MXPA00000239A - Flame retardant compositions - Google Patents

Abstract

Hindered amine compounds containing a group of formula (1) where G1 and G2 are independently alkyl of 1 to 4 carbon atoms or are together pentamethylene;Z1 and Z2 are each methyl, or Z1 and Z2 together form a linking moiety which may additionally be substituted by an ester, ether, amide, amino, carboxy or urethane group;and E is alkoxy, cycloalkoxy, aralkoxy, aryloxy;whenadded to a wide variety of polymeric substrates, particularly polyolefins and styrenic polymers, surprisingly bestow flame retardant properties to such compositions. When used with selected halogenated, phosphorus, boron, silicon and/or antimony compounds which themselves are known to be effective flame retardants, selected combinations of these flame retardants with the instant hindered amines afford enhanced or synergistic flame retardancy to some polymer substrates.

Description

COMBUSTION RETARDANT COMPOSITIONS The present invention pertains to a method for retarding the combustion of a polymeric substrate by adding thereto an effective combustion retarding amount of a selected hindered amine compound.

Background of the Invention Hindered amines have long been recognized as stabilizers and / or heat stabilizers for a host of organic materials subjected to degradation induced by oxygen, heat or actinic light. Patent literature and academic publications are replete with references to those hindered amine compounds and their valuable destabilizing efficacy. It is not mentioned or suggested in any such reference that the hindered amines themselves are also combustion retardants per se. Particularly relevant are U.S. Patent Nos. 5,004,770; 5,096,950; 5,204,473 and 5,300,544, as well as the application Serial No. 08 / 885,613, co-pending. These references belong to several hindered amines substituted with N-hydrocarbyloxy (the so-called hindered amines with NOR) and several compositions stabilized therewith. As mentioned above, none of these references describes or makes indirect reference to the fact that the compositions stabilized with the amines hindered with ÑOR are flame retardants. This inherent property was never discovered, even serendipitously, until the invention was made. That is to say, there is evidence that even those of considerable experience in the technique of hindered amine stabilizers were very surprised by this unexpected discovery. Accordingly, the method for converting a combustion retardant polymer substrate incorporated therein to a hindered amine with OR is surprising, unexpected and clearly not obvious to those skilled in the stabilizer art. This invention provides a public and valuable method for retarding the combustion of polymers which can not be obtained from any of the references of the prior art. U.S. Patent No. 5,393,812 describes polyolefin compositions which render combustion retardant by means of a combination of a halogenated hydrocarbyl phosphate or phosphate ester combustion retardant in combination with a hindered functional alkoxyamine amine, but do not exist suggestions that the hindered amine itself be responsible for retarding combustion, but that the hindered amine is to prevent tarnish and other undesirable effects from occurring in those polyolefin compositions. European Application No. 0 792 911 A2, published after the filing date of the provisional application originating Serial No. 60 / 051,331, discloses that the hindered functional alkoxyamine amines can be used to increase the efficacy in the retardation of the combustion of retardants from the combustion of tris (trihalogenopentyl) phosphate. The market of combustion retardants (FR) today is comprised of products which function to interfere with the combustion process by chemical and / or physical means. Mechanically it has been proposed that these FR operate during the combustion of an article in the gas phase, the condensed phase or both. It is proposed that the organohalogens generate halogenated species (for example HX) which interfere in the gas phase with the organic "fuel" with free radicals of the polymeric substrate. It is proposed that the synergists react with HX to form additional chemical species which interfere with the combustion in the gas phase, such as in the reaction of antimony oxide with HX to form antimony halide and water vapor. It is also proposed other types of combustion retardants that impart efficiency in the "condensed" phase by forming a protective carbonized layer on the polyester, or by forming an intumescence or foam on the polyester surface. It is thought that the carbonized or intumescent layer prevents the organic fuel from migrating from the polyester to the vapor phase where it can burn the fuel, or the carbonized layer can act as a thermal barrier to protect the underlying polymer article from thermally induced decomposition and fuel generation. Phosphorus compounds of various kinds (eg, halo or non-halogenated) are an example. Moreover, it is proposed that other classes of compounds operate in the condensed and / or vapor phases. It is proposed that metal hydrates or metal oxides generate water vapor under thermal conditions, the water acts to dilute the fuel mixture in the combustion zone and to remove heat from the flame zone via the conversion of water to steam. It is reported that alumina trihydrate, magnesium hydroxide or oxide, and other compounds work in this way. This state of the chemistries of the techniques described above have several detrimental aspects in addition to the effective, mentioned, retarding combustion attributes. Certain organobrominated compounds are under governmental safety due to the generation of toxic byproducts during production or combustion such as the dioxanes of the polybrominated diphenyl oxides.

Certain combustion retardants containing metals, notably antimony oxides, are safe for reasons of exposure and toxicity to workers. Antimony oxides often contain trace amounts of arsenic compounds that are suspected to be carcinogens. In addition, there has been a growing concern about the generation of smoke and toxic gases, which are released from these combustion retardants during a fire. Although classical FRs can be effective combustion suppressants, the toxic gases they form pose risks to human exposure. The present invention alleviates some of the detrimental aspects of the current state of the art possessed by commercial combustion retardants. The amines hindered with OR of the present are not halogenated and free of heavy metals, thus avoiding the generation of corrosive HX gases and avoiding exposure to toxic metals. In some applications, the present invention provides direct replacement of current FR systems, while in another case ÑOR compounds of the present provide the complementary or synergistic enhancement system for heavy metals (for example the replacement of antimony oxide in ABS) where a good combustion retardation can be achieved using less classical FR agent in the presence of a ÑOR compound hereof.

Accordingly, it has now been found that those amine-hindered amine compounds also have a totally unknown and totally unexpected property, namely that, when incorporated into a variety of polymeric substrates, they confer sufficient polymer retardation to the polymer composition. so that the polymeric compositions can pass the recognized combustion delay selection test procedures.

