Flame retardant composition, polymer composition containing the 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 a novel flame-retardant composition, which can be used to produce a polymer composition with improved flame retardancy. The present invention also relates to an improved polymer composition, which can be molded into thin products such as polyolefin sheets and films, and polyolefin fibers. [Background technology]

[0002] Polymers such as polyolefins are increasingly being used in applications requiring flame retardancy. 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 to very specific situations.

[0003] Phosphorus-containing flame retardants require large quantities to be used, and their effectiveness is often low in thin products such as fibers, sheets, and films.

[0004] Patent Document 1 (US6,599,963A) describes a polymer substrate containing a flame retardant system comprising a sterically hindered amine and a brominated flame retardant.

[0005] Patent document 2 (WO1999 / 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 amino ether. The document describes polyethylene sheets and films that meet 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 amino ether obtained from a sterically hindered amine and a fine phosphonate salt. While this combination significantly improves flame retardancy, a transparent flame-retardant film could not be obtained.

[0008] Patent document 5 (WO2011 / 117266) describes polymeric materials containing phosphinic acid salts and tetraalkylpiperidine or tetraalkylpiperazine derivatives. Polypropylene achieves fire classification V-2 with the addition of 8% flame retardant. This mixture is unsuitable for sheets, films, and fibers due to its high filler content and the large particle size of the phosphinate 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 either absent or mild when processing plastic materials without flame retardants.

[0009] The problem with incorporating sterically hindered amines, as described in Patent Document 6 (WO1999 / 000450), into sheets, films, or fibers is that odor and discoloration occur during the compounding process. Furthermore, there is a possibility that low molecular weight compounds may leach from the plastic material.

[0010] Various phosphorus-containing compounds have already been investigated for their suitability as flame retardant additives. Polyphosphonates and phosphonate oligomers also exhibit flame retardancy in many plastics. However, even when general melamine-based synergies are added, these polyphosphonates require large amounts to be added to thermoplastic resins (Patent Document 7: US2009 / 0043013A).

[0011] 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or (6H-dibenz[c,e][1,2]oxaphosphorine-6-oxide) (hereinafter also referred to as "DOPO") is an ester of phosphinic acid in which phosphorus and oxygen atoms are incorporated into the basic structure of phenanthrene. DOPO is flame retardant and is a basic compound for a variety of 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 under the decomposition of hydrogen chloride. When DOP-Cl is heated at high temperatures in the presence of water, DOPO is produced quantitatively and in high purity.

[0013] DOPO is a white crystalline solid and 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, numerous DOPO derivatives with high hydrolysis stability and remarkably high melting points have been synthesized, particularly for use in epoxy resins for electrical and electronic applications. DOPO and its derivatives are well-known flame retardants in polymers such as polyester.

[0015] Patent documents 8 (DE 10330774) and 9 (EP 2,284,208) indicate that flame-retardant polyesters with various phosphorus content can be obtained by reacting DOPO with an unsaturated dicarboxylic acid and then copolymerizing it with other phosphorus-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 standalone flame-retardant polyesters in engineering plastics.

[0016] Furthermore, Patent Document 10 (WO2015 / 140105) discloses a hybrid material comprising a covalently bonded DOPO unit and a pentaerythritol phosphate alcohol (hereinafter also referred to as "PEPA") unit. These compounds can be considered as "hybrid flame retardants" based on the combination of DOPO and PEPA parts, and exhibit a combination of properties that are highly desirable 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 mixing), a high melting point of at least about 150°C, which is slightly lower than the melting temperature of most polyesters, thereby enabling more uniform dispersion of the additive in 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

Patent Document 8

Patent Document 9

Patent Document 10

Summary of the Invention

Problems to be Solved by the Invention

[0018] Surprisingly, it has been found that the combination of a selected amino ether and a DOPO-PEPA derivative improves the flame retardant effect in polymers, preferably in polyolefins. With a small addition amount, various flame retardant classifications can be achieved, and the adverse effect on physical properties is small. Therefore, an object of the present invention is to provide a new combination of flame retardant materials and a polymer, preferably a polyolefin, which does not have the existing drawbacks of current amino ether-based flame retardants and has better performance than the known combinations of flame retardants.

