2O.sub.3), the only stable form of aluminium oxide, does not have such a chemically active surface and is not used as a sorbent.

[0077] Fumed and silica/alumina mixed oxides are also known and used frequently in catalytic applications such as in catalyst washcoats, in extrudates or as raw material for the synthesis of specialty zeolites.

[0078] The activity of metal oxides like silica or alumina as synergic flame retardant is also known in the art.

[0079] Surprisingly it has been found that only silica or alumina characterized by an acidic pH are very effective in increasing the flame retardant effect of the claimed compositions. When silicon and aluminium oxide have an acidic pH, the high surface is most covered by —OH groups, being effective active in adsorbing both liquids and gases. Without being bound to any theory, it is believed that when under the flame effect, acidic silica or alumina covered by —OH groups adsorb the melt polymer and gas degradation product, retarding the flame propagation.

[0080] d) Thermoplastic Polyolefin or Polar Olefin

[0081] Polyolefins, preferably polyethylene and polypropylene, can be prepared by 2 different methods: by radical polymerisation (normally under high pressure and at elevated temperature) or by catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. Mixtures of the polymers mentioned are also in the object of the present invention, for example mixtures of polypropylene with polyethylene (PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (LDPE/HDPE, LDPE/LLDPE, LLDPE/HDPE or LLDPE/EVA).

[0082] e) Fillers and/or Reinforcing Fibers

[0083] Example of fillers are glass beads, hollow glass spheres, amorphous silica, chalk, mica, calcinated kaolin, wollastonite, talc, magnesium carbonate, barium sulphate or similar products. They also may have been surface treated with fatty acids or the like, or may have been milled in the presence of fatty acids or the like. Any particulate substance currently available in the market as filler for thermoplastic resins, may be used in the compositions according to the present invention, provided that the average particle size of the powder, when measured by laser instrument, is in the range of about 2 microns to 20 microns.

[0084] Examples of preferred reinforcing fibers is glass fibers to be used in the commercially available form of chopped glass. In order to improve compatibility with thermoplastic resins, the reinforcing fiber may have been surface treated with a silane compound. Coupling agents like polypropylene grafted maleic anhydride is normally used to improve mechanical properties. Reinforcing fibers are used in the range from 10% to 50%, preferably from 20% to 35% by weight on the weight of the resin: if the amount of reinforcing fiber is lower than 10%, no advantage is observed in the mechanical properties of the final product, while if the amount is higher than 50% by weight, viscosity of the melt is found too high.

[0085] f) Other Conventional Additives

[0086] Novel thermoplastic compositions may also contain one or more of the following compounds: processing aids, heat and process stabilizers, UV stabilizers, antidripping agents, pigments, dispersing agents, mould release additives, nucleating agents, partially crosslinked elastic polymers used as impact modifiers, and their mixtures.

EXPERIMENTAL PART

[0087] In the following examples, the below listed components were used:

[0088] FR (main flame retardant component):

[0089] Aluminium hypophosphite (Phoslite IP-A, by Italmatch Chemicals), hereafter “IP-A”

[0090] Calcium hypophosphite (Phoslite IP-C, by Italmatch Chemicals), hereafter “IP-C”

[0091] FR for comparative examples:

[0092] Aluminium salt of di ethyl phosphinic acid (Exolit OP1240, by Clariant), hereafter “OP1240”

[0093] Ammonium polyphosphate (Exolit AP 422), hereafter “APP” FRSYN1 (first flame retardant synergic component)

[0094] Bis (1-octyloxy-2,2,6,-tetramethyl-4-piperidyl) sebacate (Tinuvin 123, by BASF), hereafter “T123”

[0095] CAS number: 129757-67-1

[0096] Chemical formula:

##STR00003##

[0097] 4-Piperidinol, 2,2,6,6-tetramethyl-1-(undecyloxy)-, 4,4′-carbonate (ADK STAB LA81, by Adeka), hereafter “LA81”

[0098] CAS number: 705257-84-7

[0099] Chemical formula:

##STR00004##

[0100] FRSYN for Comparative Examples

[0101] 1,6-Hexanediamine,N1,N6-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, polymer with 2,4,6-trichloro-1,3,5-triazine, reaction products with 3-bromo-1-propene,N-butyl-1-butanamine and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine, oxidized, hydrogenated (Tinuvin NOR371, by BASF), hereafter “NOR371”

##STR00005##

[0102] N-alkoxy Hindered Amine Reaction Products CAS 191680-81-6 (Flamestab NOR 116, by BASF), hereafter “NOR116”

##STR00006## [0103] where R′ is

##STR00007##

[0104] In the following table 1 are reported the molecular weight and molecular weight equivalents of N-alkoxy groups in the different synergics used. We highlight that the number of N-alkoxy groups in the different molecules is substantially the same, as a consequence a similar flame retardancy activity would be expected. Surprisingly, only the claimed synergics have shown to be effective. Without being bound to any theory, it has been hypotized that the tertiary amines groups present in the comparative examples N-alkoxyamine act as a powerful radical scavenger decreasing the overall efficiency of the molecule as flame retardant.