Detailed Description The present invention pertains to a method for retarding combustion of a polymeric substrate and adding thereto an effective amount for retarding the combustion of a hindered amine compound containing a group of the formula where Gi and G2 are independently alkyl of 1 to 4 carbon atoms or together are pentamethylene, Zi and Z are each methyl, or Zi and Z2 together form a linking moiety which can be further substituted by an ester, ether, amide group , amino, carboxy or urethane, and E is Ci-Cis alkoxy, C5-C2 cycloalkoxy, C7-C25 aralkoxy, Cg-C2 aryloxy, and the corresponding use. Preferably Zi and Z2 as a linking moiety together with the structure are bonded to form a 6 membered ring, especially a substituted piperidine ring. A preferred hindered amine compound is a substituted 2, 2, 6,6-tetramethylpiperidine. Preferably E is alkoxy, cycloalkoxy, or aralkoxy, especially methoxy, propoxy, cyclohexyloxy or octyloxy. More preferably E is propoxy, cyclohexyloxy or octyloxy. Preferably, when the polymeric substrate is polypropylene, the hindered amine is not bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, and the combustion retardant is not a phosphate or phosphonate of halogenated hydrocarbyl. More particularly, the present invention relates to a method of a combustion retardant polymeric substrate which comprises adding to the substrate an effective amount of the retardant of the combustion of a hindered amine of a hindered amine compound having a formula of AR structure where E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbon atoms, R is hydrogen or methyl, m is 1 to 4, when it is 1, R2 is hydrogen, C? -Ci8 alkyl or alkyl optionally interrupted by one or more oxygen atoms, CC? 2 alkenyl, Ce-Cio aryl, CC? aralkyl, glycidyl, a monovalent acyl radical of an aliphatic, cycloaliphatic carboxylic acid or aromatic, or a carbamic acid, preferably an acyl radical of an aliphatic carboxylic acid having 2-18 carbon atoms, a cycloaliphatic carboxylic acid having 5-12 carbon atoms or an aromatic carboxylic acid having 7- 15 C atoms, or where x is 0 or 1, where y is 2-4; when m is 2, R 2 is C 1 -C 12 alkylene, C 4 -C 2 alkenylene, xylylene, a divalent acyl radical of a dicarboxylic acid or of an aliphatic, cycloaliphatic or araliphatic dicarbamic acid, preferably an acyl radical of a aliphatic dicarboxylic acid having 2-18 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms; O O II -c- -Nh (CH2) d- NH- where Di and D2 are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, an aryl or aralkyl radical including the 3,5-di-t-butyl radical -4-hydroxybenzyl, D3 is hydrogen, or an alkyl or alkenyl radical containing up to 18 carbon atoms, and d is 0-20; when m is 3, R 2 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid; when m is 4, R 2 is tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid including 1, 2, 3, 4-butacarboxylic acid, 1,2,4,4-but-2-en-tetracarboxylic acid, and 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic acid; p is 1, 2 or 3, R3 is hydrogen, C? -C12 alkyl, C5-C7 cycloalkyl, C-Cg aralkyl, C2-C8 alkanoyl, alkenoyl or C3-C5 benzoyl; when p is 1, R4 is hydrogen, C? -C? 8 alkyl, C5-C7 cycloalkyl / C2-C8 alkenyl, unsubstituted or substituted by a cyano, carbonyl or carbamide, aryl, aralkyl, or glycidyl group , a group of the formula -CH 2 -CH (OH) -Z of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or a group of the formula or where h is 0 or 1, R3 and 4 together, when p is 1, they can be alkylene of 4 to 6 carbon atoms or cyclic acyl radical of 2-oxo-polyalkylene of a 1,2- of 1,3-dicarboxylic acid aliphatic or aromatic when p is 2, R4 is a direct bond or is alkylene of C? -C? 2, arylene of C6? C? 2, xylylene, a group -CH2CH (OH) -CH2 or a group -CH2-CH (OH) -CH2-0-X-0-CH2-CH (OH) -CH2- wherein X is C2-C6 alkylene, C6-C6 arylene or Cs-C2 cycloalkylene; or, knowing that R3 is not alkanoyl, alkenoyl or benzoyl, R4 can also be a divalent acyl radical of a dicarboxylic acid or aliphatic, cycloaliphatic or aromatic dicarbamic acid, or it can be the group -CO-; or R4 is where T8 and 9 are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T8 and Tg together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene, preferably T8 and Tg together are -oxapentamethylene; when p is 3, R 4 is 2,4,6-triazinyl, n is 1 or 2, when n is 1, s and '5 are independently are C 1 -C 12 alkyl, C 2 -C 2 alkenyl, C 7 aralkyl C 2, or R 5 is also hydrogen or R 5 and R 5 together are C 2 -C 8 alkylene or C 4 -C 22 hydroxyalkylene or acyloxyalkylene; when n is 2, R5 and R'5 together are (-CH2) 2C (CH2-) 2; R6 is hydrogen, C1-C12 alkyl, allyl, benzyl, glycidyl or C2-C6 alkoxyalkyl; when n is 1. R7 is hydrogen, C1-C12 alkyl, C3-C5 alkenyl, C7-Cg aralkyl, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-C6 alkoxyalkyl, C5-Cyl aryl , glycidyl, a group of the formula - (CH2) t-COO-Q or of the formula - (CH2) t-0-CO-Q where t is 1 or 2, and Q is Cx-C alkyl, or phenyl; or when n is 2, R7 is C2-C2 alkylene, C6-C2 arylene, a group -CH2CH (OH) -CH2-0-X-0-CH2-CH (OH) -CH2- where X is C2-C? Alkylene, C6-C15 arylene or CQ-Ci2 cycloalkylene, or a group -CH2CH (OZ ') CH2- (0CH2-CH (OZ') CH2) 2- where Z 'is hydrogen , C? -C? 8 alkyl, allyl, benzyl, C2-C? 2 alkanoyl or benzoyl; Qi is -N (R8) - or -0-; E7 is C1-C3 alkylene, the group -CH2-CH (Rg) -0- wherein Rg is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond; Rio is C? -C? 8 alkyl hydrogen, R8 is hydrogen, C? -C? 8 alkyl, C5-C7 cycloalkyl, C7-C12 aralkyl, cyanoethyl, C? -Ci aryl, the -CH2 group -CH (R9) -OH where Rg has the meaning defined above; a group of the formula or a group of the formula where G is C2-C6 alkylene, or C6-C2 arylene; or R8 is a group -E7-CO-NH-CH2-OR? 0; Formula F denotes a recurring structural unit of a polymer where T3 is ethylene or 1,2-propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; preferably a copolymer of ethylene and ethyl acrylate, and wherein k is 2 to 100; T4 has the same meaning as R4 when p is 1 or 2, 5 is methyl, T6 is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene, preferably T5 and T6 are each methyl, M and Y are independently methylene or carbonyl, and T is ethylene where n is 2; T7 is the same as R7, and T7 is preferably octamethylene where n is 2, Tio and Tu are independently alkylene of 2 to 12 carbon atoms, or Tu is -12 is piperazinyl, -NRn- (CH2) d-NR11 -NR (CH2) - N (CH2) - N [(CH2) - N] fH where Rp is the same as R3 or is also a, b and c are independently 2 or 3, and f is 0 or 1, preferably a and c are each 3, b is 2 and f is i; and e is 2, 3 or 4, preferably 4; T13 is the same as R2 with the proviso that T13 can not be hydrogen when n is 1; Ei and E2 are different, each being -CO- or -N (E5) -where E5 is hydrogen, C? -C? 2 alkyl or C4? C22 alkoxycarbonylalkyl, preferably Ei is -CO- and E2 is -N (E5) -, E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or phenylalkyl substituted by alkyl of 1 to 4 carbon atoms, E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E3 and E4 together are polymethylene from 4 to 17 carbon atoms, or such polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms, preferably methyl, Eß is a tetravalent aliphatic or aromatic radical, R2 of formula (N) is one previously defined when m is 1; Gi a direct bond, alkylene of C? ~ C? 2, phenylene or -NH-G'-NH where G 'is alkylene of C? -C? 2; or wherein the hindered amine compound is a compound of the formula I, II, III, IV, V, VI, VII, VIII, IX, X or XI Ei, E2 / E3 and E4 are independently alkyl of 1 to 4 carbon atoms, or Ei and E2 are independently alkyl of 1 to 4 carbon atoms and E3 and E4 taken together are pentamethylene, or Ei and E2; and E3 and E4 each taken together are pentamethylene, Ri is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, a radial bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or such aryl substituted by one to three alkyl of 1 to 8 carbon atoms, R 2 is hydrogen or a straight or branched chain alkyl of 1 to 12 carbon atoms, R 3 is alkylene of 1 to 8 carbon atoms, or R3 is -CO-, -C0-R4-, -C0NR2-, or -CO-NR2-R4-, R is alkylene of 1 to 8 carbon atoms, Rs' is hydrogen , a straight or branched chain alkyl of 1 to 12 carbon atoms, or or when R4 is ethylene, two methyl substituents of Rs can be linked by a direct bond "so that the triazine bridge group -N (R5) -R4-N (R5) - is a piperazin-1, -diyl moiety Re is alkylene of 2 to 8 carbon atoms or R6 is with the proviso that Y is not -OH when R5 is the structure described above, A is -O- or -NR7- where R7 is hydrogen, a straight or branched chain alkyl of 1 to 12 carbon atoms, or R7 is T is phenoxy, phenoxy substituted by one or two alkyl groups of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms or -N (R2) 2 with the proviso that R2 is not hydrogen, or T is X is -NH2, -NCO, -OH, -O-glycidyl, or -NHNH2, and Y is -OH, -NH9, -NHR2 where R2 is not hydrogen; or Y is -NCO, -COOH, oxiranyl, -O-glycidyl, or -Si (OR2) 3; or the combination R3-Y- is -CH2CH (OH) R2 where R2 is alkyl or such alkyl interrupted by one to four oxygen atoms, or R3-Y- is -CH2OR2; or wherein the hindered amine compound is a mixture of N, N ', N "' -tris. {2, 4-bis- [(1-hydroxycarbyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-tracin-6-yl.} - 3, 3'-ethylenediiminodipropylamine; N, N ', N "-tris. { 2, -bis [(1-hydrocarbyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} -3,3'-ethylenediiminodipropylamine, bridged derivatives as described by the formulas I, II IIA and III R? NH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (I) T-Ei-Ti (II) T-Ei (HA) GE? -G? -E? -G2 (III) wherein in the tetraamine of formula I Ri and R2 are the E portion of s-triazine; and one of R3 and R4 is the E portion of s-triazine with the other of R3 or R4 being hydrogen, E is R is methyl, propyl, cyclohexyl or octyl, preferably cyclohexyl, R5 is alkyl of 1 to 12 carbon atoms, preferably n-butyl, where in the compound of formula II or HA when R is propyl, cyclohexyl or octyl , T and Ti are each substituted by R? -R4 as defined by formula I, where (1) one of the E-triazine portions in each tetraamine is replaced by the Ei group which forms a bridge between two tetraamines T yi, Ei is (2) group Ei can have both terminals in the same tetraamine T as in the formula HA where two of the E portions of the tetraamine are replaced by a group Ei, or (3) all three s-triazine substituents of the tetraamine T can be Ei so that one Ei links to T and Tx and a second Ei has both terminals in tetraamine T, L is propandiyl, cyclohexanediyl or octandiyl; where in the compound of formula III G, Gi and G2 are each tetraamines substituted by R1-R4 as defined by formula I, except that G and G2 each have one of the E-portions of s-triazine replaced by Ei, and Gi has two E portions of triazine replaced by Ei, so that is a bridge between G and G, and a second bridge between Gi and G2; mixture which is prepared by reacting two to four equivalents of 2,4-bis [(1-hydrocarbyloxy-2, 2,6,6-pipendin-4-yl) butylamino] -6-chloro-s-triazine with a equivalent of N, N'-bis (3-aminopropyl) ethylenediamine. In the structures A to R, if any substituents are alkyl they are mainly C 1 -C 8 alkyl, for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Typically cycloalkyl groups include cyclopentyl and cyclohexyl; typically cycloalkenyl groups include cyclohexenyl; although typically the aralkyl groups include benzyl, alpha-methyl-benzyl, alpha, alpha-dimethylbenzyl or phenethyl. C? -C? 2 alkyl is preferred. When aryl is mentioned, it means mainly C 6 -C 2 aryl, preferably phenyl or naphthyl, especially phenyl. Aralkyl is usually as defined alkyl, which is substituted by the above alkyl; preferably phenylalkyl of C-Cu. The alky (il) aryl is the above aryl substituted by alkyl; preferably it is phenyl mono-, di- or trisubstituted by C 1 -C 4 alkyl. Groups which may be unsubstituted or substituted by selected radicals such as C6-C12 aryl or C5-C12 cycloalkyl, such as a phenyl or a cyclohexyl ring, are preferably unsubstituted or mono-, di-trisubstituted, especially preferred are those unsubstituted or mono- or disubstituted groups. If R 2 is a monovalent acyl radical of a carboxylic acid, this is for example an acyl radical of acetic acid, stearic acid, salicylic acid, benzoic acid or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic If R 2 is a divalent acyl radical of a dicarboxylic acid, this is for example an acyl radical of oxalic acid, adipic acid, succinic acid, suberic acid, sebacic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid or butyl- (3, 5-di-tert-butyl-4-hydroxybenzyl) -malonic, or bicycloheptendicarboxylic acid, with succinates, sebacates, phthalates and isophthalates being preferred. If R2 is a divalent acyl radical of a dicarbamic acid, it is for example an acyl radical of hexamethylenedicarbamic acid or 2,4-toluylenedicarbamic acid. The NOR-hindered amine compounds of the present as described above are mostly known in the prior art and are prepared as taught or by analogy with the methods described in U.S. Patent Nos. 5,004,770; 5,096,950; 5,204,473 and 5,300,544 and in copending United States patent application Serial No. 08/885, 613. Those compositions claiming the references where the effective stabilizing amount of the amine hindered with NOR is up to 5% by weight based on the polymeric substrate. As much as the amount of the OR compound in the present invention can be up to 10% by weight of the polymeric substrate, the present invention also pertains to the combustion retardant compositions which comprises (a) a polymer, and (b) 5.1 at 10% (preferably from 5.1 to 9%, more preferably 5.1 to 8%) by weight of a hindered amine with NOR as described above based on the weight of such polymer. Although the polymeric substrate can be any of a wide variety of polymeric types including polyolefins, polystyrenes, and PVC, but preferably the polymeric substrate is selected from the group of resins consisting of polyolefins, thermoplastic olefins, styrenic polymers and copolymers, ABS and polymers which contain in them double bond atoms or aromatic rings, for example: 1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-l-ene, polyisoprene or polybutadiene, as well as cycloolefin polymers, for those present of cyclopentene or norbornene, polyethylene (which may be optionally crosslinked), for example high density polyethylene (HDPE), high density polyethylene and high molecular weight (HDPE-HMW) , high density polyethylene and ultra high molecular weight (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), low density branching polyethylene (BLDPE). The polyolefins, i.e., the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods: a) radical polymerization (usually under high pressure and high temperature) ). b) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or HIV of the Periodic Table. These metals usually have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls which may be either coordinated. These metal complexes may be in free form or fixed on substrates, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or additional activators can be used, typically metal alkyls, metal halides, metal alkyl halides, metal alkyl oxides, or metal alkyloxanes, such metals are elements of the groups. and / or Illa of the Periodic Table. The activators can be conveniently modified with additional ester, ether, amine or silyl ether groups. These catalytic systems are usually thermal, Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC). 2. The mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (for example LDPE / HDPE). 3. Copolymers of monoolefins and diolefins with each or with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), copolymers of propylene / but-1-ene, propylene / isobutylene copolymer, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, copolymers of propylene / butadiene, 5 copolymers of isobutylene / isoprene, copolymers of ethylene / alkyl acrylate, copolymers of ethylene / alkyl methacrylate, copolymers of ethylene / vinyl acetate and their copolymers with carbon monoxide or ethylene / acrylic acid copolymers and their you go out (ionomers) as well as terpolymers of ethylene with propylene and ^ a diene such as hexadiene, dicyclopentadiene or ethylidene norbornene; and mixtures of such copolymers with others and with the polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, copolymers of LDPE / ethylene vinyl acetate (EVA), copolymers of LDPE / ethylene-acrylic acid (EAA), LLDPE / EVA, LLDPE / EAA and random or alternating copolymers of polyalkylene / carbon monoxide and mixtures thereof with ^ other polymers, for example polyamides. 4. Polystyrene, poly (p-methylstyrene), poly (a-methylstyrene). 5. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, for example styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, Styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of styrene copolymers of high impact strength and another polymer, for example a polyacrylate, a polymer of »5 diene or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / - propylene / styrene. 6. Grafted copolymers of styrene or α-methylstyrene, for example copolymers of styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; > styrene and acrylates or alkyl methacrylates on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS polymers (acrylonitrile / butadiene / styrene), MBS, ASA or AES. 7. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, and chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo and copolymers of epichlorohydrin, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate Especially preferred are polypropylene, polyethylene, thermoplastic olefin (TPO), ABS and high impact polystyrene; more preferably polypropylene, polyethylene, thermoplastic olefin (TPO). The retarding amount of the effective combustion of a hindered amine is that which is needed to show the efficiency of the combustion retardation as measured by one of the standard methods used to evaluate the combustion retardation. These include the NFPA 701 Standard Methods of Fire Tests for Flame-Resistant Textiles and Films, 1989 and 1996 editions; the UL 94 Test for Flammability of Plastic Materials for Parts in Devices and Appliances, 5th Edition, October 29, 1996; Limiting Oxygen Index (LOI), ASTM D-2863; and Cone Calorimetry, ASTM E-1354. The effective amount of the hindered amine to give the combustion retardation is obtained from 0.25 to 10% by weight based on the polymeric substrate; preferably from 0.5 to 80% by weight; even more preferably from 0.5 to 2% by weight. While hindered amines with OR of the present generally possess the efficiency for combustion retardation, the preferred hindered amines are those where E is alkoxy, cycloalkoxy or aralkoxy; more preferably where E is methoxy, propoxy, octyloxy or cyclohexyloxy, especially cycloalkyloxy. This is surprising since amines hindered with NOR possess this combustion retarding activity. The present invention also pertains to a combustion retardant composition, which comprises (a) a polymeric substrate, (b) an effective retardant amount of combustion of a synergistic mixture of (i) a hindered amine as described above, and (ii) a combustion retardant compound selected from halogenated compounds, phosphorus, boron, silicon and antimony, metal hydroxides, metal hydrates, metal oxides or mixtures thereof; with the proviso that when the polymeric substrate is polypropylene, the hindered amine is not bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate and the combustion retardant is not hydrocarbyl phosphate or phosphonate halogenated Preferably, when the polymeric substrate is polypropylene, the hindered amine is not functionally hindered alkoxyamine and the flame retardant is not a halogenated hydrocarbyl phosphate or phosphonate. A combustion retardant composition of the present invention also comprises conventional additives such as those described in W096 / 28431 on page 20, line 5, to page 29, line 14, and the publications cited therein; these conventional additives comprise, for example, antioxidants, UV absorbers, hindered amine photostabilizers, metal deactivators, phosphites or phosphonites, thiosynthetists and fillers. Preferred conventional additives include a phosphorus compound selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2 ', 2"-nitrile [triethyl-tris- (3, 3', 5, 5 '-tetra-tert-butyl-1,1' -biphenyl-2, 2'-diyl) phosphite], tetracis ( 2,4-di-butylphenyl) 4,4'-biphenylenediphosphonium, tris (nonylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythrityl diphosphite, 2,2'-ethylidenebis (2,4) fluorophosphite. -di-tert-butylphenyl) and 2-butyl-2-ethylpropan-1,3-diyl 2,4,6-tri-tert-butylphenyl phosphite or a UV absorbent selected from the group consisting of 2- (2 -hydroxy-3, 5-di-a-cumylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3,5-di) -ter-butylphenyl) -2H-benzo-triazole, 2- (2-hydroxy-3,5-di-ter-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3-a-cumyl-5-ter) -octylphenyl) -2H-benzotriazole, 3,5-di-tert-butyl-4-hydroxybenzoate of 2, -di-tert-butylphenyl or, 2-hydroxy-4-n-octyloxybenzophenone and 2, -bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine. The effective combustion retarding amount of the synergist mixture (b) contains components (i) and (ii) is conveniently 0.5 to 30% by weight based on component (a). Wherein the synergistic mixture (b), the retarding amount of the effective combustion of a hindered amine is conveniently 0.5 to 10% by weight based on component (a); and preferably 0.5 to 8% by weight based on component (a). Wherein the synergist mixture (b), the effective flame retardant amount of a combustion retardant compound is conveniently 0.5 to 20% by weight based on component (a); and preferably it is from 0.5 to 16% by weight based on the component (to) . In the composition and method of the combustion retardant according to the present invention, preferably the combustion retardant of the halogenated hydrocarbyl phosphate or phosphonate class, such as halogenated phosphate or phosphonate esters, is not used; more preferably, tris (trihaloneopentyl) phosphate is not used. In the compositions and methods of the present invention of particular technical interest, the hindered amine employed is preferably not an ester of a dicarboxylic acid with 1-octyloxy-2, 2, 6, 6-tet ramet il-4-hydroxypiper idine, such as a compound of formula A wherein m is 2; more preferably it is not bis- (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate or succinate, especially is not bis- (1-octyloxy-2, 2, 6, 6-tet ramet ilpiperidin-4-yl) -sebacate. In general, hindered amine compounds for use in this invention include (a) the mixture of the compounds of formula I, II, HA and III wherein R is cyclohexyl; (b) l-cyclohexyloxy-2,4,6,6-tetramethyl-4-octa-decylaminopiperidine; (c) bis (l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; (d) 2, -bis [(1-cyclohexyloxy-2, 2,6,6-tetramethyl-piperidin-4-yl) butylamino] 6- (2-hydroxyethylamino-s-triazine; (e) bis (1-cyclohexyloxy) -2, 2,6,6,6-tetramethylpiperidin-4-yl) adipate; (f) the oligomeric compound which is the condensation product of 4,4'-hexamethylenebis (amino-2,6,6,6-tetramethylpiperidine) ) and 2,4-dichloro-6- [(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine; (g) the oligomeric compound which is the product of the condensation of 4,4'-hexamethylenebis (amino-2, 2,6,6,6-tetramethylpiperidine) and 2,4-dichloro-6- [ (1-cyclohexyl-oxy-2, 2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine; or (h) 2, 4-bis [(1-cyclohexyloxy-2, 2,6,6-piperidin-4-yl) -butylamino] -6-chloro-s-triazine. More particularly, the combustion retarding compounds useful in the present invention is selected preferi of the group consisting of tetraphenyl resorcinol diphosphite (FYROLFLEX® RDP, Akzo Nobel), chloroalkyl phosphate esters (ANTIBLAZE® AB-100, Albright & Wilson; FYROL® FR-2, Alzo Nobel) polybrominated diphenyl oxide (DE-60F, Great Lakes Corp. decabromodiphenyl oxide (DBDPO; SAYTEX® 102E) antimony trioxide (Sb203), antimony pentaoxide (Sb205), tris [3-bromo-2, 2- (bromomethyl) propyl] phosphate (PB 370®, FMC Corp .), triphenyl phosphate, bis (2, 3-dibromopropyl ether) of bisphenol A (PE68), ammonium polyphosphate (APP) or (HOSTAFLAM® AP750), oligomeric resorcinol diphosphate (RDP), brominated epoxy resin, ethylene- bis (tetrabromophthalimide) (BT93), bis (hexachlorocyclopentadiene) cyclooctane (DECLORANE PLUS®), calcium sulphate chlorinated pads, magnesium carbonate, melamine phosphates, melamine pyrophosphates, molybdenum trioxide, zinc oxide, 1, 2 -bis (tribro ofenoxi) ethane (FF680), tetrabromo-bisphenol A (SAYTEX® RB 100), magnesium hydroxide, alumina trihydrate, zinc borate, ethylenediamine diphosphate (EDAP) silica, silicones, calcium silicate, and silicate of magnesium. The following examples are for illustrative purposes only and were not constructed to limit the scope of this invention in any way. Coaditives useful for use with the NOR-hindered amine compounds herein in the combustion retardant compositions are as follows: Phosphorus Compounds: tris (2, -di-tert-butylphenyl) phosphite, (IRGAFOS® 168, Ciba Specialty Chemicals Corp.); bis (2, 4-di-tert-butyl-6-methylphenyl) ethyl phosphite, (IRGAFOS® 38, Ciba Specialty Chemicals Corp.); 2,2 ', 2"-nitrile [triethyl-tris- (3,3', 5,5 ', -tetra-tert-butyl-1', 1-biphenyl-2, 2'-diyl) phosphite], (IRGAFOS® 12, Ciba Specialty Chemicals Corp.), tetracis (2,4-di-butylphenyl), 4 ', -biphenylenediphosphono-, (IRGAFOS® P-EPQ, Ciba Specialty Chemicals Corp.); tris (nonylphenyl) phosphite, (TNPP, General Electric); diphosphite of bis (2,4-di-tert-butylphenyl) pentaerythrityl, (ULTRANOX® 626, General Electric); 2-, 2'-ethylidenebis (2,4-di-tert-butylphenyl) fluorophosphite, (ETHANOX® 398, Ethyl Corp.) 2-butyl-2-ethylpropan-l, 3-diyl 2,4,6- phosphite tri-tert-butylphenol, (ULTRANOX® 641, General Electric).