[0019] Surprisingly, it has been found that the combination of a selected sterically hindered amino ether-based amine compound (e.g., Hostavin NOW) and a DOPO-PEPA hybrid material can be applied as a very efficient flame retardant for polymers. Instead of DOPO, DOPO containing a 10-hydroxy group (also called DOPO-OH) or its thio analog can also be used as a component of the hybrid material with a PEPA-unit.

[0020] DOPO or DOPO-OH or their thio analogs correspond to the following formula (I): <00者が、ポリマーにおいて、好ましくはポリオレフィンにおいて、難燃性作用が改善されることが見出された。少ない添加量で、様々な難燃性分類を達成することができ、物理的特性への悪影響は小さい。したがって、本発明の目的は、現在のアミノエーテルベースの難燃剤が持つ既存の欠点を有さず、これまでに知られている難燃剤の組み合わせよりも性能が優れている、新しい難燃材料の組み合わせと、それを含むポリマー、好ましくはポリオレフィンを提供することである。

[0019] 驚くべきことに、選択されたアミノエーテル系立体障害アミン化合物(例えばHostavin NOW)およびDOPO-PEPAハイブリッド材料の組み合わせが、ポリマー用の非常に効率的な難燃剤として適用できることが見出された。DOPOの代わりに、10-ヒドロキシ基を含むDOPO(DOPO-OHとも呼ばれる)またはそのチオ類似体も、PEPA-ユニットとのハイブリッド材料の成分として使用することができる。

[0020] DOPOまたはDOPO-OHまたはそれらのチオ類似体は、以下に示す式(I)に相当する:

Chemical Formula

Means for Solving the Problem

[0021] The present invention relates to a flame-retardant composition comprising the following: a) a compound containing an N-oxyamine group, and b) a compound of the following formula (II), (III) or (IV).

Chemical formula

[0022] Component a) is a radical generating agent. Preferably, component a) is an N-oxyamine-containing compound containing the structural unit of formula (V). [ka] (In the formula, R8 is an 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 a hydrogen or optionally substituted alkyl, cycloalkyl, aryl, heteroaryl or acyl, or two R 10 The groups, together with the atoms to which they are bonded (preferably five or four ring carbon atoms and one ring nitrogen atom), form a ring structure and are optionally substituted with ester, ether, amino, amide, carboxyl, 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-octadecylaminopiperidine, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl) sebacate; 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-butyl-amino]-6-(2-hydroxyethyl-amino-S-triazine); bis(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidine-4-yl) adipate; 2,4-bis[(1-cyclohex Siloxy-2,2,6,6-tetramethylpiperidine-4-yl)-butylamino]-6-chloro-S-triazine; 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-tetra Methylpiperidine-4-yl)-sebacate; bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)-adipate; 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl]-N-butylamino}-6-(2-hydroxy-ethylamino)-S-triazine); 4-piperidinol-2,2,6,6-tetramethyl-1-(undecyloxy)-4,4'-carbonate; 2,4-bis[(1-cyclohexyloxy-2,2 [,6,6-tetramethyl-piperidine-4-yl)butylamino]-6-chloro-S-triazine is a reaction product of N,N'-bis-(3-aminopropyl-ethylenediamine); it is an oligomeric compound that is a condensation product of 4,4'-hexamethylene-bis-(amino-2,2,6,6-tetramethylpiperidine) and 2,4-dichloro-6-[(1-cyclohexyloxy-2,2,6,6-tetramethyl-4-yl)butylamino]-S-triazine, in which the terminal position is closed by 2-chloro-4,6-bis(dibutylamino)-S-triazine;Aliphatic hydroxylamines, e.g., distearylhydroxylamine; and compounds of the following formula (where n is 1 to 15): [ka] or JPEG0007884146000005.jpg74153

[0025] Some of the above compounds are commercially available and can be purchased under the following trade names: BASF's FLAMESTAB NOR 116 (registered trademark), TINUVIN NOR 371 (registered trademark), IRGATEC CR76 (registered trademark), Clariant's Hostavin NOW (registered trademark), or Adeka's ADK Stab LA 81 (registered trademark).

[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-tetramethylpiperidine-4-yl-hexadecanoate and / or 2,2,6,6-tetramethylpiperidine-4-yl-octadecanoate) and polyethylene oxide. The reaction product is a compound of the following formula. [ka] (In the formula, C 15 H 31 / C 17 H 35 (This is the main component, and the average molecular weight of the NO-crosslinked alkyl radicals is approximately 2000.)

