ES2806550T3 - NOR-HALS compounds as flame retardants - Google Patents

Abstract

Composition, comprising a) at least one NOR-HALS compound of formula ** (See formula) ** in which R1 and R2 represent n-undecyl; b) at least one flame retardant compound selected from the group consisting of tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate and melamine phenylphosphonate; and c) a polymeric substrate.

Description

DESCRIPTION

NOR-HALS compounds as flame retardants

The present invention relates to the use of the NOR-HALS compound of formula (I) in admixture with tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate or melamine phenylphosphonate in polymeric compositions retarding the call. These compositions are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers, especially homo- and copolymers of polyolefin, polycondensates, such as polyamines or polyesters, and duroplastic polymers, such as polyepoxides.

Flame retardants are added to polymeric materials (synthetic or natural) to enhance the flame retardant properties of polymers. Depending on their composition, flame retardants can act in the solid, liquid or gaseous phase, either chemically, for example as a foaming agent by releasing nitrogen, and / or physically, for example by producing a foam coating. Flame retardants interfere during a particular phase of the combustion process, for example during heating, decomposition, ignition or propagation of the flame.

There is still a need for flame retardant compositions with improved properties that can be used on different polymeric substrates. Increased standards regarding safety and environmental requirements result in stricter regulations. The known halogen-containing flame retardants in particular no longer fulfill all the necessary requirements. Therefore, halogen-free flame retardants are preferred, particularly in view of their better performance in terms of smoke density associated with fire. Improved thermal stability and less corrosive behavior are additional benefits of halogen-free flame retardant compositions. NOR-HALS compounds are known from EP 1 731 508 as stabilizers for synthetic resins to protect these substrates from degradation caused by the action of chemicals and acid rain.

WO 08/03602 refers to NOR-HALS compounds that can also be used as flame retardants. WO 99/00450 further discloses additional common flame retardants.

It has surprisingly been found that thermoplastic or duroplastic polymers with excellent flame retardant properties are prepared in the event that selected NOR-HALS compounds are added to the polymeric substrate.

These compositions have excellent thermal stability and are therefore especially suitable for application in epoxy laminates and thermoplastic engineering materials used for the manufacture of electrical and electronic parts and devices. By using instant flame retardant additives in thermoplastic and duroplastic resins, conventional halogen-containing flame retardants and halogenated epoxy resins, antimony compounds, and inorganic fillers can be greatly reduced or replaced.

The present invention relates to a composition, comprising

a) at least one NOR-HALS compound of formula

wherein R1 and R2 represent n-undecyl;

b) at least one flame retardant compound selected from the group consisting of tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate and melamine phenylphosphonate; Y

c) a polymeric substrate.

The polymeric compositions in which the compounds (I) are present, as defined above, achieve the desirable classifications related to established flame retardant test methods, especially in polyolefin compositions.

This compound (I) is preferably contained in the flame retardant compositions according to the invention in an amount of from about 0.005-90.0% by weight, preferably about 0.02-20.0% by weight, most preferably between 0.10-15.0% by weight, based on the total weight of the composition.

The terms polymer and substrate include within their scope thermosetting materials and thermoplastic and duroplastic polymers.

The following is a list of suitable thermoplastic polymers:

1. Polymers of monoolefins and diolefins, for example thermoplastic polyolefins (TPO), such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyvinylcyclohexane, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for example from cyclopentene or norbornene, polyethylene (which can optionally be cross-linked), for example high density polymethylene (HDPE), high density high molecular weight polyethylene (HDPE-HMW), high density ultrahigh molecular weight polyethylene (HDPE) -UHMW), Medium Density Polyethylene (MDPE), Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), (VLDPE) and (ULDPE). Polyolefins, that is, the polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene, can be prepared by different methods and especially the following:

a) Radical polymerization (usually at high pressure and at elevated temperature).

b) Catalytic polymerization using a catalyst that normally contains one or more than one metal from groups IVb, Vb, Vlb or VIII of the Periodic Table. These metals usually have one or more than one ligand, usually oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls that can be coordinated with either a or n bonds. These metal complexes can be in free form or fixed on substrates, usually on activated magnesium chloride, titanium (III) chloride and silicon oxide or alumina. These catalysts can be soluble or insoluble in the polymerization medium. The catalysts can be used alone in the polymerization or additional activators can be used, usually metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of the groups la, Ila and / or IIIa of the Periodic table. Activators can conveniently be modified with additional ester, ether, and amine or silyl ether groups. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler-Natta, TNZ (DuPont), metallocene, or single site catalysts (SSC).