Combustion retardants: tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate, (PB 370®, FMC Corp.) decabromodiphenyl oxide, (DBDPO); ethylene bis- (tetrabromophthalimide), (SAYTEX® BT-93); ethylene bis- (dibromo-norbornandicarboximide), (SAYTEX® BN-451) UV Absorbers: 2- (2-hydroxy-3,5-di-a-cumylphenyl) -2H-benzotriazole, (TINUVIN® 234, Ciba Specialty Chemicals Corp.); 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, (TINUVIN® P, Ciba Specialty Chemicals Corp.); 5-chloro-2- (2-hydroxy-3,5-di-tert-butylphenyl) -2H-benzotriazole, (TINUVIN® 327, Ciba Specialty Chemicals Corp.); 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzo-triazole, (TINUVIN® 328, Ciba Specialty Chemicals Corp.); 2- (2-hydroxy-3-a-cumyl-5-tert-octylphenyl) -2H-benzo-triazole, (TINÜVIN® 928, Ciba Specialty Chemicals Corp.); 3, 5-di-tert-butyl 14-hydroxybenzoate from 2,4-di-tert-butylphenyl, (TINUVIN® 120, Ciba Specialty Chemicals Corp.); 2-hydroxy-4-n-octyloxybenzophenone, (CHIMASSORB® 81, Ciba Specialty Chemicals Corp.); 2, 4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-octyloxy-phenyl) -s-triazine, (CYASOIRB® 1164, Cytec).