[0027] The thermal stability of the compounds of formulas (II), (III), and (IV), which are component b), is preferably 270°C to 335°C, more preferably 280°C to 330°C, and 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, and most preferably 170°C to 230°C. When in contact with a flame or fire, the compounds of formulas (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 in this specification with respect to compounds is understood to be characterized by “decomposition temperature,” which is the threshold temperature at which substantial thermal decomposition of the compound (a 5% weight loss under an inert atmosphere) begins.

[0029] Unless otherwise specified, the term “alkyl” as used herein includes, but is not limited to, saturated monovalent hydrocarbon radicals having a linear or branched portion, such as methyl, ethyl, propyl, isopropyl, butyl, and isobutyl.

[0030] Unless otherwise specified, the term "alkylene" as used herein includes, but is not limited to, saturated divalent hydrocarbon radicals having a straight or branched portion, 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 aromatic hydrocarbons by removing one hydrogen atom, such as phenyl or naphthyl.

[0032] Unless otherwise specified, the term "arylene" as used herein includes, but is not limited to, aromatic divalent radicals derived from aromatic hydrocarbons by removing two hydrogen atoms, such as phenylene.

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

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

[0035] The compound of formula (II), (III), or (IV), which is component b), is preferably such that n and m are 0, Y is oxygen or sulfur, R4 is methylene or ethylene, t is 1, and W is oxygen.

[0036] The compound of formula (II), (III), or (IV), which is component b), is preferably such that R1 and R2 are each independently hydrogen or a C1-C6-alkyl group.

[0037] The compound of formula (II), (III), or (IV), which is component b), is preferably such that 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] The compound of formula (II), (III), or (IV), which is component b), 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 the following formulas: (VI) (DOPO-PEPA) or (VII) (DOPS-PEPA). [ka]

[0040] The compounds of formulas (II), (III), and (IV) are known compounds and can be produced by known manufacturing methods.

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

[0042] Surprisingly, the flame-retardant composition containing components a) and b) exhibits excellent flame retardancy, along with excellent transparency, UV resistance, flowability, extrudeability, and moldability, in a variety of plastic products (preferably polymers derived from ethylenically unsaturated monomers).

[0043] This invention relates to a flame-retardant polymer composition comprising the following: a) N-oxyamine group-containing compounds as defined above, b) Compounds of formula (II), (III), or (IV) as defined above, and c) Polymer.

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

[0045] The amount of flame retardant b) in the flame-retardant polymer composition of the present invention can be varied over 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 amount of the polymer composition.

[0046] The amount of polymer c) in the flame-retardant polymer composition of the present invention can be varied over 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 amount of the polymer composition.

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

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

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

[0050] Furthermore, mixtures of two or more polymers, particularly thermoplastic resins and / or thermosetting resins, can 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) may be any of the broad range of polymer types, including polyolefins, polystyrene, and PVC. Polymer c) is preferably selected from the group consisting of polyolefins, thermoplastic elastomer 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 as follows: 1. Polymers of monoolefins and diolefins, such as polypropylene, polyisobutylene, polybuto-1-ene, poly-4-methylpento-1-ene, polyisoprene or polybuta-diene, 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), and branched low-density polyethylene (BLDPE).

[0054] Polyolefins (i.e., polymers of monoolefins as exemplified in the previous paragraph, preferably polyethylene and polypropylene) can be produced by different methods, particularly the following methods: a) Radical polymerization (usually under high pressure and high temperature), or b) Catalytic polymerization using a catalyst typically comprising one or more metals from groups IYb, Vb, VIb, or VIII of the periodic table. These metals typically have one or more ligands and are typically oxides, halides, alkoxides, esters, ethers, amines, alkyls, alkenyls, and / or aryls, which may be 1t- or α-coordinated. These metal complexes may be in free form or immobilized on a support, typically on 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 polymerization, or it may be used with an activator, typically a metal alkyl, metal hydride, metal alkyl halide, metal alkyl oxide, or metal alkyloxane, wherein the metal is an element from groups Ia, IIa, and / or IIIa of the periodic table. The activator may be further modified as appropriate with an ester, ether, amine, or silyl ether group. These catalytic 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 described in item 1 above, for example, a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (e.g., PP / HDPE, PP / LDPE), and a mixture 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 mixtures thereof with low-density polyethylene (LDPE), propylene / buto-1-ene copolymers, propylene / isobutylene copolymers, ethylene / buto-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 of carbon monoxide having carbon monoxide or ethylene / acrylic acid copolymers and their salts (ionomers), and terpolymers of ethylene with propylene and dienes (e.g., hexadiene, dicyclopentadiene or ethylidene norbornene); mixtures of such copolymers with each other and with the polymers described in 1 above, e.g., mixtures of ethylene, polypropylene / ethylene-propylene copolymer, 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 of them with other polymers, e.g., polyamides.