2. Mixtures of the polymers mentioned in 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP / HDPE, PP / ^l D ^p E) and mixtures of different types of polyethylene (for example LDPE / HDPE) .

3. Copolymers of monoolefins and diolefins with each other and with other vinyl monomers, for example ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and blends thereof with low density polyethylene (LDPE), propylene / but copolymers -1-ene, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, ethylene / vinylcyclohexane copolymers , ethylene / cycloolefin copolymers (eg ethylene / norbornene as COC), ethylene / 1-olefin copolymers, where the 1-olefin is generated in situ; propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / vinylcyclohexene copolymers, ethylene / alkyl acrylate copolymers, such as ethylene-acrylate or n-butyl methacrylate, ethylene / alkyl methacrylate copolymers, ethylene / alkyl methacrylate copolymers, vinyl acetate or ethylene / acrylic acid copolymers and their salts (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 each other and with polymers mentioned in 1) above, for example polypropylene / ethylene-propylene copolymers, LDPE / ethylene vinyl acetate (EVA) copolymers, LDPE / ethylene-acrylic acid (EAA) copolymers, LLDPE / EVA, LLDPE / EAA and polyalkylene / carbon monoxide alternate or random copolymers and blends thereof with other polymers, for example polyamides.

4. Hydrocarbon resins (eg C5-C9) including hydrogenated modifications thereof (eg tackifiers) and mixtures of polyalkylenes and starch. The homopolymers and copolymers mentioned above can have a stereo structure including syndiotactic, isotactic, hemi-isotactic or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).

6. Aromatic homopolymers and copolymers derived from vinyl aromatic monomers including styrene, amethylstyrene, all vinyl toluene isomers, especially p-vinyl toluene, all ethyl styrene, propyl styrene, vinyl biphenyl, vinyl naphthalene, and vinyl anthracene, and mixtures thereof. Homopolymers and copolymers can have a stereo structure including syndiotactic, isotactic, hemi-isotactic, or atactic; where atactic polymers are preferred. Stereoblock polymers are also included;

a) Copolymers including the aforementioned vinyl aromatic monomers and comonomers selected from ethylene, propylene, dienes, nitriles, acids, maleic anhydrides, maleimides, vinyl acetate and vinyl chloride or acrylic derivatives and mixtures thereof, for example styrene / butadiene, styrene / acrylonitrile, styrene / ethylene (interpolymers), styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; high impact blends of copolymers of styrene and another polymer, for example a polyacrylate, a diene polymer or an ethylene / propylene / diene terpolymer; and styrene block copolymers such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene or / ethylene / propylene or / styrene.

b) Hydrogenated aromatic polymers derived from the hydrogenation of polymers mentioned in 6), including especially polycyclohexylethylene (PCHE) prepared by hydrogenation of atactic polystyrene, often referred to as polyvinylcyclohexane (PVCH).

c) Hydrogenated aromatic polymers derived from the hydrogenation of polymers mentioned in 6a). Homopolymers and copolymers can have a stereo structure including syndiotactic, isotactic, hemi-isotactic, or atactic; where atactic polymers are preferred. Stereoblock polymers are also included.

7. Graft copolymers of vinyl aromatic monomers, such as styrene or α-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; 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 alkyl acrylates or 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 in 6), for example the copolymer mixtures known as ABS, MBS, ASA polymers or AES.

8. Halogen-containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, homo and copolymers of epichlorohydrin, especially polymers of compounds of halogen-containing vinyl, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride / chloride copolymers vinylidene, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate.

9. Polymers derived from a, p-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; poly (methyl methacrylates), polyacrylamides and polyacrylonitriles, impact modified with butyl acrylate.

10. Copolymers of the monomers mentioned in 9) with each other or with other unsaturated monomers, for example acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylate or acrylonitrile / vinyl halide copolymers. alkyl methacrylate / butadiene.

11. Polymers derived from unsaturated amines and alcohols or acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl (vinyl maleate), polyvinylbutyral, poly (allyl phthalate) or polyallyl melamine; as well as their copolymers with olefins mentioned in 1 above.

12. Homopolymers and copolymers of cyclic esters such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.

13. Polyacetals such as polyoxymethylene and those polyoxymethylenes that contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.