Test Methods Methods Standard NFPA 701 of Fire Tests for Flame-Resistant Textiles and Films, 1989 and 1996 editions; UL 94 Test for Flammability of Plastic Materials for Parts in Devices and Appliances, 5th Edition, October 29, 1996; Oxygen Limit Index (LOI), ASTM D-2863; Cone Calorimetry, ASTM E-l or ASTM E 1354; ASTM D 2633-82, oven test.

Test Compounds HA-1 is N, N ', N ", N"' -tetracis [4,6-bis (butyl-1,2,2,6,6-pentamethylpiperidin-4-yl) amino-s-triazine -2-il] -1,10-diamino-4,7-diazadecane (CHIMASSORB3® 119, Ciba Specialty Chemicals Corp.). HA-2 is bis (2, 2, 6, 6-tetramethylpiperidin-4-yl) sebacate, (TINUVINV 770, Ciba Specialty Chemicals Corp.). NOR-1 is the mixture of the compounds of formula I, II, HA and III where R is cyclohexyl. NOR-2 is l-cyclohexyloxy-2, 2,6,6,6-tetramethyl-4-octadecylaminopiperidine. NOR-3 is bis (l-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) sebacate, (TINUVIN® 123, Ciba Specialty Chemicals Corp.). NOR-4 is 2, 4-bis [(1-cyclohexyloxy-2, 2,6,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine.) NOR-5 is bis adipate. (l-cyclohexyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) NOR-6 is the oligomeric compound which is the product of the condensation of 4, '-hexamethylenebis (amino-2, 2, 6, 6-tetramethylpiperidine) and 2,4-dichloro-6- [(1-octyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine NOR-7 is the oligomeric compound which is the product of the condensation of 4,4 '-hexamethylenebis (amino-2, 2,6,6,6-tetramethylpiperidine) and 2-dichloro-6 - [(1-cyclohexyl-oxy-2, 2,6,6-tetramethylpiperidin-4-yl) butylamino] -s-triazine capped with 2-chloro-4,6-bis (dibutylamino) -s-triazine. 8 is 2, 4-bis [(1-cyclohexyloxy-2, 2,6,6-piperidin-4-yl) -butylamino] -6-chloro-s-triazine FR-1 is tris phosphate [3-bromine] -2, 2-bis (bromomethyl) propyl], (PB 370®, FMC Corp.). FR-2 is p ammonium oliphosphate (APP). FR-3 is bis (2,3-dibromopropyl) ether of tetrabromobisphenol A (PE68). FR-4 is ammonium polyphosphate / synergistic mixture HOSTAFLAM® AP750. FR-5 is decaphenyl odiphenyl oxide, SAYTEX® 102E. FR-6 is ethylene bis- (tetrabromof alimide), (SAYTEX® BT-93).

Example 1 The fiber grade polypropylene, which contains 0.05% by weight of calcium stearate and 0.05% of tris (2, -di-tert-butylphenyl) phosphite and 0.05% of a N, N-dihydroxylamine made by the direct oxidation of N, N-di (hydrogenated bait) amine was mixed dry with the test additives and then melted at 23 ° C (450 ° F) in granules. The fully granulated formulated resin was then spun at 246 ° C (475 ° F) fiber using a fiber model extruder from the Hills laboratory. The skein of 41 filament yarn was stretched at a ratio of 1: 3.2 to give a final denier of 615/41. Sleeves of the stabilized polypropylene fibers were woven in a Lawson-Hemphill Analysis Weaver and tested under the NFPA 701 vertical combustion process. The time in seconds for the woven wizard to extinguish to remove insulting flame was reported as "After the flame". Both the maximum time for any replication and the total time for the ten replicas are shown in the following table. Efficiency as a retardant of combustion was demonstrated when low flame time was observed in relation to the blank sample that did not contain combustion retardant.

After the Flame (time in seconds) Total maximum formulation White 55 177 HA-1 (%; 131 231 brominated flame retardants FR-1 (3%; FR-1 (1%) 10 27 hindered amines with OR NOR-1 (1%) NOR-2 (1%) NOR-3 (1%) 15 43 Surprisingly, although conventional hindered amines have essentially a neutral effect on combustion retardation, the hindered amines with 1-hydrocarbyloxy (OR) hereof are as effective as the brominated flame retardants in combustion. one third of the concentration level. Those hindered amines with OR do not have the detrimental effects associated with inorganic combustion retardants.

Example 2 Following the procedure set forth in Example 1, stabilized polypropylene fibers were prepared. Sleeves of stabilized polypropylene fiber were woven in a Lawson-Hemphill Analysis Weaver and tested under the NFPA vertical combustion process 701. Several other types of hindered amines were compared with the hindered amines with OR as potential combustion retardants using the NFPA 701 test procedure. The results are given in the following table.

After the Flame (time in seconds) Maximum total formulation White 26 69 FR-1 (3%) FR-2 (0.5%) 32 70 amines not hindered with OR HA-1 (1%) 39 175 HA-2 (1%) 52 144 amines hindered with ÑOR NOR-4 (1%) NOR-5 (1%) NOR-6 (1%) 10 NOR-1 (1%) NOR-7 (1%) hindered amines with ÑOR (continued) NOR-8 (1%) NOR- 1 (1%) 0 NOR-1 (0 .5%) NOR- 1 (0 .25%; 18 33 It is clear that the hindered amines with OR are a group as effective as some retarders of phosphorus combustion since they provide the retardation of combustion to the polypropylene fibers, and are effective in the reduction after the flame at levels as low as 0.25% by weight.

Example 3 Dry molding grade polypropylene was mixed with the test additives and then melt-compounded into granules. The fully granulated formulated resin was then compression molded into the test specimens using an abash compression molder. The test plates were tested under UL-94 Vertical Combustion test conditions. The average time in seconds for the test samples to be extinguished after removing the insulting flame was reported. The efficiency as a retardant of combustion was demonstrated when the low flame times were observed in relation to the white sample that did not contain combustion retardant. All samples containing the NOR-hindered amines of the present were self-extinguished after the application of the first flame. This shows that ÑOR compounds of the present exhibit discernible efficacy as combustion retardants that is essentially the same as that conferred by a halogenated or phosphate combustion retardant. The white burned completely after the application of the first flame.