[0057] 4. Polystyrene, poly(p-methylstyrene), poly(α-methylstyrene). 5. Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives, e.g., 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, e.g., polyacrylate, mixtures with diene polymers or ethylene / propylene / diene polymers; and block copolymers of styrene, e.g., styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene.

[0058] 6. Graft copolymers of styrene or α-methylstyrene, e.g., 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 polymer; styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate; styrene and acrylonitrile on acrylate / butadiene copolymer, and mixtures thereof with the copolymers described in 6., e.g., copolymer mixtures known as ABS (acrylonitrile / butadiene / styrene), MBS, ASA, or AES polymers.

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

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

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

[0062] The amount of component d) can vary widely. A typical amount of component e) is 0 to 60% by weight, preferably 1 to 50% by weight, and more preferably 5 to 30% by weight, based on the total amount of the flame-retardant polymer composition.

[0063] Examples of additives d) include antioxidants, foaming agents, further flame retardants, light stabilizers, heat stabilizers, impact modifiers, processing aids, lubricants, processing aids, nucleating agents and clearing agents, antistatic agents, lubricants such as calcium stearate and zinc stearate, viscosity and impact modifiers, compatibilizers and dispersants, dyes or pigments, anti-dropping agents, laser marking additives, 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, and even more preferably a functionalized polyethylene wax. An example of a functionalized polyethylene wax is 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 functionalized polyethylene wax.

[0066] The flame-retardant polymer composition of the present invention preferably contains additional fillers. These 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 powder, cellulose powder, carbon black, graphite, and chalk.

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

[0068] These additives d) can impart other desired properties to the polymer composition of the present invention. In particular, mechanical stability can be improved by reinforcement with fibers (preferably glass fibers).

[0069] The flame-retardant polymer composition of the present invention is preferably prepared by the steps of preparing components a), b), c) and optionally d), for example, by mixing or compounding them 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 pre-mixing all components, which are powders and / or granules, in a mixer, and then homogenizing them in a polymer molten material using a compounding device (e.g., a twin-screw extruder). The molten material is usually drawn out as strands, cooled, and granulated. Components a), b), and optional component d) can also be fed separately into the compounding device directly via a weighing system. Alternatively, components a), b), and optional component d) can be mixed with the finished polymer granules or powder, and the mixture can be directly processed into molded articles, for example, using an injection molding machine.

[0071] The production of the flame-retardant polymer composition is characterized by compounding components a), b) and optional component d) into polymer pellets (optionally together with other additives) in a compounding apparatus at high temperature and homogenizing them. 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] Similarly, components a) and b) and optional component d) can be mixed with the prepared polymer pellets / powder (component c), and the mixture can be processed directly, for example, in a blow film production line or a fiber spinning line.

[0073] Preferably, the compounding apparatus is selected from the group consisting of a single-screw extruder, a multi-zone screw extruder, or a twin-screw extruder.

[0074] The flame-retardant polymer composition according to the present invention is suitable for the manufacture of molded articles such as films, sheets, threads, and fibers by methods such as injection molding, extrusion molding, blow molding, or press molding.

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

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

[0077] The polymer composition according to the present invention is particularly suitable for the manufacture of blown films. The blown films are characterized by very high film adhesion, and especially high puncture resistance and tear resistance. The blown films may be sheets and films consisting of only a single layer (so-called single-layer blown films), or sheets and films manufactured from multiple layers (so-called co-extruded blown films). In the case of co-extruded blown films, the advantageous properties of different materials can be combined into a single 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 an optional component d) for the production of polymer molding materials, preferably polyolefin molding materials, and most preferably polyolefin films or polyolefin fibers. [Examples]

