Flame retardant polymer composition

专利摘要:
PURPOSE: A flame retardant polymer composition is provided to obtain good light stability and flame retardancy to a thermoplastic polymer by comprising a certain flame retardant containing a sterically hindered amine of the hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine class and optionally further stabilizers. CONSTITUTION: The process for imparting light stability and flame retardancy to a thermoplastic polymer(a) by addition of a flame retardant(b) and a sterically hindered amine(c), is characterized in that the flame retardant(b) is selected from the group consisting of b1) melamin based flame retardants and/or ammonium polyphosphate, b2) bis-(hexachlorocyclopentadieno)cyclooctane, b3) tris-(2,3-dibromopropyl)-isocyanurate, b4) ethylene-bis-tetrabromophthalimide, b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecan, b6) ethane-1,2-bis(pentabromophenyl); and the sterically hindered amine(c) is selected from sterically hindered amine light stabilizers of the hydrocarbyloxyamine and of the hydroxyhydrocarbyloxyamine class, provided that the flame retardant is not (b4) if the sterically hindered amine is of the hydroxyhydrocarbyloxy class.
公开号:KR20020046204A
申请号:KR1020010077708
申请日:2001-12-10
公开日:2002-06-20
发明作者:징위르크；링크위르겐
申请人:시바 스폐셜티 케미칼스 홀딩 인코포레이티드；
IPC主号:

专利说明:

Flame retardant polymer composition
[1] The present invention relates to thermoplastic organic polymers which are stabilized against the harmful effects of light, oxygen and heat and which contain specific hindered amines of hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines and optionally further stabilizers, In particular polyolefins such as thermoplastic polyolefins (TPO); The use of the flame retardant and sterically hindered amine to impart both light stabilizing and flame retardant properties; And corresponding methods for improving the light stability and flame retardancy of thermoplastic organic polymers.
[2] U. S. Patent No. 5,393, 812 describes polyolefin compositions which are made flameproof by the addition of halogenated hydrocarbyl phosphate or phosphonate ester flame retardants and stabilized from aging by alkoxyamine functional hindered amines. EP-A-792911 proposes the use of alkoxyamine functional hindered amines to improve the flame retardant properties of polyolefins. The function of alkoxyamine functional hindered amine anisotropic agents is described in WO 99/00450.
[3] It is a technical problem of the present invention to improve the flame retardant polymer composition to have good stability from aging.
[4] Good stabilization properties for UV light and aging, and especially for outdoor use, are characterized by the presence of certain hindered amine stabilizers in thermoplastic polymers, in particular in their combinations such as polyolefins, polyolefin copolymers or impact modified polyolefins or thermoplastic polyolefins (TPOs). It has recently been found that it can be combined when used in combination with certain flame retardants. Therefore, the present invention is to provide both the aging stability and flame retardancy to the thermoplastic polymer (a),
[5] (b1) melamine based flame retardants and / or ammonium polyphosphates,
[6] (b2) bis- (hexachlorocyclopentadieno) cyclooctane,
[7] (b3) tris- (2,3-dibromopropyl) -isocyanurate,
[8] (b4) ethylene-bis-tetrabromophthalimide,
[9] (b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecane,
[10] (b6) a flame retardant selected from ethane-1,2-bis (pentabromophenyl); And
[11] (c) the use of a combination of sterically hindered amine light stabilizers of hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines, provided the flame retardant is not (b4) unless the sterically hindered amine is not hydroxyhydrocarbyloxy; .
[12] The hindered amine light stabilizer of component (c) hydrocarbyloxyamine or hydroxyhydrocarbyloxyamines is characterized by having a substituent E ₁ -O- on the amino nitrogen atom (see formula below) E ₁ in the hindered amines of hydrocarbyloxyamines is preferably C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl; In the sterically hindered amines of hydroxyhydrocarbyloxyamines, E ₁ is preferably C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -each substituted by 1 to 3 OH groups in the aliphatic moiety. C ₁₅ aralkyl. The following types of compounds containing reactive OH groups can be used in the form of their reaction products.
[13] The hindered amine light stabilizers of the hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines of component (c) are often compounds containing groups of the formula:
[14]
[15] In the food,
[16] G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms or collectively pentamethylene, and
[17] E ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl; Or E ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl, each substituted by a 1-3 OH group in the aliphatic moiety; Or reaction products thereof. Preference is given to cyclic hindered amines corresponding to formula (1)
[18]
[19] In the food,
[20] G ₁ , G ₂ and E ₁ are as defined above;
[21] T is required to complete formula (1) to combine the hindered amine nitrogen atom and two quaternary carbon atoms substituted by G ₁ and G ₂ to form a 5- or 6-membered aliphatic ring structure, especially a piperidine ring. It is an organic group; Or oligomers prepared by the reaction of a dialkyl ester or isocyanate with a compound of formula (1) wherein E ₁ contains one OH group and T is -CH ₂ -CH (OH) -CH _2- A polymerizable hindered amine molecule; Or a simple diester or urethane derivative of a compound of formula (1) wherein E ₁ contains one OH group and T is —CH ₂ —CH (OH) —CH ₂ —.
[22] In general, the effective stabilizing amount of the compound of component (c) is from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 2% by weight, based on the amount of polymer component (a).
[23] The hindered amines of component (c) are well known as light stabilizers (US Patents 5,004,770; US Patents 5,096,950; US Patents 5,204,473; US Patents 5,096,950; US Patents 5,300,544; US Patents 6,117,995; US Patents). 6,271,377).
[24] Flame retardants of component (b) are commercially available compounds. Most preferred is tris- (2,3-dibromopropyl) -isocyanurate (b3).
[25] Flame retardant (b1) having no halogen is used in an amount of 1 to about 50% by weight of polymer (a), preferably 5 to 50% by weight of polymer (a). (b1): (c) The ratio is most preferably in the range 20: 1 to 250: 1.
[26] Halogenated flame retardants (b2), (b3), (b4), (b5) and / or (b6) are usually from 0.5 to 40% by weight of polymer (a); More preferably used in an amount of 3 to 40%, most preferably 5 to 35% by weight of polymer (a).
[27] The most preferred amount of flame retardant (b) in the composition of the present invention is as follows:
[28] (b1) 20 to 50% of melamine based flame retardant and / or ammonium polyphosphate;
[29] (b2) 5 to 20% bis- (hexachlorocyclopentadieno) cyclooctane;
[30] (b3) 2-10% of tris- (2,3-dibromopropyl) -isocyanurate;
[31] (b4) 10 to 40% of ethylene-bis-tetrabromophthalimide;
[32] (b5) 1,2,5,6,9, 10-hexabromo-cyclo-dodecane 2-20%;
[33] (b6) ethane-1,2-bis (pentabromophenyl) 2-20%;
[34] Each amount is in weight percent based on the weight of polymer (a).
[35] In the present invention, tris (3-bromo-2,2- (bromomethyl) propyl) phosphate (b7; see below), which is a flame retardant, is most preferably 2 to 20% by weight based on the weight of the polymer (a), It is particularly important to use in amounts of 2 to 10% by weight.
[36] The ratio of halogenated flame retardants (b2), (b3), (b4), (b5), (b6) or (b7): (c) is most preferably in the range from 5: 1 to 100: 1.
[37] Advantageously, halogenated flame retardants such as (b2), (b3), (b4), (b5), (b6) and / or (b7) are 0.5 to 20% by weight based on the weight of the polymer (a) It can be used in combination with a suitable synergist such as antimony compounds (often Sb ₂ O ₃ ) which are often added in amounts.
[38] Component (a) is selected from the following thermoplastic polymers:
[39] 1. Polymers of monoolefins and diolpins, such as polypropylene (PP), polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefins Polymers (eg cyclopentene or norbornene), polyethylene (which may optionally be crosslinked) such as high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultra high molecular weight polyethylene (HDPE) -UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), (VLDPE) and (ULDPE).
[40] The polyolefins, ie the polymers of the monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be produced in various ways, in particular by the following method:
[41] a) radical polymerization reaction (normally under high pressure and high temperature)
[42] b) Catalytic polymerization using catalysts which normally comprise at least one of IVb, Vb, VIb or Group VIII metals of the periodic table. Such metals generally have one or more ligands, such as oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and / or aryls, which may be π- or σ-coordinated. Such metal complexes may be in glass form or immobilized on a substrate, typically on activated magnesium chloride, titanium (III) chloride, alumina or silicon oxide. Such catalysts may be soluble or insoluble in the polymerization medium. These catalysts can be used independently in the polymerization or by using additional active agents such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, where the metal is an element of the groups Ia, IIa and / or IIIa of the periodic table. Can be. These activators can be conveniently modified with additional ester, ether, amine or silyl ether groups. The catalyst system is generally referred to as Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or cationic catalyst (SSC).
[43] 2. 1) Mixtures of the polymers mentioned hereinafter such as mixtures of polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of various types of polyethylene (eg LDPE / HDPE).
[44] 3. Copolymers of monoolefins and diolefins with each other or with other vinyl units, such as ethylene / propylene copolymers, linear low density polyethylene (LLDPE) and mixtures of these with low density polyethylene (LDPE), propylene / but-1-ene air Copolymer, propylene / isobutylene copolymer, ethylene / but-1-ene copolymer, ethylene / hexene copolymer, ethylene / methylpentene copolymer, ethylene / heptene copolymer, ethylene / octene copolymer, propylene / butadiene copolymer 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 salts thereof (Ionomers), as well as ethylene and propylene and dienes (eg hexadiene, dicyclopentadiene or ethylidene-norbornene) Dimer; And mixtures of such copolymers and mixtures of such copolymers with the polymers mentioned in 1), such as polypropylene / ethylene-propylene copolymers, LDPE / ethylene-vinyl acetate copolymers (EVA), LDPE / ethylene-acrylic acid copolymers. (EAA), LLDPE / EVA, LLDPE / EAA and alternating or random polyalkylene / carbon monoxide copolymers and mixtures thereof with other polymers such as polyamides.
[45] 4. Blends of the aforementioned polymers (polyblends), such as PP / EPDM.
[46] In the following the term polyolefin refers to pure polyolefin homopolymers as well as copolymers and blends thereof.
[47] Preferably, the polyolefin or thermoplastic olefin or polyolefin (TPO) is the only organic polymer present in the composition; Mainly polyethylene (PE) or polypropylene (PP), in particular LDPE, LLDPE or PP, or a copolymer of PP and PE.
[48] Especially preferred as component (a) are polypropylenes or polyethylenes, or heterophasic copolymers containing polymers known as thermoplastic (poly) olefins (TPO), such as elastomeric components such as impact modifiers or EPRs, such as W Neissl group, Kunstoffe 83, No. 8, 1993).
[49] Examples of polymeric compositions in which the compounds of the present invention are effective include flame retardant polyolefins, ceiling membranes, greenhouse membranes, and agricultural mulch membranes in which acidic residues obtained from decomposition of halogenated flame retardants deactivate sterically hindered amines having no N-OR groups. Acid residues from insecticides interfere with the activity of normal hindered amine stabilizers and in thermoplastic polyolefins where the pigments interact with the basic hindered amine stabilizers.
[50] Preferably, the compound of component (c) of the present invention is a cyclic hindered amine containing a group of formula (2) and / or (3):
[51]
[52]
[53] In the food,
[54] G is hydrogen or methyl, and
[55] G ₁ and G ₂ are independently hydrogen, methyl or combined to form substituent = 0.
[56] Examples of sterically hindered amines of component (c) of the present invention are described in the following (a ') to (m').
[57] (a ') A compound of formula (1a)
[58]
[59] In the food,
[60] n ₁ is a number from 1 to 4,
[61] G and G ₁ are independently hydrogen or methyl,
[62] G ₁₁ is O., hydroxy, C ₁ -C ₁₈ alkoxy, C ₅ -C ₁₂ cycloalkoxy, C ₇ -C ₁₅ phenylalkoxy; Or G ₁₁ is C ₁ -C ₁₈ alkoxy, C ₅ -C ₁₂ cycloalkoxy or C ₇ -C ₁₅ phenylalkoxy, each substituted by 1 to 3 OH groups in the aliphatic moiety; G ₁₁ is preferably C ₁ -C ₁₂ alkoxy or cyclohexyloxy or C ₂ -C ₈ hydroxyalkoxy, in particular octyloxy, cyclohexyloxy or 2-hydroxy-2-methylpropoxy, and
[63] G ₁₂ is ₁ if n = 1, hydrogen, unless a medium comprising a one or more oxygen atoms, COO and / or CONH, or include, or C ₁ -C ₁₈ alkyl, or cyanoethyl, benzoyl, glycidyl, aliphatic, Monovalent or monovalent silyl groups of cycloaliphatic, aliphatic, unsaturated or aromatic carboxylic acids, carbamic acid or phosphorus-containing acids, preferably aliphatic carboxylic acid groups having 2 to 18 carbon atoms, cycloaliphatic carboxylic acids having 7 to 15 carbon atoms Groups or α, β-unsaturated carboxylic acid groups having 3 to 5 carbon atoms or aromatic carboxylic acid groups having 7 to 15 carbon atoms, each carboxylic acid having 1 to 3 -COOZ ₁₂ groups in the aliphatic, cycloaliphatic or aromatic moiety , Z ₁₂ may be substituted by H, C ₁ -C ₂₀ alkyl, C ₃ -C ₁₂ alkenyl, C ₅ -C ₇ cycloalkyl, phenyl or benzyl,
[64] G ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, xylylene, aliphatic, cycloaliphatic, aliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid when n ₁ = 2 Divalent or divalent silyl groups, preferably aliphatic dicarboxylic acid groups having from 2 to 36 carbon atoms, or cycloaliphatic or aromatic dicarboxylic acid groups having from 8 to 14 carbon atoms, or aliphatic, cycloaliphatic having from 8 to 14 carbon atoms Or an aromatic dicarbamic acid group, each dicarboxylic acid may be substituted by one or two -COOZ ₁₂ groups at an aliphatic, cycloaliphatic or aromatic moiety,
