Flame retardant composition, polymer composition containing same and use thereof

Abstract

The present disclosure is a flame retardant composition that includes a) a compound that includes an N-oxyamine group, and b) a compound of formula (II), (III), or (IV): [chemical 2] JPEG2025533889000017.jpg194153 (wherein R1 and R2 are, independently of one another, hydrogen, C1-C6-alkyl, -P(O)(OR5)2, -P(O)OR5R6, -P(O)(R5)2, where R5 and R6 are, independently of one another, C1-C4-alkyl, C6-C 12 -Aryl, C7-C 15 -Aralkyl or C7-C 15 -alkaryl, or R1 and R2 together form an unsaturated cyclic ring optionally substituted by alkyl groups; k is an integer from 1 to 2; Y is O or S; X is C1-C4-alkylene, C6-C 12 -Arylene, C7-C 15 -Aralkylene or C7-C 15 -alkarylene, where n is 0, 1 or 2, or X is -O- or -NR7-, where n is 1; R7 is hydrogen or C1-C4-alkyl; R3 is C1-C4-alkylene, C6-C 12 -Arylene, C7-C 15 -Aralkylene or C7-C 15 -alkarylene; m is 0, 1, or 2, provided that when X is -O- or -NR7-, then m is 1 or 2; R4 is C1-C4-alkylene; t is an integer from 1 to 2; and W is oxygen or sulfur. The composition can be used as a flame retardant in polymer compositions to enhance flame retardancy.

Description

[Technical Field]

[0001] The present invention relates to novel flame retardant compositions that can be used to prepare polymer compositions with improved flame retardancy. The invention also relates to improved polymer compositions that can be formed into thin articles, particularly polyolefin sheets and films, and polyolefin fibers. [Background technology]

[0002] Polymers such as polyolefins are increasingly being used in applications where flame retardancy is required. Flame retardancy is usually achieved by adding bromine or phosphorus compounds. However, bromine compounds significantly reduce the photostability of olefins, limiting their use in outdoor applications.

[0003] Phosphorus-containing flame retardants must be used in large quantities, and are often less effective in thin products such as fibers, sheets, and films.

[0004] US Pat. No. 6,599,963A describes a polymer substrate containing a flame retardant system comprising a sterically hindered amine and a brominated flame retardant.

[0005] WO 1999 / 000450 describes the use of sterically hindered amine compounds as flame retardants for polymers.

[0006] Patent Document 3 (WO2010 / 026230) describes a mixture of a cyclic phosphonate, one or more 1,3,5-triazine compounds, and a sterically hindered aminoether. The document also describes polyethylene sheets and films that meet the fire classification DIN 4102 B2. A drawback is that transparent sheets and films cannot be produced.

[0007] Patent Document 4 (WO2015 / 010775) discloses a combination of an aminoether derived from a sterically hindered amine and a finely divided phosphonate salt. This combination significantly improves flame retardancy, but does not produce a transparent flame-retardant film.

[0008] Patent Document 5 (WO 2011 / 117266) describes a polymeric material containing a salt of phosphinic acid and a tetraalkylpiperidine or tetraalkylpiperazine derivative. Polypropylene achieves a fire classification of V-2 with the addition of 8% flame retardant. This mixture is not suitable for sheets, films, or fibers due to the high filler content and large particle size of the phosphinic acid salt used. Due to the chemical reactivity required for flame retardancy at high temperatures, flame retardants can impair the processing stability of plastic materials. For example, accelerated polymer decomposition, crosslinking reactions, gas release, and discoloration may occur. These effects are absent or only minor when processing plastic materials without flame retardants.

[0009] Problems with compounding the sterically hindered amines described in Patent Document 6 (WO1999 / 000450) into sheets, films, or fibers include odor and discoloration during compounding, and the possibility that low molecular weight compounds may leach out of the plastic material.

[0010] Various phosphorus-containing compounds have been investigated for their suitability as flame retardant additives. Polyphosphonates and phosphonate oligomers have also demonstrated flame retardancy in many plastics. However, these polyphosphonates require large amounts of additives in thermoplastic resins, even when combined with common melamine-based synergists (see US 2009 / 0043013A).

[0011] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or (6H-dibenz[c,e][1,2]oxaphosphorine-6-oxide) (hereafter also referred to as "DOPO") is an ester of phosphinic acid in which phosphorus and oxygen atoms are incorporated into the phenanthrene basic structure. DOPO has flame-retardant properties and is the basis for a variety of different halogen-free and highly effective flame retardants for polymers.

[0012] DOPO can be synthesized by reacting 2-phenylphenol with phosphorus trichloride in the presence of zinc chloride. The reaction product, 6-chloro(6H)dibenz[c,e][1,2]oxaphosphorine (DOP-Cl), is produced in high yield at high temperatures by decomposition of hydrogen chloride. Heating DOP-Cl at high temperatures in the presence of water produces DOPO quantitatively in high purity.

[0013] DOPO is a white crystalline solid that exists as two tautomers: 6H-dibenzo[c,e][1,2]oxaphosphorin-6-one (tautomer I) and 6-hydroxy-(6H)-dibenzo-[c,e][1,2]oxaphosphorin (tautomer II). The latter compound hydrolyzes to 2'-hydroxydiphenyl-2-phosphinic acid in the presence of water.