Fiery Formulation Flame (average in seconds) White 172 FR-3 (1.75%) + Sb203 (V- FR-4 (25%) Fiery Formulation Flame (average in seconds) NOR-1 (1%) NOR-1 (5%) NOR-1 (10%) Example 4 Dry fiber grade polyethylene was mixed with the test additives and then compounded by melting into granules. The fully granulated formulated resin was then blown at 205 ° C using an MPM Superior Blown film extruder. The films were tested to retard combustion under the NFPA 701 test conditions. Films containing the compounds with NOR of the present showed retardation of combustion. The film grade polypropylene was handled in a similar manner and the polypropylene films containing the ÑOR compounds of the present also showed retardation of combustion.

Example 5 Molded test specimens were prepared by injection molding thermoplastic olefin granules (TPO) containing a hindered amine compound with NOR. The TPO formulations may also contain a pigment, a phosphite, a phenolic antioxidant or hydroxylamine, a metal stearate, a UV absorber or a hindered amine stabilizer or a mixture of hindered amine and UV absorber. The pigmented TPO formulation is composed of polypropylene blend with a rubber modifier, where the rubber modifier is a copolymer that reacts in situ or a blended product containing the copolymers of propylene and ethylene with or without a tertiary component such as ethylidene norbornene stabilized with a basic stabilization system consisting of an N, N-dialkylhydroxylamine or a mixture of hindered phenolic antioxidant and an organophosphorus compound. The TPO plates were tested to retard combustion using UL-94 Vertical Combustion conditions. A minimum of three replicas were tested. The effectiveness as a retardant of the comparison was measured in relation to a blank sample that did not contain combustion retardant. The TPO formulations containing a hindered amine with OR of the present showed efficacy in the combustion delay.

EXAMPLE 6 Film grade ethylene / vinyl acetate (EVA) copolymers containing 20 percent or less of vinyl acetate were mixed dry with the test additives and then compounded by pelletization. The fully granulated formulated resin was then blown on a film at 205 ° C using an MPM Superior Blown film extruder. The films were tested for combustion retardation under NFPA 701 test conditions. Films containing the NOR-hindered amine compounds of the present showed retardation of combustion. Low density polyethylene film grade (LDPE) containing some linear low density polyethylene (LLDPE) and / or ethylene / vinyl acetate (EVA) were dry mixed with test additives and blown onto films as described above for the EVA copolymer resin . The films were tested for combustion retardation under test conditions NFPA 701 and those containing the amines prevented with NOR showed retardation of combustion.

Example 7 Dry fiber grade polypropylene was mixed with the test additives and then melt compounded at 204 ° C (400 ° F). In addition to the NOR-hindered amine compounds of the present, halogenated combustion retardants were included in the formulations. Typical formulations contain the NOR compounds herein and a combustion retardant such as bis (2,3-dibromopropyl) ether of bisphenol A (PE68), decabromodiphenyloxide (DBDPO), ethylene bis-tetrabromophthalimide (SAYTEX BT-93) ) or ethylene bis-dibromonorbornandicarboximide (SAYTEX BN-451). Other formulations may contain antimony trioxide in addition to brominated flame retardants. Other formulations may contain phosphorus-based combustion retardants such as ethylenediamine diphosphate (EDAP) or ammonium polyphosphate (APP). Fibers from these formulations were extruded using a hill-scale fiber extruder at 2465 ° C (275 ° F) laboratory. The sleeves of these fibers were woven and tested for combustion retardation according to the NFPA 701 vertical combustion test conditions. The fibers containing the amine compounds prevented with NOR showed retardation of combustion.

Example 8 Dry molding grade polypropylene was mixed with the test additives and then melt-compounded into granules. In addition to the NOR-hindered amine compounds also selected combustion retardants were included. The fully granulated formulated resin was then compression molded into test specimens using a Wabash Compression Molder. The plates were tested under the UL-94 Vertical Combustion conditions. A minimum of three replicas were tested. The average time in seconds for the test sample to be extinguished after a first and a second insulting flame was reported. The effectiveness as a retardant of combustion was demonstrated when low flame times were observed.

Time Flame Time 2nd Flame Time Formulation (average in seconds) (average in seconds) White 172 FR-3 (1.75%) + Sb203 (1%) 22 FR-3 (1.75%) + Sb203 (1%) + ler Flame Time 2nd Flame Time Formulation (average in seconds) (average in seconds) NOR-1 (5í FR-4 (10%; 103 FR-4 (10%) + NOR- 1 (5%) 5 4 ** The time for the 2nd flame is not shown since the sample was completely consumed after the application of the first flame.

All samples containing the ÑOR compound of the present together with a combustion retardant were destroyed after the application of the first and second flames. Additionally, the combustion time decreases significantly compared to the formulation containing only combustion retardant. This shows that the compounds with OR of the present increase the retardation of the combustion of a retardant of the halogenated combustion or of phosphate.

Example 9 Molded test specimens were prepared by injection molding thermoplastic olefin granules (TPO) as described in Example 5. Typical formulations containing the NOR compounds herein and a combustion retardant such as tris [3-bromo-2,2,2-bis (bromomethyl) propyl phosphate. ] (PB370), bis (2,3-dibromopropyl) ether or tetrabromobisphenol A (PE68), decabromodiphenyloxide (DBDPO), ethylene bis-tetrabromophthalimide (SAYTEX BT-93) or ethylene bis-dibromonorbornandicarboximide (SAYTEX BN-451). Other formulations may contain antimony trioxide in addition to the brominated flame retardants. Other formulations may contain phosphorus compounds based on combustion retardants such as ethylene diamine diphosphate (EDAP). The plates were tested under the UL-94 test method. A minimum of three replicas were tested. The average time in seconds for the test sample to extinguish after removing a first and second insulting flames was reported. The NOR-hindered amine compounds of the present increase the retardation of the combustion of a halogenated or phosphate combustion retardant compared to the comparison retarder used alone.

Example 10 Dry film grade polyethylene was mixed with test additives and then melt-compounded into granules. In addition to the NOR-hindered amine compounds of the present, combustion retardants were also included in the formulation. Typical formulations contain the NOR compounds and a combustion retardant such as tetra (2,2-dibromopropyl) ether of tetrabromobisphenol A (PE68), decabromodiphenyloxide (DBDPO) or ethylene bis-tetra-10-bromophthalimide (SAYTEX BT-93). Other formulations can Wr contain antimony trioxide in addition to brominated flame retardants. Other formulations may contain phosphorus-based combustion retardants such as ethylenediamine diphosphate (EDAP) or ammonium polyphosphate '15 (APP). The fully granulated formulated resin was then blown into films at 250 ° C using a Superior Blown Film extruder. The test specimens were tested under the NFPA 701 test conditions. The hindered amines with ÑOR 20 of the present promote the retardation of the combustion of a halogenated combustion retardant or of phosphate.

Example 11 Thermoplastic resins were mixed dry including polypropylene, polyethylene homopolymer, polyolefin copolymer or elastomeric olefins (TPO), high impact polystyrene (HIPS) and ABS with the NOR compounds herein and were then compounded into granules. The fully granulated formulated resin was then processed into a useful article such as fiber extrusion; extrusion by blowing or molding in films; blow molding in bottles; injection molding in molded articles, thermoformed articles in moldings, extruded in wire or cable housings or rotation molding in hollow articles. The articles containing the ÑOR compounds of the present exhibit combustion retardation when tested by a known standard test method to evaluate the combustion delay. Polyethylene wire and cable applications were tested to determine the combustion retardation according to the ASTM D-2633-82 combustion test method. The materials containing the ÑOR compounds of the present show retardation of combustion.

Example 12 The articles prepared according to Example 11, which additionally contain an organophosphorus stabilizer selected from the group consisting of tris (2,4-di-tert-butyl-phenyl) phosphite, bis (2, -di) phosphite -tert-butyl-6-methylphenyl) ethyl, 2, 2 ', 2"-nitrile- [triethyl-tris- (3, 3', 5,5'-tetra-tert-butyl-1,1 '-biphenyl- 2, 2'-diyl) phosphite], 4, '-biphenylenediphosphonate of tetracis (2,4-di-butylphenyl), tris (nonylphenyl) phosphite, diphosphite of bis (2,4-di-tert-butylphenyl) pentaerythrityl, 2,2'-ethylidenebisbis (2, -di-tert-butylphenyl) fluorophosphite and 2, 4,6-tri-tert-butylphenylphosphite of 2-butyl-2-ethylpropan-1,3-diyl as well as the amine compounds NOR inhibited present good properties of retarding combustion.

Example 13 The articles prepared according to Example 11, which additionally contain a UV absorber of o-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or an o-hydroxyphenyl-s-triazine selected from the group consisting of 2- (2 -hydroxy-3, 5-di-a-cumylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3,5-di) -tert-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-2-a-cumyl-5-tert-octylphenyl) ) -2H-benzotriazole, 3,5-di-tert-butyl-4-hydroxybenzoate of 2, -di-tert-butylphenyl, 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis (2,4-dimethylphenyl) - 6- (2-hydroxy-4-octyloxyphenyl) -s-triazine as well as the NOR-hindered amine compounds of the present exhibit good combustion retardation.