[65] G ₁₂ is a trivalent group of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, a trivalent group of aromatic tricarbamic acid, phosphorus-containing when n ₁ = 3, which may be substituted by an -COOZ ₁₂ group in an aliphatic, cycloaliphatic or aromatic moiety Trivalent or trisilyl groups of the acid, preferred groups include triacyl groups of triacetic acid with nitrile of benzene tricarboxylic acid, and
[66] G ₁₂ is an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid doctor when n ₁ = 4.
[67] The carboxylic acid groups described above should be understood to mean groups of the formula (-CO) _x R, wherein x is as defined in n ₁ and the meaning of R is as defined above.
[68] Alkyl having up to 20 carbon atoms is for example methyl, ethyl, n-propyl, n-butyl, secondary butyl, tert-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n -Undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[69] C ₁ -C ₁₈ alkoxy G ₁₁ is, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dode Siloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Preference is given to C ₆ -C ₁₂ alkoxy, in particular heptoxy and octoxy.
[70] C ₅ -C ₁₂ cycloalkoxy G ₁₁ are, for example, cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Preference is given to C ₅ -C ₈ cycloalkoxy, in particular cyclopentoxy and cyclohexoxy.
[71] C ₇ -C ₉ phenylalkoxy is for example benzyloxy.
[72] As C ₁ -C ₁₈ alkoxy, C ₅ -C ₁₂ cycloalkoxy or C ₇ -C ₁₅ phenylalkoxy which is substituted by a 1-3 OH group in the aliphatic moiety G ₁₁ is preferably 2-methyl-2-propanol (tert-butanol ), 2-propanol, 2,2-dimethyl-1-propanol, 2-methyl-2-butanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1-nonanol, 1 -Decanol, 1-dodecanol, 1-octadecanol, 2-butanol, 2-pentanol, 2-ethyl-1-hexanol, cyclohexanol, cyclooctanol, allyl alcohol, phenylethyl alcohol or 1- Phenyl-1-ethanol; 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propane Diols, 1,2-cyclohexanediol, 1,3-cyclohexanediol or 1,4-cyclohexanediol; Glycerol, 1,1,1-tris (hydroxymethyl) methane, 2-ethyl-2- (hydroxymethyl) -1,3-propanediol, 1,2,4-butanetriol or 1,2,6 -Group formed by removing carbon-bonded hydrogen atoms from hexanetriol.
[73] More preferably, G ₁₁ is 2-methyl-2-propanol or cyclohexanol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-cyclohexanediol, 1,3 -Cyclohexanediol or 1,4-cyclohexanediol. Most preferably hydroxy substituted G ₁₁ is 2-hydroxy-2-methylpropoxy.
[74] Examples of some G ₁₂ groups are shown below.
[75] If G ₁₂ is a monovalent group of carboxylic acid, for example, acetyl, caproyl, stearoyl, acryloyl, methacryloyl, benzoyl or β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl Qi.
[76] If G ₁₂ is a monovalent silyl group, for example, it is a group of the formula-(C _j H _2j ) -Si (Z ') ₂ Z ", where j is an integer from 2 to 5 and Z' and Z" are independently C _1- C ₄ alkyl or C ₁ -C ₄ alkoxy.
[77] If G ₁₂ is a divalent group of dicarboxylic acid, for example malonyl, succinyl, glutaryl, adipoyl, subveroyl, sebacoyl, maleoyl, itaconyl, phthaloyl, dibutylmalonyl, dibenzylmalonyl , Butyl (3,5-di-tert-butyl-4-hydroxybenzyl) malonyl or bicycloheptenedicarbonyl groups or formula It is the flag of.
[78] If G ₁₂ is a trivalent group of tricarboxylic acid, it is, for example, trimellitoyl, citryl or nitrilotriacetyl group.
[79] When G ₁₂ is a tetravalent group of tetracarboxylic acid, it is, for example, a tetravalent group of butane-1,2,3,4-tetracarboxylic acid or a tetravalent group of pyromellitic acid.
[80] If G ₁₂ is a divalent group of dicarbamic acid, it is, for example, hexamethylenedicarbamoyl or 2,4-toluylenedicarbamoyl group.
[81] Preference is given to compounds of the formula (1a) in which G and G ₁ are hydrogen, G ₁₁ is hydrogen or methyl, n ₁ is 2 and G ₁₂ is a diacyl group of aliphatic dicarboxylic acid having 4 to 12 carbon atoms.
[82] (b ') A compound of formula (1b):
[83]
[84] In the food,
[85] n ₂ is a number of 1, 2 or 3, and G, G ₁ and G ₁₁ are as defined under (a ′) above, G ₁₃ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₅ hydroxide Oxyalkyl, C ₅ -C ₇ cycloalkyl, C ₇ -C ₈ aralkyl, C ₁ -C ₁₈ alkanoyl, C ₃ -C ₅ alkenoyl, benzoyl or formula It is a group of
[86] G ₁₄ is substituted by hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₈ alkenyl, C ₅ -C ₇ cycloalkyl, hydroxy, cyano, alkoxycarbonyl or carbamide group when n ₂ = 1 C ₁ -C ₄ alkyl or a group of formula -CONH-Z, or G ₁₄ is glycidyl, a group of formula -CH ₂ -CH (OH) -Z or a group of formula -CONH-Z wherein Z is Hydrogen, methyl or phenyl) or a group of CH ₂ -OZ ₁₄ , wherein Z ₁₄ is hydrogen or C ₁ -C ₁₈ alkyl;
[87] G ₁₄ is C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, xylene, -CH ₂ -CH (OH) -CH ₂ group or -CH ₂ -CH (OH) if n ₂ = 2; -CH ₂ -ODO- group wherein D is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene, C ₆ -C ₁₂ cycloalkylene, provided that G ₁₃ is an alkanoyl, alkenoyl or benzoyl Otherwise G ₁₄ may be a di- or -CO- group of 1-oxo-C ₂ -C ₁₂ alkylene, aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid,
[88] If G ₂ is n ₂ = 3, Or when n ₂ = 1, G ₁₃ and G ₁₄ may be combined to be a divalent group of aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.
[89] Some examples of G ₁₃ , G ₁₄ and D are shown below.
[90] Optional alkyl substituents are as defined under (a ') above.
[91] Any C ₅ -C ₇ cycloalkyl substituent is especially cyclohexyl.
[92] C ₇ -C ₈ aralkyl G ₁₃ is especially phenylethyl or especially benzyl.
[93] C ₂ -C ₅ hydroxyalkyl G ₁₃ is especially 2-hydroxyethyl or 2-hydroxypropyl.
[94] C ₁ -C ₁₈ alkanoil G ₁₃ is, for example, formyl, acetyl, propionyl, butyryl, octane oil, dodecane oil, hexadecane oil, octadecane oil, but is preferably acetyl and C ₃ -C ₅ alkenes Oil G ₁₃ is in particular acrylic oil.
[95] C ₂ -C ₈ alkenyl G ₁₄ is, for example, allyl, metallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
[96] G ₁₄ as hydroxy-, cyano-, alkoxycarbonyl- or carbide-substituted C ₁ -C ₄ alkyl is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-cyanoethyl, methoxy Carbonylmethyl, 2-ethoxycarbonylethyl, 2-aminocarbonylpropyl or 2- (dimethylaminocarbonyl) ethyl.
[97] Any C ₂ -C ₁₂ alkylene group is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
[98] Any C ₆ -C ₁₅ arylene substituent is for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[99] C ₆ -C ₁₂ cycloalkylene is especially cyclohexylene.
[100] 1-oxo -C ₂ -C ₁₂ alkylene G ₁₄ as is preferably the general formula It is the flag of.
[101] (c ') A compound of formula (1c)
[102]
[103] In the food,
[104] when n ₃ is 1 or 2, G, G ₁ and G ₁₁ are as defined under (a '), and G ₁₅ and G' ₁₅ are n ₃ = 1, independently of each other, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkenyl, C ₇ -C ₁₂ aralkyl, or G ₁₅ is also hydrogen, or G ₁₅ and G ′ ₁₅ are combined to form C ₂ -C ₈ alkylene, C ₅ -C ₁₅ alkenylene, C ₂ -C ₈ hydroxyalkyl alkylene or C ₄ -C ₂₂ acyloxy-alkylene, is also n ₃ = 2, G ₁₅ and G _'15 is combined _{(-CH 2) 2 C (CH} 2 -) 2 giim .
[105] C ₂ -C ₈ alkylene or C ₂ -C ₈ hydroxyalkylene G ₁₅ and G ′ ₁₅ are, for example, ethylene, 1-methylethylene, propylene, 2-ethylpropylene or 2-ethyl-2-hydroxymethylpropylene .
[106] C ₄ -C ₂₂ acyloxyalkylene G ₁₅ and G ′ ₁₅ are, for example, 2-ethyl-2-acetoxymethylpropylene.
[107] (d ') A compound of formula (1da), (1db) or (1dc):
[108]
[109]
[110]
[111] In the food,
[112] n ₄ is 1 or 2, G, G ₁ and G ₁₁ are as defined under (a '), and G ₁₆ is hydrogen, C ₁ -C ₁₂ alkyl, allyl, benzyl, glycidyl or C _2- a C ₆ alkoxyalkyl, and G ₁₇ is ₄ when n = 1, hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl, C ₂ -C ₆ alkoxyalkyl, C ₆ -C ₁₀ aryl, glycidyl or a group of the formula-(CH ₂ ) _p -COO-Q or-(CH ₂ ) _p -O- Group is CO-Q, wherein p is 1 or 2 and Q is C ₁ -C ₄ alkyl or phenyl, and if G ₁₇ is n ₄ = 2, C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₆ -C ₁₂ arylene, a group of the formula -CH ₂ -CH (OH) -CH ₂ -O-D'-O-CH ₂ -CH (OH) -CH _2- , wherein D ′ is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene, or In which D ″ is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl,
[113] T ₁ and T ₂ independently of one another are hydrogen, C ₁ -C ₁₈ alkyl or unsubstituted or halogen- or C ₁ -C ₄ alkyl-substituted C ₆ -C ₁₀ aryl or C ₇ -C ₉ aralkyl, or
[114] T ₁ and T ₂ combine with the carbon atoms to which they are attached to form a C ₅ -C ₁₄ cycloalkane ring.
[115] Any C ₁ -C ₁₂ alkyl substituent is, for example, methyl, ethyl, n-propyl, n-butyl, secondary butyl, tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
[116] Optional C ₁ -C ₁₈ alkyl substituents are, for example, the groups described above, and others are, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
[117] Any C ₂ -C ₆ alkoxyalkyl substituent is for example methoxymethyl, ethoxymethyl, propoxymethyl, tert-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert-butoxyethyl, isopro Oxyethyl or propoxypropyl.
[118] C ₃ -C ₅ alkenyl G ₁₇ is for example 1-propenyl, allyl, metalyl, 2-butenyl or 2-pentenyl.
[119] C ₇ -C ₉ aralkyl G ₁₇ , T ₁ and T ₂ are especially phenethyl or especially benzyl. When T ₁ and T ₂ combine with a carbon atom to form a cycloalkane ring, it may be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
[120] C ₂ -C ₄ hydroxyalkyl G ₁₇ is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
[121] C ₆ -C ₁₀ aryl G ₁₇ , T ₁ and T ₂ are especially phenyl or α- or β-naphthyl which may be unsubstituted or substituted by halogen or C ₁ -C ₄ alkyl.
[122] C ₂ -C ₁₂ alkylene G ₁₇ is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.
[123] C ₄ -C ₁₂ alkenylene G ₁₇ is especially 2-butenylene, 2-pentenylene or 3-hexenylene.
[124] C ₆ -C ₁₂ arylene G ₁₇ is for example o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
[125] C ₂ -C ₁₂ alkanoyl D ″ is, for example, propionyl, butyryl, octanoyl, dodecane oil, but is preferably acetyl.
[126] C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene D ′ may be one of the meanings defined for D, for example under (b ′).
[127] (e ') A compound of formula (1e)
[128]
[129] In the food,
[130] n ₅ is 1 or 2, and G ₁₈ is a chemical formula
[131] Is the flag of,
[132] G and G ₁₁ are as defined under (a '), and G ₁ and G ₂ may be hydrogen, methyl or combined may be substituent = 0;
[133] E is -O- or -ND "'-,
[134] A is C ₂ -C ₆ alkylene or-(CH ₂ ) ₃ -O- and
[135] x ₁ is 0 or 1,
[136] D ″ ′ is hydrogen, C ₁ -C ₁₂ alkyl, C ₂ -C ₁₂ alkylene-N (D ^V ) ₂ , C ₂ -C ₅ hydroxyalkyl or C ₅ -C ₇ cycloalkyl, wherein D ^V is Independently hydrogen or butyl,
[137] G ₁₉ is the same as G ₁₈ or is one of -N (G ₂₁ ) (G ₂₂ ), -OG ₂₃ , -N (H) (CH ₂ OG ₂₃ ) or -N (CH ₂ OG ₂₃ ) ₂ groups ,
[138] G ₂₀ is equal to G ₁₈ or G ₁₉ if n ₅ = 1 and n ₅ = 2 is an -ED ^IV -E- group, where D ^IV is C ₂ -C ₈ alkylene or 1 or 2 in between C ₂ -C ₈ alkylene containing two -NG ₂₁ -groups,
[139] G ₂₁ is hydrogen, C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl or
[140] Is the flag of,
[141] G ₂₂ is C ₁ -C ₁₂ alkyl, cyclohexyl, benzyl or C ₁ -C ₄ hydroxyalkyl, and
[142] G ₂₃ is hydrogen, C ₁ -C ₁₂ alkyl or phenyl, or G ₂₁ and G ₂₂ are combined to form a C ₄ -C ₅ alkylene or C ₄ -C ₅ oxaalkylene, such as —CH ₂ CH ₂ —O—CH ₂ CH ₂ -or a group of the formula -CH ₂ CH ₂ -N (G ₁₁ ) -CH ₂ CH _2- .
[143] Examples of some variables in the above formula (1e) are as defined below.
[144] Any C ₁ -C ₁₂ alkyl substituent is, for example, methyl, ethyl, n-propyl, n-butyl, secondary butyl, tertiary butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
[145] Optional hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.
[146] Any C ₅ -C ₇ cycloalkyl substituent is, for example, cyclopentyl, cyclohexyl or cycloheptyl. Cyclohexyl is preferred.
[147] C ₂ -C ₆ alkylene A is for example ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.
[148] If G ₂₁ and G ₂₂ are taken together and C ₄ -C ₅ alkylene or oxaalkylene, these are, for example, tetramethylene, pentamethylene or 3-oxapentamethylene.
[149] (f ') A compound of formula (1f):
[150]
[151] In the formula, G ₁₁ is as defined under (a ').
[152] (g ') oligomeric or polymeric compounds in which the repeating structural unit contains 2,2,6,6-tetraalkylpiperidinyl groups, in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, poly Aminotriazines, poly (meth) acrylates, poly (meth) acrylamides and copolymers containing these aforementioned groups.
[153] Examples of 2,2,6,6-tetraalkylpiperidine compounds from the above class are compounds of the formula m ₁ to m ₁₄ are numbers from 2 to about 200, preferably 2 to 100, such as 2 to 50, 2 to 40, 3 to 40 or 4 to 10.
[154] The meaning of the end groups saturating free values in the oligomeric or polymeric compounds listed below depends on the process used to prepare the compounds described above. The end groups can also be modified after synthesis of the compound.
[155] Examples of polymerizable compounds are as follows:
[156] 1) A compound of formula (1 g):
[157]
[158] Wherein G ₂₄ , G ₂₅ , G ₂₆ , G ₂₇ and G ₂₈ are each independently a direct bond or C ₁ -C ₁₀ alkylene, G ₁₁ is as defined under (a ') and m ₁₇ is 1 Number from 50 to 50.
[159] In the compounds of the formula (1 g), the terminal groups bonded to the> C═O groups are for example
[160] And end groups bonded to oxygen, for example
[161] Can be.
[162] 2) a compound of formula (2 g):
[163]
[164] In the food,
[165] The index m ₁₈ is a number from 1 to 15;
[166] R ₁₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylene-di (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or 1,4-piperazindiyl, -O or> NX _{1 in which} X ₁ Is C ₄ -C ₁₂ alkylene comprising C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl) or has one of the definitions of R ₁₄ defined below except hydrogen Or R ₁₂ is a group of formula (2g ') or (2g ");