[0014] In recent years, many DOPO derivatives with high hydrolytic stability and remarkably high melting points have been synthesized, especially for use in epoxy resins for electrical and electronic applications. DOPO and its derivatives are well-known flame retardants in polymers, such as polyesters.

[0015] From DE 10330774 and EP 2,284,208, it is known that flame-retardant polyesters with various P contents can be obtained by reacting DOPO with unsaturated dicarboxylic acids and then copolymerizing it with other P-containing derivatives suitable for forming ester bonds. These DOPO-based polymers can be used, for example, as flame-retardant additives for polyethylene terephthalate (PET) in textile applications or as the sole flame-retardant polyester in engineering plastics.

[0016] Furthermore, Patent Document 10 (WO 2015 / 140105) discloses hybrid materials containing covalently bonded DOPO and pentaerythritol phosphate alcohol (hereinafter also referred to as "PEPA") units. These compounds, based on the combination of DOPO-type and PEPA-type moieties, can be considered "hybrid flame retardants" and exhibit a highly desirable combination of properties as flame retardant compounds, particularly as flame retardant additives for thermoplastic polyesters. Such advantageous properties include, but are not limited to, high thermal stability (enabling melt blending) and a high melting point of at least about 150°C, slightly below the melt processing temperature of most polyesters, thereby allowing for more uniform dispersion of the additive within the polyester polymer matrix. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] US6,599,963A [Patent Document 2] WO1999 / 000450 [Patent Document 3] WO2010 / 026230 [Patent Document 4] WO2015 / 010775 [Patent Document 5] WO2011 / 117266 [Patent Document 6] WO1999 / 000450 [Patent Document 7] US2009 / 0043013A [Patent Document 8] DE 10330774 [Patent Document 9] EP2,284,208 [Patent Document 10] WO2015 / 140105 Summary of the Invention [Problem to be solved by the invention]

[0018] Surprisingly, it has been found that the combination of selected aminoethers and DOPO-PEPA derivatives improves the flame retardancy of polymers, preferably polyolefins. Various flame retardancy classifications can be achieved at low dosages, with minimal adverse effects on physical properties. Therefore, the object of the present invention is to provide a novel flame retardant material combination and a polymer, preferably polyolefin, containing the same, which does not have the drawbacks of current aminoether-based flame retardants and has superior performance compared to previously known flame retardant combinations.

[0019] Surprisingly, we found that the combination of selected aminoether-based sterically hindered amine compounds (e.g., Hostavin NOW) and DOPO-PEPA hybrid materials can be applied as highly efficient flame retardants for polymers. Instead of DOPO, DOPO containing a 10-hydroxy group (also called DOPO-OH) or its thio analogue can also be used as a component of the hybrid materials with PEPA units.

[0020] DOPO or DOPO-OH or their thio analogs correspond to formula (I) shown below: [ka] (wherein Y is O or S, and R is hydrogen or OH.) [Means for solving the problem]

[0021] The present invention relates to a flame retardant composition comprising: a) compounds containing an N-oxyamine group, and b) A compound of formula (II), (III) or (IV): [ka] (In the formula, R1 and R2 are, independently of one another, hydrogen, C1-C6-alkyl, -P(O)(OR5)2, -P(O)OR5R6, -P(O)(R5)2, where R5 and R6 are, independently of one another, C1-C4-alkyl, C6-C 12 -Aryl, C7-C 15 -Aralkyl or C7-C 15 -alkaryl, or R1 and R2 together form an unsaturated cyclic ring optionally substituted by alkyl groups; k is an integer from 1 to 2; Y is O or S; X is C1-C4-alkylene, C6-C 12 -Arylene, C7-C 15 -Aralkylene or C7-C 15 -alkarylene, where n is 0, 1 or 2, or X is -O- or -NR7-, where n is 1; R7 is hydrogen or C1-C4-alkyl; R3 is C1-C4-alkylene, C6-C 12 -Arylene, C7-C 15 -Aralkylene or C7-C 15 -Alkarren; m is 0, 1 or 2, provided that when X is -O- or -NR7-, then m is 1 or 2; R4 is C1-C4-alkylene; t is an integer between 1 and 2; W is oxygen or sulfur.

[0022] Component a) is a radical generator. Preferably, component a) is an N-oxyamine-containing compound comprising a structural unit of formula (V): [ka] (In the formula, R8 is alkoxy, aryloxy, cycloalkoxy, aralkoxy, or acyloxy; R9 is optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl, preferably a C1-C4-alkyl group, most preferably methyl or ethyl; R 10 is hydrogen or optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl, or two R 10 The groups form a ring structure together with the atoms to which they are attached (preferably 5 or 4 ring carbon atoms and 1 ring nitrogen atom) and are optionally substituted with ester, ether, amino, amide, carboxy, or urethane groups.

[0023] Preferably, component a) is a compound containing an N-alkoxyamine group.

