TW201202325A - Flame retardant compositions of phosphinic acid salts and nitroxyl derivatives - Google Patents

Abstract

The present invention relates to flame retardant polymer compositions which comprise mixtures of salts of phosphinic acids and 2, 2, 6, 6-tetraalkylpiperidines. The mixtures are especially useful for the manufacture of flame retardant compositions based on thermoplastic polymers.

Description

201202325 VI. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a flame retardant polymer composition comprising a combination of a phosphinate and a so-called sterically hindered nitrate derivative. These compositions are especially useful in the preparation of flame retardant compositions based on thermoplastic polymers, especially based on polyolefin homopolymers and copolymers and copolymers thereof with vinyl monomers. [Prior Art] A flame retardant is added to a polymeric material (synthetic or natural material) to enhance the flame retardancy of the polymer. Depending on its composition, the flame retardant can be acted upon in a solid phase, a liquid phase or a gas phase in a chemical manner (e.g., in the form of a foam by releasing nitrogen), and/or in a physical manner (e.g., by creating a foam covering). The flame retardant interferes during the special stages of the combustion process (for example during heating, decomposition, ignition or flame propagation). There is still a need in the industry for flame retardant compositions having improved properties that can be used in different polymer matrices. Increased standards for safety and environmental requirements have led to stricter regulations. In particular, known flame retardants containing the elements do not meet all the necessary requirements. Therefore, halogen-free flame retardants are preferred, especially in terms of their preferred properties for flame-related density. Improved thermal stability and less rot behavior are other benefits of flame retardant compositions that are not dentate. Surprisingly, it has been found that a polymer composition having excellent flame retardancy can be prepared by adding a combination of a phosphinate and a so-called sterically hindered amine to a polymer matrix. Other benefits of the compositions of the present invention are improved electrical properties compared to the use of a toothed fr system (CT compared to the tracking index) and improved light stability 154949.doc 201202325. In addition, the 'flame retardant composition is resistant The so-called leaching. Contact with water does not reduce its flame retardant activity. Surprisingly, it has been found that by using the flame retardant composition of the present invention, halogen-containing flame retardants such as decyl diphenyl oxide, hydrazine compound, and filler can be greatly reduced or replaced. SUMMARY OF THE INVENTION The present invention is directed to a composition, particularly a flame retardant composition, comprising: a) a phosphinate 'as represented by the following structural formula: , Π ίί π R-P-OH (I) HO-P —Rip - 〇H (II),

X2 11 U

R or RR wherein: one of R1 and R2 represents hydrogen or (: 丨-(:8 alkyl; or both R and r2 represent Ci-Cs alkyl; and R3 represents C^-Cw alkyl) a c2_c alkylene group having a pendant phenyl group, a phenyl group, a (cvc:4 alkyl group), a 3-phenylene group, or a phenyl-Ci_C4 alkyl group; b) selected from the group consisting of Tetraalkylhexahydropyridine or tetraalkylhexahydropyrazine derivative: 2,2,6,6-tetraalkylhexahydropyridine-indole-oxide, hydroxy-2,2,6,6-tetradecane Hexahydropyridine, 1·alkoxy 2,2,6,6-tetraalkyl hexahydrogen ratio, 1 -decyloxy-2,2,6,6-hexahydropyrene ratio bite, 1 _Phenyl-2,2,6,6-tetraalkylhexahydropyrazine, 1-alkoxy-2,2,6,6-tetraalkylhexahydro-D-rhodium, and 1-methoxy- 2,2,6,6-hexahydro-n-ratio; and c) polymer matrix. 154949.doc 201202325 Another embodiment of the invention is a composition as defined above for use as a flame retardant. [Embodiment] A preferred embodiment of the present invention relates to a composition, particularly a flame retardant composition, comprising: a) an aluminum salt of diethylphosphinic acid (I), as represented by the following formula:

b) A tetraalkylhexahydropyridine derivative of the group consisting of: 2,2,6,6-tetraalkyl hexahydro-β ratio.定_1_Oxide, 1·trans group 2,2,6,6_tetrakilyl hexamethylene bismuth, 1-alkoxy-2,2,6,6-tetraalkyl hexahydro 1-decyloxy-2,2,6,6-hexahydropyrene ratio bite; and c) thermoplastic polymer matrix. The composition of the present invention exhibits excellent flame retardancy at the lower concentrations of components a) and b). UL-94 (Underwriter's Laboratories) can be obtained by looking at the concentrations of components a) and b) in the polymer matrix.

Subject 94)) V-2 grade and other excellent grades in the relevant test methods. The composition as defined above comprises the following components: Component a) The term phosphinic acid includes within its scope derivatives of phosphinic acid H2p(=〇)〇h, wherein one or two are directly bonded to the phosphorus atom A hydrogen atom has been substituted with an organic substituent such as a Cj-Cs alkyl group. 154949.doc 201202325 A tautomeric form of a hydrogen atom such as (:)-(:8-alkane phosphinic acid also encompasses HP(OH) 2, wherein an organic substituent such as a group directly bonded to a phosphorus atom is substituted. The term phosphinate preferably includes a metal salt in its range, for example, an alkali metal or a soil metal metal salt such as sodium I potassium salt, magnesium salt, Or a calcium or iron (II) salt, an iron (in) salt, a zinc salt or a boron salt. Defined as a linear chain of C,-C8 leuco or, if possible, a branched alkyl group and is, for example, a Base, ethyl, n-propyl, n-butyl 't-butyl, t-butyl, n-hexyl, n-octyl, or 2 ethylhexyl. defined as an alkyl group of the r3 chain or (if possible a branched Ci_c alkylene group, such as methylene, ethyl, 1,2- or 153, propyl, 2, 1,3- or 1,4 butyl. a phenyl group (^-(:) R3 is an alkyl group of, for example, a moiety or a divalent group thereof, wherein the dotted line points to a bonded carbon atom. The R3 group defined as a phenyl group is a 1,2-phenylene group. , 1,3-phenylene or hydrazine, 4, phenyl. The R3 system defined as (C--C4 alkyl) 丨·3 phenyl is substituted, for example, by 1-3 methyl or ethyl. 1,2-phenylene, 1,3-phenylene or 1,4-phenylene. R3 as defined as phenyl-Ci-C4 alkylene (for example) Ci-substituted Ci- One of the Cs alkyl groups. According to a preferred embodiment, the composition comprises an aluminum salt of diethyl hypophosphorous acid. According to an alternative embodiment, the term salt includes a non-metal salt, for example, by 154949.doc 201202325 phosphine. An acid addition salt obtained by the reaction of an acid with ammonia, an amine or a decylamine, such as (CrC^alkyl)4N+, (CVC4 alkyl)3NH+, (C2-C4 alkyl OH)4N+, (c2-c4 alkyl OH) 3NH+, (C2-C4 alkyl OH) 2N(CH3)2+, (c2-c4 alkyl OH)2NHCH3+, (C6H5)4N+, (C6H5)3NH+, (C6H5CH3)4N+, (C6H5CH3)3NH+, NH4+, Melamine or pulverized salt. In these acid addition salts, 'Synthesis, (C)-C4 alkyl) 1_ 4 or (2-ethyl)! 4 ammonium (such as tetradecylammonium, tetraethylammonium, 2-hydroxyethyltriammonium), melamine or phosphonium salt is particularly preferred. According to a preferred embodiment The salt of phosphinic acid (I) is represented by the following formula:

0 ,II r—ρ-σ

Wherein: one of R1 and R2 represents hydrogen or C^-Cs alkyl; or both R1 and R2 represent C丨-C 8 alkyl, Μ represents (C]-C4 炫) 4N, ( C1-C4 alkyl)3NH, (C2-C4, oh) 4n, (c2-c4 alkyl 〇h) 3nh, (c2-c4 alkyl 〇H) 2N(CH3)2, (c2-c4 alkyl OH)2NHCH3, (c6h5)4n, (c6h5)3nh, (C6H5CH3)4N, (C6H5CH3)3NH, NH4, melamine, vein, metal or alkaline earth metal ion, or aluminum, rhodium, iron or boron ion; m system 1 a value of -3 and indicating the number of positive charges on the ;; and η is a value of 1-3 and represents the number of sub-scale cations corresponding to Mm+. 0 154949.doc 201202325 According to a preferred embodiment, component a) The phosphinic acid (1) salt is represented by the following formula