[167] (2 g ')
[168] (2g ")
[169] In the food,
[170] X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; In addition
[171] Group X ₃ is independently C ₂ -C ₁₂ alkylene,
[172] Group A is independently —OR ₁₃ , —N (R ₁₄ ) (R ₁₅ ) or formula (2 g ″ ′)
[173] (2g "'),
[174] The same or different R ₁₃ , R ₁₄ and R ₁₅ are hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl or —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino at the 2, 3 or 4 position or the formula (2g ^IV )
[175] Group (2g ^IV) (wherein, Y is _{-O-, -CH 2 -, -CH 2} CH 2 - or> N-CH ₃ Im) or a C ₂ -C ₄ alkyl substituted by or -N (R ₁₄ ) (R ₁₅ ) is additionally a group of formula (2g ^IV );
[176] X is -O- or> NR ₁₆ ;
[177] R ₁₆ is hydrogen, C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl, Formula (2 g ^V )
[178] C ₂ -C ₄ substituted with a group of (2g ^V ) or —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (2g ^IV ) at the 2, 3 or 4 position Alkyl;
[179] R ₁₁ is one of the meanings defined in R ₁₆ ; In addition
[180] The group B is independently one of the meanings given for A.
[181] 3) a compound of formula (3 g):
[182]
[183] In the food,
[184] G ₁₁ is as defined under (a '), and G ₂₉ and G ₃₂ are independently direct bonds or -N (X ₁ ) -CO-X ₂ -CO-N (X ₃ )-groups, wherein X ₁ and X ₃ independently of one another is hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl, C ₇ -C ₉ phenylalkyl or formula (3 g)
[185] And X ₂ is a direct bond or C ₁ -C ₄ alkylene, and G ₃₀ , G ₃₁ , G ₃₄ and G ₃₅ are independently of each other hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl Or phenyl, G ₃₃ is hydrogen, C ₁ -C ₃₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₇ -C ₉ phenylalkyl, phenyl or a group of formula (3 g), and m ₁₉ is a compound of 1 to 50 Appointment.
[186] In the compound of formula (3 g), the terminal group bonded to the 2,5-dioxopyrrolidine ring can be for example hydrogen and the terminal group bonded to the -C (G ₃₄ ) (G ₃₅ )-group is for example
[187] Can be.
[188] 4) A product obtained by reacting an intermediate product obtained by reacting a polyamine of formula (4 g) with cyanuric chloride with a compound of formula (4 g '):
[189] (4 g)
[190] (4g ')
[191] In the food,
[192] m _'20 , m " ₂₀ and m"' ₂₀ are independently of each other a number from 2 to 12, G ₃₆ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₁₂ cycloalkyl, phenyl or C ₇ -C ₉ Phenylalkyl and G ₁₁ is as defined under (a ').
[193] In general, the reaction product can be represented by the following three compounds. It may also be in the form of a mixture of these three compounds:
[194]
[195]
[196]
[197] 5) A compound of formula (5 g):
[198]
[199] In the food,
[200] G ₁₁ is as defined under (a '), G ₃₇ is C ₁ -C ₁₀ alkyl, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl-substituted C ₅ -C ₁₂ cycloalkyl, phenyl or C ₁ -C ₁₀ alkyl-substituted phenyl, G ₃₈ is C ₃ -C ₁₀ alkylene and m ₂₁ is a number from 1 to 50.
[201] In the compound of the formula (5g), the end group bonded to the silicon atom may be, for example, (G ₃₇ ) ₃ Si-O-, and the end group bonded to oxygen may be, for example, Si (G ₃₇ ) ₃ .
[202] The compound of formula (5g) may be in the form of a cyclic compound if m ₂₁ is a number from 3 to 10, ie the free valency shown in the above formula forms a direct bond.
[203] 6) A compound of formula (6 g):
[204]
[205] In the food,
[206] E is —O— or —ND ″ ′ as defined under (e ′), T ₃ is ethylene or 1,2-propylene and is derived from an alpha-olefin copolymer with alkyl acrylate or methacrylate Repeating structural unit, preferably a copolymer of ethylene and ethyl acrylate, wherein k is 2 to 100.
[207] 7) A compound of formula (7 g):
[208]
[209] In the food,
[210] m is 1 to 100;
[211] G ₅₀ is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cycloalkenylene having 5 to 8 carbon atoms, alkenylene having 3 to 18 carbon atoms, phenyl or Straight or branched chain alkylene having 1 to 4 carbon atoms substituted by phenyl substituted by 1 or 2 alkyl with 1 to 4 carbon atoms, provided that the series of hindered amine residues in formula (7 g) Can be arranged in head or head-to-tail fashion;
[212] T ₄ is hydrogen or
[213] T ₄ is Is;
[214] G ₅₅ is straight or branched chain alkylene having 1 to 18 carbon atoms, cycloalkylene or cycloalkenylene having 5 to 8 carbon atoms, phenylene or 5-amino-1-aminomethyl-1,3,3-trimethyl -NH-alkylene-NH- of 2 to 18 carbon atoms, including cyclohexane and -NH-xylylene-NH-;
[215] T ₅ is alkyl of 1 to 4 carbon atoms; being.
[216] In the oligomeric and polymeric compounds exemplified above, examples of alkyl are methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, 2-ethylbutyl, n-pentyl, isopentyl, 1 -Methylpentyl, 1,3-dimethylbutyl, n-hexyl, 1-methylhexyl, n-heptyl, isoheptyl, 1,1,3,3-tetramethylbutyl, 1-methylheptyl, 3-methylheptyl, n -Octyl, 2-ethylhexyl, 1,1,3-trimethylhexyl, 1,1,3,3-tetramethylpentyl, nonyl, decyl, undecyl, 1-methylundecyl, dodecyl, 1,1,3 , 3,5,5-hexamethylhexyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, iconic and docosyl; Examples of cycloalkyl are cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl; An example of C ₇ -C ₉ phenylalkyl is benzyl; Examples of alkylene are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene, hexamethylene, trimethylhexamethylene, octamethylene and decamethylene.
[217] (h ') A compound of formula (1h):
[218]
[219] In the food,
[220] n ₆ is 1 or 2, G and G ₁₁ are as defined under (a ') and G ₁₄ is as defined under (b'), while G ₁₄ is -CONH-Z and -CH ₂ -CH ( OH) -CH ₂ -ODO-.
[221] (i ') A compound of formula (Ii)
[222]
[223] Wherein the groups G ₃₉ are independently of one another the formula (1i-1) Group of (1i-1), wherein G ₄₀ is C ₁ -C ₁₂ alkyl or C ₅ -C ₁₂ cycloalkyl, G ₄₁ is C ₂ -C ₁₂ alkylene and G ₄₂ is as defined above in G ₁₁ same.
[224] Alkyl is for example C ₁ -C ₄ alkyl, in particular methyl, ethyl, propyl or butyl.
[225] Cycloalkyl is preferably cyclohexyl.
[226] Alkylene is for example ethylene, propylene, trimethylene, tetramethylene, pentamethylene, 2,2-dimethyltrimethylene or hexamethylene.
[227] Alkenyl is preferably allyl.
[228] Phenylalkyl is preferably benzyl.
[229] Acyl is preferably acetyl.
[230] (j ') A compound of formula (1j):
[231]
[232] In the food,
[233] G, G ₁₁ are as defined above and
[234] If n ₇ = 1, T ₇ is hydrogen, C ₁ -C ₁₂ alkyl, C ₃ -C ₅ alkenyl, C ₇ -C ₉ aralkyl, C ₅ -C ₇ cycloalkyl, C ₂ -C ₄ hydroxyalkyl , C ₂ -C ₆ alkoxyalkyl, C ₆ -C ₁₀ aryl, glycidyl, a group of formula-(CH ₂ ) _t -COO-Q or a group of formula-(CH ₂ ) _t -O-CO-Q Where t is 1 or 2 and Q is C ₁ -C ₄ alkyl or phenyl; or
[235] If n ₇ = 2, T ₇ is a C ₂ -C ₁₂ alkylene, C ₆ -C ₁₂ arylene, -CH ₂ CH (OH) -CH ₂ -OXO-CH ₂ -CH (OH) -CH ₂ -group Wherein X is C ₂ -C ₁₀ alkylene, C ₆ -C ₁₅ arylene or C ₆ -C ₁₂ cycloalkylene, or -CH ₂ CH (OZ ') CH _2- (OCH ₂ -CH (OZ' ) CH ₂ ) ₂ -wherein Z 'is hydrogen, C ₁ -C ₁₈ alkyl, allyl, benzyl, C ₂ -C ₁₂ alkanoyl or benzoyl.
[236] (k ') A compound of formula (1k):
[237]
[238] In the formula, G, G ₁₁ are as defined above.
[239] (l ') A compound of formula (1L)
[240]
[241] In the formula, G, G ₁₁ are as defined above.
[242] (m ') A compound of formula (1m)
[243]
[244] Wherein G is as defined above, n ₈ is 1, 2 or 3,
[245] if n ₈ = 1, G ₅₁ is -G ₅₀ -O-CO-G ₅₆ ; G ₅₂ is -O-CO-G ₅₆ ; And G ₅₃ is hydrogen; G ₅₆ is alkyl of 1 to 18 carbon atoms or —NH-alkyl or —NH-cycloalkyl of 5 to 8 carbon atoms;
[246] If n ₈ = 2, G ₅₁ is alkylene having 1 to 18 carbon atoms, hydroxyalkylene having 3 to 18 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, cyclo having 5 to 8 carbon atoms 1-4 carbon sources substituted by alkylene or hydroxycycloalkylene, alkenylene having 3 to 18 carbon atoms, or phenyl substituted by phenyl or by 1 or 2 alkyl having 1 to 4 carbon atoms Straight or branched chain alkylene having a molecule or hydroxyalkylene having 2 to 4 carbon atoms; Or G ₅₁ is an aliphatic, cycloaliphatic, aromatic aliphatic or divalent acyl group of aromatic dicarboxylic acid or dicarbamic acid, preferably aliphatic dicarboxylic acid having 2 to 18 carbon atoms or cycloaliphatic or aromatic di having 8 to 14 carbon atoms Acyl group of carboxylic acid,
[247] If n ₈ = 3, G ₅₁ is _alkanetriyl having 1 to 18 carbon atoms, hydroxyalkantriyl having 3 to 18 carbon atoms, cycloalkantriyl having 5 to 8 carbon atoms, 5 to 8 carbon atoms Cycloalkentriyl having, alkentriyl having 3 to 18 carbon atoms, straight chain having 1 to 4 carbon atoms substituted by phenyl substituted by phenyl or by 1 or 2 alkyl having 1 to 4 carbon atoms Or branched alkanetriyl;
[248] If n ₈ = 2 or 3,
[249] G ₅₂ is ; Or one of the formula
[250] Group;
[251]
[252]
[253] In G ₅₃ is hydrogen, or G ₅₂ = -OG ₁₅ is O-G _'15, and; or
[254] G ₅₂ and G ₅₃ are taken together = O or formula Wherein G ₁₁ and G ₁₂ are as defined above under (a ′) when n ₁ = 1; G ₁₃ and G ₁₄ are as defined above under (b ′) when n ₂ = 1; G ₁₅ and G ′ ₁₅ are as defined above under (c ′) when n ₃ = 1; G ₁₈ , G ₁₉ , A, E, D ^IV , x ₁ are as defined above under (e ′); T ₇ is as defined above under (j ′) when n ₇ = 1; G ₅₄ is as defined for G ₁₂ under (a ′) when n ₁ = 2; G ₅₅ is as defined for G ₁₄ under (b ′) when n ₂ = 2; G ₅₆ is as defined for T ₇ under (j ′) when n ₇ = 2.
[255] Hydroxyhydro, wherein E ₁ is preferably C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl each substituted by 1 to 3 OH, in particular one OH group, in the aliphatic moiety The hindered amine light stabilizers of carbyloxyamines are of particular technical importance.
[256] Therefore, the present invention,
[257] (a) polyolefins; And
[258] (b) (b1) melamine based flame retardant and / or ammonium polyphosphate, (b2) bis- (hexachlorocyclopentadieno) cyclooctane, (b3) tris- (2,3-dibromopropyl) -isocy Anurate, (b4) flame retardant selected from ethylene-bis-tetrabromophthalimide; And
[259] (c) A flame retardant composition stabilized from adverse effects of light and aging comprising a hindered amine light stabilizer of hydroxyhydrocarbyloxyamines.
[260] The present invention also relates to adding a hindered amine light stabilizer of tris- (2,3-dibromopropyl) -isocyanurate and hydrocarbyloxyamine or hydroxyhydrocarbyloxyamine as a flame retardant to a thermoplastic polymer. It relates to a method for imparting photostability and flame retardancy to a thermoplastic polymer, including. hindered amine light stabilizers of (a) polyolefins, (b) tris- (2,3-dibromopropyl) -isocyanurate as flame retardant, and (c) hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines Flame-retardant photostabilized composition comprising a is a preferred object of the present invention.
[261] Preferred components (a) and (c) and amounts thereof in the novel process and novel composition of the present invention are as described below.
[262] Components (b) and (c) of the present invention and any other components may be readily incorporated into the polymer by conventional techniques in any convenient process prior to making the molded article. For example, the additive may be mixed with the polymer in dry powder form, or the suspension or emulsion of the stabilizer may be mixed with the solution, suspension or emulsion of the polymer. The additives may be added to component (a) individually or mixed with each other. If desired, the individual components can be mixed with each other in the form of melt (melt mixing) before they are incorporated into the material to be stabilized. Components (b) and / or (c) and any additional additives may be incorporated, for example, by incorporation of a stabilizer mixture incorporated or dissolved or dispersed before or after molding into the material to be stabilized and then optionally by evaporating the solvent. Can be. Additives as well as additional additives of components (b) and / or (c) may be added to the material to be stabilized in the form of a masterbatch containing these components at a concentration of, for example, 2.5% to about 25% by weight; In this operation, the polymer can be used in powder, granule, solution, suspension or latis form.
[263] Incorporation may be effected prior to or during the molding operation, or may be carried out by applying a dissolved or dispersed compound to the polymer and then optionally evaporating the solvent. In the case of elastomers, they can be stabilized as latiss. The possibility for incorporating the stabilizers of the invention into the polymer can be added before, during or immediately after the polymerization of the corresponding monomers. When added before or during the polymerization, the stabilizers of the invention can act as chain length regulators (chain terminators) of the polymer.
[264] Components (b) and (c) of the present invention can be incorporated by the following methods:
[265] As emulsions or dispersants (such as in latis or emulsion polymers)
[266] As a dry mixture while mixing additional components or polymer mixtures,
[267] By direct introduction into processing equipment (eg extruders, internal mixers, etc.),
[268] As a solution or melt.
[269] Additive combinations of the present components (b) and (c) are useful for many applications, especially for outdoor use including:
[270] Thermoplastic olefins (TPO) such as applicable thermoplastic olefins
[271] Polypropylene Molded Articles
[272] Polyethylene membrane
[273] Molded Polypropylene with Brominated Flame Retardants
[274] Molded Thermoplastic Olefin With Brominated Flame Retardants