14. Polyphenylene sulfides and oxides, and mixtures of polyphenylene oxides with styrene or polyamide polymers.

15. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams, for example polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6 , 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylenediamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic and / or terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4, -trimethylhexamethylene-terephthalamide or poly-m-phenylene-isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, chemically bonded or graft ionomers or elastomers; or with polyethers, for example with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).

16. Polyureas, polyimides, polyamido-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids and diols and / or hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, poly (butylene terephthalate), poly (1,4-dimethylolcyclohexane terephthalate), poly (naphthalate) alkylene) (PAN) and polyhydroxybenzoates, as well as block copolyether-esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.

18. Policetonas.

19. Polysulfones, polyethersulfones, and polyetherketones.

20. Combinations of the polymers mentioned above (polycombinations), for example PP / EPDM, polyamide / EPDM or ABS, PVC / EVA, PVC / ABS, PVC / MBS, PC / ABS, PBTP / ABS, PC / ASA, PC / PBT, PVC / CPE, PVC / acrylates, thermoplastic POM / PUR, thermoplastic PC / PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO , PBT / PC / ABS or PBT / PET / PC.

21. Polycarbonates that correspond to the general formula:

Such polycarbonates can be obtained by interfacial processes or by melting processes (catalytic transesterification). The polycarbonate can be either branched or linear in structure and can include any functional substituent. Polycarbonate copolymers and polycarbonate blends are also within the scope of the invention. The term polycarbonate should be interpreted as inclusive of copolymers and combinations with other thermoplastic compounds. Methods for the manufacture of polycarbonates are known, for example, from US Patent Specifications Nos. 3,030,331, 3,169,121, 4,130,458, 4,263,201, 4,286,083, 4,552,704, 5,210. 268 and 5,606,007. A combination of two or more polycarbonates of different molecular weights can be used.

Polycarbonates that can be made by reacting a diphenol, such as bisphenol A, with a carbonate source are preferred. Examples of suitable diphenols are:

bisphenol F:

bisphenol M:

bisphenol P:

bisfenol

bisphenol

bisphenol

bisphenol Z:

4,4 '- (2-norbomylidene) bis (2,6-dichlorophenol); or fluorene-9-bisphenol:

The carbonate source can be a carbonyl halide, a carbonate ester, or a haloformate. Suitable carbonate halides are phosgene or carbonyl bromide. Suitable carbonate esters are dialkyl carbonates, such as dimethyl or diethyl carbonate, diphenyl carbonate, phenyl-alkylphenyl carbonate, such as phenyl-tolyl carbonate, dialkyl carbonates, such as dimethyl or diethyl carbonate, di - (halophenyl), such as di- (chlorophenyl) carbonate, di- (bromophenyl) carbonate, di- (trichlorophenyl) carbonate or di- (trichlorophenyl) carbonate, di- (alkylphenyl) carbonate, such as carbonate di-tolyl, naphthyl carbonate, dichloronaphthyl carbonate and others.

The above-mentioned polymeric substrate, comprising polycarbonates or polycarbonate blends, is a polycarbonate copolymer, in which isophthalate / terephthalate-resorcinol segments are present. Such polycarbonates are commercially available, for example Lexan® SLX (General Electrics Co. USA). Other polymeric substrates of component b) may additionally contain in the form of additives or as copolymers a wide variety of synthetic polymers including polyolefins, polystyrenes, polyesters, polyethers, polyamides, poly (meth) acrylates, thermoplastic polyurethanes, polysulfones, polyacetals and PVC, including suitable compatibilizing agents. For example, the polymeric substrate may additionally contain thermoplastic polymers selected from the group of resins consisting of polyolefins, thermoplastic polyurethanes, styrene polymers, and copolymers thereof. Specific embodiments include polypropylene (PP), polyethylene (PE), polyamide (PA), poly (butylene terephthalate) (PBT), poly (ethylene terephthalate) (PET), glycol-modified poly (cyclohexylene methylene terephthalate) (PCTG). ), polysulfone (PSU), poly (methyl methacrylate) (PMMA), thermoplastic polyurethane (TPU), acrylonitrile-butadiene-styrene (ABS), acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-ethylene-propylene-styrene (AES), styrene -maleic anhydride (SMA) or high impact polystyrene (HIPS).