Based on the weight of the polymer matrix component c), the component a) is preferably contained in the amount of οι wt〇 / e 45 · 0 wt. %, preferably 1 wt % - 3 0.0 wt %. The content of the 'component' in the fuel composition is preferably 〇.05 wt%_5 〇wt%, preferably 0.1 wt.%-2.0 wt%. The preferred ratio of components a):b) is 5〇:1_ 1:5, preferably 20:1-1: 2. Another embodiment of the invention relates to a mixture comprising: a) a phosphinate, as represented by structural formula (1) or (π): wherein: one of R and R2 represents hydrogen or Ci_c8 alkyl; or Ri And R2 both represent C-C8 alkyl; and R3 represents C^c丨Q alkyl, heterophenyl phenyl 2C2_Ci() alkyl, phenyl, (Cl-C4 alkyl) 1- 3 phenyl, or phenyl-(VC4 alkyl); and b) a tetraalkylhexahydropyridine derivative selected from the group consisting of: 2'2,6,6-tetraalkylpyridinium oxide , hydroxy-tetraalkyl/hydropyridine, 1-alkoxy-2,2,6,6-tetraalkylhexahydropyridine and 1-decyloxy-2,2,6,6-hexahydro'• ratio. set. This mixture can be used to impart flame retardancy to the polymer matrix. Another embodiment of the invention relates to the method of imparting flame retardancy to a polymer matrix 154949.doc 201202325, which comprises adding to components a) and b) of the polymer matrix of component c) mixture. Component b) Suitable tetraalkylhexahydropyridine or tetraalkylhexahydropyrazine derivatives are selected from the group consisting of 2,2,6,6-tetraalkylhexahydropyridine_丨-oxide, hydroxy group _2,2,6,6_four-compartment hexahydro-μ, alkoxy 2,2,m_tetra-burning six-gas oxime, brewing oxy-2,2, Μ·hexahydroanthracene, _经····················································· The compounds can be represented by the following formula:

R2 R, (c) 0.-N N- (d) or ~巳, 2, 1-R4 represents a Cl-C4 alkyl group, preferably a methyl group or an ethyl group. According to the preferred embodiment, the one in RAR2 and the one in m4 are *ethyl and the other groups represent methyl or all Ri_R4 represent methyl; and represent hydrogen Cl C2Q, C5_(:6 naphthenic Or an additional substituent jC2-C2Q, a c5_c6 cycloalkyl or a c2_c2〇 dilute group; or a fluorenyl group of a c丨-' monocarboxylic acid or a C2-C2Q dicarboxylic acid. Corresponding to a partial formula & In the compound, the dotted line in the 4 position of hexahydroindole is such that the * represents the bond of the hydrogen filament substituent, and the other represents the bond to the 0-substituent or the C-substituent. The two dotted lines of the hexahydropyridine are both indicated by the bond to the 154949.doc 201202325 hydrogen, hydrazine-substituent or c-substituent or the double bond to the oxygen. Among the compounds corresponding to the moiety b, six Hydrogen. The nitrogen in the 4-position of the azine is bonded to a hydrogen or carbon substituent. The representative structural formula is as follows:

Ο--Rj m (eight)

(B) (C)

154949.doc -10- 201202325 ·

R

g Τ5 Μ- Τ, T. _Ν Ν一Ο一ΕΤ, Τ6

COO. Τ7 (G) (Η)

l^CI^COO

(I)

Τη Τ5 Τ6 (J) 154949.doc • 11 - 201202325

1^0

(N)

I54949.doc -12- 201202325

〇 (R) H3C E— Ο — Ϊ

H3C In the compounds (A)-(R), E represents hydrogen, q-CM alkyl, Cs-C6 cycloalkyl or C2-C2G alkyl, C5-C6 cycloalkyl or C2 with additional substituents -C2G alkenyl; or represents Ci-Cz. The monocarboxylic acid or the thiol group of the C^-Cm dicarboxylic acid; or alternatively, the group >Ν-0-Ε is replaced by the group >N-〇. Alkyl linear or branched alkyl and is, for example, methyl, ethyl, n-propyl, n-butyl, t-butyl, t-butyl, n-hexyl, n-octyl, 2-ethyl Hexyl, n-decyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl. The % alkyl group contains a cyclopentyl group and a cyclohexyl group; a typical cycloalkene group contains a cyclohexene methyl-membered group, a dimethylbenzyl group; and a typical aralkyl group contains a benzyl group or a phenethyl group. The sulfhydryl group defined as a monocarboxylic acid is preferably selected from

-C(=〇)-NH-CrC6 154949.doc •13· 201202325 Burning base, -C(=〇)-NH-C6-Ci〇aryl group and -C(=〇)-N(C〗-C6 institute Base) 2. An E system, defined as a fluorenyl group of a C2-C2 fluorene dicarboxylic acid, for example, is derived from a dihydric group having a C group and a monobasic organic acid of two acid functional groups, such as derived from an aliphatic, aromatic or cycloaliphatic group. A diindenyl group of a dicarboxylic acid. Suitable aliphatic dicarboxylic acids have 2 to 40 C atoms, such as oxalic acid, malonic acid, dimethylmalonic acid, succinic acid, pimelic acid, adipic acid, trimethyl adipic acid, sebacic acid, Azelaic acid and dimer acid (dimerized product of unsaturated aliphatic carboxylic acid such as oleic acid), alkylated malonic acid and succinic acid (for example octadecyl succinic acid). Suitable cycloaliphatic dicarboxylic acid systems (for example) 1,3-cyclobutanedicarboxylic acid, 1,3-cyclopentane dicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 14-cyclohexanedicarboxylic acid , 13- and 1,4-(dihydroindenyl) cyclohexane or 4,4 |-dicyclohexyl dinonanoic acid. Preferred members of this group include a thiol group of the following groups: oxalic acid, adipic acid, vitreic acid, suberic acid, azelaic acid, phthalic acid, dibutylmalonic acid, dibenzylpropane Acid or butyl-(3,5-di-t-butyl-4-yl-hydroxybenzyl)-malonic acid, or bicycloheptene dicarboxylic acid, of which specific examples are succinate, sebacate, ortho-benzene Dicaprate and isophthalate. If the lanthanide is a divalent fluorenyl group of a diamino decanoic acid, it is, for example, a hexamethylenediamine decanoic acid or a fluorenyl 2,4-toluenediamine decanoic acid; the lanthanide has 1 to 18 a linear or branched alkyl group of a c atom, a cycloalkyl group having 5 to 18 C atoms, a cycloalkenyl group having from 8 to 8 c atoms, and having 1 substituted by the following group a linear or branched alkyl group of 4 C atoms or a phenyl group substituted with an alkyl group having 1 to 4 C atoms; 154949.doc • 14-201202325 and at b 2 b is 1, 2 or 3, provided that b does not exceed the number of C atoms in T or 3 'each C is bonded to a different C atom of T; R is hydrogen or methyl; and m is 1 to 4. In the above compound, when the variable „! is 1, I is hydrogen, CkC” alkyl (or the alkyl group optionally contains one or more oxygen atoms), C2-C12 dilute group, (VC, aryl group, a monovalent fluorenyl group of a C7-C18 aralkyl group, a glycidyl group, an aliphatic, a cycloaliphatic or aromatic carboxylic acid, or an aminocarboxylic acid (for example, an aliphatic carboxylic acid having 2 to 18 C atoms, having 5_ a ruthenium group of 2 c atoms of a cycloaliphatic carboxylic acid or an aromatic carboxylic acid having 7 to 5 C atoms, or a group representing the following formula:

Where X is 0 or 1,

Where y is 2-4; when m is 2, Han 2 series (VC) 2 extended alkyl, c4-c12 extended alkenyl, xylylene, fat 154949.doc • 15· 201202325 ethnic group, aromatic a divalent fluorenyl group of a family or aromatic dicarboxylic acid or diamino decanoic acid, for example, an aliphatic dicarboxylic acid having one C atom, a cycloaliphatic or aromatic dicarboxylic acid having 8 to 14 C atoms, or having a aryl group of 814 c atoms of an aliphatic, cycloaliphatic or aromatic diaminocarbamic acid; or a group representing the following formula:

Wherein: 〇 and 〇2 are independently hydrogen, Ci_c8 alkyl, aryl or aralkyl, and the sound contains 3,5·di-t-butyl-4-hydroxyl group; D3 is hydrogen, Ci-C18 alkane Or C丨-C2Q alkenyl; and d is 0·20; when m is 3, R2 is an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic triterpenoid trivalent sulfhydryl; At 4 o'clock, it is a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid (including 1,2,3, alkanetetracarboxylic acid, 1,2,3,4-but-2-enetetracarboxylic acid, and 1,2,3 , a 5-valent base of 5-pentanose 1 and 1,2,4,5-pentene tetradecanoic acid; in the above compounds, when the variable p is 1, 2 or 3'

R3 is hydrogen, CrC12 alkyl, C5-C7 cycloalkyl, C7-C9 aralkyl, U 154949.doc • 16· 201202325 alkanoyl, c3-c5 olefinic or benzamidine; at p is 1 When R4 is hydrogen, Ci-Cu alkyl, C5-C7 cycloalkyl, c2-c8 alkenyl (unsaturated or substituted by cyano, perfusate or gland)' or aryl, aryl, or shrinkage a group of a glyceryl group, a moiety of the formula -CH2_CH(OH)-Z or a moiety of the formula _c〇_Z4_c〇NH_Z, wherein the Z is hydrogen, methyl or phenyl, or a group representing the following formula:

Wherein h is 0 or 1; when p is 1, R_3 and I together represent an alkylene group having 4 to 6 C atoms, or a 2-sided oxy-polyalkylene group, or an aliphatic or aromatic oxime, a cyclic sulfhydryl group of 2_dicarboxylic acid or 1,3-dicarboxylic acid; when p is 2, R·4 is a direct bond or a Ci-Ci2 exudyl group, a C6_C!2 exoaryl group, and a dimethyl group , -CH2CH(OH)-CH2 group or a moiety of the formula -CH2-CH(0H)-CH2-0-X-0-CH2_CH(0H)-CH2- where X is (:2-(:10) Alkyl, 154949.doc •17- 201202325