[275] Polyethylene Membrane with Brominated Flame Retardant
[276] Thermoplastic Elastomers with Other Co-Stabilizers
[277] Grease-filled wire and cable insulation
[278] Coating on Plastic Substrate
[279] Polyolefin tanks or vessels containing chemicals
[280] Polyolefin Membrane with Mist
[281] Polyolefin membranes with IR thermal fillers such as hydrotalcites such as DHT4A
[282] Polyolefin membrane with antistatic agent
[283] Flame Retardant Molded Polypropylene Articles
[284] Flame Retardant Molded Thermoplastic Olefin
[285] Flame retardant polyethylene membrane
[286] Preformed Film for Lamination on Plastic Substrates
[287] Electronic device
[288] Containers, boxes, bins for storage and transport
[289] For automotive use, eg instrument clusters, back boards
[290] Furniture such as stadium chairs, public chairs
[291] Ceiling sheet
[292] Ceiling material membrane
[293] Flooring
[294] Liner
[295] Profiles, especially window and door profiles
[296] Geomembrane.
[297] The materials containing the stabilizers described above can be used for the production of moldings, extrudates, rotomolds, injection moldings, blow moldings, single layer and multilayer films, extrusion profiles, surface coatings and the like.
[298] The resulting stabilized compositions of the invention may optionally contain various conventional additives, such as the substances or mixtures thereof listed below, preferably from 0.01 to 10% by weight, more preferably from about 0.025 to about 0.05% by weight of component (a). 2 weight percent, especially about 0.1 to about 1 weight percent.
[299] 1. Antioxidant
[300] 1.1. Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6 -Di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, straight chain or Nonylphenol branched from the side chain such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundec-1'-yl) phenol, 2,4-dimethyl- 6- (1'-methylheptadec-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) phenol and mixtures thereof.
[301] 1.2. Alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol , 2,6-di-dodecylthiomethyl-4-nonylphenol.
[302] 1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl- 4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3 , 5-di-tert-butyl-4-hydroxyphenyl stearate, bis (3,5-di-tert-butyl-4-hydroxyphenyl) adipate.
[303] 1.4. Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol, δ-tocopherol and mixtures thereof (vitamin E)
[304] 1.5. Hydroxylated thiodiphenyl ethers such as 2,2'-thiobis (6-tert-butyl-4-methylphenol), 2,2'-thiobis (4-octylphenol), 4,4'-thio Bis (6-tert-butyl-3-methylphenol), 4,4'-thiobis (6-tert-butyl-2-methylphenol), 4,4'-thiobis (3,6-di-secondary amylphenol) , 4,4'-bis (2,6-dimethyl-4-hydroxyphenyl) disulfide.
[305] 1.6. Alkylidenebisphenols such as 2,2'-methylenebis (6-tert-butyl-4-methylphenol), 2,2'-methylenebis (6-tert-butyl-4-ethylphenol), 2,2'- Methylenebis [4-methyl-6- (α-methylcyclohexyl) -phenol], 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-methylenebis (6-nonyl -4-methylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2 ' -Ethylidenebis (6-tert-butyl-4-isobutylphenol), 2,2'-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2'-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol], 4,4'-methylenebis (2,6-di-tert-butylphenol), 4,4'-methylenebis (6-tert-butyl-2-methyl Phenol), 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methyl Phenol, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n Dodecyl mercaptobutane, Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate], bis (3-tert-butyl-4-hydroxy-5-methyl-phenyl) dicyclopentadiene, bis [2- (3'-tert-butyl-2'-hydroxy-5'-methylbenzyl) -6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis- (3,5-dimethyl-2- Hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4-hydroxyphenyl) propane, 2,2-bis- (5-tert-butyl-4-hydroxy-2-methylphenyl) 4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-tert-butyl-4-hydroxy-2-methylphenyl) pentane.
[306] 1.7. O-, N- and S-benzyl compounds , for example 3,5,3 ', 5'-tetra-tert-butyl-4,4'-dihydroxy-dibenzyl ether, octadecyl-4-hydroxy- 3,5-dimethylbenzyl mercaptoacetate, tridecyl-4-hydroxy-3,5-di-tert-butylbenzyl mercaptoacetate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) amine, Bis (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) dithioterephthalate, bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, isooctyl-3,5 Di-tert-butyl-4-hydroxybenzyl mercaptoacetate.
[307] 1.8. Hydroxybenzylated malonates , for example dioctadecyl-2,2-bis (3,5-di-tert-butyl-2-hydroxybenzyl) malonate, di-octadecyl-2- (3-tert-butyl 4-hydroxy-5-methylbenzyl) -malonate, di-dodecylmercaptoethyl-2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, bis [4- (1,1,3,3-tetramethylbutyl) phenyl] -2,2-bis (3,5-di-tert-butyl-4-hydroxybenzyl) malonate.
[308] 1.9. Aromatic hydroxybenzyl compounds such as 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 1,4-bis (3, 5-di-tert-butyl-4-hydroxybenzyl) -2,3,5,6-tetramethylbenzene, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) phenol .
[309] 1.10. Triazine compounds such as 2,4-bis (octylmercapto) -6- (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-jade Tylmercapto-4,6-bis (3,5-di-tert-butyl-4-hydroxyanilino) -1,3,5-triazine, 2-octylmercapto-4,6-bis (3,5 -Di-tert-butyl-4-hydroxyphenoxy) -1,3,5-triazine, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenoxy) -1, 2,3-triazine, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3- Hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxyphenylethyl) -1,3,5-triazine, 1 , 3,5-tris (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexahydro-1,3,5-triazine, 1,3,5-tris (3,5-dicyclo Hexyl-4-hydroxybenzyl) isocyanurate.
[310] 1.11. Benzylphosphonates such as dimethyl-2,5-di-tert-butyl-4-hydroxybenzyl phosphonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, di Octadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzyl phosphonate, 3,5-di-tert Calcium salt of butyl-4-hydroxybenzyl-phosphonic acid monoethyl ester.
[311] 1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
[312] 1.13. Esters of mono- or polyhydric alcohols with β- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionic acid such as methanol, ethanol, n-octanol, i-octanol, octadecanol, 1, 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) iso Cyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha- Ester with 2,6,7-trioxabicyclo [2.2.2] octane.
[313] 1.14. Esters of mono- or polyhydric alcohols with β- (5-tert-butyl-4-hydroxy-3-methylphenyl) -propionic acid , for example methanol, ethanol, n-octanol, i-octanol, octadecanol, 1 , 6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) Isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha -2,6,7-trioxabicyclo [2.2.2] octane; 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [ 5.5] -Undecan.
[314] 1.15. Esters of mono- or polyhydric alcohols with β- (3,5-dicyclohexyl-4-hydroxyphenyl) -propionic acid , for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1 , 9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (hydroxyethyl) oxamide, 3-thiaoundaneol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7- Ester with trioxabicyclo [2.2.2] octane.
[315] 1.16. Esters of monohydric or polyhydric alcohols with 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid, for example methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonane Diol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris (hydroxyethyl) isocyanurate, N, N'-bis (Hydroxyethyl) oxamide, 3-thiaoundanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxa bicyclo [2.2.2] esters with octane
[316] 1.17. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexa Methylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4 -Hydroxyphenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxide (Naugard ^R XL- 1, supplied by Uni-Royal).
[317] 1.18. Ascorbic acid (vitamin C)
[318] 1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-secondarybutyl-p-phenylenediamine, N, N'-bis (1,4-dimethylpentyl ) -p-phenylenediamine, N, N'-bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N'-bis (1-methylheptyl) -p-phenylenediamine, N, N'-dicyclohexyl-p-phenylenediamine, N, N'-diphenyl-p-phenylenediamine, N, N'-bis (2-naphthyl) -p-phenylenediamine, N- Isopropyl-N'-phenyl-p-phenylenediamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, N- (1-methylheptyl) -N'-phenyl- p-phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N'-di- Secondary butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octylphenyl) -1 -Naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butyla Minophenol, 4-butyrylaminophenol, 4-nonanylaminophenol, 4-dodecane oilaminophenol, 4-octadecane oilaminophenol, bis (4-methoxyphenyl) amine, 2,6-di-tertiary Butyl-4-dimethylaminomethylphenol, 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, N, N, N ', N'-tetramethyl-4,4'-di -Aminodiphenylmethane, 1,2-bis [(2-methylphenyl) amino] ethane, 1,2-bis (phenylamino) propane, (o-tolyl) biguanide, bis [4- (1 ', 3 '-Dimethylbutyl) phenyl] amine, tertiary octylated N-phenyl-1-naphthylamine, mixture of mono- and dialkylated tert-butyl / tert-octyldiphenylamine, mixture of mono- and dialkylated nonyldiphenylamine, Mixtures of mono- and dialkylated nonyldiphenylamines, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexylphenylamines, mono- and dialkylated tert-butyldiphenylamines Mixture, 2,3-di-hydro-3,3-di Methyl-4H-1,4-benzothiazine, phenothiazine, mixture of mono and dialkylated tert-butyl / tert-octylphenothiazine, mixture of mono- and dialkylated tert-octyl-phenothiazine, N-allylphenothiazine , N, N, N ', N'-tetraphenyl-1,4-diaminobut-2-ene, N, N-bis (2,2,6,6-tetramethyl-piperid-4-yl- Hexamethylenediamine, bis (2,2,6,6-tetramethylpiperid-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6, 6-tetramethylpiperidin-4-ol.
[319] 2. UV absorbers and light stabilizers
[320] 2.1. 2- (2'-hydroxyphenyl) benzotriazole , for example 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2 '-Hydroxyphenyl) benzotriazole, 2- (5'-tertbutyl-2'-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-(1,1,3,3 -Tetramethylbutyl) phenyl) benzotriazole, 2- (3 ', 5'-di-tert-butyl-2'-hydroxyphenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl- 2'-hydroxy-5'-methylphenyl) -5-chloro-benzotriazole, 2- (3'-secondarybutyl-5'-tert-butyl-2'-hydroxyphenyl) benzotriazole, 2- (2 '-Hydroxy-4'-octyloxyphenyl) benzotriazole, 2- (3', 5'-di-tert-amyl-2'-hydroxyphenyl) benzotriazole, 2- (3 ', 5'- Bis- (α, α-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole, 2- (3'-tertbutyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) phenyl ) -5-chlorobenzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5-chlorobenzo T Azole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chlorobenzotriazole, 2- (3'-tert-butyl-2' -Hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) benzotriazole, 2- (3'-tert-butyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl) phenyl ) Benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) carbonylethyl] -2'-hydroxyphenyl) benzotriazole, 2- (3'- Dodecyl-2'-hydroxy-5'-methylphenyl) benzotriazole, and 2- (3'-tertbutyl-2'-hydroxy-5 '-(2-isooctyloxycarbonylethyl) phenylbenzotria Sol, 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene glycol 300 and 2- [3'-tert-butyl Transesterification product of -5 '-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole; R is 3'-tert-butyl-4'-hydroxy-5' -2H-benzotriazol-2-ylphenyl , 2- [2'-hydroxy-3 '-(α, α-dimethylbenzyl) -5'-(1,1,3,3-tetramethylbutyl) phenyl] -benzotriazole; 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) phenyl] benzotriazole.
[321] 2.2. 2-hydroxybenzophenones , for example 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[322] 2.3. Esters of unsubstituted or substituted benzoic acid , for example 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butylbenzoyl) resorcinol, Benzoyl resorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
[323] 2.4. Acrylates such as ethyl α-cyano-β, β-diphenylacrylate, isooctyl α-cyano-β, β-diphenylacrylate, methyl α-carbomethoxycinnamate, methyl α-cya No-β-methyl-p-methoxycinnamate, butyl α-cyano-β-methyl-p-methoxycinnamate, methyl α-carbomethoxy-p-methoxycinnamate and N- (β-carr Bomethoxy-β-cyanovinyl) -2-methylindolin.
[324] 2.5. 2,2'-thiobis [4- (1,1,3,3) with a nickel compound , for example with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, where appropriate -Tetramethylbutyl) phenol] (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl benzyl phosphonic acid monoalkyl ester Nickel salts of (eg methyl esters or ethyl esters), nickel complexes of ketoximes (eg 2-hydroxy-4-methylphenyl undecylketoxime), 1-phenyl-4-lauroyl with additional ligands where appropriate Nickel complex of -5-hydroxypyrazole.