[0080] The following examples illustrate the present invention. Materials used in the examples Component a) Hostavin(registered trademark) NOW: Reaction product of 2,2,6,6-tetramethylpiperidine-4-yl-hexadecanoate and 2,2,6,6-tetramethylpiperidine-4-yl-octadecanoate with polyethylene oxide wax, Clariant GmbH, Frankfurt, Germany (hereinafter referred to as HALS-NO wax). Flamestab (registered trademark) NOR116: Reaction product of 1,3-propanediamine, N,N''-1,2-ethanediylbis-, cyclohexane, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine-2,4,6-trichloro-1,3,5-triazine peroxide, CAS No. 191680-81-6, BASF (Ludwigschafen, Germany)

[0081] component b) DOPO-PEPA with approximately 15.7% by weight phosphorus content; a transparent, highly fluid polymer with a glass transition temperature of approximately 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, Netherlands (hereinafter referred to as LDPE)

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

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

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

[0086] The flame retardancy of the sheets and films was measured in accordance with DIN4102B2 as follows: A 190 × 90 mm sample was used, clamped vertically, and its lower end was exposed to a gas burner flame at a height of 20 mm for 15 seconds. The test was considered passed (Yes) if the tip of the flame did not reach the reference mark on the sample, which was 150 mm above the lower end of the sample, for 20 seconds.

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

[0088] [Table 1]

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

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

[0091] Table 2 compares the DOPO-PEPA and amino ether combination of the present invention with the combination of phosphinate and non-polymerized phosphonate and amino ether. Transparent sheets and films can only be obtained when the phosphonate polymer and amino ether of the present invention are combined. Table 3 shows that transparency can be further improved by adding a compatibilizer to the film. Discoloration and odor during processing can be further prevented by using HALS-NO wax. 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 example. The sheets and films according to the present invention exhibit improved mechanical properties (tensile test). The transparency of the sheets and films is significantly higher than that of the standard material.

[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(hydride tallow)amine) was dry-formed with the test additives DOPO-PEPA and Hostavin® NOW, and then melt-kneaded at 234°C (4500P) to form pellets. The fully formed resin pellets were formed into fibers at 246°C (475°P) using a Hills laboratory model fiber extruder. The spun tow of 41 filaments was stretched in a ratio of 1:3.2, resulting in a final denier of 615 / 41.

[0095] Socks were knitted from stabilized polypropylene fibers using a Lawson-Hemphill analytical knitting machine and tested according to the NFPA 701 vertical combustion test procedure. The effectiveness of the flame retardancy is demonstrated by a shorter afterflame time compared to a blank sample without flame retardant.

[0096] Molded polypropylene: Example 8 Molding-grade polypropylene was dry-formed with the test additives DOPO-PEPA and Flamestab® NOR 116, and then melt-kneaded to form pellets. The fully formed resin pellets were compressed into test specimens using a Wabash compression molding machine.

[0097] Test plaques were tested under UL-94 vertical combustion test conditions. After removing the test flame, the average time until the test sample extinguished was recorded in seconds. The effectiveness of the flame retardant was demonstrated by shorter burning times compared to blank samples without the flame retardant. All samples containing NOR-based hindered amines self-extinguished after initial ignition. This indicates that the NOR compound exhibits a clear flame retardant effect essentially equivalent to that imparted by halogenated or phosphoric acid-based flame retardants. The blank samples burned completely after initial ignition.

[0098] EVA blow film: Example 9 Film-grade ethylene / vinyl acetate (EVA) copolymer (vinyl acetate content 20% by weight or less) was dry-formed with the test additives DOPO-PEPA and Flamestab® NOR 116, and then melt-kneaded to form pellets. The pelletized complete resin was blow-molded into film at 205°C using an MPM Superior Blown-film extruder.

[0099] The films were subjected to flame retardancy tests under NFPA701 test conditions. Films containing the composition of the present invention exhibited flame retardancy. Film-grade low-density polyethylene (LDPE) (partially containing linear low-density polyethylene (LLDPE) and / or ethylene / vinyl acetate (EVA)) was dry-formed with test additives and blow-molded into films in the same manner as the EVA copolymer resin described above. These films were subjected to flame retardancy tests under NFPA701 test conditions, and those containing the composition of the present invention exhibited high flame retardancy.