TABLE-US-00001 Tab. 1 FRSYN1 T123 LA81 NOR371 NOR 116 Molecular Weight (g/mol) 737 681 2890 2261** (xn = 2)* Number of N-alkoxy groups 2 2 8 6 N-alkoxy groups (g/mol) 369 341 361 377 *Chemicals Notification and Assessment File No.: NA/910 (August 2011) **Technical Datasheet BASF

[0105] FRSYN2 (Second Flame Retardant Synergic Component)

[0106] Fumed silica (Cab-o-sil M5, by Cabot) with pH=3.6-4.3 (4% in H.sub.2O), hereafter “Cab-o-sil M5”

[0107] Fumed alumina (Aeroxide Alu 130, by Evonik) with pH=4.4-5.4 (4% in H.sub.2O), hereafter “Aeroxide Alu 130”

[0108] Fumed silica (Aerosil 200, by Evonik) with pH=3.7-4.7 (4% in H.sub.2O), hereafter “Aerosil 200”

[0109] Fumed mixed alumina/silica (Aerosil MOX 170, by Evonik) with pH=3.6-4.5 (4% in H.sub.2O), herafter called “Aerosil MOX 170”

[0110] FRSYN2 for Comparative Examples

[0111] Amorphous Silica (Sidistar T120, by Elkem) with pH=7-9 (4% in H.sub.2O), hereafter “Sidistar T120”

[0112] Alumina (Martoxid™ 2250, by Huber) with pH=7-9 (4% in H.sub.2O), hereafter “Martoxid™ 2250”

[0113] Polymers:

[0114] Polyolefins

[0115] HDPE: Eraclene ML 70 (Medium-low molecular weight HDPE homopolymer from slurry process, MFR 190° C./2.16 kg=2-3 gr/10′, density=0.951 grlcc) LDPE: Riblene MP 30 (Medium molecular weight LDPE, MFR 190° C./2.16 kg=7.5 gr/10′, density=0.925 grlcc)

[0116] LLDPE: Flexirene FG30 (Medium molecular weight ethylene-butene copolymer, MFR 190° C./2.16 kg=1 gr/10′, density=0.92 gr/cc)

[0117] PP: Moplen HP500N (PP homopolymer, MFR 230° C. 2.16 kg=12 gr/10′)

[0118] PP glass fiber reinforced (Rialglass H07S30G, Polypropylene homopolymer 30% glass fiber reinforced, chemically coupled)

[0119] Polar Polyolefins

[0120] EVA: Greenflex ML 30 (Ethyelene Vinyl Acetate copolymers with VA=9%; MFR 190° C./2.16 kg=2.5 gr/10′)

[0121] Stabilizers:

[0122] Hindered phenol heat stabilizer (Irganox 1010, by Ciba), hereafter “Irg. 1010”

[0123] Phosphite process stabiliser (Irgaphos 168, by Ciba), hereafter “lrg. 168” Examples according to the invention (from E.1 to E. 18) and Comparative Examples (from C.1 to C.20) are reported in the tables below

[0124] Experimental Procedure

[0125] All components reported in Examples and Comparative Examples are extruded in a 24 mm twin screw extruder with a temperature profile in the range 220-230° C. Polymer pellets are previously cut mechanically to lower size in a high speed milling machine. Grinded polymers, liquids and solid additives are premixed in a low speed lab internal mixer and add to first hopper of the twin screw extruder. The extruded polymer pellets are dried in an oven at 90° C. before injection moulding in UL-94 specimens at 1.6 mm and 5 specimens were conditioned for 24 hours at 23° C. and 50% humidity. Flammability have been reported according to UL-94 procedure. When tests do not meet V0, V1 and V2 an NC classification has been given,

[0126] Comments to Table 1 (Example from C.1 to C.14)

[0127] In table 1 (C.1 to C.12) combinations are shown according to previous art (WO 2011/117266) where a thermoplastic polymer is made flame retardant by an organic or inorganic phosphinate and one sterically hindered N-alkoxy amine. However, the comparative examples here reported show that the combinations fail to fulfil the high flame retardancy level in HDPE. Examples reported in WO 2011/117266 refers only to PP.

[0128] Comparative example C.13 and C.14 are according to compositions claimed in WO2013/136285. Mixtures of inorganic phosphorus compound (APP) in oxidation state +5 and N-alkoxyamine with a structure claimed in the present invention, fail to obtain a good flame behaviour when used in HDPE.

[0129] Comments to Table 2 (Example from E.1 to E.6 and Comparative Example from C.15 to C.20)

[0130] In table 2 (E.1 to E.6) it is reported that the addition of silicon oxide (Cab-o-sil M5) to inorganic hypophosphite (IP-A) and N-alkoxyamine with the specific structure claimed (T123 and LA81) surprisingly shows an high level of flame retardancy in HDPE polymer.