[325] 2.6. Common hindered amines , for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) Succinate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) n- Butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid Condensate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-tri Linear or cyclic condensates of azine, tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperi Dill) -1,2,3,4-butanetetracarboxylate, 1,1 '-(1,2-ethanediyl) -bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl -2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis (1, 2,2,6,6-pentamethylpiperidyl) -2-n-butyl-2- (2-hydroxy-3,5-di-tert-butylbenzyl) malonate, 3-n-octyl-7, 7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, N, N'-bis (2,2,6,6-tetramethyl-4-pi Ferridyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine linear or cyclic condensates, 2-chloro-4,6-bis (4-n-butyl Condensate of amino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 2-chloro-4,6- Condensation of di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane Water, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro [4.5] decane-2,4-dione, 3-dodecyl-1- ( 2,2,6,6-tetramethyl-4-piperidyl) pyrrolidine-2,5-dione, 3-dodecyl-1- (1,2,2,6,6-pentamethyl-4- Piperidyl) pyrrolidine-2,5-dione, 5- (2-ethylhexanoyl) -oxymethyl-3,3,5-trimethyl -2-morpholino, 1,3,5-tris (N-cyclohexyl-N- (2,2,6,6-tetramethylpiperazin-3-one-4-yl) amino) -s-tri Azine, 1,3,5-tris (N-cyclohexyl-N- (1,2,2,6,6-pentamethylpiperazin-3-one-4-yl) amino) -s-triazine, 4 A mixture of -hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, N, N'-bis- (2,2,6,6-tetramethyl-4- Condensates of piperidyl) hexamethylenediamine and 4-cyclohexylamino-2,6-di-chloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2, Condensates of 4-butylamino-2,2,6,6-tetramethylpiperidine as well as 4,6-trichloro-1,3,5-triazine (CAS Reg. No. [136504-96-6 ]); N, N-dibutylamine and 4-butylamino-2,2,6,6-tetramethylpy, as well as 1,6-hexanediamine and 2,4,6-trichloro-1,3,5-triazine Condensates of ferridine (CAS Reg. No. [192268-64-7]; N- (2,2,6,6-tetramethyl-4-piperidyl) -n-dodecylsuccinimide, N- (1,2,2,6,6-pentamethyl-4-piperidyl) -n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3 , 8-diaza-4-oxo-spiro [4,5] decane, 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxosispiro Reaction product of [4,5] decane and epichlorohydrin, 1,1-bis (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl) -2- (4-meth Methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, 4-methoxymethylenemalon Acid and diesters of 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly- [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4 Piperidyl)] siloxane, maleic anhydride-α-olefin Of the copolymer with 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-amino-reaction product of piperidine.
[326] 2.7. Oxamides , for example 4,4'-dioctyloxyoxananilide, 2,2'-diethoxyoxananilide, 2,2'-dioctyloxy-5,5'-di-tert-butoxananilide, 2, 2'-didodecyloxy-5,5'-di-tert-butoxananilide, 2-ethoxy-2'-ethyloxaanilide, N, N'-bis (3-dimethylaminopropyl) oxaamide, 2- Ethoxy-5-tert-butyl-2'-ethoxananilide and mixtures thereof with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide, o- and p-methoxy- Mixtures of double substituted oxaanilides and mixtures of o- and p-ethoxy-disubstituted oxaanilides.
[327] 2.8. 2- (2-hydroxyphenyl) -1,3,5-triazine , for example 2,4,6-tris (2-hydroxy-4-octyloxyphenyl) -1,3,5-triazine , 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2,4-dihydroxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4- Dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-octyloxyphenyl) -4,6-bis (4-methylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-dodecyloxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-tridecyloxy Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxypropoxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxypropyloxy) phenyl]- 4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxypropoxy) Phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- (2-hydroxy-4-hexyloxy) phenyl-4,6-diphenyl-1 , 3,5-triazine, 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2,4,6-tris [2-hydrate Hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl] -1,3,5-triazine, 2- (2-hydroxyphenyl) -4- (4-methoxyphenyl) -6 -Phenyl-1,3,5-triazine, 2- {2-hydroxy-4- [3- (2-ethylhexyl-1-oxy) -2-hydroxypropyloxy] phenyl} -4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazine.
[328] 3. Metal deactivators such as N, N'-diphenyloxaamide, N-salicyl-N'-salicyloylhydrazine, N, N'-bis (salicyloyl) hydrazine, N, N ' -Bis (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis (benzylidene) oxalyl dihydrazide, oxa Anilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N, N'-diacetyladifoyl dihydrazide, N, N'-bis (salicyloyl) oxalyl dihydrazide, N, N ' Bis (salicyloyl) thiopropionyl dihydrazide.
[329] 4. Phosphites and phosphonites such as triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, disdis Tearylpentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol depot Spite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol diphosphite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite , Tetrakis (2,4-di-tert-butyl Nil) 4,4'-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz [d, g] -1,3,2-di Oxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl) ethylphosphite, 6-fluoro-2,4 , 8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, 2,2 ', 2 "-nitrilo [triethyltris (3, 3 ', 5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3', 5,5'-tetra-tertiary Butyl-1,1'-biphenyl-2,2'-diyl) phosphite, 5-butyl-5-ethyl-2- [2,4,6-tri-tert-butylphenoxy) -1,3,2 -Dioxaphosphiran.
[330] Particular preference is given to the following phosphites:
[331] Tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ^R 168, manufactured by Ciba-Geigy), tris (nonylphenyl) phosphite,
[332]
[333] 5. Hydroxylamines such as N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N , N-ditetedecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl- N-octadecylhydroxylamine, N, N-dialkylhydroxylamine derived from hydrogenated resin.
[334] 6. Nitrons , eg N-benzyl-alpha-phenylnitron, N-ethyl-alpha-methylnitron, N-octyl-alpha-heptylnitron, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecylnitrone, N-hexadecyl-alpha-pentadecylnitrone, N-octadecyl-alpha-heptadecylnitrone, N-hexadecyl-alpha-heptadecylnitrone, N- N, N'-dialkylhydroxylamine derived from octadecyl-alpha-pentadecylnitrone, N-heptadecyl-alpha-heptadecylnitrone, N-octadecyl-alpha-hexadecylnitrone, hydrogenated resin amine Nitron derived from.
[335] 7. Thio synergists , for example dilauryl thiodipropionate or distearyl thiodipropionate.
[336] 8. Peroxide decomposing compounds , for example esters of β-thiodipropinic acid, such as lauryl, stearyl, myristyl or tridecyl esters, zinc salts of mercaptobenzimidazole or 2-mercaptobenzimidazole, di Butyldithiocarbamate zinc, dioctadecyl disulfide, pendaerythritol tetrakis (β-dodecylmercapto) propionate.
[337] 9. Polyamide stabilizers such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.
[338] 10. Basic co-stabilizers , for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids Such as calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatechol or tin pyrocatechol.
[339] 11. Nucleating agents , for example inorganic substances (eg talc), metal oxides (eg titanium dioxide or magnesium oxide), preferably phosphates, carbonates or sulfates of alkaline earth metals; Organic compounds (mono- or polycarboxylic acids) and salts thereof such as 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; Polymeric compounds such as ionic copolymers ("ionomers"). 1,3: 2,4-bis (3 ', 4'-dimethylbenylidene) sorbitol, 1,3: 2,4-di (paramethyldibenzylidene) sorbitol and 1,3: 2,4-di (Benzylidene) sorbitol.
[340] 12. Fillers and reinforcing agents , for example powders of calcium carbonate, silicates, glass fibers, glass spheres, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood powder and other natural products or Fiber, synthetic fiber.
[341] 13. Other additives , for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow control agents, optical brighteners, flame retardants, antistatic agents and blowing agents.
[342] 14. Benzofuranone and indolinones, for example US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US- A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 As disclosed in the heading or 3- [4- (2-acetoxyethoxy) phenyl] -5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3- -(2-stearoyloxyethoxy) phenyl] benzofuran-2-one, 3,3'-bis [5,7-di-tert-butyl-3- (4- [2-hydroxyethoxy]- Phenyl) benzofuran-2-one], 5,7-di-tert-butyl-3- (4-ethoxyphenyl) benzofuran-2-one, 3- (4-acetoxy-3,5-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (3,5-dimethyl-4-pivaloyloxyphenyl) -5,7-di-tert-butyl-benzofuran-2-one , 3- (3,4-dimethylphenyl) -5,7-di-tert-butyl-benzofuran-2-one, 3- (2,3-di-methylphenyl) -5,7-di-tert-butylphenyl-benzo Furan-2-one.
[343] 15. Amine oxides such as amine oxide derivatives, such as didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide as described in US Pat. Nos. 5,844,029 and 5,880,191. US Pat. Nos. 5,844,029 and 5,880,191 disclose the use of saturated hydrocarbon amine oxides for the stabilization of thermoplastics. The thermoplastic composition may further comprise a stabilizer or a mixture of stabilizers selected from phenolic antioxidants, hindered amine light stabilizers, ultraviolet light absorbers, organophosphorus compounds, alkaline metal salts of fatty acids and thio synergists. The use of amine oxides and other stabilizers together to stabilize polyolefins is not illustrated.
[344] More preferred compositions comprise further additives, in particular phenolic antioxidants, light stabilizers or process stabilizers, in addition to components (b) and (c).
[345] Particularly preferred additives are phenolic antioxidants (list 1 above), hindered amines (2.6 listed above), photostabilizers of benzotriazoles and / or hydroxyphenyltriazines (2.1 and 2.8 listed above), phosphite And phosphonites (4 of the above list) and peroxide destroying compounds (5 of the above list).
[346] Particularly preferred further additives (stabilizers) are benzofuran-2-ones, for example as described in US-A-4,325,863, US-A-4,338,244 or US-A-5,175,312.
[347] The composition of the present invention may also contain other UV absorbers selected from the group consisting of s-triazines, oxanilides, hydroxybenzophenones, benzoates and α-cyanoacrylates. In particular, the compositions of the present invention comprise an effective stabilizing amount of at least one 2-hydroxyphenyl-2H-benzotriazole; Tris-aryl-s-triazine; Or sterically hindered amines or mixtures thereof. Pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling agents, basic co-stabilizers, other light stabilizers such as UV absorbers and / or hindered amines, metal deactivators, metal oxides, organophosphorus compounds, hydroxylamines, and these Mixtures, in particular pigments, phenolic antioxidants, calcium stearate, zinc stearate, 2- (2'-hydroxyphenyl) benzotriazole and 2- (2-hydroxyphenyl) -1,3,5-tria Preference is given to further components selected from the group consisting of anti-UV UV absorbers and hindered amines.
[348] In the present invention, the thermoplastic polymer contains a combination of a high molecular weight hindered amine and a low molecular weight hindered amine of hydroxyhydrocarbyloxyamines in addition to the flame retardant to improve performance in both light stability and flame retardancy. Is one of the discoveries. Therefore, the present invention,
[349] (A) thermoplastic polymer,
[350] (B) an flame retardant selected from ammonium polyphosphate, halogenated and / or melamine based flame retardants, and
[351] Light and aging comprising a combination of (C) a low molecular weight hindered amine of (C1) hydroxyhydrocarbyloxyamines, and (C2) a hindered amine light stabilizer comprising conventional high molecular weight hindered amines It relates to a flame retardant composition stabilized from the adverse effects of.
[352] Preferred polymers (A) in the composition are as described above in (a).
[353] Halogenated flame retardants useful as component (B) in the compositions of the present invention are organic aromatic halogenated compounds, such as halogenated benzenes, biphenyls, phenols, ethers or esters thereof, bisphenols, diphenyloxides, aromatic carboxylic acids or polyacids, Anhydrides, amides or imides thereof; Organic cycloaliphatic or polycycloaliphatic halogenated compounds; And organic aliphatic halogenated compounds such as halogenated paraffins, oligo- or polymers, alkylphosphates or alkylisocyanurates. These components are well known in the art. See, for example, US Pat. No. 4,579,906 (columns 3, lines 30-41), US Pat. No. 5,393,812; Plastics Additives Handbook, edited by H. Zweifel, 5 ^th Ed, Hanser Publ., Munich 2001, pp. See 681-698.
[354] Halogenated flame retardants can be selected, for example, from chlorinated or brominated compounds, such as the following compounds:
[355] Chloroalkyl phosphate esters (ANTIBLAZE ^R AB-100, Albright &Wilson; FYROL ^R FR-2, Akzo Nobel),
[356] Polybrominated diphenyl oxide (DE-60F, manufactured by Great Lakes Corporation),
[357] Decabromodiphenyl oxide (DBDPO; SAYTEX ^R 102E),
[358] Tris [3-bromo-2,2-bis (bromomethyl) propyl] phosphate (PB 370 ^R , FMC Corporation),
[359] Bis (2,3-dibromopropyl ether) of bisphenol A (PE68)
[360] Brominated epoxy resin,
[361] Ethylene-bis (tetrabromophthalimide) (SAYTEX ^R BT-93),
[362] Bis (hexachlorocyclopentadieno) cyclooctane (DECLORANE PLUS ^R ),
[363] Chlorinated paraffin,
[364] 1,2-bis (tribromophenoxy) ethane (FF680),
[365] Tetrabromo-bisphenol A (SAYTEX ^R RB100),
[366] Ethylene bis- (dibromo-norborandidicarboximide) (SAYTEX ^R BN-451),
[367] Bis- (hexachlorocyclopentadieno) cyclooctane,
[368] Tris- (2,3-dibromopropyl) -isocyanurate,
[369] Ethylene-bis-tetrabromophthalimide.
[370] Preferred as component (B) are brominated flame retardants.
[371] The most preferred flame retardant (B) in the composition of the present invention is
[372] (B1) melamine based flame retardants and / or ammonium polyphosphates,
[373] (B2) bis- (hexachlorocyclopentadieno) cyclooctane,
[374] (B3) tris- (2,3-dibromopropyl) -isocyanurate,