[0024] Component a) is more preferably 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylamino-piperidine, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-butyl-amino]-6-(2-hydroxyethyl-amino-S-triazine; bis(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl) adipate; 2,4-bis[(1-cyclohexyloxy 1-(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-tetramethylpiperidine) Methylpiperidin-4-yl)-sebacate;Bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl)-adipate;2,4-Bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-S-triazine;4-Piperidinol-2,2,6,6-tetramethyl-1-(undecyloxy)-4,4'-carbonate;2,4-Bis[(1-cyclohexyloxy-2,2 reaction products of 4,4'-hexamethylene-bis-(amino-2,2,6,6-tetramethylpiperidine) with 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)butylamino]-S-triazine with N,N'-bis-(3-aminopropyl-ethylenediamine); oligomeric compounds which are condensation products of 4,4'-hexamethylene-bis-(amino-2,2,6,6-tetramethylpiperidine) with 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)butylamino]-S-triazine, the terminal positions of which are capped with 2-chloro-4,6-bis(dibutylamino)-S-triazine;Aliphatic hydroxylamines, such as distearylhydroxylamine; and compounds of the formula: (n is 1 to 15). [ka] or JPEG2025533889000006.jpg74153

[0025] Some of the above compounds are commercially available and are available under the trade names: FLAMESTAB NOR 116®, TINUVIN NOR 371®, IRGATEC CR76® from BASF, Hostavin NOW® from Clariant, or ADK Stab LA 81® from Adeka.

[0026] Component a) is particularly preferably a reaction product of a fatty acid ester of 4-hydroxy-2,2,6,6-tetramethylpiperidine (e.g., 2,2,6,6-tetramethylpiperidin-4-yl hexadecanoate and / or 2,2,6,6-tetramethylpiperidin-4-yl octadecanoate) with polyethylene oxide, which reaction product is a compound of the formula: [ka] (In the formula, C 15 H 31 / C 17 H 35 The main component is NO-bridged alkyl radicals with an average molecular weight of approximately 2000.

[0027] The thermal stability of the compounds of formulae (II), (III) and (IV) which are component b) is preferably 270°C to 335°C, more preferably 280°C to 330°C, most preferably 290°C to 325°C, and the melting point is preferably 150°C to 260°C, more preferably 160°C to 240°C, most preferably 170°C to 230°C. When in contact with a flame or fire, the compounds of formulae (II), (III) and (IV) exhibit hybrid flame retardant activity simultaneously in the gas phase and the condensed phase.

[0028] Unless otherwise specified, the term "thermal stability" as used herein with respect to a compound is characterized by a "decomposition temperature", which is understood to be the threshold temperature at which substantial thermal decomposition of the compound begins (5% weight loss under an inert atmosphere).

[0029] Unless otherwise indicated, the term "alkyl," as used herein, includes, but is not limited to, saturated monovalent hydrocarbon radicals having straight or branched moieties, such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.

[0030] Unless otherwise indicated, the term "alkylene," as used herein, includes, but is not limited to, saturated divalent hydrocarbon radicals having straight or branched moieties such as methylene, ethylene, propylene, isopropylene, butylene, or isobutylene.

[0031] Unless otherwise specified, the term "aryl" as used herein includes, but is not limited to, aromatic radicals derived from an aromatic hydrocarbon by removing one hydrogen, such as phenyl or naphthyl.

[0032] Unless otherwise specified, the term "arylene," as used herein, includes, but is not limited to, an aromatic divalent radical derived from an aromatic hydrocarbon by removing two hydrogens, such as phenylene.

[0033] Unless otherwise indicated, the term "aralkyl" as used herein means It refers to "aryl-alkyl-" groups such as, but not limited to, benzyl (C6H5-CH2-) or methylbenzyl (CH3-C6H4-CH2-).

[0034] Unless otherwise indicated, the term "alkaryl" as used herein refers to an "alkyl-aryl-" group such as, but not limited to, methylphenyl (CH3-C6H4-), dimethylphenyl ((CH3)2-C6H3-), or isopropylphenyl ((CH3)2C-C6H4-).

[0035] Component b) is a compound of formula (II), (III) or (IV), preferably wherein n and m are 0, Y is oxygen or sulfur, R4 is methylene or ethylene, t is 1, and W is oxygen.

[0036] Component b) is a compound of formula (II), (III) or (IV), preferably wherein R1 and R2 are each independently hydrogen or C1-C6-alkyl.

[0037] Component b) is a compound of formula (II), (III) or (IV), preferably wherein X is methylene, n is 1, m is 0, Y is oxygen, R4 is methylene or ethylene, t is 1, and W is oxygen.

[0038] Component b), a compound of formula (II), (III) or (IV), is preferably such that Y is oxygen or sulfur, X is -O-oxygen or -NH-, n is 1, R3 is methylene or ethylene, m is 2, R4 is methylene, t is 1, and W is oxygen.

[0039] More preferably, component b) is a compound of formula (IV). Most preferably, component b) is a compound of formula (VI) (DOPO-PEPA) or (VII) (DOPS-PEPA). [ka]

[0040] The compounds of formulae (II), (III) and (IV) are known compounds and can be prepared by known methods of preparation.

[0041] In the flame-retardant mixture of the present invention, component a) is present in an amount of 50 to 99.5 wt. % and component b) is present in an amount of 0.5 to 50 wt. Preferably, component a) is present in an amount of 60 to 70 wt. % and component b) is present in an amount of 30 to 40 wt. These percentages are based on the total amount of the flame-retardant mixture.

[0042] Surprisingly, the flame retardant compositions comprising components a) and b) exhibit excellent flame retardancy in various plastic products (preferably in polymers derived from ethylenically unsaturated monomers) together with excellent transparency, UV resistance, flowability, extrudability and moldability.