A preferred embodiment of the invention relates to the use of the inventive compositions in thermoplastic polymers. Preferred thermoplastic polymers include polyamides, polyesters, and polycarbonates.

Another preferred embodiment of the invention relates to a composition, in which component c) is a duroplastic polymeric substrate of the polyepoxide type.

A highly preferred embodiment of the invention relates to the use of the inventive compositions to induce flame retardancy in polymers.

The combination of the compound NOR-HALS (I) and the additional flame retardants defined above is preferably contained in the flame retardant compositions according to the use defined above in a amount of from about 0.005-90.0% by weight, preferably about 0.02-20.0% by weight, most preferably between 0.10-15.0% by weight, based on weight total composition.

The present invention further relates to the use of the compositions defined above comprising, in addition to the components defined above, optional components, such as additional flame retardants and / or additional additives selected from the group consisting of tetraalkylpiperidine additives, suppressors of smoke, polymer stabilizers, fillers, reinforcing agents and so-called anti-drip agents that reduce melt flow from thermoplastic polymers and reduce droplet formation at higher temperatures.

Such additional flame retardants are phosphorus-containing flame retardants, selected for example from the group consisting of phosphorus and / or nitrogen-containing flame retardants, organohalogen-containing flame retardants and inorganic flame retardants.

Phosphorous-containing flame retardants are, for example, resorcinol phenylphosphate oligomer (Fyrolflex® RDP, Akzo Nobel), triphenyl phosphate, bisphenol A phenylphosphate oligomer (Fyrolflex® BDP), tris (2.4 -ditert-butylphenyl), ethylenediamine diphosphate (EDAP), tetra (2,6-dimethylphenyl) resorcinol diphosphate, diethyl-N, N-bis (2-hydroxyethyl) -aminomethyl phosphonate, hydroxyalkyl esters of phosphoric acids, salts hypophosphoric acid (H3PO2), particularly the Ca2 +, Zn2 + or Al3 + salts, tetrakis (hydroxymethyl) phosphonium sulfide, triphenylphosphine, triphenylphosphine oxide, tetraphenyldiphosphine monoxide, phosphazenes and 9,10-dihydro-9-oxa 10-oxide -10-phosphorylphenanthrene (DOPO) and its derivatives, such as 2- (9,10-dihydro-9-oxa-10-phosphaphenanthrene 10-oxide) -1,4-benzenediol.

Nitrogen-containing flame retardants are, for example, isocyanurate flame retardants, such as polyisocyanurate, isocyanuric acid esters or isocyanurates. Representative examples are hydroxyalkyl isocyanurates, such as tris- (2-hydroxyethyl) isocyanurate, tris (hydroxymethyl) isocyanurate, tris (3-hydroxy-n-proyl) isocyanurate, or triglycidyl isocyanurate.

Nitrogen-containing flame retardants further include melamine-based flame retardants. Representative examples are: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine ammonium polyphosphate, melamine ammonium pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate.

Additional examples are: benzoguanamine, allantoin, glycoluril, urea cyanurate, ammonium polyphosphate, and a melamine condensation product of the melem, melam, melon series and / or a higher consensus compound or a reaction product of melamine with phosphoric acid. or a mixture thereof.

Representative organohalogen flame retardants are, for example: polybrominated diphenyl oxide (DE-60F, Chemtura Corp.), decabromodiphenyl oxide (DBDPO; Saytex® 102E), tris [3-bromo-2,2- phosphate bis (bromomethyl) propyl] (PB 370®, FMC Corp.), tris (2,3-dibromopropyl) phosphate, tris (2,3-dichloropropyl) phosphate, chloendic acid, tetrachlorophthalic acid, tetrabromophthalic acid, poly (chloroethyl triphosphonate), tetrabromobisphenol A bis (2,3-dibromopropyl ether) (PE68), brominated epoxy resin, ethylene-bis (tetrabromophthalimide) (Saytex® BT-93), bis (hexachlorocyclopentadiene) cyclooctane (Declorane Plus®), Chlorinated paraffins, octabromodiphenyl ether, 1,2-bis (tribromophenoxy) ethane (FF680), tetrabromo-bisphenol A (Saytex® RB100), ethylene-bis- (dibromonorbornanedicarboximide) (Saytex® BN-451), bis- (hexachlorocyclopentane) , PTFE, tris- (2,3-dibromopropyl) isocyanurate and ethylene-bis-tetrabromophthalimide.