Example 14 The articles prepared according to Example 11, which additionally contain a UV absorber of o-hydroxyphenyl-2H-benzotriazole, a hydroxyphenyl benzophenone or an o-hydroxyphenyl-s-triazine selected from the group consisting of 2- (2 -hydroxy-3, 5-di-a-cumylphenyl) -2H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) -2H-benzotriazole, 5-chloro-2- (2-hydroxy-3,5-di) -ter-butylphenyl) -2H-benzotriazole, 2- (2-hydroxy-3,5-di-tert-amylphenyl) -2H-benzotriazole, 2- (2-hydroxy-2-a-cumyl-5-tert-octylphenyl) ) -2H-benzotriazole, 3,4-di-tert-butylphenyl, 2-hydroxy-4-n-octyloxybenzophenone and 2,4-bis (2,4-dimethylphenyl), 3,5-di-tert-butyl-4-hydroxybenzoate -6- (2-hydroxy-4-octyloxyphenyl) -s-triazine as well as NON-hindered amine compounds herein and a combustion retardant such as tris phosphate [3-bromo-2, 2, -bis] (bromomethyl) propyl] (PB370), bis (2, 3-dibromopropyl) ether of tetrabromobisphenol A (PE68), decabromodiphenyloxide (DBDPO), ethylene bis-tetrabromo Phthalimide (SAYTEX BT-93) or ethylene bis-dibromonorbornandicarboximide (SAYTEX BN-451) exhibit good combustion retarding properties.

Another formulation may contain antimony trioxide in addition to brominated flame retardants. Other compositions may contain phosphorus-based combustion retardants such as ethylenediamine diphosphate (EDAP).

Example 15 ABS polymer (Dow 342EZ) was mixed with the stabilizers and test additives, and was compounded in a twin screw extruder at a die temperature of 220 ° C and the extrudate was granulated. The granules were injection molded in a BOY 50 machine to produce bars with the following dimensions: 12.7 cm L x 1.27 cm W x 0.3175 cm D (5"L x 0.5" W x 0.125"D) Optionally, the ABS granules are compression molded at 220 ° C to produce test boards of 10.16 cm L x 10.16 cm W x 0.3175 cm D (4"L x 4" W x 0.125"D) for the conical calorimetric test. The conical calorimetry test of the compression molded plates was carried out according to ASTM E 1354. The results of the tests are shown below.

TO Sample * - »-» Test Test Test Test Test Test Test Test Test 1 2 1 2 1 2 1 2 PHR 1240 1273 1007 1085 1209 1265 1200 1265 HRR Prom 740 745 393 394 652 653 435 476 HR Total 97 96 44 47 86 85 48 53 r of CO Prom 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 r of C02 Prora 2.4 2.4 0.8 0.9 2.3 2.3 1.4 1.5 * PHRR - average heat release rate HRR Average - average heat release rate during the test time HR Total - total heat evolved (area under the calorimetric curve) r of CO Average - average carbon monoxide yield r of C02 Average - average carbon dioxide yield Sample A is white with no retardant of combustion present. Sample B contains 15 parts by weight of FR-5 and 4 parts by weight of antimony trioxide. Sample C contains 4 parts by weight of NOR-1.

Sampling D contains 15 parts by weight of FR-5 and 4 parts by weight of NOR-1. Inspection of the results in the table shows that Sample C containing the NOR-1 gives an unexpected reduction in the average heat release rate and a reduction in total heat evolution compared to the unstabilized ABS blank of Sample A. Almost equivalent values of the average heat release rate and total heat evolution were observed when compared to a commercial FR system as observed in Sample B with the combination of FR-5 and NOR-1 as it is observed in Sample D.

In that case the NOR-1 compound of the present was used to replace the antimony oxide. In this way it is advantageous to remove a heavy metal (antimony) from the system and not sacrifice the excellent operation of the combustion delay that can be achieved with the FR system of the state of the art.

Example 16 Following the general procedure of Example 15, high impact polystyrene polymer (HIPS) was made (STYRON® 484C, Dow Chemical Co.) with the NOR-hindered amine herein, was granulated and then molded by injection or compression into plates. Those plates were tested to determine the effectiveness of the combustion retardant using conical calorimetry, LOI or UL-94 test method. Plates containing the ÑOR compound exhibit retardation of combustion. HIPS retardant combustion polymers find application in commercial machine housings.

Example 17 This Example shows the efficacy of the ÑOR compound present in PVC formulations. Such formulations are useful in flexible or rigid PVC and in wire and cable applications. Typical formulations are seen below: Component parts parties parts PVC resin 100 100 100 100 Tin Mercaptide 1.5 2.0 Tin Carboxylate 2.5 2.0 Process support 1.5 1.5 2.0 2.0 Impact module 6.0 6.0 7.0 7.0 Paraffin wax 1.0 0.3 1.0 1.0 Component parts parts parts parts Polyethylene wax 0.1 0.1 0.2 0.2 Stearate of Ca 1.0 0.8 Pigment 1.0 0.9 5.0 5.0 The fully formulated PVC containing the ÑOR compound was granulated and then injection molded into test plates to examine the combustion retardation using the UL-94 or LOI test method. The PVC plates containing the ÑOR compound of the present demonstrate retardation of combustion.

Example 18 Polypropylene, the base resin containing 0.05% by weight of calcium stearate, 0.1% by weight of tris (2,4-di-tert-butyl-phenyl) phosphite and 0.05% by weight of neopentantetrail tetracis (3, 5-di-tert-butyl-4-hydroxyhydrazinamate), was melt-compounded in a single screw extruder at 425 ° F (218 ° C) with the respective additives to form the formulations given in the table below. They were compression molded at 400 ° F (204 ° C) 125 mil plate (3175 μm). The plates were tested to determine the combustion delay by the UL 94V coarse cutting test.

Time Flame Time 2nd Flame Time Formulation (average in seconds) (average in seconds) FR-4 (5%) 252 ** FR-4 (10% 103 ** FR-5 (5%) + NOR-1 (5%) 83 FR-4 (10%) + NOR-1 (5%) FR-4 (25%) 11 ** The time for the 2nd flame is not shown since the sample was completely consumed after the application of the first flame. It is clear that the combination of the hindered amine NOR-1 with inorganic combustion retardant at the same total concentration enhances the effectiveness of the inorganic combustion retardant by allowing a lower concentration of the inorganic combustion retardant when combined with the inorganic combustion retardant. hindered amine component. This a synergistic effect. Even when the inorganic combustion retardant is used at very high levels alone, it can not provide both combustion retardation and combustion retardant combination with the hindered amine at such a low total concentration.

Example 19 Following the procedure of Example 18, 10 mil (254 μm) polypropylene films were compression molded from the combustion retardant formulations at 400 ° F (204 ° C). Those films were tested to determine the combustion delay using the NFPA 701 test of 1989 and 1996.

Test NFPA 701 of 1996 Formulation Trickle by Combustion Weight Loss Pass / Fail Criteria to Pass < 2 sec < 40% White > 2 sec 39% Fail N0R-1 (1%) < 2 sec 7% Pass NOR-1 (5%) > 2 sec 31% Failure N0R-1 (10%;> 2 sec 57% Failure NFPA test 701 of 1989 Formulation After the Flame Trickle by Combustion Length of the Pass / Fail Carbonized Layer Criterion to Pass < 2 sec 0 sec 5.5 inches (13.97 cm) White 28 sec. > 2 sec 10 inches Fail (25.4 cm) NOR-1 (1%) < 2 sec 0 sec 3.4 inches Pass (8.6 cm) NOR-1 (5%) 24 sec > 2 sec 9.3 inches Fail (23.6 cm) NOR-1 (10%) 21 sec > 2 sec 10 inches Fail (25.3 cm) Example 20 Dry fiber grade polyethylene was mixed with test additives and melt compounded at 400 ° F (204 ° C). Fibers of this formulation were extruded using a Hills laboratory scale fiber extruder. Sleeves of the fibers were woven and tested for combustion retardation according to the NFPA 701 vertical combustion method. Fibers containing the NOR compounds of the present show retardation of combustion.

Example 21 Polyethylene fibers were prepared as seen in Example 20 containing a NOR compound herein in combination with a conventional combustion retardant such as decabromodiphenyl oxide (DBDPO); bis (2,3-dibromopropyl) ether of tetrabromobis phenol A (PE68); ethylene bis-tetrabromophthalamide (SAYTEX® BT-93) and the like. These formulated fibers were tested for combustion retardation according to MFPA 701. Fibers containing both a ÑOR compound and a halogenated combustion retardant or classic phosphorus exhibit better combustion retardation compared to the retardation of the combustion. Classic combustion alone.

Example 22 Polyethylene (LDPE) was melt-compounded on a twin-screw extruder at 450 ° F (232 ° C) with the respective additives to form the formulations given in the following table. 125 mil (3175 μm) plates at 400 ° F (204 ° C) were compression molded. The plates were tested for combustion retardation by the UL 94V coarse cutting test.

Time Flame Time 2nd Flame Time Formulation (average in seconds) (average in seconds) White 163 NOR-1 (1%) 149 NOR-1 (5%) 124 FR-6 (3%) + Sb203 (1%) 250 ler Flame Time 2nd Flame Time Formulation (average in seconds) (average in seconds) FR-6 (3%) + Sb203 (1%) + NOR-1 (5%) 11 FR-4 (10% 198 FR-4 (5%) + NOR-1 (5%) 118 FR-4 (10%) + NOR-1 (5%) 1 64 ** the time for the 2nd flame is not shown since the sample was completely consumed after the application of the first flame.

It is clear that the combination of the hindered amine NOR-1 with inorganic combustion retardant at the same total concentration enhances the effectiveness of the inorganic combustion retardant allowing a lower concentration of inorganic combustion retardant to be used when combined with the inorganic combustion retardant. hindered amine component. This a synergistic effect.

Example 23 Polyethylene (LDPE) was melt compounded in a twin screw extruder at 450 ° F (232 ° C) with the respective additives to form the formulations given in the following table. 2 mil (50.8 μm) thick films were blow molded in an MPM extruder at 400 ° F (204 ° C). The films were tested to determine the combustion delay by the NFPA 701 test.