[0043] The present invention relates to a flame retardant polymer composition comprising: a) an N-oxyamine group-containing compound as defined above; b) a compound of formula (II), (III) or (IV) as defined above, and c) Polymers.

[0044] The amount of flame retardant a) in the flame retardant polymer composition of the present invention can vary within a wide range. Typically, the amount of component a) is 0.2 to 10% by weight, preferably 0.5 to 5% by weight, most preferably 0.2 to 2% by weight, based on the total weight of the polymer composition.

[0045] The amount of flame retardant b) in the flame retardant polymer composition of the present invention can vary within a wide range. Typically, the amount of component b) is 0.1 to 20% by weight, preferably 0.1 to 5% by weight, more preferably 0.2 to 2% by weight, and most preferably 0.5 to 2% by weight, based on the total weight of the polymer composition.

[0046] The amount of polymer c) in the flame retardant polymer composition of the present invention can vary within a wide range. Typically, the amount of component c) is 70 to 99.7% by weight, preferably 80 to 99.7% by weight, more preferably 90 to 99.3% by weight, and most preferably 94 to 99.2% by weight, based on the total weight of the polymer composition.

[0047] Component c) of the flame-retardant polymer composition of the present invention can be any natural or synthetic polymer, including those modified by chemical treatment. Polymer blends can also be used. Suitable polymers a) include thermoplastic polymers, thermoplastic elastomeric polymers, elastomers, or thermosetting polymers.

[0048] Preferably, a thermoplastic polymer is used as component c), and preferred thermoplastic polymers are selected from the group consisting of polyamides, polycarbonates, polyesters, polyolefins, polystyrene, polyvinyl chloride, polyvinyl esters, polyvinyl alcohol, polybutadiene copolymers such as ABS, and polyurethanes.

[0049] Furthermore, thermosetting polymers can be used, which are preferably selected from the group consisting of epoxy resins, phenolic resins and melamine resins.

[0050] Additionally, mixtures of two or more polymers, especially thermoplastic and / or thermosetting resins, may also be used.

[0051] Preferably, component c) in the polymer composition of the present invention is a polymer obtained by polymerization of one or more ethylenically unsaturated monomers.

[0052] Polymer c) can be any of a wide range of polymer types, such as polyolefins, polystyrene, and PVC. Polymer c) is preferably selected from the group of polyolefins, thermoplastic elastomeric polyolefins (TPO), styrene-based polymers and copolymers, polybutadiene copolymers such as ABS, and polymers containing heteroatom double bonds or aromatic rings (e.g., polyimides or polyamides, e.g., aromatic polyamides).

[0053] Examples of these preferred polymers c) are: 1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, and polymers of cycloolefins such as cyclopentene and norbornene, polyethylene (optionally crosslinked), such as high density polyethylene (HDPE), high density, high molecular weight polyethylene (HDPE-HMW), high density, ultra high molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).

[0054] Polyolefins (i.e. the polymers of monoolefins exemplified in the previous paragraph, preferably polyethylene and polypropylene) can be prepared by different methods, in particular by the following methods: a) radical polymerization (usually under high pressure and temperature), or b) Catalytic polymerizations typically using catalysts containing one or more metals from Groups I, Yb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls, and / or aryls, which may be either t- or α-coordinated. These metal complexes may be in the free form or immobilized on a support, typically activated magnesium chloride, titanium(III) chloride, alumina, or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalyst may be used alone in the polymerization, or an activator may be used, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide, or metal alkyl oxane, where the metal is an element from Groups Ia, IIa, and / or IIIa of the periodic table. The activator may be further modified with ester, ether, amine, or silyl ether groups, as appropriate. These catalyst systems are commonly referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single-site catalysts (SSC).

[0055] 2. Mixtures of the polymers mentioned in 1 above, such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (e.g. PP / HDPE, PP / LDPE) and mixtures of different types of polyethylene (e.g. LDPE / HDPE).

[0056] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, such as ethylene-propylene copolymers, linear low-density polyethylene (LLDPE) and their mixtures with low-density polyethylene (LDPE), propylene / but-1-ene copolymers, propylene / isobutylene copolymers, ethylene / but-1-ene copolymers, ethylene / hexene copolymers, ethylene / methylpentene copolymers, ethylene / heptene copolymers, ethylene / octene copolymers, propylene / butadiene copolymers, isobutylene / isoprene copolymers, ethylene / alkyl acrylate copolymers, ethylene / alkyl methacrylate copolymers, ethylene / vinyl acetate copolymers, and Copolymers thereof with carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), as well as terpolymers of ethylene with propylene and dienes (for example hexadiene, dicyclopentadiene or ethylidene norbornene); mixtures of such copolymers with each other and with the polymers mentioned in 1 above, for example mixtures of ethylene, polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymer (EVA), LDPE / ethylene-acrylic acid copolymer (EAA), LLDPE / EVA, LLDPE / EAA, and alternating or randomly bonded polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

[0057] 4. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene). 5. Copolymers of styrene or α-methylstyrene with dienes or acrylic derivatives, such as styrene / butadiene, styrene / acrylonitrile, styrene / alkyl methacrylate, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene / maleic anhydride, styrene / acrylonitrile / methyl acrylate; mixtures of impact-resistant styrene copolymers with other polymers, such as polyacrylates, diene polymers or ethylene / propylene / diene terpolymers; and block copolymers of styrene, such as styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

[0058] 6. Graft copolymers of styrene or α-methylstyrene, such as 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 alkyl acrylate or methacrylate on polybutadiene; styrene and acrylonitrile on ethylene / propylene / diene terpolymers; styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile on acrylate / butadiene copolymers, and mixtures thereof with the copolymers described under 6., such as the copolymer mixtures known as ABS (acrylonitrile / butadiene / styrene), MBS, ASA or AES polymers.