[375] (B4) ethylene-bis-tetrabromophthalimide,
[376] (B5) 1,2,5,6,9,10-hexabromo-cyclo-dodecane,
[377] (B6) ethane-1,2-bis (pentabromophenyl),
[378] (B7) tris (3-bromo-2,2- (bromomethyl) propyl) phosphate.
[379] Particularly preferred flame retardant (B) in the composition of the present invention is as described first with respect to component (b).
[380] Flame retardant (B) is often contained in an amount of 0.5 to 50% by weight of the polymerizable substrate (A); More preferred dosages of the most preferred flame retardant (B) are as described above for component (b).
[381] The (B) :( C) ratio in the composition is preferably in the range from 20: 1 to 250: 1.
[382] The (C1) :( C2) ratio in the composition ranges from 1: 5 to 5: 1. If the polymerizable substrate (A) is a polyolefin, the low molecular weight component (C1) is for example 40 to 95 based on 100 parts by weight of the component (C) consisting of (C1) and (C2) in the same amount or in a larger amount than (C2). Used in parts by weight.
[383] In polyolefins with main component polyethylene, the amount of low molecular weight portion (C1) is often from about half of the total amount of component (C), such as from about 40 to about 70 weight percent of the total component (C), more particularly from 45 to about 55 Weight percent.
[384] In polyolefins with main component polypropylene, the amount of low molecular weight portion (C1) is often at least 1/2 of the total amount of component (C), such as from about 50 to about 90 weight percent of the total component (C), more particularly from 60 to about 85 wt%.
[385] Under such conditions in the polyolefin, the low molecular weight component (C1) may be hydrocarbyloxyamines. Therefore, another object of the present invention,
[386] (A) polyolefin,
[387] (B) a flame retardant selected from ammonium polyphosphate, halogenated and / or melamine based flame retardants, and
[388] (C) 40 to 95 parts by weight of low molecular weight hindered amines of (C1) hydrocarbyloxyamines and (C2) 5 to 60 parts by weight of conventional high molecular weight hindered amines based on 100 parts by weight of the total component (C) It also relates to a composition comprising a combination of hindered amine light stabilizers.
[389] The low molecular weight hindered amines of hydroxyhydrocarbyloxyamine or optionally hydrocarbyloxys (C1) range from 200 to 1000 g / mol, in particular from 300 to 800 g / mol molecular weight. It may be a compound or a mixture of compounds satisfying the molecular weight condition. Particularly preferred are, for example,
[390] 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylaminopiperidine;
[391] Bis (1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate;
[392] Bis (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) adipate;
[393] 1- (2-hydroxy-2-methylpropoxy) -4-octadecanoyloxy-2,2,6,6-tetramethylpiperidine.
[394] High molecular weight sterically hindered amines (C2) are either unsubstituted by nitrogen atoms ((secondary hindered amines) or substituted by alkyl, especially methyl (alkylated tertiary hindered amines) or part of the polymer backbone (polymeric tertiary hindered amines). Is a common type containing 2,2,6,6-tetramethyl-4-piperidyl residues whose molecular weight is usually 1200 to 10000 g / mol, especially 1500 to 5000 g / mol. Examples of such compounds useful in the compositions can be found in the compounds listed under 2.6 above, such as the following compounds:
[395] Examples of high molecular weight secondary hindered amines
[396]
[397] Wherein n ranges from 3 to 5.
[398] Examples of high molecular weight methylated tertiary hindered amines
[399]
[400] (n is as defined above)
[401] being.
[402] Examples of high molecular weight polymerizable tertiary hindered amines
[403]
[404] Particularly preferred compounds of component (C2) are those containing 2,2,6,6-tetramethyl-4-piperidyl residues which are unsubstituted or substituted by alkyl, in particular methyl by nitrogen atoms. Particularly preferred compounds of component (C2) are compounds containing triazine residues as structural backbones.
[405] In general, component (C) is contained in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, in particular 0.1 to 3% by weight, based on polymer component (A). The weight ratio of (C1) :( C2) is in the range of 1:10 to 10: 1, most preferably 1: 1 to 10: 1.
[406] The components optionally used in the compositions of the present invention and methods of using them are as described above.
[407] The following examples are for illustrative purposes only and do not limit the invention in any sense. Room temperature represents a temperature in the range of 20-25 ° C. % Is by weight unless otherwise indicated.
[408] The abbreviations are as follows:
[409] v Skin
[410] w weight part
[411] Nuclear Magnetic Resonance (NMR) of ¹ Hnmr ¹ H
[412] m / z mass spectrometer (atomic unit)
[413] amu molecular weight (g / mol) (atomic unit)
[414] Number average of M _n molecular weight (typically measured by GPC)
[415] PP polypropylene
[416] PE polyethylene
[417] PE-LD Low Density Polyethylene (LDPE)
[418] The hindered amines of hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines (component c) for use in the examples are the following compounds:
[419] c1: as described in Example 73 of US Pat. No. 6,271,377
[420]
[421] c2: the main component of the formula Mixtures of phosphorus compounds: wherein _{three of} R ₁ , R ₂ , R ₃ and R ₄ are
[422] And one of R ₁ , R ₂ , R ₃ and R ₄ is hydrogen.
[423] (c2 is described in Example 3 of US Pat. No. 5,844,026)
[424] c3:
[425]
[426] c4:
[427]
[428] (Example 2 of US Pat. No. 6,117,995)
[429] Further stabilizers used in the examples are the following compounds:
[430] A:
[431] Where R is Term.
[432] B: poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [[(2,2,6,6- Tetramethyl-4-piperidyl) imino] hexamethylene [(2,2,6,6-tetramethyl-4-piperidyl) imino]] (CAS-No. 70624-18-9)
[433] C: bis (2,2,6,6-tetramethylpiperidin-4-yl) -sebacate (CAS-No. 52829-07-9)
[434] D: oligomer of formula (CAS-No. 65447-77-0)
[435]
[436]
[437]
[438] Compounds c2, c3 and A-G are stabilizers sold by Ciba Specialty Chemicals.
[439] Example 1
[440] Sample Preparation: The polymer powder and stabilizer were premixed (Henkel mixer, 800 rpm, room temperature), the pigment powder and flame retardant were added to the PP as a concentrate and homogenized in a drum mixer. Homogenization and granulation was carried out by an extruder (Collin ^R twin screw extruder, up to 200 ° C., 100 rpm). The mixture was then processed into a flat membrane using a single screw extruder (up to 200 ° C., 70 rpm) with a corresponding nozzle (sample size 2 mm thick, 10 cm wide).
[441] Aging : Punched samples were exposed to accelerated aging (Atlas ^R WOM Ci 65, 0.35 W / m ² (340 nm), 102 minutes dry, 18 minutes water spray, 63 ° C. black panel temperature). The effect of the aging test on the surface was evaluated as follows:
[442] Neck observation of choking (choking indicates disintegration on the surface)
[443] Gloss: minolta; Decomposition of the surface reduces the reflection of polarized light (60 ° gloss as defined in DIN 67530).
[444] ΔE: Color change (measured according to DIN 6174).
[445] Formulations :
[446] 84 parts by weight of polypropylene-ethylene copolymer (Novolen ^R PPG1022),
[447] 15 parts by weight of a PE-based flame retardant masterbatch containing 51% by weight of ethylene-bis-tetrabromophthalimide (b4) and 17% by weight of Sb ₂ O ₃ ,
[448] 1 part by weight of TiO ₂ , and
[449] 0.2 part by weight of blue pigment (Cromophtal blue 4GNP)
[450] And stabilizers shown in the tables below (amounts expressed in weight percent of total formulation).
[451] The results are shown in the table below.
[452] Table : Surface evaluation after aging for 2000 hours
[453]
[454] Samples containing a combination of flame retardant and hindered amines of the present invention exhibit no choking and exhibit excellent gloss and significantly lower color change compared to samples in which component c has been replaced with other hindered amines.
[455] Example 2
[456] Samples were prepared and subjected to an accelerated aging test as described in Example 1.
[457] Formulations :
[458] 89 parts by weight of polypropylene-ethylene copolymer (Novolen ^R PPG1022),
[459] 10 parts by weight of a PE-based flame retardant masterbatch containing 30% by weight of tris- (2,3-dibromopropyl) -isocyanurate (b3) and 15% by weight of Sb ₂ O ₃ ,
[460] 1 part by weight of TiO ₂ , and
[461] 0.2 part by weight of blue pigment (Cromophtal blue 4GNP)
[462] And stabilizers shown in the tables below (amounts expressed in weight percent of total formulation).
[463] The results are shown in the table below.
[464] Table : Surface evaluation after aging for 2000 hours
[465]
[466] Replacing the compound c3 with the same amount of c2 or c4 in this example shows better properties.
[467] Example 3
[468] Sample Preparation: The polymer powder, flame retardant and stabilizer were premixed (Henkel mixer, 800 rpm, room temperature), pigment was added as a concentrate in PE-LD and homogenized in a drum mixer. Homogenization and granulation was carried out by extrusion (Berstorff ^R twin screw extruder (up to 220 ° C., 100 rpm)). Test samples (44 x 68 x 2 mm) were obtained by Engeling at plasticization temperatures of up to 200 ° C and molding temperatures of 50 ° C. These samples were subjected to accelerated aging testing and evaluation as described in Example 1.
[469] Formulations :
[470] 73 parts by weight of polypropylene-ethylene copolymer (Appryl ^R 3060),
[471] 25 parts by weight of melamine polyphosphate (flame retardant b1, Melapur ^R P 46),
[472] 2 parts by weight of a blue pigment masterbatch (10% Cromophtal blue 4GNP in PE-LD),
[473] Of commercially available phenolic antioxidants (tris (2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) 1: 1 mixture), 0.15 parts by weight of Ciba Specialty Chemicals)
[474] Stabilizers shown in the table below (amounts expressed in weight percent of total formulation).
[475] The results are shown in the table below.
[476] Table : surface evaluation after aging for 1000 hours
[477]
[478] Example 4
[479] Sample preparation, accelerated aging and evaluation of the samples were performed as described in Example 3.
[480] Formulations :
[481] 82 parts by weight of polypropylene-ethylene copolymer (Appryl ^R 3060),
[482] 12 parts by weight of bis- (hexachlorocyclopentadieno) cyclooctane (flame retardant b2, Dechloran Plus ^R ),
[483] 4 parts by weight of Sb ₂ O ₃ ,
[484] 2 parts by weight of a blue pigment masterbatch (10% Cromophtal blue 4GNP in PE-LD),
[485] Of commercially available phenolic antioxidants (tris (2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) 1: 1 mixture), 0.15 parts by weight of Ciba Specialty Chemicals)
[486] Stabilizers shown in the table below (amounts expressed in weight percent of total formulation).
[487] The results are shown in the table below.
[488] Table : surface evaluation after aging for 1000 hours
[489]
[490] Example 5
[491] Sample preparation, accelerated aging and evaluation of the samples were performed as described in Example 3. The formulation was identical to the formulation of Example 3 except for replacing the melamine polyphosphate flame retardant with the same amount of ammonium polyphosphate (flame retardant b1; Exolith ^R AP 752). The results are shown in the table below.
[492] Table : Surface evaluation after aging for 1500 hours
[493]
[494] Example 6
[495] Sample preparation, accelerated aging and evaluation of the samples were performed as described in Example 3.
[496] Formulations :
[497] 92 parts by weight of polypropylene-ethylene copolymer (Appryl ^R 3060),
[498] 4 parts by weight of tris (3-bromo-2,2,-(bromomethyl) propyl) phosphate (flame retardant, FR 372, manufactured by Dead Sea Bromine),
[499] Sb ₂ O ₃ 2 parts by weight,
[500] 2 parts by weight of a blue pigment masterbatch (10% Cromophtal blue 4GNP in PE-LD),
[501] Of commercially available phenolic antioxidants (tris (2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) 1: 1 mixture), 0.15 parts by weight of Ciba Specialty Chemicals)
[502] Stabilizers shown in the table below (amounts expressed in weight percent of total formulation).
[503] The results are shown in the table below.
[504] Table : Surface evaluation after aging for 1500 hours
[505]
[506] Example 7
[507] Sample preparation, accelerated aging and evaluation of the samples were carried out as described in Example 3.
[508] Formulations :
[509] 88 parts by weight of polypropylene-ethylene copolymer (Appryl ^R 3060),
[510] 8 parts by weight of ethane-1,2-bis (pentabromophenyl) (flame retardant b6, Saytex ^R 8010),
[511] 4 parts by weight of Sb ₂ O ₃ ,
[512] 2 parts by weight of a blue pigment masterbatch (10% Cromophtal blue 4GNP in PE-LD),
[513] Of commercially available phenolic antioxidants (tris (2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) 1: 1 mixture), 0.15 parts by weight of Ciba Specialty Chemicals)
[514] Stabilizers shown in the table below (amounts expressed in weight percent of total formulation).
[515] The results are shown in the table below.
[516] Table : Surface evaluation after aging for 750 hours
[517]
[518] The thermoplastic polymer composition according to the invention contains hindered amines of hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines and optionally further stabilizers, which are stabilized and flame retardant from the harmful effects of light and aging.