NFPA test 701 of 1989 Formulation After the Flame Drip by Ccpibustion Length of the Pass / Fail Carbonized Layer Criterion to Pass < 2 sec 0 sec < 5 . 5 inches (13, 97 cm) White 0-14 sec 0-2 sec 1. 5 inches Fail (21. 9 cm) NFPA Test 701 of 1989 (continued) Formulation After the Flame Dripping by Ccupustus Length of the Raisin / Failure Carbonised Layer NOR-1 (1%) 0 sec 0 sec 4. 8 inches Pass (12.2 cm) NOR-1 (5%) 0 sec 0 sec 4. 8 inches Pass (12.2 cm) NOR-1 (10%) 0 sec 0 sec 7. 9 inches Fail (20 cm) Example 24 Dry poly (ethylene terephthalate) (PET) grade fiber was mixed with test additives, then melt compounded at 550 ° F (288 ° C) and then granulated. The polyester granules were dried at 175 ° F (79 ° C) for 24 hours under vacuum. The dried granules were extruded into fibers using a Hills laboratory scale fiber extruder at 550 ° F (288 ° C). Sleeves of these fibers were woven and tested for combustion retardation according to test method NFPA 701. The polyester fibers containing the ÑOR hindered amine compound of the present show retardation of combustion.

Example 25 Polyester fibers (PET) prepared as seen in Example 24 containing the ÑOR compound herein in combination with a conventional combustion retardant. These formulated fibers were tested for combustion retardation according to the NFPA 701 vertical combustion test method. Fibers containing both a ÑOR compound and a classic halogen or classic phosphorus combustion retardant increased the combustion retardation compared to the classic combustion retardant only.

EXAMPLE 26 Dry foam grade polyethylene was mixed with test additives and then melt-compounded into granules. The fully granulated formulated resin was then blown into a foam. Test specimens' cut from the foam were tested under the UL-94 combustion test specification. The foam containing the ÑOR compound of the present exhibits combustion retardation.

Example 27 Polyethylene foam prepared as seen in Example 26 containing a ÑOR compound hereof in combination with a conventional combustion retardant. The formulated foam was tested for combustion retardation according to the UL-94 combustion test method. Foam that contains both a ÑOR compound and a classic combustion retardant exhibits increased combustion retardation compared to the classic halogenated or classical phosphorus combustion retardant alone.

Example 28 Wire-grade polyethylene and dry cable were mixed with test additives and then melt-compounded into granules. The fully granulated formulated resin was then extruded onto a wire. The test specimens were tested for combustion retardation using the combustion test conditions ASTM D 2633-82. The formulations containing the ÑOR compounds of the present show retardation of combustion.

Example 29 Polyethylene grade wire and dry cable were mixed with test additives and then melt-compounded into granules. The fully granulated formulated resin was then extruded onto wire.

The test specimens were tested for combustion retardation using the combustion test conditions ASTM D 2633-82. Formulations containing both a NOR compound and a conventional combustion retardant exhibit a greater combustion retardation compared to the conventional halogen or phosphorus combustion retardant alone.

Example 30 Dry fiber grade polyethylene was mixed with hindered amine test additives. Non-woven fabrics of a polymer blend formulation were produced by a granulation or meltblowing process. The non-woven fabrics thus made were tested for combustion retardation according to the specifications of the NFPA 701 vertical combustion test. Fabrics containing hindered amine compounds exhibit combustion retardation.

Example 31 Dry fiber grade polyethylene was mixed with test additives. In addition to a hindered amine, selected combustion retardants were also included in the different formulations. Non-woven fabrics were produced from the polymer blend formulation by meltblown or meltblown processes. The non-woven fabrics thus made were tested for the combustion retardation according to the NFPA 701 vertical combustion test specifications. The fabrics containing the hindered amine compounds and the combustion retardants selected exhibit combustion retardation. .

Example 32 Dry fiber grade polyethylene was mixed with hindered amine test additives. Non-woven fabrics of the polymer blend formulation were produced by a meltblown or meltblown process. Non-woven fabrics made from these were tested for combustion retardation according to the specifications of the NFPA 701 vertical combustion test. Fabrics containing hindered amine compounds exhibited combustion retardation.

Example 33 Dry fiber grade polyethylene was mixed with test additives. In addition to a hindered amine, selected combustion retardants were also included in the different formulations. Non-woven fabrics were produced from the polymer blend formulation by meltblown or meltblown processes. The non-woven fabrics thus made were tested for the combustion retardation according to the NFPA 701 vertical combustion test specifications. The fabrics containing the hindered amine compounds and the combustion retardants selected exhibit combustion retardation. .

Example 34 Dry molding grade polystyrene was mixed with hindered amine test additives and then melt compounded. The specimens were injection molded of those test formulations. The specimens were tested for combustion retardation according to the specifications of the UL-94 combustion test. The molded specimens containing the hindered amine compounds exhibit retardation of combustion.

Example 35 Dry molding grade polystyrene was mixed with test additives and then melt compounded. In addition to the hindered amines, selected combustion retardants were also included in the test formulations. The specimens were injection molded of those test formulations. The specimens were tested for combustion retardation according to the specifications of the UL-94 combustion test. The molded specimens containing the hindered amine compounds and the combustion retardants selected exhibit retardation of combustion. v Example 36 Dry foam grade polystyrene was mixed with hindered amine test additives and then melt compounded. The foamed polystyrene specimens were prepared from these test formulations. The specimens were tested for combustion retardation according to the specifications of the UL-94 combustion test. The molded specimens containing the hindered amine compounds exhibit retardation of combustion.

EXAMPLE 37 Dry foam grade polystyrene was mixed with test additives and then melt compounded.

In addition to the hindered amines, combustion retardants selected in those test formulations were also included. The foamed polystyrene specimens were prepared from these test formulations.The specimens were tested for combustion retardation according to UL-94 combustion test specifications.The foamed specimens containing the hindered amine compounds and combustion retardant exhibit combustion retardation.

Claims (10)

1. The use of a hindered amine compound, which contains a group of the formula where Gi and G2 are independently alkyl of 1 to 4 carbon atoms or together are pentamethylene, Zi and Z2 are each methyl, or Zi and Z2 together form a linking moiety which can be further substituted by an ester, ether, amide group , amino, carboxy or urethane, and E is C? -C? 8 alkoxy, C5-C? 2 cycloalkoxy, C7-C25 aralkoxy, C6-C? 2 aryloxy, as a combustion retardant for a substrate polymeric 2. The use according to claim 1, wherein the hindered amine compound is one of the formula where E is alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 5 to 15 carbon atoms, R is hydrogen or methyl, m is 1 to 4, where m is 1, R2 is hydrogen , Ci-Ciß alkyl or alkyl optionally interrupted by one or more oxygen atoms, C 2 -C 2 alkenyl / C 6 -C 0 aryl, C 7 -C 8 aralkyl, glycidyl, a monovalent acyl radical of an aliphatic, cycloaliphatic or aromatic carboxylic acid, or a carbamic acid, preferably an acyl radical of an aliphatic carboxylic acid having 2-18 carbon atoms, a cycloaliphatic carboxylic acid having 5-12 carbon atoms or an acid aromatic carboxylic having 7-15 C atoms, or where x is 0 or 1, where y is 2-4; when m is 2, R 2 is C 1 -C 2 alkylene, C -C 12 alkenylene, xylylene, a radical. divalent acyl of a dicarboxylic acid or of an aliphatic, cycloaliphatic or araliphatic dicylamic acid, preferably an acyl radical of an aliphatic dicarboxylic acid having 2-18 carbon atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 atoms of C, or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms; O or II II C-NH (CH2) -NH-C, where Di and D2 are independently hydrogen, an alkyl radical containing up to 8 carbon atoms, an aryl or aralkyl radical including the 3,5-di-t-butyl-4-hydroxybenzyl radical, D3 is hydrogen, or an alkyl radical or alkenyl containing up to 18 carbon atoms, and d is 0-20; when m is 3, R 2 is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid; when m is 4, R 2 is tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid including 1, 2, 3, -butetracarboxylic acid, 1,2,4,4-but-2-en-tetracarboxylic acid, and 1,2,3,5- and 1,2,4,5-pentanetetracarboxylic; p is 1, 2 or 3, R3 is hydrogen, C? -C? 2 alkyl, C5-C7 cycloalkyl, C7-Cg aralkyl, C2-C? 8 alkanoyl, alkenoyl or C3-Cs benzoyl; when p is 1, R is hydrogen, C 1 -C 8 alkyl, C 5 C cycloalkyl, C 2 -C 8 alkenyl, unsubstituted or substituted by a cyano, carbonyl or carbamide, aryl, aralkyl, or glycidyl group , a group of the formula -CH 2 -CH (OH) -Z of the formula -CO-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or a group of the formula where h is 0 or 1, R3 and R4 together, when p is 1, can be alkylene of 4 to 6 carbon atoms or cyclic acyl radical of 2-oxo-polyalkylene of a 1,2- of 1,3-carboxylic acid aliphatic or aromatic when p is 2, R4 is a direct bond or is alkylene of C? -C? 2, arylene of C6-C12, xylylene, a group -CH2CH (OH) -CH or a group -CH2-CH (OH) ) -CH2-0-X-0-CH2-CH (OH) -CH2- where X is C2-C10 alkylene, C6-C arylene or cycloalkylene of Ce-C2; or, knowing that. R3 is not alkanoyl, alkenoyl or benzoyl, R4 can also be a divalent acyl radical of a dicarboxylic acid or aliphatic, cycloaliphatic or aromatic dicarbamic acid, or it can be the group -C0-; or R4 is where T8 and Tg are independently hydrogen, alkyl of 1 to 18 carbon atoms, or T8 and Tg together are alkylene of 4 to 6 carbon atoms of 3-oxapentamethylene, preferably T8 and Tg together are -oxapetamethylene; when p is 3., R 4 is 2,4,6-triazinyl, n is 1 or 2, when n is 1, R 5 and R 5 are independently C 1 -C 12 alkyl / C 2 -C 2 alkenyl, C 7 -C 2 aralkyl, or R 5 is also hydrogen or R 5 and R 5 together are C 2 -C 8 alkylene or C 4 -C 22 hydroxyalkylene or acyloxyalkylene; when n is 2, R5 and R'5 together are (-CH2) 2C (CH2-) 2; R 6 is hydrogen, C 1 -C 2 alkyl, allyl, benzyl, glycidyl or C 2 -C 6 alkoxyalkyl, "when n is 1. R is hydrogen, C 1 -C 2 alkyl, C 3 -C 5 alkenyl, C 7 aralkyl -Cg, C5-C7 cycloalkyl, C2-C4 hydroxyalkyl, C2-Cd alkoxyalkyl, cycloalkyl, glycidyl, a group of the formula - (CH2) t-COO-Q or of the formula - (CH2 ) t-0-CO-Q where t is 1 or 2, and Q is C 1 -C 4 alkyl, or phenyl, or when n is 2, R 7 is C 3 -C 12 alkylene, C 6 -C 2 arylene, a group -CH2CH (OH) -CH2-0-X-0-CH2-CH (OH) -CH2- where X is C2-C6 alkylene, C6-C5 arylene or C6-C cycloalkylene? 2, or a group -CH2CH (OZ ') CH2- (OCH2-CH (OZ') CH2) 2- where Z 'is hydrogen, C? -C? 8 alkyl, allyl, benzyl, C2-Ci2 alkanoyl or benzoyl; Qi is -N (R8) - or -0-; E is C1-C3 alkylene, the group -CH-CH (Rg) -0- where Rg is hydrogen, methyl or phenyl, the group - (CH2) 3-NH- or a direct bond: Rio is hydrogen or C? -C? 8 alkyl, R8 is hydrogen, C? -C? 8 alkyl, C5-C7 cycloalkyl, aralkyl of C7-C? , cyanoethyl, C6-C6 aryl, the group -CH2-CH (R9) -OH where Rg has the meaning defined above; a group of the formula or a group of the formula where G4 is C2-C6 alkylene, or C6-C2 arylene; or R8 is a group -E7-CO-NH-CH2-OR? 0; Formula F denotes a recurring structural unit of a polymer where T3 is ethylene or 1,2-propylene, is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; preferably a copolymer of ethylene and ethyl acrylate, and wherein k is 2 to 100; T4 has the same meaning as R when p is 1 or