[0059] 7. Halogen-containing polymers, such as polychloroprene, chlorinated rubber, chlorinated and brominated isobutylene-isoprene copolymers (halobutyl rubbers), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, polymers of halogen-containing vinyl compounds, such as polyvinyl chloride (PVC), polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, and copolymers thereof, such as vinyl chloride / vinylidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymers.

[0060] Particularly preferred are polypropylene, polyethylene, thermoplastic elastomeric olefin (TPO), ABS, and high impact polystyrene; most preferred are polypropylene, polyethylene, and thermoplastic elastomeric olefin (TPO).

[0061] The flame retardant polymer composition of the present invention may further comprise an additive as component d).

[0062] The amount of component d) can vary within a wide range. Typical amounts of component e) are 0 to 60 wt. %, preferably 1 to 50 wt. %, more preferably 5 to 30 wt. %, based on the total weight of the flame retardant polymer composition.

[0063] Examples of additives d) include antioxidants, blowing agents, further flame retardants, light stabilizers, heat stabilizers, impact modifiers, processing aids, lubricants, processing aids, nucleating and clarifying agents, antistatic agents, lubricants such as calcium stearate or zinc stearate, viscosity and impact modifiers, compatibilizers and dispersants, dyes or pigments, anti-dripping agents, additives for laser marking, hydrolysis stabilizers, chain extenders, softeners and / or plasticizers, fillers and / or reinforcing agents.

[0064] The flame retardant polymer composition of the present invention preferably comprises as component d) a wax, more preferably a polyethylene wax, even more preferably a functionalized polyethylene wax, such as Licocene PE MA 4351 available from Clariant, which is a highly maleic acid grafted metallocene polyethylene wax and is preferably used in combination with polyethylene as a compatibilizer.

[0065] The flame retardant polymer composition of the present invention preferably comprises polyethylene and a functionalized polyethylene wax.

[0066] The flame retardant polymer composition of the present invention preferably contains additional fillers, which are preferably selected from the group consisting of metal hydroxides and / or metal oxides, preferably alkaline earth metals (e.g. magnesium hydroxide, aluminum hydroxide, silicates), preferably layered silicates (bentonite, kaolinite, muscovite, pyrophyllite, marcasite and talc) or other minerals (silica such as wollastonite, quartz, mica, feldspar and titanium dioxide), alkaline earth metal silicates and alkali metal silicates, carbonates, preferably calcium carbonate and talc, clay, mica, silica, calcium sulfate, barium sulfate, pyrite, glass beads, glass particles, wood flour, cellulose powder, carbon black, graphite and chalk.

[0067] The flame-retardant polymer composition of the present invention preferably contains a reinforcing agent, more preferably a reinforcing fiber. The reinforcing agent is preferably selected from the group consisting of glass fiber, carbon fiber, aramid fiber, and potassium titanate whisker, and is preferably glass fiber. The reinforcing agent can be incorporated into the molding composition in either a continuous strand (roving) or chopped form (short glass fiber). To improve compatibility with the polymer matrix, the reinforcing fiber used can be provided with a sizing agent and an adhesion promoter. The diameter of commonly used glass fiber is usually in the range of 6 to 20 microns.

[0068] These additives d) can impart other desirable properties to the polymer compositions of the invention, in particular improving the mechanical stability by means of reinforcement with fibres, preferably glass fibres.

[0069] The flame retardant polymer composition of the present invention is preferably prepared by providing components a), b), c) and optionally d), for example by mixing or compounding into a masterbatch, and compounding components a), b) and optionally d) into a polymer or polymer mixture.

[0070] Components a), b), and optional component d) can be incorporated into polymer c) by premixing all components as powders and / or granules in a mixer and then homogenizing them into the polymer melt in a compounding device (e.g., a twin-screw extruder). The melt is usually drawn off as a strand, cooled, and granulated. Components a), b), and optional component d) can also be added separately to the compounding device directly via a metering system. It is also possible to mix components a), b), and optional component d) with finished polymer granules or powder and process the mixture directly into molded articles, for example, in an injection molding machine.

[0071] The preparation of the flame-retardant polymer composition is characterized by blending and homogenizing components a), b), and optional component d) (with optional other additives) into polymer pellets in a compounding apparatus at elevated temperatures. The resulting homogenized polymer melt is then formed into strands, cooled, and divided. The resulting granules are dried, for example, at 90°C in a convection oven.

[0072] It is also possible to mix components a) and b) and optional component d) with pre-prepared polymer pellets / powder (component c) and process the mixture directly, for example in a blown film production line or a fiber spinning line.