[0100] Polyethylene fibers: Example 10 Fiber-grade linear low-density polyethylene (LLDPE) (containing 10.4% by weight of DOPO-PEPA and 1.60% of Hostavin® NOW) was dry-formed with test additives, and then melt-kneaded at 240°C to form pellets. The pelletized resin was dry-formed with 10.0% by weight of Licocene® PE MA 4351 and melt-spun into fibers at 195°C using a custom-made pilot melt-spinning line. The spun monofilaments were stretched at a ratio of 1:4 to obtain a final fineness of 173 tex.

Claims

1. a) Compounds containing an N-oxyamine group, b) Compounds of the following formulas (II), (III), or (IV), and c) A flame-retardant polyolefin composition containing polyolefin. 【Chemistry 2】 (In the formula, R 1 and R 2 are, independently of each other, 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, independently 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 an alkyl group; k is an integer between 1 and 2; Y is either O or S; X is C 1 -C 4 -Alkylene, C 6 -C 12 - Alliren, C 7 -C 15 - Aralkylene or C 7 -C 15 -Alkali-Lene, 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 -It is alkyl; R 3 C 1 -C 4 -Alkylene, C 6 -C 12 - Alliren, C 7 -C 15 - Aralkylene or C 7 -C 15 -It is alkaline elenium; m is 0, 1, or 2, where X is -O- or -NR 7 - If so, m is 1 or 2; R 4 C 1 -C 4 -It is alkylene; t is an integer between 1 and 2; W is either oxygen or sulfur.

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

3. Component a) is 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine, bis(1-octyloxy-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-butyl-amino]-6-(2-hydroxyethyl-amino-S-triazine, bis(1-cyclohexyloxy-2,2,6,6-tetramethyl (Tyl-piperidine-4-yl)-adipate, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidine-4-yl)-butylamino]-6-chloro-S-triazine, 1-(2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetramethylpiperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethyl-piperidine, 1-(2-hydroxy-2-methylpropoxy)-4-oxo-2,2,6,6-tetramethyl-piperidine Lupropoxy)-4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)-sebacate, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethylpiperidine-4-yl)-adipate, 2,4-bis{N-[1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetramethyl [Piperidin-4-yl]-N-butylamino}-6-(2-hydroxyethylamino)-S-triazine), 4-piperidinol-2,2,6,6-tetramethyl-1-(undecyloxy)-4,4'-carbonate; reaction product of 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethyl-piperidine-4-yl)-butylamino]-6-chloro-S-triazine and N,N'-bis-(3-aminopropyl-ethylenediamine);A composition according to claim 2, selected from oligomers, aliphatic hydroxylamines such as distearylhydroxylamine, which are condensation products 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; and compounds of the following formula (wherein n is 1 to 15). 【Chemistry 4】 or 【change】

4. 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 and polyethylene oxide.

5. Component b) is a compound of formula (II), (III), and / or (IV), where n and m are 0, Y is oxygen or sulfur, and R is 0. 4 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), and R 1 and R 2 Each of them is independently of hydrogen or C 1 -C 6 -The composition according to claim 1, wherein it is 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 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 m is methylene or ethylene, m is 2, R 4 The composition according to claim 1, wherein is methylene, t is 1, and W is oxygen.

9. The composition of claim 1, wherein component b) is a compound of formula (IV).

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

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

12. The composition according to claim 1, wherein the amount of component a) is 0.2 to 10% by weight, the amount of component b) is 0.1 to 20% by weight, and the amount of component c) is 70 to 99.7% by weight, where these percentages are based on the total amount of the composition.

13. The composition of claim 1, wherein component c) is selected from the group of monoolefin and diolefin polymers, and copolymers of monoolefin and diolefin with each other or with other vinyl monomers.

14. Furthermore, d) the composition of claim 1, comprising an additive.

15. The composition of claim 14, wherein the additive d) is a filler and / or reinforcing agent.

16. The composition of claim 14, wherein the additive d) is a functionalized polyethylene wax.

17. The composition according to claim 1, wherein the polymer c) is polyethylene.

18. A molded article comprising components a), b), and c) of claim 1.

19. A molded article according to claim 18, which is a transparent sheet with a thickness of 50 to 500 μm.

20. A molded article according to claim 18, which is a film, yarn, or fiber.

21. A molded article according to claim 18, which is a blow film.

22. Use of the composition of claim 1 as a flame retardant.

23. Use of the composition of claim 1 for the manufacture of polyolefin molding materials.

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