The organohalogen flame retardants mentioned above are routinely combined with an inorganic oxide synergist. The most common for this use are zinc or antimony oxides, for example Sb2O3 or Sb2O5. Boron compounds are also suitable.

Representative inorganic flame retardants include, for example, aluminum trihydroxide (ATH), boehmite (AIOOH), magnesium dihydroxide (MDH), hydrotalcite, zinc borates, CaCO3, layered silicates (organically modified), double hydroxides in layers (organically modified), and mixtures thereof.

The aforementioned additional classes of flame retardant are advantageously contained in the composition of the invention in an amount of from about 0.5% to about 75.0% by weight of the organic polymeric substrate; for example from about 10.0% to about 70.0%; for example from about 25.0% to about 65.0% by weight, based on the total weight of the composition.

According to another embodiment, the invention relates to compositions that additionally comprise as an additional component so-called anti-drip agents.

These anti-drip agents reduce the flow of the thermoplastic polymer melt and inhibit the formation of droplets at high temperatures. Various references, such as US Patent Specification No. 4,263,201, describe the addition of anti-drip agents to flame retardant compositions.

Suitable additives that inhibit droplet formation at high temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon fibers, glass spheres.

The addition of polysiloxanes of different structures has been proposed in various references; see US Patent Specification Nos. 6,660,787, 6,727,302, or 6,730,720.

According to a further embodiment, the invention relates to compositions which additionally comprise fillers and reinforcing agents as additional components. Suitable fillers are, for example, glass powder, glass microspheres, silica, mica, wollastonite, and talc.

The stabilizers are preferably halogen-free and are selected from the group consisting of nitroxyl stabilizers, nitrone stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphite and phosphonite stabilizers, quinone methylated stabilizers, and monoacrylate ester stabilizers. of 2,2'-alkylidenebisphenol.

As mentioned above, the composition according to the invention may additionally contain one or more conventional additives, for example selected from the group consisting of pigments, colorants, plasticizers, antioxidants, thixotropic agents, leveling assistants, basic costabilizers, metal passivators, oxides metals, organophosphorus compounds, UV absorbing compounds and additional light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate and UV absorbers of the 2-hydroxy-benzophenone groups, 2 - (2'-hydroxyphenyl) benzotriazole and / or 2- (2-hydroxyphenyl) -1,3,5-triazine and benzoate, such as 2,4-di 3,5-di-tert-butyl-4-hydroxybenzoate -tert-butylphenyl (TINUVIN 120) or hexadecyl 3,5-bis-tert-butyl-4-hydroxybenzoate (Cytec Cyasorb®UV 2908).

Additional preferred additives for the compositions as defined above are processing stabilizers, such as the phosphites and phenolic antioxidants mentioned above, and light stabilizers, such as benzotriazoles. Specific preferred antioxidants include octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (IRGANOX 1076), tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ( ⁱ R ^g ANOX 1010), tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate (IRGANOX 3114), 1,3,5-trimethyl-2,4,6-tris ( 3,5-di-tert-butyl-4-hydroxybenzyl) benzene (IRGANOX 1330), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (IRGANOX 245) and N, N'-hexane-1,6-diyl-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionamide] (IRGANOX 1098). Specific processing stabilizers include tris (2,4-di-tert-butylphenyl) phosphite (IRGAFOS 168), 3,9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10- tetraoxa-3,9-diphosfaspiro [5.5] undecane (IRGAFOS 126), 2,2 ', 2 "-nitrile [triethyl-tris (3,3', 5,5'-tetra-tert-butyl-1, 1'-biphenyl-2,2'-diyl)] (IRG ^to F ^or S 12) and 4,4'-diylbiphosphonite from tetrakis (2,4-di-tert-butylphenyl) - [1,1-biphenyl] (IRGAFOS P -EPQ) Specific light stabilizers include 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (TINUVIN 234), 2- (5-chloro (2H) -benzotriazol-2-yl) -4- (methyl) -6- (tert-butyl) phenol (TINUVIN 326), 2- (2H-benzotriazol-2-yl) -4- (1,1,3 , 3-tetramethylbutyl) phenol (TINUVIN 329), 2- (2H-benzotriazol-2-yl) -4- (tert-butyl) -6- (secbutyl) phenol (TINUVIN 350), 2,2'-methylenebis (6 - (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol) (TINUVIN 360) and 2- (4,6-diphenyl-1,3,5-triazin-2- yl) -5 - [(hexyl) oxy] -phenol (TINUVIN 1577), 2- (2'-hydroxy-5'-methylphenyl) benzotriazole (TINUVIN P), 2-hydroxy-4- (oc tyloxy) benzophenone (CHl-MASSORB 81), 1,3-bis - [(2'-cyano-3 ', 3'-diphenylacryloyl) oxy] -2,2-bis - {[(2'-cyano-3' , 3'-diphenylacryloyl) oxy] methyl} -propane (UVINUL 3030, BASF), ethyl 2-cyano-3,3-diphenylacrylate (UVINUL 3035, BASF) and 2-cyano-3,3-diphenylacrylate (2-ethylhexyl ) (UVINUL 3039, BASF).