[0073] Preferably, the compounding device is selected from the group of single screw extruders, multi-zone screw or twin screw extruders.

[0074] The flame-retardant polymer compositions according to the invention are suitable for the production of moldings such as films, sheets, threads and fibers, for example by injection molding, extrusion, blow molding or press molding.

[0075] The present invention also relates to a molded article made from a composition comprising components a), b), c), and optional component d). In one embodiment, the polymer composition is processed into a transparent sheet, e.g., having a thickness of 50 to 500 μm.

[0076] The molded articles are preferably films, threads and fibers and comprise as component c) polyolefins such as polyethylene, polypropylene, ethylene-vinyl acetate, etc.

[0077] The polymer composition according to the present invention is particularly suitable for producing blown films.Blown films are characterized by very high film adhesion and particularly high resistance to puncture and tearing.Blown films can be sheets and films consisting of only a single layer (so-called monolayer blown films) or sheets and films made from multiple layers (so-called coextruded blown films).In the case of coextruded blown films, the advantageous properties of different materials can be combined in one sheet.

[0078] The present invention further relates to the use of a composition comprising components a) and b) as a flame retardant.

[0079] Finally, the present invention relates to the use of a polymer composition comprising components a), b), c) and optional component d) for the production of polymer moldings, preferably polyolefin moldings, and most preferably polyolefin films or polyolefin fibers. [Example]

[0080] The following examples illustrate the invention. Materials used in the examples Component a) Hostavin® NOW: 2,2,6,6-tetramethylpiperidin-4-yl-hexadecanoate and 2,2,6,6-tetramethylpiperidin-4-yl-octadecanoate, reaction products with oxidized polyethylene wax, Clariant AG, Frankfurt, Germany (hereinafter referred to as HALS-NO wax). Flamestab® NOR116: 1,3-propanediamine, N,N″-1,2 ethanediylbis-, reaction product with cyclohexane and N-butyl-2,2,6,6-tetramethyl-4-piperidinamine-2,4,6-trichloro-1,3,5-triazine peroxide, reaction product, CAS No. 191680-81-6, BASF AG, Ludwigshafen, Germany

[0081] component b) DOPO-PEPA with a phosphorus content of about 15.7% by weight; a clear, high-flow polymer with a glass transition temperature of about 105° C., supplied by FRX Polymers, Chelmsford, MA (USA).

[0082] Ingredient c) Sabic LDPE 2102 Z 500, low-density polyethylene, MFR 1.7-2.2g / 10min, Sabic, Gereen, The Netherlands (hereafter referred to as LDPE).

[0083] Materials used in the comparative examples Exolit® OP935 (hereinafter referred to as Depal d50 2-3 μm): aluminum diethylphosphinate, particle size d95<10 μm, particle size d50-2-3 μm, Clariant GmbH, Frankfurt, Germany Aflammit® PCO800: melamine salt of phosphinic acid, Thor GmbH, Speyer, Germany Others: Nofia® HM-1100, Aflammit® PCO 900

[0084] Sample Production The polymer (component c) and additives (components a and b) were mixed in an Arenz KL 1 single screw extruder at a temperature of 180-210°C.

[0085] Polyethylene film: Examples (Ex. 1 to Ex. 6) and comparative examples (CE1 to CE6) Blown films with thicknesses of 50 to 200 μm were produced using a Collin BL 180 / 400 blown film production apparatus at 160 to 200°C.

[0086] The flame retardancy of sheets and films was measured in accordance with DIN 4102B2 as follows: A 190 x 90 mm test piece was clamped vertically and its bottom end was exposed to a 20 mm high flame from a gas burner for 15 seconds. The test was considered passed if the tip of the flame did not reach a reference mark on the test piece 150 mm high from the bottom end within 20 seconds.

[0087] The films were ignited in the longitudinal direction and transverse to the film extrusion direction. The transparency of the films was measured under neutral gray light using a Dr. Lange LT 12 transmittance measuring device (Neuss, Germany). Calibration was performed at 100% without sample and a gray filter was used. Table 1: 200-µm LDPE films containing aminoethers and DOPO-PEPA

[0088] [Table 1]

[0089] Only the combination of DOPO-PEPA and aminoether flame retardants was able to pass the DIN 4102 B2 flammability test in both the extrusion direction and the transverse direction of the film. Furthermore, the film according to the present invention showed good transparency and no color change. No odor was observed during the processing of the film. Table 2: 50, 100, and 200-μm LDPE films containing aminoethers and DOPO-PEPA

[0090] [Table 2] CE7 = Comparative example according to WO-A-2015 / 010775 CE8 = Comparative example according to WO-A-2010 / 026230

[0091] Table 2 compares the combination of DOPO-PEPA and aminoethers of the present invention with a combination of phosphinate and non-polymerized phosphonate and aminoether. Transparent sheets and films are only obtained when the phosphonate polymers of the present invention are combined with aminoethers. Table 3 shows that transparency can be further improved by adding a compatibilizer to the film. The use of HALS-NO wax further prevents discoloration and odor during processing. Table 3: Permeability of 200 μm LDPE film

[0092] [Table 3]

[0093] The DOPO-PEPA combination exhibits significantly lower haze values ​​compared to the comparative examples. The sheets and films according to the invention exhibit improved mechanical properties (tensile test). The transparency of the sheets and films is significantly higher compared to the standard materials.