Ce-c!5 aryl or C6_Cu cycloalkyl; or R3 is not an alkyl, diasteryl or phenyl fluorenyl group, then R4 additionally represents an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or a divalent fluorenyl group of a diamino decanoic acid, or a group -CO-; or R4 represents a group of the following formula:

N / , V τ9 where 'and A are independently hydrogen, c】_Ci8 alkyl, or butyl 8 and butyl 9 together with a C4-C8 alkyl or 3 oxapentanylene group, for example, 8 and butyl 9 together are 3-oxapentamethylene; when P is 3, R·4 is 2,4,6-triazinyl; η is 1 or 2; when η is 1,

Rs and 11'5 are independently Cl_Ci2 alkyl, C2-Ci2 dilute, C7_Ci2 aromatic base ' or Rs additionally denotes hydrogen' or heart and ruler 5 together with C2_C8 alkyl or hydroxy extension or C4_C24 Alkylalkyl; when η is 2, R5 and R'5 are a moiety of the formula (_CH2)2C(CH2_)22; R6 is hydrogen, Cl-ci2, propyl, benzyl, glycidol Or a C2-C6 alkoxyalkyl group; or when η is 1, R7 is hydrogen, C|-c>2 alkyl, c3_c5 alkenyl, c7_c^alkyl, c5_c^ 154949.doc 201202325

a group of a glyceryl group, a moiety of the formula -(CH2)t-C00-Q or a moiety of the formula _(CH2)t_〇c〇_Q, wherein t is 1 or 2, and the Q is an alkyl group or a phenyl group; When η is 2, R·7 is a C2_Ci2 extended alkyl group, a C^-Ci2 extended aryl group, and a partial formula of -CH2CH(OH)-CH2-〇-X-0-CH2-CH(OH)-CH2- a group, wherein the X-based C2-C10 alkylene group, the cvc15 extended aryl group or the c6-C12 extended ring leuko group, or the partial formula -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- Group, wherein Z is nitrogen, Ci-Ci8 alkyl, propyl, benzyl, C2-C12 or phenyl hydrazide; QA-N(R8)· or alkyl, group-CH2-CH (R9)-0-, wherein r9 is hydrogen, fluorenyl or phenyl, group -(ch2)3-nh_ or direct bond; R10 is hydrogen or CVCu alkyl, R8 is hydrogen, C丨-C is 8 Alkyl, (: 5-(:7-cycloalkyl, C7-Ci2 aralkyl-cyanoethyl, c6-C丨〇 aryl, group -CH2-CH(R9)-OH, wherein R9 has The meaning of the definition of the text; or the basis of the following partial formula

Wherein, G4 is a C2-C6 alkylene group or a group of (6-(:12-aryl); or 118-line part 154949.doc -19-201202325-E7_CO-NH-CH2-OR]; A structural unit representing a recurring occurrence of a polymer, wherein τ3 is ethylene or 1,2-propylene' is a repeating structural unit derived from a copolymer of an alpha olefin and an alkyl acrylate or methacrylic acid group; for example, ethylene And a copolymer of acetoacetate, wherein k is 2 to 1 〇〇; when p is 1 or 2, Τ'4 has the same meaning as R4; T5 is fluorenyl; τό fluorenyl or ethyl 'or τ5 and τ6—starting with tetradecyl or penta-indenyl, for example, butyl 5 and hydrazine 6 are each methyl; hydrazine and hydrazine are independently methylene or carbonyl, and butyl 4 is ethyl Wherein η is a butyl 7 as defined by R_7 and is, for example, an octadecyl group, wherein η is 2; Τ10 and Τπ are independently an alkylene group having 2 to 12 C atoms; or Τη The following partial groups:

Y Τ! 2 is a hexahydropyrazine group, or a group representing the following formula: -NR丨丨-(CH2)d-NR丨丨- or Η abcf where 'Rn is as defined by R·3 or otherwise Groups of the following formula: 154949.doc 20- 201202325

a, b and c are independently 2 or 3, and f is 0 or 1, for example, & and c are each 3, b is 2 and f is 1; and e is 2, 3 or 4 (eg 4 Τη is the same as R2, provided that T13 is not hydrogen when η is 1; Ε!&Ε2 is different from each other -C0- or -Ν(Ε5)-, where ε5 is hydrogen, CVCu alkyl or C4- C24 alkoxycarbonylalkyl, for example, EHg-CO- and E2-N(E5)-;

Eg is hydrogen, C^-Cm alkyl, phenyl, naphthyl (the phenyl or the naphthyl group is substituted by chlorine or a C1-C4 alkyl group), or a C7-Ci2 phenyl group, or the phenyl group Substituted by an alkyl group having 1 to 4 C atoms; E4 is hydrogen, an alkyl group having 1 to 30 C atoms, a phenyl group, a naphthyl group or a phenylalkyl group having 7 to 12 C atoms, or E3 And E4 is a polymethylene group having 4 to 17 C atoms, or the polyarylene group is substituted with up to 4 alkyl groups (for example, fluorenyl groups); E6 is an aliphatic or aromatic tetravalent group; When m is 1, '112 of formula (N) is as defined above;

The Gi line is a direct bond, Ci-C 2 is a thiol group, a stilbene group, or -NH-G'-NH, wherein the G' system is a Ci-C12 extension group. Suitable for the four-alkyl hexahydropyrene ratio biting or tetraalkyl hexahydropyridinium hydrazine derivative (for example) the compound of the formula 1-12: 154949.doc • 21- 201202325

154949.doc 22- 201202325

154949.doc -23- 201202325

R· R. 0·

N τ Ο

(12) wherein: E!, E2, E3 and E4 are independently Ci_C4 alkyl, or ^ and 匕 are independently C-C4 alkyl and E3 and E4 are quinone, or hydrazine, And 匕 and E4 are each associated with the Wuya 曱 base;

Ri system C]-C丨8 alkyl, CVCi2 cycloalkyl, 154949.doc with 7 to 12 carbon atoms •24- 201202325 double %· or two J chen group, C7-C15 phenyl leukoyl group, a C6_Ci aryl group, or the aryl group is substituted with 1 to 3 C!-C8 alkyl groups; R2 is an oxygen or a straight bond or has a branched C1-C12 alkyl group, and R3 is an alkylene having 1 to 8 carbon atoms. Base, or r3 series -CO-, co-r4-, -CONR2-, *_c〇, NR2-R4; extension base; R5 system 虱, straight bond or branch-bearing Ci-Ci2 alkyl group' or the following part Group of:

Alternatively, when R4 is extended to an ethyl group, two R5 methyl substituents may be bonded to the triazine bridging group via a direct bond to form a hexahydropyrazine-1,4-diyl group; R.6 system C2- C8 extended or a group representing the following formula:

It is not mentioned that when the structure is as shown above, γ is not _〇H; A is -0- or -NR7·, wherein R? is hydrogen, linear or branched 匸丨/^ alkyl; or R? The following group of parts: 154949.doc -25- 201202325

i-C8 alkoxy substituted; or butyl is a τ-based oxy group, one or two CrQ alkyl groups or a phenoxy group of c or -N(R2) 2, the limiting condition & is not hydrogen Group: c

R, X is -NH2, -NC0, -OH, -〇-glycidyl, or ·NH2, and Y is -OH, -NH2, -ship 2, wherein R2 is not hydrogen; or gamma-NCO, _C00H , an oxiranyl group, a glycidyl group, or -Si(OR2)3; or a combination of RrY-system-CH2CH(〇H)R2, wherein the r2 alkyl group or the alkyl group has 1 to 4 An oxygen atom, or R3_y_s_Ch2〇r2; or a mixture of hindered amine compounds of the following: Ν, Ν·, Ν", _叁{2,4-bis[(1-hydrocarbyloxy_2,2,6,6 -tetradecyl hexahydropyridin-4-yl)alkylamino]----triazin-6-yl}-3,3'-extended ethyldiimidodipropylamine, hydrazine, hydrazine, hydrazine ''-Volume {2,4-bis[(1.hydrocarbyloxy-2,2,6,6-tetramethylhexahydro 0-pyridin-4-yl)alkylamino]-iso-triazine_ 6_Kib 3,3,_Ethyldiimidodipropylamine, and a bridged derivative of the formula: 154949.doc •26- 201202325 R,NH-CH2CH2CH2NR2CH2CH2NR3CH2CH2CH2NHR4 (13) Τ-Ε, -Τ, (14) (15) GE^G^E^Ga (16) wherein, in the tetraamine (13), R丨 and R2 are each a triazine moiety E; and one of the rulers 3 and R4 a s-triazine moiety E, and the other of & or R4 is hydrogen;

R is a methyl group, a propyl group, a cyclohexyl group or an octyl group, such as a cyclohexyl group; R5 is a C1 · C12 alkyl group, such as n-butyl group; wherein, among the compounds of the formulae (14) and (15), in the For the base or cyclohexyl group, & T and τ 咚 are R, R4 substituted tetraamines as defined for formula 13, one is replaced by the group E1, and thus (1) the parent-tetramine The triazine moiety is in the form of a bridge between two tetraamines T and T丨; E is the group of the following formula: 154949.doc •27· 201202325