[0131] Comparing C.15, C.16 to E.1 it is shown how the flame retardant effectiveness needs the presence of three components IP-A, Cab-o-sil M5 and T123 Comparative Examples C.17 to C.20 show that Cab-o-sil M5 and IP-A with N-alkoxyamine not represented by the structure here claimed (NOR371 and NOR116) does not reach good level of flame retardancy.

[0132] Comments to Table 3 (Examples from E. 7 to E.9 e Comparison Examples C.21 and C.22)

[0133] In Examples E.7, E8, E9 it is demonstrated the high effectiveness of different grades silicon oxide and aluminium oxide and mixtures with acidic pH. Comparison examples C.21, C.22 demonstrate that silicon oxide (Sidistar T120) and aluminium oxide (Martoxid™ 2250) with basic pH do not show the high flame retardancy effect.

[0134] Comments to Table 4 (Examples from E.10 to E.18)

[0135] In Examples from E.10 to E.16 it is demonstrated the high effectiveness of combinations according to present invention on different polyolefins and polar polyolefins polymers (LLDPE, LDPE, PP and EVA). Example E.18 show the effectiveness of combinations here claimed also in a PP glass fibre compound.

TABLE-US-00002 TABLE 1 C.1 C.2 C.3 C.4 C.5 C.6 C.7 C.8 C.9 C.10 C.11 C.12 C.13 C.14 HDPE 88.9%  88.2%  88.9%  88.2%  88.9%  88.2%  88.9%  88.2%  88.9%  88.2%  78.9%  78.2%  88.9%  88.2%  IP-A  10%  10%  10%  10%  10%  10%  10%  10% — —  20%  20% — — OP1240 — — — — — — — —  10%  10% — — APP  10%  10% NOR371 0.7% 1.4% — — — — — 0.7% 1.4% 0.7% 1.4% NOR116 — — 0.7% 1.4% — — — — — — — — — — T123 — — — — 0.7% 1.4% — — — — — — — LA81 — — — — — 0.7% 1.4% — — — — 0.7% 1.4% Irg. 1010 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% Irg. 168 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% UL-94 NC NC NC NC NC NC NC NC NC NC NC NC NC NC 1.6 mm

TABLE-US-00003 TABLE 2 C. 15 C. 16 E.1 E.2 E.3 E.4 E.5 E.6 C.17 C.18 C.19 C.20 HDPE 79.6%  88.2%  88.2%  88.2%  88.2%  88.2%  88.2%  88.2%  88.2%  86.8%  88.2%  86.8%  IP-A  20%  10%  10%  10%  10%  10%  10%  10%  10%  10%  10%  10% T123 0.7% 0.4% 1.0% — — — — — LA81 — — — 0.7% 0.4% 1.0% — — — — NOR371 — — — — — — — 0.7% 1.4% — — NOR116 — — — — — — — — — 0.7% 1.4% Cab-o-sil M5 1.4% 0.7% 1.0% 0.4% 0.7% 1.0% 0.4% 0.7% 1.4% 0.7% 1.4% Irg. 1010 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% Irg. 168 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% UL-94 NC NC V2 V2 V2 V2 V2 V2 NC NC NC NC 1.6 mm

TABLE-US-00004 TABLE 3 E.7 E.8 E.9 C.21 C.22 HOPE 88.2%  88.2%  88.2%  88.2%  88.2%  IP-A  10%  10%  10%  10%  10% LA81 0.7% 0.7% 0.7% 0.7% 0.7% Aeroxide Alu 130 0.7% — — — — Aerosil 200 — 0.7% — — — Aerosil MOX 170 — — 0.7% — — SidistarT120 — — — 0.7% — Martoxid TM 2250 — — — — 0.7% Irg.1010 0.1% 0.1% 0.1% 0.1% 0.1% Irg.168 0.3% 0.3% 0.3% 0.3% 0.3% UL-94 1.6 mm V2 V2 V2 NC NC

TABLE-US-00005 TABLE 4 E.10 E.11 E.12 E.13 E.14 E.15 E.16 E.17 E.18 LLDPE 90.6%  90.6%  — — — — 90.6%  — — LDPE — 90.6%  90.6%  — — — — — EVA — — — 90.6%  90.6%  — — — PP 95.1 — PP GF30% — 95.1%  IP-A   8%   8%   8%   8%   8%   4%   4% IP-C — — — — —   8%   8% — — T123 0.6% — 0.6% — — — — — — LA81 — 0.6% — 0.6% 0.6% 0.6% 0.6% 0.3% 0.3% Cab-o-sil M5 0.4% 0.4% 0.4% 0.4% 0.4% 0.4% 0.4% 0.2% 0.2% Irg. 1010 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% 0.1% Irg. 168 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% 0.3% UL-94 V2 V2 V2 V2 V2 V2 V2 V2 V2 1.6 mm