[0094] Polypropylene Fiber: Example 7 Fiber-grade polypropylene (containing 0.05 wt.% calcium stearate, 0.05 wt.% tris(2,4-di-tert-butylphenyl)phosphite, and 0.05 wt.% N,N-dihydroxylamine produced by direct oxidation of N,N-di(hydrogenated tallow)amine) was dry-blended with the experimental additives DOPO-PEPA and Hostavin® NOW, then melt-mixed at 234°C (4500°F) and pelletized. The fully compounded resin pellets were formed into fibers at 246°C (475°F) using a Hills Laboratory Model Fiber Extruder. The 41-filament spun tow was stretched at a ratio of 1:3.2 to a final denier of 615 / 41.

[0095] Socks were knitted from the stabilized polypropylene fibers using a Lawson-Hemphill analytical knitting machine and tested using the NFPA 701 vertical burn test procedure. Flame retardant effectiveness is demonstrated by a short afterflame time compared to a blank sample containing no flame retardant.

[0096] Molded Polypropylene: Example 8 Molding grade polypropylene was dry compounded with the test additives DOPO-PEPA and Flamestat® NOR 116, then melt compounded and pelletized. The fully compounded resin pellets were compression molded into test specimens using a Wabash compression molder.

[0097] The test plaques were tested under UL-94 vertical burn test conditions. After the test flame was removed, the average time in seconds for the test samples to extinguish was recorded. The effectiveness of the flame retardants was demonstrated by shorter burn times compared to blank samples containing no flame retardant. All samples containing NOR-based hindered amines self-extinguished after initial ignition, demonstrating that the NOR compounds exhibit a pronounced flame retardant effect essentially equivalent to that imparted by halogenated or phosphate-based flame retardants. The blank sample burned completely after initial ignition.

[0098] EVA blown film: Example 9 Film-grade ethylene / vinyl acetate (EVA) copolymer (vinyl acetate content 20% by weight or less) was dry-blended with the experimental additives DOPO-PEPA and Flamestab® NOR 116, then melt-mixed and pelletized. The pelletized fully compounded resin was blown into film at 205°C using an MPM Superior Blown-film extruder.

[0099] The films were flame-retardant tested under NFPA 701 test conditions. Films containing the compositions of the present invention exhibited flame retardancy. Film-grade low-density polyethylene (LDPE) (containing a portion of linear low-density polyethylene (LLDPE) and / or ethylene / vinyl acetate (EVA)) was dry-blended with the test additives and blown into films, similar to the EVA copolymer resins described above. The films were flame-retardant tested under NFPA 701 test conditions, and those containing the compositions of the present invention exhibited high flame retardancy.

[0100] Polyethylene fiber: Example 10 Fiber-grade linear low-density polyethylene (LLDPE) (containing 10.4 wt% DOPO-PEPA and 1.60% Hostavin® NOW) was dry-blended with the test additives, then melt-mixed at 240°C and pelletized. The pelletized compounded resin was dry-blended with 10.0 wt% Licocene® PE MA 4351 and melt-spun into fiber at 195°C using a custom-built pilot melt-spinning line. The spun monofilament was stretched at a 1:4 ratio to a final fiber size of 173 tex.

Claims

1. a) a compound containing an N-oxyamine group, and b) A flame retardant composition comprising a compound of the following formula (II), (III) or (IV): 【Chemistry 2】 (In the formula, R1 and R2 are independently hydrogen, C 1 -C 6 -Alkyl, -P(O)(OR 5 ) 2 , -P(O)OR 5 R 6 , -P(O)(R 5 ) 2 where R 5 and R 6 are independent of each other, C 1 -C 4 -Alkyl, C 6 -C 12 -aryl, C 7 -C 15 -Aralkyl or C 7 -C 15 -alkaryl or R 1 and R 2 together form an unsaturated cyclic ring optionally substituted by alkyl groups; k is an integer from 1 to 2; Y is O or S; X is C 1 -C 4 -Alkylene, C 6 -C 12 -Arylene, C 7 -C 15 -Aralkylene or C 7 -C 15 -alkarylene, where n is 0, 1, or 2, or X is -O- or -NR 7 - and n is 1; R 7 is hydrogen or C 1 -C 4 - alkyl; R 3 is C 1 -C 4 -Alkylene, C 6 -C 12 -Arylene, C 7 -C 15 -Aralkylene or C 7 -C 15 -alkarylene; m is 0, 1 or 2, provided that X is -O- or -NR 7 -, m is 1 or 2; R 4 is C 1 -C 4 - alkylene; t is an integer from 1 to 2; W is oxygen or sulfur.

2. 2. The composition of claim 1, wherein component a) is an N-oxyamine-containing compound comprising a structural unit of formula (V): 【Chemistry 3】 (In the formula, R 8 is alkoxy, aryloxy, cycloalkoxy, aralkoxy or acyloxy; R 9 is optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl; R 10 is hydrogen or optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl, or two R 10 The groups, together with the atoms to which they are attached, form a ring structure and are optionally substituted with an ester, ether, amino, amide, carboxy, or urethane group.