权利要求:
Claims (19)
[1" claim-type="Currently amended] For imparting both aging stability and flame retardancy to the thermoplastic polymer (a),
(b) (b1) melamine based flame retardants and / or ammonium polyphosphates,
(b2) bis- (hexachlorocyclopentadieno) cyclooctane,
(b3) tris- (2,3-dibromopropyl) -isocyanurate,
(b4) ethylene-bis-tetrabromophthalimide,
(b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecane,
(b6) one or more flame retardants selected from ethane-1,2-bis (pentabromophenyl); And
(c) Combination of hindered amine light stabilizers of hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines, provided the flame retardant is not (b4) unless the hindered amine is hydroxyhydrocarbyloxy.
[2" claim-type="Currently amended] The combination of claim 1 for imparting outdoor aging stability and flame retardancy to the polyolefin.
[3" claim-type="Currently amended] The combination of claim 1, wherein the hindered amine light stabilizer of component (c) is a cyclic hindered amine corresponding to formula (1):
(One)
In the food,
G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms or collectively pentamethylene, and
E ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl; Or E ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl each substituted by 1 to 3 OH groups in the aliphatic moiety,
T is required to complete formula (1) to combine the hindered amine nitrogen atom and two quaternary carbon atoms substituted by G ₁ and G ₂ to form a 5- or 6-membered aliphatic ring structure, especially a piperidine ring. It is an organic group; Or oligomers prepared by the reaction of a dialkyl ester or isocyanate with a compound of formula (1) wherein E ₁ contains one OH group and T is -CH ₂ -CH (OH) -CH _2- A polymerizable hindered amine molecule; Or a simple diester or urethane derivative of a compound of formula (1) wherein E ₁ contains one OH group and T is —CH ₂ —CH (OH) —CH ₂ —.
[4" claim-type="Currently amended] A combination according to claim 1 comprising from 0.01 to 10% by weight of component (c) based on the weight of polymer (a).
[5" claim-type="Currently amended] The process according to claim 1, wherein 1 to 50% by weight of component (b1) or 0.5 to 20% by weight of components (b2), (b3) and (b4), based on the weight of the polymer (a) according to claim 1 , (b5), a combination comprising at least one of (b6).
[6" claim-type="Currently amended] The combination of claim 1 for imparting aging stability and flame retardancy to polyethylene, polypropylene, or copolymers or mixtures thereof.
[7" claim-type="Currently amended] The compound according to claim 1, which is a pigment, dye, plasticizer, antioxidant, thixotropic agent, leveling agent, basic co-stabilizer, UV absorber and / or hindered amines, metal deactivators, metal oxides, organic compounds, Hydroxylamine, and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, zinc stearate, hindered amines, 2- (2'-hydroxyphenyl) benzotriazole and 2- (2-hydroxy A combination comprising at least one additional component selected from the group consisting of UV absorbers of phenyl) -1,3,5-triazines.
[8" claim-type="Currently amended] Thermoplastic polymer comprising adding to the thermoplastic polymer tris- (2,3-dibromopropyl) -isocyanurate and the hindered amine light stabilizer hydrocarbyloxyamine or hydroxyhydrocarbyloxyamines To impart photostability and flame retardancy.
[9" claim-type="Currently amended] (a) polyolefins,
(b) a flame retardant tris- (2,3-dibromopropyl) -isocyanurate and
(c) Flame retardant and photostabilized compositions comprising hydrocarbyloxyamines or hydroxyhydrocarbyloxyamines which are hindered amine light stabilizers.
[10" claim-type="Currently amended] (a) polyolefins;
(b) (b1) melamine based flame retardants and / or ammonium polyphosphates,
(b2) bis- (hexachlorocyclopentadieno) cyclooctane,
(b3) tris- (2,3-dibromopropyl) -isocyanurate,
(b5) 1,2,5,6,9,10-hexabromo-cyclo-dodecane,
(b6) a flame retardant selected from ethane-1,2-bis (pentabromophenyl); And
c) Flame-retardant photostabilized composition comprising a hindered amine light stabilizer of hydroxyhydrocarbyloxyamines.
[11" claim-type="Currently amended] The flame-retardant photostabilized composition of claim 10, wherein component (c) is a compound of formula (1):
(One)
In the food,
G ₁ and G ₂ are independently alkyl having 1 to 4 carbon atoms or collectively pentamethylene, and
E ₁ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₁₅ aralkyl each substituted by 1 to 3 OH groups in the aliphatic moiety,
T is required to complete formula (1) to combine the hindered amine nitrogen atom and two quaternary carbon atoms substituted by G ₁ and G ₂ to form a 5- or 6-membered aliphatic ring structure, especially a piperidine ring. It is an organic group; Or oligomers prepared by the reaction of a dialkyl ester or isocyanate with a compound of formula (1) wherein E ₁ contains one OH group and T is -CH ₂ -CH (OH) -CH _2- A polymerizable hindered amine molecule; Or a simple diester or urethane derivative of a compound of formula (1) wherein E ₁ contains one OH group and T is —CH ₂ —CH (OH) —CH ₂ —.
[12" claim-type="Currently amended] (a) a thermoplastic polymer,
(b) an flame retardant selected from ammonium polyphosphate, halogenated and / or melamine based flame retardants, and
(c) a hindered amine light stabilizer comprising (c1) low molecular weight hindered amines of hydroxyhydrocarbyloxyamines, and (c2) conventional high molecular weight secondary or alkylated or polymerizable tertiary hindered amines. Flame retardant composition stabilized from the adverse effects of light and aging, including the combination.
[13" claim-type="Currently amended] 13. The composition of claim 12 wherein component (a) is a polyolefin.
[14" claim-type="Currently amended] (a) polyolefins,
(b) a flame retardant selected from ammonium polyphosphate, halogenated and / or melamine based flame retardants, and
(c) 40 to 95 parts by weight of a low molecular weight hindered amine of (c1) hydrocarbyloxyamines and (c2) a secondary, alkylated or polymerizable tertiary of a common high molecular weight, based on 100 parts by weight of the total component (c) A flame retardant composition stabilized from the adverse effects of light and aging, comprising a combination of sterically hindered amine light stabilizers comprising from 5 to 60 parts by weight of hindered amines.
[15" claim-type="Currently amended] The method according to claim 12 or 14, wherein component (b)
(b1) melamine based flame retardants and / or ammonium polyphosphates,
(b2) bis- (hexachlorocyclopentadieno) cyclooctane,
(b3) tris- (2,3-dibromopropyl) -isocyanurate,
(b4) ethylene-bis-tetrabromophthalimide,
(b5) 1,2,5,6,9, 10-hexabromo-cyclo-dodecane,
(b6) ethane-1,2-bis (pentabromophenyl),
(b7) a composition selected from tris (3-bromo-2,2- (bromomethyl) propyl) phosphate.
[16" claim-type="Currently amended] The low molecular weight hindered amine (c1) of the hydrocarbyloxyamine or the hydroxyhydrocarbyloxyamines has a molecular weight in the range of 200 to 1000 g / mol and has a high molecular weight hindered amine. (c2) has a molecular weight of 1200 to 10000 g / mol.
[17" claim-type="Currently amended] The method according to claim 9, 10, 12 or 14, wherein the amount of component (b) is 0.5 to 50% by weight based on the weight of component (a), and the amount of component (c) is 0.01 to 10. Composition by weight.
[18" claim-type="Currently amended] 15. The method of claim 9, 10, 12 or 14, wherein the pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling agents, other co-stabilizers, and / or sterically hindered amines, such as UV absorbers, Metal deactivators, metal oxides, organophosphorus compounds, hydroxylamines, light stabilizers, and mixtures thereof, in particular pigments, phenolic antioxidants, calcium stearate, zinc stearate, hindered amines, 2- (2'- A composition containing at least one additional component selected from the group consisting of hydroxyphenyl) benzotriazole and UV absorbers of 2- (2-hydroxyphenyl) -1,3,5-triazines.
[19" claim-type="Currently amended] 15. A molded or extruded article comprising the composition of any one of claims 9, 10, 12 or 14.

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同族专利:

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FR2817873B1|2005-02-11|

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GB2373507A|2002-09-25|

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BR0106359A|2002-08-20|

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2000-12-12|Priority to EP00811174

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2000-12-12|Priority to EP00811174.2

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2001-12-10|Application filed by 시바 스폐셜티 케미칼스 홀딩 인코포레이티드

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2002-06-20|Publication of KR20020046204A

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2008-02-20|Application granted

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2008-02-20|Publication of KR100805296B1

优先权:

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申请号 | 申请日 | 专利标题

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EP00811174|2000-12-12|

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EP00811174.2|2000-12-12|