(3) all three of the tetraamines T are all substituted by the mesin, and the substituents are all attached, so that E丨 is bonded to τ and τ丨 and both ends of the second oxime are in the tetraamine τ; L is a propylenediyl group, a cyclohexanediyl group or a octyldiyl group; wherein, in the compound (16), each of the G and GJG2 (4) is substituted with a tetraamine as defined for the formula (10): Ει replaces the three. One of the Qin parts, and G, has two of the three parts, replaced by E, thereby creating a bridge between 〇 and 〇, and creating a second bridge between G|&G2; The mixture is obtained by making 2 to 4 equivalents of 2,4_bis[(1-nicotinyloxy-2,2,6,6-tetrafyl-based, octa- 4-yl)butylamino group ]_6_chloro-homo-triazine is reacted with ^ equivalent of N,N._bis(3-aminopropyl)ethylenediamine; or 'hindered amine system (17) compound: 154949.doc • 28 - 201202325

A

N-R

R1T

(17), wherein the subscript η is between 1 and 15; r12 is a c2-c12 exudyl group, a c4-c12 alkenyl group, a C5_c7 exocyclic ring, a C5-C7 exocyclic group-two ( CVC4 extended alkyl), Ci_C4 alkylene bis (be extended cyclic alkyl), phenyl-di(CVC4 alkyl) or 7 mixed with 1,4-hexahydro" bis-diyl, -0- Or a C4-C12 extension odor, wherein the thiol or (Ci-Ci2 alkoxy) number group has the following formula; the definition of ^^ is not one of the gases; or the base of the R12 system group:

Wherein X2 is a Ci-Ci8 alkyl group, a C5_Ci2 cycloalkyl group (unsubstituted or substituted by 1, 2 or 3 CkCU alkyl groups); a phenyl group (unsubstituted or via 1, 2 or 3 C^-C) ^alkyl or (^-0:4 alkoxy substituted); 匚7. phenylalkyl (unsubstituted or substituted on the phenyl by 1, 2 or 3 C1-C4 leuko) ' and Group X3 is independent of each other by CrC!2; I54949.doc -29·201202325 R13, R14 and Ri5 are the same or different, which are hydrogen, c^-Cu alkyl, Cs-Cu cycloalkyl (unsubstituted Or substituted by 1, 2 or 3 CVC4 alkyl groups, C3-Ci8 alkenyl, phenyl (unsubstituted or substituted by 1, 2 or 3 (^-(:4 alkyl or alkoxy)), C7_C : 9 stupid base (unsubstituted or substituted with 1, 2 or 3 C丨-C4 alkyl groups on the phenyl group); tetrahydroindenyl or C2-C4 alkyl, in the 2, 3 or 4 position Substituted by -OH, Ci-Cs alkoxy, bis(Ci-C4 alkyl)amine or a group of the following formula:

Where Y is -0-, -CH2-, ·ΟΗ2(:Η2-4)=Ν-(:Η3, or -N(R14)(R15)

Further group; group A is independently of each other - 〇R丨3, -N(R!4)(Rl5) or a group of the following formula:

Wherein: X series-0-4>N-Ri6; R16 is hydrogen, Ci-Cu alkyl, C3-C18 alkenyl, C5_Cl2 cycloalkyl (unsubstituted or via 1, 2 or 3 (^-(: 4 alkyl group substituted); C7-C9 base group * (unsubstituted or substituted by 1, 2 or 3 CrC4 alkyl groups on the aryl group), tetrahydroindenyl, 154949.doc -30- 201202325 a group of the formula: HX CH3 γΚ —(N-〇-CHrCH2-CH3 h3c ch3 5 or C2-C4 alkyl, which is azoxy-, C^-Cs alkoxy, di(Ci) at the 2, 3 or 4 position -C4 alkyl)amino group or a group of the following formula:

Ri 1 has one of the definitions given for Ri6; and the groups B independently of one another have one of the definitions given for A. Tetraalkylhexahydropyridines and tetraalkylhexahydropyrazine compounds are well known in the art and are also known as N-alkoxy hindered amines and NOR-hindered amines or NOR-hindered amine light stabilizers or NOR-HALS, For example, it is disclosed in U.S. Patent Nos. 5,004,770, 5,204,473, 5,096,950, 5,300,544, 5,112,890, 5,124,378, 5,145,893, 5,216,156, 5,844,026, 6,117,995 or 6,271,377. US Patent Specification No. 6,271,377, and published US Publication No. 09/505,529 (filed on Feb. 17, 2000), and No. 9/794,710 (filed on February 27, 2001) disclose blocked Hydroxyalkoxyamine stabilizer. Blocked trans-alkoxyamine stabilizers are also known as N-hydroxy alkoxy hindered amines, or NOR〇l-HALS. The representative structure is as follows: 154949.doc •31_ 201202325

Wherein R and R' are defined as N-, 0- or C. substituents. In the case of the group E--0-C(0)-Ci-Ci8 alkyl group, the compound is via a base amine. The hydroxylamine is reacted with an acid derivative to form the final hydroxylamine ester. These methods have been well known and described in the literature. The preparation of particularly suitable compounds is described in International Patent Application No. 01/90113. According to a preferred embodiment, the tetraalkylhexahydropyridine derivative is selected from the group consisting of 2,2,6,6-tetraalkylhexahydropyridinium 0t-indole-oxide of the formula:

1-hydroxy-2,2,6,6-tetraalkylpiperidine of the formula:

1-alkoxy-2,2,6,6-tetraalkylhexahydroacridine of the formula: 154949.doc -32- 201202325

The formula 1-silanoxy-2,2,6,6-hexahydro. ratio. Set: F R R.

Wherein: one of 1^ and 1^ represents a hydrogen or N. substituent and the other represents a hydrazine substituent or a hydrazine substituent; or both Ra and Rb represent a hydrogen, a hydrazine substituent or a hydrazine _ substitution a group; R represents not (^-C2. alkyl, Cs-C6 cycloalkyl or c2_c^ alkyl having an additional substituent, c5-c6 cycloalkyl*c2_C2Galkenyl;

Ac represents a fluorenyl group of a CrCw monocarboxylic acid or a Ci_C2G dicarboxylic acid; and R1 to R4 each represent a CVC4 alkyl group; and R5 and R6 independently of each other represent hydrogen or are selected from a Ci_C4_alkyl 'Ci_C3 alkylphenyl group and a phenyl group. a substituent of the group; and R_5 and R0 together represent a pendant oxy group.

among them:

One of Ra and Rb represents hydrogen or an N-substituent and the other represents a fluorene-substituent or a C-substituent; or 154949.doc •33·201202325 1 and Rb both represent hydrogen, hydrazine-substituent Or a C-substituent; R represents a CrCs alkyl group, a C5-C6 cycloalkyl group or a c2_C8 alkyl group having an additional substituent, (: 5-(:6-cycloalkyl or C2-C8-alkenyl;

Ac is not C--C8 tartile base; and R1-R4 are each a fluorenyl group; and R5 and R6 each represent hydrogen. According to a preferred embodiment, the composition comprises at least one tetraalkyl hexahydroacridine derivative III a, III b, III c or III d as component b), wherein:

One of Ra and Rb represents hydrogen or an N-substituent and the other represents a hydrazine- or a C-substituent; or both Ra and Rb are a 7F fluorene-substituted or C-substituent; CrCs alkyl, C5-C6 cycloalkyl or substituted by hydroxy (: 2-(:8 alkyl, 匕-(:6 cycloalkyl or C2-C8 alkenyl;

Ac represents a thiol group of a C!-C8 carboxylic acid; and each of R1 to R4 is a methyl group; and each of the ruthenium 5 and R6 represents hydrogen. According to a preferred embodiment, component b) consists of at least one tetraalkylhexahydropyridine derivative IIIc4incl selected from the group consisting of: cyclohexyloxy-2,2,6,6-tetradecyl- 4-octadecylamine hexahydropyridinium, bis(1-octyloxy-2,2,6,6-tetradecylhexahydropyridin-4-yl) sebacate (Tinuvin NOR 371® ), 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetradecylhexahydropyridin-4-yl)butyl 154949.doc •34- 201202325 arylamino]-6- (2-Phenylethylamino-homo-trimium, adipic acid bis(1-cyclohexyloxy-2,2,6,6-tetradecyl hexa-1° ratio -4-yl) 酉Purpose, 2.4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl)butylamino]-6-gas-homo-triterpenoid, 1- (2-hydroxy-2-methylpropoxy)-4-hydroxy-2,2,6,6-tetradecylhexahydropyridyl, 1-(2-hydroxy-2-mercaptopropoxy)- 4-sided oxy-2,2,6,6-tetramethylhexafluoro 0-bite, 1-(2-hydroxy-2-mercaptopropoxy)_4-octadecyloxy-2,2 ,6,6-tetramethylhexahydrogen ratio, bis(1-(2-hydroxy-2-mercaptopropoxy)-2,2,6,6-tetramethylhexahydropyridine 4-yl)ester, adipic acid bis(1-(2-hydroxyl) -2-methylpropoxy)_2,2,6,6-tetradecylhexahydro 0 to 0-1,4-isyl), 2.4-bis{1^-[1-(2-hydroxy-2) - mercaptopropoxy)_2,2,6,6-tetramethylhexahydropyridin-4-yl]-indole-butylamino}_6_(2.hydroxyethylamino)-s-triazine , 2.4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl)butylamino]-6-gas-tetrazine with hydrazine, hydrazine , the reaction product of _bis(3-aminopropyl)ethylenediamine), 2.4-bis[(1-%hexyloxy-2,2,6,6-tetramethylhexahydropyridinyl-4-yl) Butylamino]-6-(2-hydroxyethylamino-s-triazine, oligomeric compound, which is 4,4|_hexamethylene bis(amino-2,2,6,6• Tetramethylhexahydropyridine) and 2-chloro-4,6-bis(dibutylamino)-s-triazine capped 154949.doc -35· 201202325 ' A:6 [(1_咏己基a condensation product of oxy-2,2,6,6-tetramethylhexahydropyridine-4. ylaminobutyl]-ho-triazine, a compound of the formula:

(Irgatec CR 76®) and compounds of the formula:

/, medium η is 1 to 15 (Flamestab NOR 116®). Some of the above compounds are commercial products. Representative compounds are sold by cibaU under the following trade names: Flamestab NOR 116®, Tinuvin NOR 371® or Irgatec CR 76® 〇 component c) 154949.doc • 36· 201202325 The term polymer matrix includes thermoplastic polymers or Thermoset material. A list of suitable thermoplastic polymers is shown below: 1_Polyolefins and polymers of diolefins, such as polypropylene, polyisobutylene, polybutene-1-ene, poly-4-indolyl-1-ene, polyethylene a cyclohexane, polyisoprene or polybutadiene; and a polymer of a cyclic olefin, such as a polymer of cyclopentene or norbornene; polyethylene (which can be crosslinked as needed), such as high density poly Ethylene (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), straight Chain low density polyethylene (LLDPE), (VLDPE) and (ULDPE). T-sparse, that is, the polymer of a single-deep hydrocarbon exemplified in the paragraph, preferably polyether and polypropylene, can be obtained by different methods and especially by the following method: a radical polymerization (usually High pressure and high temperature). b) Catalytic polymerization using a catalyst which typically contains one or more metals of Group ivb, Group 9%, Group VIb or Group of the Periodic Table of Elements. The metals generally have one or more ligands (through* are oxides, halides, alcoholates, esters, ethers, amines 'alkyl's and/or aryl groups), which may be a-h bonds Coordination. These: the complex may be in free form or immobilized on a substrate, usually solidified in broadened magnesium chloride, vaporized titanium (10), alumina or cerium oxide. The catalyst such as the side is soluble or insoluble in the polymerization medium. The 4 catalyst may be used by itself in the polymerization 154949.doc •37·201202325 reaction or other activators may be used, usually metal-based compounds, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkane. Metal alkyl oxanes 'Elements of Group 13, Na, and/or Ilia of the Periodic Table of the Metals, such activators may conveniently be passed through other esters, ethers, and amines or A decyl ether group is modified. Such catalyst systems are commonly referred to as metallocene or unit catalyst (SSC) (Phillips, Standard Oil Indiana, Ziegler (Natta), TNZ (DuPont)). 2. Mixtures of the polymers mentioned in 1), such as a mixture of polypropylene and polyisobutylene, a mixture of polypropylene and polyethylene (eg pp/HDPE, PP/LDPE) and a mixture of different types of polyethylene ( For example LDPE/HDPE). 3. Copolymers of monoolefins and diolefins with each other or copolymers thereof with other vinyl monomers such as ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and low density polyethylene (LDPE) Mixture, propylene/but-1-ene copolymer, propylene/isobutylene copolymer, ethylene/butylene copolymer, ethylene/hexene copolymer, ethylene/methylpentene copolymer, ethylene/glycol copolymer, Ethylene/octene copolymer, ethylene/vinylcyclohexane copolymer, ethylene/cycloolefin copolymer (such as ethylene/norbornene, such as COC), ethylene/1-olefin copolymer, wherein b Produced; propylene/butadiene copolymer, isobutylene/isoprene copolymer, ethylene/vinylcyclohexene copolymer, ethylene/alkyl acrylate copolymer, ethylene/mercapto acrylate copolymer , ethylene/vinyl acetate 154949.doc • 38 - 201202325 base copolymer or ethylene/acrylic acid copolymer and its salt (ionomer) and ethylene and propylene and such as hexamethylene dichloride, dicyclopentadiene or ethylene a terpolymer of a diene such as norbornene; and the copolymer Mixtures thereof and mixtures thereof with the polymers mentioned in 1) above, for example 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 polyamine. 4. A hydrocarbon resin (for example, Cs-C9) comprising a hydrogenated modified product (e.g., an adhesive) and a mixture of a polyalkylene group and a starch; the above homopolymer and copolymer may have a three-dimensional structure, and the three-dimensional structure comprises A stereoregular, isotactic, semi-isotactic or atactic structure in which an atactic polymer is preferred. Also included are stereoblock polymers. 5. Polystyrene, poly(p-methylstyrene), poly(α-mercaptostyrene 6. Aromatic homopolymers and copolymers obtained from vinyl aromatic monomers, such vinyl aromatics The body comprises styrene, α-mercaptostyrene, all isomers of vinyl oxime (especially for vinyl toluene), all isomers of ethyl styrene, propyl styrene, vinyl biphenyl, ethylene The naphthalene, and the vinyl anthracene, and mixtures thereof. The homopolymers and copolymers may have a stereostructure comprising a syndiotactic, isotactic, semi-isotactic or atactic structure; Wherein the atactic polymer is preferred. It also comprises a stereoblock polymer; 154949.doc •39·201202325 a) a copolymer comprising the above vinyl aromatic monomer and a comonomer selected from the group consisting of ethylene, Propylene, disaccharide, nitrile, acid, maleic acid needle, maleimide, vinyl acetate and ethylene or its acrylic derivatives and mixtures, such as styrene/butadiene, styrene/acrylonitrile , styrene/ethylene (interpolymer), styrene/alkyl methacrylate, styrene/butyl Alkene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene, acrylonitrile/methyl acrylate; high impact strength styrene copolymer and another polymer (for example, a mixture of polyacrylate, diene polymer or ethylene/propylene/diene terpolymer); and block copolymer of styrene, such as styrene/butadiene/styrene, styrene/isoprene Diene/styrene, styrene/ethylene/butadiene/styrene or styrene/ethylene/propylene/styrene. b) a hydrogenated aromatic polymer obtained from the hydrogenation reaction of the polymer mentioned in 6.), especially comprising polycyclohexylethylene (PCHE) obtained by hydrogenating atactic polystyrene, which is usually called It is a hydrogenated aromatic polymer obtained by hydrogenation of a polymer mentioned in 6a.) of polyvinylcyclohexane (PVCH) 〇c). The homopolymers and copolymers may have a steric structure comprising syndiotactic, isotactic, semi-isotactic or atactic structures; wherein the atactic polymer is preferred. Also included are stereoblock polymers. 7. A graft copolymer of a vinyl aromatic monomer (for example, styrene or α-mercaptostyrene), such as styrene on polybutadiene, located in polybutadiene - 154949.doc -40· 201202325 Styrene on styrene or polybutadiene-acrylonitrile copolymer; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene and propylene on polybutadiene Nitrile and methyl methacrylate; styrene and maleic anhydride on polybutadiene; ethylene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on butadiene; styrene and alkyl acrylate or methacrylic acid ester on polybutadiene; located on ethylene/propylene/diene terpolymer Styrene and acrylonitrile; styrene and acrylonitrile on polyacrylic acid ester or poly(meth) acrylate, styrene and acrylonitrile on acrylate/butadiene copolymer, And a mixture thereof with the copolymers listed in 6) (for example, a copolymer called ABS, MBS, ASA or AES polymer) Matter). 8. Halogen-containing polymers such as polychloroprene, gasified rubber, isobutylene-isoprene chlorinated and brominated copolymers (self-butyl rubber), gasified or chlorosulfonated polyethylene, ethylene Copolymers with vaporized ethylene, epoxidized homopolymers and copolymers, especially polymers containing dentate ethylene compounds (eg, polyethylene, polydiethylene, polyvinyl fluoride, polydifluoroethylene) Ethylene), and copolymers thereof (for example, vinyl chloride / ethylene diethylene glycol, vinyl chloride / vinyl acetate or diethylene vinyl / vinyl acetate copolymer). 9. Polymers obtained from α,β-unsaturated acids and derivatives thereof, such as polyacrylates and polymethacrylates; poly(methyl methacrylate), polypropylene decylamine modified by butyl acrylate Polyacrylonitrile. 10. The copolymers of the monomers mentioned in 9) or their copolymers with other unsaturated monomers 154949.doc 41 201202325, such as acrylonitrile/butadiene copolymer, acrylonitrile/alkyl acrylate copolymerization , acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/ethylene-based copolymer or acrylonitrile/alkyl methacrylate/butadiene terpolymer. 11. Polymers obtained from unsaturated alcohols and amines or their mercapto derivatives or acetals, such as polyvinyl alcohol, polyvinyl acetate, vinyl polystearate, vinyl polybenzoate, poly Vinyl maleate, polyvinyl butyrate, polyallyl phthalate or polypropyl melamine; and copolymers thereof with the above mentioned dilute hydrocarbons. 1 2. Ring-like homopolymers and copolymers' such as a polyphenol, polyethylene oxide, polypropylene oxide, or a copolymer thereof with bisglycidyl ether. 13. Polyacetals such as polyacetal and their polyacetals containing ethylene oxide as a comon; polyacetals modified with thermoplastic polyamine phthalates, acrylates or Mbs. 14. Polyphenylene Ethers and polyphenylene sulfides, and mixtures of polyphenylene ethers with styrene polymers or polyamines. 15. Aspects derived from hydroxyl terminated polyethers, polyesters or polybutadienes and on the other hand derived from fats A polyamino phthalate of a family or aromatic polyisocyanate, and precursors thereof. 16. Polyamines and copolyamines derived from monoamines and a rebel and/or amino-reactive acid or corresponding internal amines, such as polyamides 4, polyamines 6, polyamines 0/6, 6 /10, 6/9, 6/12, 4/6, 12/12, polyamine u, polyamine 12, aromatic polyamine starting from m-diphenylene diamine and adipic acid; Polyamides, such as poly-2,4, prepared from sulfhydryl monoamines and isophthalic acid and/or terephthalic acid and having 154949.doc •42-201202325 with or without the use of elastomers as modifiers , 4,-tridecylhexamethylene-p-xylylenediamine or poly(m-xylylenediphenyl) m-phenylenediamine; and the above polyamine and polyolefin, olefin copolymer, ionomer or chemical bond a block copolymer of a knot or graft elastomer; or a block copolymer with a polyether (for example, polyethylene glycol, polypropylene glycol or polytetramethylene glycol); and a polyamide or copolymer modified with EPDM or ABS Indoleamine; and polyamidamine (RIM polyamine system) condensed during processing. 17. Polyurea, polyimine, polyamidimide, polyetherimine, polyesterimine, polyethylurea and polybenzimidazole 1 8. From dicarboxylic acid and diol And/or a polyester obtained from a hydroxycarboxylic acid or a corresponding lactone, such as polyethylene terephthalate, polybutylene terephthalate, 1,4-dimethylpolybutylene terephthalate , polyalkylene naphthalate diester (PAN) and polyhydroxybenzoate, and block copolyetherester obtained from a hydroxyl terminated polyether; and polycarbonate or MBS modified polyester. 19. Polyketone. 20. Polysulfone, polyether oxime and polyether ketone. 21. Blends (poly blends) of the above polymers, such as PP/EPDM, polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS, PC /ASA, PC/PBT, PVC/CPE, PVC/acrylic acid vinegar, POM/thermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, 154949.doc • 43 - 201202325 PA/PPO, PBT/ PC/ABS or PBT/PET/PC 〇 22. Polycarbonate corresponding to the following formula: *—R-0-C-0 * η . η L Ο These polycarbonates can be obtained by interface methods or by A melting method (catalytic transesterification) is obtained. The polycarbonate may be branched or linear in structure and may contain any functional substituent. Polycarbonate copolymers and polycarbonate blends are also within the scope of the invention. The term polycarbonate is understood to include copolymers and blends with other thermoplastic materials. For example, U.S. Patent Nos. 3,030,331, 3,169,121, 4,130,458, 4,263,201, 4,286,083, 4,552,704, 5, 21, 268, and 5 , 6〇6, 〇〇7, a method for preparing polycarbonate. A combination of two or more different molecular weight polycarbonates can be used. Preferably, the polycarbonate is obtained by the reaction of a diphenol (e.g., bisphenolphthalein) with a carbonate source. Examples of suitable diphenols are:

154949.doc -44· 201202325

OH

/=\ CH. .H〇-〇i-

OH

OH OH

Bisphenol M: Bisphenol F:

Bisphenol P : ——O——〇-〇h n

u

Bisphenol S : HO OH

OH Bisphenol Z: U U , 4,4'-(2-ylidenealkyl)bis(2,6-dichlorophenol), or -9-bisphenol:

The OH carbonate source can be a carbonyl complex, a carbonate or a halogenated formate. Suitable 154949.doc •45· 201202325 Suitable carbonate halides are phosgene or carbon ruthenium bromide. Suitable carbonate dialkyl carbonate (such as dimethyl carbonate or diethyl carbonate), diphenyl carbonate, phenyl alkyl phenyl ester (such as phenyl carbonate toluene), carbonic acid Alkyl esters (such as dimethyl carbonate or diethyl carbonate), di-(halophenyl)s carbonate (for example, di-(phenyl) carbonate, di-(bromophenyl) carbonate, carbonic acid 2. (three gas base) ester or di-(trihenylphenyl) carbonate, di-(alkylphenyl carbonate) (such as di-p-phenylene carbonate), naphthyl carbonate, carbonic acid Air naphthyl esters and others. The above polymer matrix-containing polycarbonate copolymers comprising a polycarbonate or polycarbonate blend in which an isophthalate/terephthalate-resorcinol segment is present. Such polycarbonates are commercially available, for example, Lexan® SLX (General Electrics, USA). The other polymeric matrices of component b) may additionally comprise various synthetic polymers in the form of mixtures or copolymers comprising polyolefin, polystyrene, polyester, polyether, polydecylamine, poly(meth)acrylate' thermoplastic poly Amino phthalates, polysulfones, polyacetals, and PVC, which contain suitable compatibilizers. By way of example, the polymer matrix may additionally comprise a thermoplastic polymer selected from the group consisting of polyolefins, thermoplastic polyurethanes, styrene polymers, and copolymers thereof. Specific examples include polypropylene (PP), polyethylene (PE), polydecylamine (PA), polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Glycol-modified poly(p-phenylene terephthalate) (PCTG), polyfluorene (PSU), polymethyl methacrylate (PMMA), thermoplastic polyurethane (TPU), acrylonitrile Butadiene-styrene (ABS), acrylonitrile_styrene_154949.doc •46· 201202325 Acrylic vinegar (ASA), acrylonitrile-ethylene_propylene_styrene (AES), styrene-maleic anhydride (SMA) ) or high impact polystyrene (HIps). 23. An epoxy resin consisting of a di- or polyfunctional epoxy compound, wherein at least two epoxy groups of the formula:

, which directly binds to a carbon, oxygen, nitrogen or sulfur atom, and wherein q represents 〇, both the heart and the rule 3 represent hydrogen and & represents hydrogen or methyl; or wherein q represents 0 or 1, R and R3 The formation of a _CH2_CH2 or _CH2_CH2_CH2- group and R2 represents hydrogen. Suitable hardener components are, for example, amines and anhydride hardeners, such as polyamines such as ethylenediamine, di-ethyltriamine, tri-ethyltriamine, hexamethylenediamine, methyldiamine, N _Aminoethylhexahydropyrazine, diaminodiphenylnonane [DDM], alkyl substituted derivatives of DDM, isophorone diamine [IPD], diaminodiphenyl sulfone [DDS] , 4,4,·-indenyldiphenylamine [MDA], or m-phenylenediamine [MPDA]), polydecylamine, alkyl/alkenyl imidazole, dicyandiamide [DICY], 1,6-hexamethylene Base bis-cyano hydrazine, or anhydrides such as, for example, dodecyl succinic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, phthalic anhydride, pyromellitic anhydride, and derivatives thereof . A preferred embodiment of the invention relates to a composition comprising a thermoplastic polymer as component c). Preferred thermoplastic polymers include polyolefin homopolymers and copolymers, copolymers of olefin vinyl monomers, stupid vinyl homopolymers, and their materials 154949.doc -47-201202325. Preferably, the melamine and the pulverized salts (I) and (II) are ground to a fine powder having an average particle diameter of less than 100 μm before being applied to the polymer matrix, because the small particle size is observed to improve the combination of the present invention. The flame retardancy of the material. Additional Components The present invention further relates to compositions comprising, in addition to components a), b) and c) as defined above, additional flame retardants and other additives as optional components, selected from the group consisting of A group of so-called anti-drip agents and polymer stabilizers. Representative phosphorus-containing flame retardants (for example): m-phenylene diphenyl phthalate (Fyr〇lflex® rdp, Akzo Nobel), resorcinol diester oligomer (rdp), phosphoric acid Triphenyl ester, bismuth (2,4-di-tert-butylphenyl) phosphate, ethylenediamine diphosphate (EDAP), ammonium polyphosphate, diethyl-N-N, N-bis (2) · Hydroxyethyl)-amino sulfonate, hydroxyalkyl phosphate, [RX1] hypophosphorous acid (H3p〇2) salt (especially Ca2+, Zn2+, or Al3+ salt), tetra(hydroxyindole) sulfide a derivative of squama, triphenylphosphine, 9'10-dihydro-9-oxa-10-phosphonium phenanthrene _10_oxide (D〇p〇), and a phosphazene flame retardant. The gas-containing flame retardant is, for example, a isocyanuric acid vinegar flame retardant such as polyisocyanuric acid vinegar, isocyanuric acid vinegar or isocyanuric acid vinegar. Representative examples are hydroxyalkyl urethanes such as hydrazine-(2-hydroxyethyl) isocyanurate, hydrazine (hydroxyl hydroxy) hydroxy phthalate, hydrazine isocyanurate (3-hydroxy-n-propyl) ) Ester or isocyanuric acid triglycid vinegar. The nitrogen-containing flame retardant contains other melamine-based flame retardants. Representative examples 154949.doc -48- 201202325 Examples: melamine cyanurate, melamine borate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, ammonium melamine polyphosphate, ammonium melamine pyrophosphate, dimelamine phosphate and dimelamine pyrophosphate. Other examples are: benzophenamine, hydroxyethyl ester of isocyanurate, allantoin, glycoluril, melamine cyanurate, melamine phosphate, bis-melamine phosphate, urea cyanurate, ammonium polyphosphate, melem (melem ), melam, melon series of melamine condensation products and / or highly condensed compounds or reaction products of melamine and dish acid or mixtures thereof. Representative organic dentate flame retardants (for example): polybrominated dipyridyl oxygen (DE-6OF, Great Lakes), decabromodiphenyloxy (DBDPO; Saytex® 102E), yttrium phosphate [3-bromide -2,2-bis(bromomethyl)propyl]ester (PB 370®, FMC), bismuth (2,3-dibromopropyl) phosphate, bismuth phosphate (2,3-dipropyl) Ester, chloric acid, tetrachlorophthalic acid, tetrabromophthalic acid, triphosphonic acid poly-α-gas ethyl ester mixture, tetrabromobisphenol A bis (2,3-di-propyl) (PE68), desertified epoxy resin, ethyl bis(tetrabromo-o-phenylene imino) (Saytex® BT-93), bis(hexachlorocyclopentadienyl)cyclooctane (Declorane Plus) ®), gasified paraffin, octabromodiphenyl ether, hexachlorocyclopentadiene derivative, 1,2-bis(tribromophenoxy)ethane (FF68〇), tetrabromo-bisphenol A (Saytex ® RB 100), ethyl bis(dibromo-norbornane dimethyl sulfoxide) (Saytex® BN-451), bis-(hexacyclopentadienyl) cyclooctane, PTFE, isocyanide Bismuth(5,3-dibromopropyl) urate, and ethyl bis-tetrabromophthalimide. The above organohalogen flame retardants are usually combined with an inorganic oxide synergist. Most 154949.doc •49· 201202325 Commonly used are zinc or antimony oxides such as Sb2〇3 or sb205. Boron compounds are also suitable. Representative inorganic flame retardant Qi! Including, for example, gas oxidized (ατη), soft water shale (Α100Η), argon oxidation town (MDH), sulphuric acid, Μα, (organically modified) delamination, (organized) Layered double hydroxide, and mixtures thereof. The above-mentioned type of flame retardant may be advantageously included in the composition of the present invention in an amount of from about 0.5% by weight to about 6% by weight of the organic polymer matrix; for example, about 1.0% by weight. /. To about 40.0% by weight, for example from about 5% by weight to about 〇 by weight / 0 of the polymer (or based on the total weight of the composition). According to another embodiment, the invention relates to a composition comprising an additional component - an anti-drip agent for the stomach. The anti-drip agents reduce the melt flow of the thermoplastic polymer and inhibit the formation of droplets at elevated temperatures. The addition of an anti-drip agent to a flame retardant composition is described in various references, for example, U.S. Patent Specification No. 4,263,201. Suitable additives which inhibit the formation of droplets at elevated temperatures include glass fibers, polytetrafluoroethylene (PTFE), high temperature elastomers, carbon phosphates, glass spheres, and the like. Polycethane having a different structure has been added to various references; see U.S. Patent Nos. 6,660,787, 6,727,302 or 6,730,720. The stabilizer is preferably free of dentate and is selected from the group consisting of nitroxide stabilizers, nitroxide stabilizers, amine oxide stabilizers, benzofuranone stabilizers, phosphites and hypophosphites. Agent, mashing stabilizer and 2,2,- 153949.doc -50- 201202325 bis-bisphenol monoacrylate stabilizer. As indicated above, the compositions of the present invention may additionally contain one or more customary additives, for example selected from the group consisting of pigments, dyes, plasticizers, antioxidants, thixotropic agents, leveling aids, basic co-stabilizers, Metal passivators, metal oxides, organophosphorus compounds, other light stabilizers and mixtures thereof, especially pigments, phenolic antioxidants, calcium stearate, stearic acid, 2_hydroxy-benzophenone UV absorption Agent, 2-(2,-hydroxyphenyl)benzotriazole and/or 2-(2-hydroxyphenyltriazine group. Preferred additional additives for use in the compositions defined above are treatment stabilizers ( For example, the above phosphites and phenolic antioxidants) and light stabilizers (for example, benzotriene). Preferably, the specific antioxidant comprises 3-(3,5-di-t-butyl-4-yl-phenyl) Octadecyl propionate (IRGANOX 1076), pentaerythritol _ tetra [3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate] (irgan〇x 1010) , guanidinium isocyanurate (3,5-di-t-butyl-4-hydroxyphenyl) vinegar (IRGANOX 3114), 1,3,5-trimethyl-2,4,6-anthracene (3,5 -di-tert-butyl-4-hydroxybenzyl Benzene (IRGANOX 1330), triethylene glycol-bis[3_(3_t-butyl-4-transyl-5-methylphenyl)propionate] (IRGANOX 245), and N,N' -Hexane-1,6-diyl-bis[3-(3,5-di-t-butyl-4-ylhydroxyphenyl)propanamide](IRGANOX 1098)»The specific treatment stabilizer contains Yalin Barium (2,4-di-tert-butylphenyl) ester (IRGAFOS 168), 3,9-bis(2,4-di-t-butylphenoxy)-2,4,8,10 - tetra-milk-3,9-di-scale snail [5.5]·]--alkane (IRGAFOS 126), phosphorous acid 2,2,,2,,-nitrogen [triethyl 畚

(3,3,5,5'-tetra-t-butyl-1,1'-biphenyl-2,2'-diyl)]g (irgaFOS 12), and diphosphinic acid tetra (2, 4-di-t-butylphenyl)[l,i_biphenyl]·4,4,_ 154949.doc 51 201202325 Di-based ester (IRGAFOS P-EPQ). The specific light stabilizer comprises 2_(2H_benzotrisyl-1 -yl)-4,6-bis(1-mercapto-1-phenylethyl)benzene (tinuvin 234), 2-(5 -Chloro(2H)-benzotriazol-2-yl)-4-(indolyl)-6-(t-butyl)phenol (TINUVIN 326), 2-(2H-benzotriazol-2-yl )-4-(1,ι,3,3-tetradecylbutyl)phenol (TINUVIN 329), 2-(2H-benzotrisin-2-yl)·4_(t-butyl)-6- (t-butyl)phenol (TINUVIN 350), 2,2,-methylenebis(6-(2Η-benzotris-2-yl)-4-(1,1,3,3 -tetraindole) Butyl)benzine) (TINUVIN 360), and 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[(hexyl)oxy]-phenol ( TINUVIN 1577), 2-(2,-hydroxy-5,-methylphenyl)benzotrien. Sitting (TINUVIN P), 2-hydroxy-4-(octyloxy)benzhydryl (CHIMASSORB 81), 1,3_bis_[(2,_cyano-3,3,_diphenylpropene oxime) Alkyloxy]-2,2·bis-{[(21-cyano-3,3'-diphenylpropenyl)oxy]methyl}-propane (UVINUL 3030, BASF), Acrylic Acid B Base 2_cyano_33_diphenyl ester (UVINUL 3035, BASF), and (2-ethylhexyl)-2-cyano-3,3-diphenylacrylate (UVINuL 3 039, BASF). Preferably, the above additive is present in an amount of 0.01 relative to the weight of the polymer matrix of component c). /. Up to 10.0%, especially 〇 5% to 5%. The incorporation of the components defined above in the polymer component is carried out by known means: for example, dry blending in powder form, or in solution, dispersion: suspension (for example) in an inert solvent (for example) Wet mixing in water or oil). ^ Agents M ha) and b) and other optional additives may be incorporated, for example, after molding or after ' or by incorporation of: dissolved or dispersed: : agent or additive mixture applied to the polymerization In the material, followed by evaporation or; heat generating solvent or suspension/dispersant. It can be added directly to the treatment unit (e.g., extruder, internal mixer, etc.), for example, as a dry mixture or powder 154949.doc • 52-201202325 or as a solution or dispersion or suspension or melt. The τ is added to the polymer matrix in a conventional flexing machine, and the polymer is melted and mixed with the additive. Suitable machines are well known to those skilled in the art. It is mainly a mixer, a kneader and an extruder. Preferably, the treatment is carried out in an extruder by introducing an additive during the treatment. Youjia's processing machines are single-screw list, reverse and co-rotating twin-screw extruders, planetary gear extruders, ring extruders or co-kneaders. A processing machine provided with at least one gas removal chamber can be used, to which a vacuum can be applied. Suitable extruders and kneaders are described, for example, in Handbuch der