3. Component a) is 1-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)-butyl-amino]-6-(2-hydroxyethyl-amino-S-triazine, bis(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-butyl-amino]-6-(2-hydroxyethyl-amino-S-triazine), 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethyl-piperidine, ... 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl-piperidine, 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, 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl- piperidin-4-yl]-N-butylamino}-6-(2-hydroxy-ethylamino)-S-triazine), 4-piperidinol-2,2,6,6-tetramethyl-1-(undecyloxy)-4,4'-carbonate; reaction products of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidin-4-yl)-butylamino]-6-chloro-S-triazine with N,N'-bis-(3-aminopropyl-ethylenediamine);3. The composition of claim 2, wherein the hydroxylamine is selected from the group consisting of an oligomer of the condensation product of 4,4'-hexamethylene-bis-(amino-2,2,6,6-tetramethylpiperidine) end-capped with 2-chloro-4,6-bis(dibutylamino)-s-triazine and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)-butylamino]-s-triazine, an aliphatic hydroxylamine such as distearylhydroxylamine; and a compound of the formula: wherein n is 1 to 15. 【Chemistry 4】 or 【change】

4. 3. The composition of claim 2, wherein component a) is a reaction product of a fatty acid ester of 4-hydroxy-2,2,6,6-tetramethylpiperidine (preferably 2,2,6,6-tetramethylpiperidin-4-yl-hexadecanoate and / or 2,2,6,6-tetramethylpiperidin-4-yl-octadecanoate) with oxidized polyethylene.

5. Component b) is a compound of formula (II), (III) and / or (IV), where n and m are 0, Y is oxygen or sulfur, R 4 5. The composition of claim 1, wherein is methylene or ethylene, t is 1, and W is oxygen.

6. Component b) is a compound of formula (II), (III) and / or (IV), R 1 and R 2 are each independently hydrogen or C 1 -C 6 The composition of any one of claims 1 to 4, wherein -alkyl.

7. Component b) is a compound of formula (II), (III) and / or (IV), where X is methylene, n is 1, m is 0, Y is oxygen, R 4 5. The composition of claim 1, wherein is methylene or ethylene, t is 1, and W is oxygen.

8. Component b) is a compound of formula (II), (III) and / or (IV) where Y is oxygen or sulfur, X is -O-oxygen or -NH-, n is 1, R 3 is methylene or ethylene, m is 2, R 4 5. The composition of claim 1, wherein is methylene, t is 1, and W is oxygen.

9. 9. The composition of any one of claims 1 to 8, wherein component b) is a compound of formula (IV).

10. 10. The composition of claim 1, wherein component b) is a compound of formula (VI) or (VII): 【Chemistry 6】

11. 11. The composition of claim 1, wherein component a) is present in the flame-retardant mixture in an amount of 50 to 99.5 wt. % and component b) is present in an amount of 0.5 to 50 wt. %, wherein these percentages are based on the total amount of the flame-retardant mixture.

12. 12. A flame retardant polymer composition comprising components a) and b) of any one of claims 1 to 11 and a polymer c).

13. 13. The flame retardant polymer composition of claim 12, wherein the amount of component a) is 0.2 to 10 wt. %, the amount of component b) is 0.1 to 20 wt. %, and the amount of component c) is 70 to 99.7 wt. %, wherein these percentages are based on the total amount of the polymer composition.

14. 14. The flame retardant polymer composition of claim 12 or 13, wherein component c) is a thermoplastic polymer, preferably selected from the group consisting of polyamides, polycarbonates, polyesters, polyolefins, polystyrenes, polyvinyl chlorides, polyvinyl esters, polyvinyl alcohols, polybutadiene copolymers, and polyurethanes.

15. 15. The flame retardant polymer composition of any of claims 12 to 14, wherein component c) is selected from the group of polyolefins, thermoplastic elastomeric polyolefins (TPOs), styrenic polymers and copolymers, polybutadiene copolymers, and polymers containing heteroatom double bonds or aromatic rings.

16. 16. The flame retardant polymer composition according to any of claims 12 to 15, wherein component c) is selected from the group of polymers of monoolefins and diolefins, copolymers of monoolefins and diolefins with each other or with other vinyl monomers, copolymers of polystyrene, styrene or α-methylstyrene with dienes or acrylic derivatives, graft copolymers of styrene or α-methylstyrene, or halogen-containing polymers.

17. The flame retardant polymer composition of any one of claims 12 to 16, further comprising d) an additive.

18. 18. The flame retardant polymer composition of claim 17, wherein said additive d) is a filler and / or a reinforcing agent.

19. 20. The flame retardant polymer composition of claim 17, wherein said additive d) is a functionalized polyethylene wax.

20. 20. The flame retardant polymer composition of claim 19, wherein said polymer c) is polyethylene.

21. A molded article comprising components a), b) and c) of any one of claims 12 to 20.

22. The molded article according to claim 21, which is a transparent sheet having a thickness of 50 to 500 μm.

23. 22. The molded body according to claim 21, which is a film, thread or fiber comprising a polyolefin as component c), preferably comprising polyethylene, polypropylene or ethylene vinyl acetate.

24. 22. The molded article of claim 21, which is a blown film.

25. 12. Use of a composition comprising components a) and b) of any one of claims 1 to 11 as a flame retardant.

26. Use of the flame-retardant polymer composition according to any one of claims 12 to 20 for the production of polyolefin moldings, preferably for the production of polyolefin films or polyolefin fibers.

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