2, T5 is methyl, Te is methyl or ethyl, or T5 and T6 together are tetramethylene or pentamethylene, preferably T5 and Td are each methyl, M and Y are independently methylene or carbonyl, and T4 is ethylene where n is 2; T7 is the same as R7 / and T7 is preferably octamethylene where n is 2, Tio and u are independently alkylene of 2 to 12 carbon atoms, or Tu is T 12 is piperazinyl, -NR- (CH 2) d-NR? R or -NR (CH2) - N (CH2) ^ N [(CH2) - N] fH where Ru is the same as R3 or is also a, b and c are independently 2 or 3, and f is 0 or 1, preferably a and c are each 3, b is 2 and f is i; and e is 2, 3 or 4, preferably 4; _ T? 3 is the same as R2 with the proviso that Ti3 can not be hydrogen when n is 1; Ei and E2 / are different, each being -CO- or -N (E5) -where E5 is hydrogen, C? -C? 2 alkyl or C4-C22 alkoxycarbonylalkyl, preferably Ex is -CO- and E2 is -N (E5) -, E3 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, phenyl or naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or phenylalkyl substituted by alkyl of 1 to 4 carbon atoms, E4 is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E3 and E4 together are polymethylene from 4 to 17 carbon atoms, or such polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms, preferably methyl, E6 is a tetravalent aliphatic or aromatic radical, R2 of formula (N) is one previously defined when m is 1; Gi a direct bond, alkylene of C? ~ C? 2, phenylene or -NH-G'-NH where G 'is alkylene of C? -C? 2; or wherein the hindered amine compound is a compound of the formula I, II, III, IV, V, VI, VII, HIV, IX, X or XI where Ei, E2, E3 and E are independently alkyl of 1 to 4 carbon atoms, or Ei and E2 'are independently alkyl of 1 to 4 carbon atoms and E3 and E taken together are pentamethylene, or Ei and E2; and E3 and E4 each taken together are pentamethylene, Ri is alkyl of 1 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, a radial bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or such aryl substituted by one to three alkyl of 1 to 8 carbon atoms, R 2 is hydrogen or a straight or branched chain alkyl of 1 to 12 carbon atoms, R 3 is alkylene of 1 to 8 carbon atoms, or R3 is -CO-, -C0-R4-, -C0NR2-, or -CO-NR2-R4-, R4 is alkylene of 1 to 8 carbon atoms, R5 is hydrogen, a straight or branched chain alkyl of 1 to 12 carbon atoms, or or when R4 is ethylene, two methyl substituents of Rs can be linked by a direct bond so that the triazine bridge group -N (R5) -R4-N (R5) - is a piperazin-1,4-diyl moiety RQ is alkoxy of 2 to 8 carbon atoms or Re is with the proviso that Y is not -OH when R6 is the structure described above, A is -0- or -NR7- where R7 is hydrogen, a straight or branched chain alkyl of 1 to 12 carbon atoms, or R7 is T is phenoxy, phenoxy substituted by one or two alkyl groups of 1 to 4 carbon atoms, alkoxy of 1 to 8 carbon atoms or -N (R2) with the proviso that R2 is not hydrogen, or T is X is -NH2, -NCO, -OH, -O-glycidyl, or -NHNH2, and Y is -OH, -NH2, -NHR2 where R2 is not hydrogen; or Y is -NCO, -COOH, oxiranyl, -O-glycidyl, or -Si (OR2) 3; or the combination R3-Y- is -CH2CH (OH) R2 where R2 is alkyl or such alkyl interrupted by one to four oxygen atoms, or R3-Y- is -CH20R2; or wherein the hindered amine compound is a mixture of N, N ', N "' - tris. {2, 4-bis- [(1-hydroxycarbyloxy-2, 2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-tracin-6-yl.} - 3, 3'-ethylenediiminodipropylamine; N, N ', N "-tris. { 2,4-bis [(1-alkoxy-2,2,6,6-tetramethylpiperidin-4-yl) alkylamino] -s-triazin-6-yl} 3, 3'-ethylenediiminodipropylamine, bridged derivatives as described by the formulas I, II, HA and III R? NH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (I) T-Ei-Ti (H) T-Ei (HA) G-E1- G1-E1-G2 (IH) wherein in the tetraamine of formula I Ri and R2 are the E portion of s-triazine; and one of R3 and R4 is the E portion of s-triazine with the other of R3 or R being hydrogen, E is R is methyl, propyl, cyclohexyl or octyl, R5 is alkyl of 1 to 12 carbon atoms, where in the compound of formula II or HA when R is propyl, cyclohexyl or octyl, T and Ti are each, substituted by R? ~ R4 as defined by formula I, where (1) one of the E-portions of s-triazine in each tetraamine is replaced by the group Ei which forms a bridge between two tetraamines T and Ti, Ei is (2) the group Ei can have both terminals in the same tetraamine T as in the formula HA where two of the E portions of the tetraamine are replaced by a group Ei, or (3) all three s-triazine substituents of the tetraramine T can be Ei so that one Ei links to T and Ti and a second Ei has both terminals in tetraamine T, L is propandiyl, cyclohexanediyl or octandiyl; where in the compound of formula III G, Gi and G2 are each year tetraamines substituted by R1-R4 as defined by formula I, except that G and G2 each have one of the E portions of s-triazine replaced by Ei, and Gi has two portions E of triazine replaced by Ei, so that is a bridge between G and Gx and a second bridge between Gi and G2; mixture which is prepared by reacting two to four equivalents of 2,4-bis [(1-hydrocarbyloxy-2, 2,6,6-piperidin-4-yl) butylamino] -6-chloro-s-triazine with one equivalent of N, N'-bis (3-aminopropyl) ethylenediamine.

3. The use according to claim 1, wherein the polymeric substrate is selected from the group of resins consisting of polyolefins, thermoplastic olefins, styrenic polymers and copolymers, and ABS.

4. The use of. according to claim 1, wherein the hindered amine is from 0.25 to 10% by weight based on the polymeric substrate.

5. The use according to claim 1, wherein the hindered amine is selected from the class of 2,2,6,6-tetramethylpiperidines substituted on the nitrogen atoms by alkoxy of 1 to 18 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms or aralkoxy of 7 to 15 carbon atoms.

6. The use according to claim 1, wherein, the polymeric substrate is polypropylene, the hindered amine is not bis (l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

7. The use according to claim 1, wherein, if the polymeric substrate is polyolefin, the hindered amine is not bis (l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate.

8. A combustion retardant method of a polymeric substrate characterized by the addition thereto of a retardant amount of effective combustion of a hindered amine compound according to claim 1.

9. A combustion retardant composition, characterized because it comprises (a) a polymeric substitute, (b) an effective retardant amount of combustion of a synergist mixture of (i) a hindered amine according to claim 1, and (ii) a combustion retardant compound selected from compounds halogenated, phosphorous, boron, silicon- and antimony, metal hydroxides, metal hydrates, metal oxides or mixtures thereof; with the proviso that when the polymeric substrate is polypropylene, the hindered amine is not a functional alkoxyamine hindered amine and the combustion retardant is not a halogenated hydrocarbyl phosphate or phosphonate.

10. A combustion retardant composition, characterized in that it comprises (a) a polymer, and (b) from 5.1 to 9% by weight of the polymer of a NOR-hindered amine according to claim 1.