According to a further embodiment, the compositions comprise as an optional component the additional flame retardants defined above and additives selected from the group consisting of polymer stabilizers and tetraalkylpiperidine derivatives.

Representative examples of tetraalkylpiperidine derivatives are selected from the group consisting of -cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine,

bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

2.4- bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino-s-triazine,

bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate,

2.4- bis [(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-chloro-s-triazine,

- (2-hydroxy-2-methylpropoxy) -4-hydroxy-2,2,6,6-tetramethylpiperidine,

1- (2-hydroxy-2-methylpropoxy) -4-oxo-2,2,6,6-tetramethylpiperidine,

1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine,

bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) sebacate,

bis (1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl) adipate,

, 4-bis {N- [1- (2-hydroxy-2-methylpropoxy) -2,2,6,6-tetramethylpiperidin-4-yl] -N-butylamino} -6- (2-hydroxyethylamino) -s- triazine, The reaction product of 2,4-bis [(1-cidohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6-doro-s-triazine with N, N'-bis (3- aminopropyl) ethylenediamine),

2,4-bis [(1-cyidohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -6- (2-hydroxyethylamino) -s-triazine,

The oligomeric compound which is the condensation product of 4,4'-hexamethylenebis (amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6 - [(1-cyclohexyloxy-2,2,6, 6-tetramethylpiperidin-4-yl) butylamino] -s-triazine with 2-chloro-4,6-bis (dibutylamino) -s-triazine ends,

The compound of formula

and the compound of formula

where n is a number from 1 to 15.

The above-mentioned additives are preferably contained in an amount of 0.01 to 10.0%, especially 0.05 to 5.0%, relative to the weight of the polymeric substrate of component c).

The incorporation of the components defined above into the polymeric component is carried out by known methods such as dry blending in the form of a powder, or wet blending in the form of solutions, dispersions or suspensions for example in an inert solvent, water or oil. The additive components can be incorporated, for example, before or after molding or also by applying the dissolved or dispersed additive or the mixture of additives to the polymeric material, with or without subsequent evaporation of the solvent or the suspending / dispersing agent. They can be added directly to the processing apparatus (eg extruders, internal mixers, etc.), eg as a dry mix or powder, or as a solution or dispersion or suspension or melt.

The addition of the additive components to the polymeric substrate can be carried out in conventional mixing machines in which the polymer is melted and mixed with the additives. Suitable machines are known to those skilled in the art. They are predominantly mixers, kneaders and extruders.

The process is preferably carried out in an extruder with the additive being introduced during processing.

Particularly preferred processing machines are single screw extruders, counter-rotating and co-rotating twin-screw extruders, planetary gear extruders, ring extruders or co-kneaders. Processing machines provided with at least one gas removal compartment can be used to which vacuum can be applied.

Suitable extruder and kneader presses are described, for example, in Handbuch der Kunststoffextrusion, Vol. 1 Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3-7, ISBN: 3-446-14339-4 (Vol. 2 Extrusionsanlagen 1986, ISBN 3-446-14329-7 ;.

For example, the length of the screw is 1-60 screw diameters, preferably 35-48 screw diameters. The rotational speed of the spindle is preferably 10-600 rotations per minute (rpm), preferably 25-300 rpm.

The maximum performance depends on the diameter of the spindle, the speed of rotation and the driving force. The process of the present invention can also be carried out at a level below the maximum throughput by varying the mentioned parameters or by employing scales that deliver dosage amounts.

If a plurality of components are added, these can be premixed or added individually.

The additive components and optional additional additives can also be added to the polymer in the form of a masterbatch ("concentrate") containing the components in a concentration of, for example, about 1.0% to about 80.0% and preferably 2.0% to about 60.0% by weight incorporated into a polymer. The polymer is not necessarily identical in structure to the polymer where the additives are finally added. In such operations, the polymers can be used in the form of powders, granules, solutions and suspensions or in the form of network structures.

Incorporation can take place before or during the shaping operation. The materials containing the additives of the invention described herein are preferably used for the production of molded articles, for example injection molded or rotomolded articles, injection molded articles, profiles and fibers, fusion spun nonwoven fabrics, films or foams.

A preferred embodiment relates to a process for inducing the flame retardant ability in polymers, which comprises adding to a polymeric substrate a combination of

a) at least one NOR-HALS compound of formula

in which

R1 and R2 represent n-undecyl; with

b) at least one flame retardant compound selected from the group consisting of tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate and melamine phenylphosphonate.

The polymeric substrate suitable for inducing flame retardancy has been described above.

The following example illustrates the invention:

A) Methods

The following conventional test methods are used to evaluate performance as a flame retardant: DIN 4102-Part 1

The sample is placed vertically and the ignition flame is applied to the lower edge of the sample (edge ignition test).

The classification is based on the time for the flames to spread 150 mm from the sample.

If the flame does not reach the 150mm benchmark within 20 seconds, the film under test passes the test and is classified as B2.

UL 94-VTM and UL 94-V standards

A flame is applied twice to the lower end of the vertically placed test specimen.

The UL 94-VTM standard is a well known test to classify the flame retardancy of a very fine material into 3 classes VTM-0, v Tm-1 and VTM-2. The best classification is v Tm -0.

UL Standard 94, Test for Flammability of Plastic Materials for Parts in Devices and Appliances , 5th Edition, October 29, 1996. The classifications according to the UL 94 test V are compiled in the following table (the time periods for a sample are indicated):

Table

FR-1

Ri, R2: n-undecyl

B) Application example

Example 1

Injection Molding Grade Polypropylene Flame Retardant Capability ( MFI 25) Containing FR-1 Polymeric Component: MOPLEN HP 552 R (Lyondell Basell (PP))

Flame retardant components:

ADK STAB LA-81 (ADEKA): bis (1-undekanyloxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate (FR-1)

Aflammit ®TL 1260 (THOR GROUP LIMITED): Pentaerythritol dimethylphosphonate (FR-2)

PP, FR-1, and FR-2 were premixed in the indicated amounts and melt blended to form pellets on a Berstorff 32D co-rotating twin screw extruder (lab size twin screw extruder, screw diameter 25 mm) a maximum temperature Tmax of 230 ° C.

A 1.6 mm thick test sample according to UL94-V is prepared by injection molding (Engel EK 65).

Table 1

Ref. (Reference compositions) 1, 2; Inv. (inventive composition) 1: The addition of FR-1 significantly increases the FR performance of the composition compared to reference compositions 1, 2. The effectiveness of FR-1 as a flame retardant is demonstrated by the V- classification 0.

Claims (5)

1. Composition, comprising a) at least one NOR-HALS compound of formula

in which R1 and R2 represent n-undecyl; b) at least one flame retardant compound selected from the group consisting of tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate and melamine phenylphosphonate; Y c) a polymeric substrate. Composition according to claim 1, comprising as an optional component flame retardants and additional additives selected from the group consisting of tetraalkylpiperidine additives, polymer stabilizers, fillers, reinforcing agents and so-called anti-drip agents that reduce the flow of the melt. thermoplastic polymers and reduce droplet formation at higher temperatures. Composition according to claim 2, comprising as an additional flame retardant a nitrogen-containing compound selected from the group consisting of melamine polyphosphate, ammonium polyphosphate, melamine ammonium phosphate, melamine ammonium polyphosphate, ammonium pyrophosphate and melamine, a condensation product of melamine with phosphoric acid and other reaction products of melamine with phosphoric acid, and mixtures thereof. 4. Process for inducing the flame retardancy in polymers, which comprises adding to a polymeric substrate a combination of a) at least one NOR-HALS compound of formula

in which R1 and R2 represent n-undecyl; with b) at least one flame retardant compound selected from the group consisting of tris (tribromoneopentyl) phosphate, resorcinol bis-diphenylphosphate, pentaerythritol dimethylphosphonate, guanidine phenylphosphonate and melamine phenylphosphonate. 5. Use of the composition according to claim 1 to induce the flame retardancy in polymers.