Kunststoffextrusion, Vol. 1, Grundlagen, Editors F. Hensen, W. Knappe, H. Potente, 1989, pp. 3 to 7, ISBN: 3-446 14339-4 (Vol. 2, Extrusionsanlagen 1986, ISBN 3- 446. 14329-7). For example, the length of the screw is from 1 to 60 times the diameter of the screw, preferably from 35 to 48 times the diameter of the screw. The screw speed is preferably from 10 to 600 revolutions per minute (rpm), preferably 25 to 300 rpm. The maximum flux depends on the screw diameter, the rotational speed and the driving force. The present invention may also be practiced below the maximum flux by varying the parameters mentioned or using a weighing machine in an amount that delivers the dose. If multiple components are added, the components may be pre-mixed or separately added. 154949.doc -53· 201202325 It is also possible to spray additive component a) and other optional additives onto the polymer substance b). The additive mixture can be diluted with other additives (such as the conventional additives shown above), or a melt thereof, so that it can also be sprayed onto the polymer substrate together with the additives. It is especially advantageous to add by nozzle coating during polymerization catalyst passivation; in this case, the generated steam can be used to passivate the catalyst. In the case of spherical polymeric polyolefins, the additives of the invention may, for example, be advantageously applied by spraying with other additives as needed. Additive components a) and b) and other optional additives may also be added to the polymer in the form of a masterbatch ("concentrate") containing, for example, from about 5% by weight to about 40.0% by weight and more A concentration of from about 2% by weight to about 2% by weight is included in each component of the polymer. The polymer does not necessarily have the same structure as the polymer to which the additive is finally added. In such operations, the polymer can be used in the form of a powder, granule, solution, suspension or in the form of a crystal lattice. Inclusion can be performed before or during the molding operation. Materials containing the additives of the invention described herein are preferably used in the preparation of molded articles, such as rotary molded articles, injection molded articles, profiles, and the like, and especially for the preparation of fibers, spunbonded fabrics, films or foams. body. For component a) from 0.1 wt.% to 45.0 wt.%, preferably 0.1 wt.% to 3 〇〇 wt.% and for component b) from 0.05 wt.% to 5.0 wt.%, preferably 〇. The components a) and b) are mixed with the polymer matrix c) at a concentration of from 1 wt.% to 2.0 wt.%. The preferred ratio of components a):b) ranges from 50:1 to 1:5, preferably from 20:1 to 1:2. A particularly preferred embodiment of the invention relates to a composition, in particular a flame retardant composition, comprising: a) a phosphinate, as represented by structural formula (I) or (π): 154949.doc • 54-201202325 wherein One of R1 and R2 represents hydrogen or C^-Cs alkyl; or both R and R2 represent C丨-C8 alkyl; and R3 represents C^-Cio alkyl, heterophenyl. C2-C1G alkylene, phenyl, (C^C^alkyl)ι·3 phenyl, or phenyl-cvc^alkyl; b) at least one tetraalkylhexahydropyridine derivative m ^ Or III d, which is selected from the group consisting of: 1-cyclohexyloxy-2,2,6,6-tetradecyl-4-octadecylaminopyrohydropyridine, azelaic acid bis(κ 辛氧基oxy-2,2,6,6-tetramethylhexahydropyridin-4-yl) West I , 2.4-bis[(1-cyclohexyloxy_2,2,6,6_tetraindole) Hexahydrogen D-pyridyl-4-yl-butylamino]-6-(2-hydroxyethylamino---triazine, adipic acid bis(K cyclohexyloxy-2,2,6, 6-tetramethylhexahydro.pyridin-4-yl), 2.4-bis[(1-cyclohexyloxy-2,2,6,6•tetramethylhexahydro D-pyridyl-4-yl Butylamino]-6-chloro-homo-triterpene, 1-(2-hydroxy-2-mercaptopropoxy)-4-hydroxyl -2,2,6,6-tetradecyl hexahydro 0 ratio. 1-(2. hydroxymethylpropoxy)-4- oxo-2,2,6,6-tetramethyl Hexahydrogen ratio σ, 1-(2-hydroxy-2-methylpropoxy) octadecyloxy-2,2,6,6-tetradecyl hexahydrogen bite, 154949.doc •55 - 201202325 Bis(1-(2-hydroxy-2-mercaptopropoxy)_2,2,6,6-tetradecylhexahydropyridin-4-yl) sebacate, adipic acid bis(1- (2-hydroxy-2-methylpropoxy)_2,2,6,6•tetradecylhexahydropyridin-4-yl)ester, 2.4-bis{N-[l-(2-hydroxy-2- Mercaptopropoxy)_2,2,6,6-tetradecylhexahydro.pyridin-4-yl]-N-butylaminohydroxyethylamino))-triazine, 2.4-bis [ (1-cyclohexyloxy-2,2,6,6-tetradecylhexahydron-rhenyl)-butylamino]-6-chloro-ho-triazine with hydrazine, hydrazine, _ double (3_Aminopropyl)ethylenediamine), 2.4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl)butylamine -6-(2-hydroxyethylamino)-homo-trimethyl, oligomeric compound, which is a 4,4,-hexamethylene bis (amino-2,2,6,6-tetraindole) Hexahydropyridine) and 2-chloro-4,6-bis(dibutylamino)-homo-triazine a condensation product of 2,4-dichlorocyclohexyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl)butylamino]••--triazine, a compound of the formula : 154949.doc

• 56- 201202325 and compounds of the formula:

Wherein η is from 1 to 15; and c) a thermoplastic polymer selected from the group consisting of η, and the following: a polyolefin homopolymer and a copolymer of olefins with each other or with a vinyl monomer. The following examples are illustrative of the invention', but are not to be construed as limiting its scope. Examples of components and reagents

Moplen® HF500 Ν : Commercial grade polypropylene (Base„, Germany); Tinuvin® NOR 371 (N0R 1): Commercial product (Ciba & Division, Switzerland);

Flamestab® NOR 116 (NOR 2): Commercial products (Ciba,

Switzerland);

ExolitOP® 1240: aluminum diethylphosphinate (Ciariant, Switzerland). Test method for evaluating flame retardancy About "Flammability of Plastic Materials for Parts in 154949.doc -57· 201202325

The 5th edition of Devices and Appliances”, ^^ 94 test on January 29, 1996. The UL 94 V test grades are summarized in the table below (showing the time for one sample). Grade burn-in time [sec] Combustion drip burning to clip V-0 <10 No V-1 <30 None-- —---- No V-2 <30 have '--- 益 nc < 30 nc· > 30 no nc: no classification polymerization composition preparation / extrusion reference example 1-4 reference composition And the composition of the invention of Examples 1-4: in a co-rotating twin-screw extruder at a temperature of Tmax: 230 ° C, a flux rate of 4 kg / h and a rotational speed of 1 rpm / _ minute (rpm) A polypropylene homopolymer (MOPLEN HF 500 N) was extruded over ZSK25 (Coperion Werner & Pfleiderer). Add a base grade stable composition (0.05% calcium stearate + 〇 5% IRGANOX® B225; IRGANOX® B225 is a 1:1 mixture of IRGAFOS® 168 and IRGANOX® 1010) to MOPLEN HF 500 N and in Table 1 Additives listed. After cooling in a water bath, the polymer strip was granulated. UL94-V test samples (125 x 12.5 mm rods, thickness = 1.6 mm) and 1.0 mm plates according to DIN 4102-B2 were prepared by injection molding on an Arburg 370S injection molding machine at 230 °C. The DIN 4102-B2 film was obtained by compression molding. 154949.doc • 58 - 201202325 Testing of Polymeric Compositions The flame retardant properties of the test specimens were investigated after treatment at 23 ° C and 50% relative humidity for 48 h according to UL94-V. An additional UL94-V test (leaching test) was performed after exposing the test sample to deionized water for 7 days at 70 °C. Subsequently, the test rod was dried in a vacuum oven at 105 ° C for 24 h. The results obtained after leaching are shown in Table 2. Table 1 UL94 V (1.6 mm) test results obtained using different flame retardant compositions containing polypropylene homopolymers Example No. FR Additives [wt.%] Total Burning Time [sec] Burning Drips Ignition Cotton 3) UL94 Rating (1.6 mm) Reference example 1 w/o 223 5(5) nc Reference example 2 0.5% NOR 1 278 5(5) nc Reference example 3 1.0% NOR 1 290 5(5) nc Reference example 4 6.5% EXOLIT OP 1240 222 5(5) nc Inventive Example 1 6.5% EXOLIT OP 1240+0.50% NOR 1 67 5(5) V-2 Inventive Example 2 6.5% EXOLIT OP 1240+ 1.0% melamine hydrobromide + 0.50% NOR 1 10 5(5) V-2 Inventive Example 3 7.5% EXOLIT OP 1240+ 0.50% NOR 1 58 5(5) V-2 Inventive Example 4 7.5% EXOLIT OP 1240+ 0.75% NOR 2 57 5(5) V- 2 a) Number of tests (number of 5 tests) in which the burning drip from the ignited test stick ignited the cotton placed under the test stick according to the UL94 test standard. 154949.doc -59- 201202325 From the results reported above, it can be concluded that the polymer composition of the present invention exhibits excellent flame retardancy with self-extinguishing properties. While the reference to a single additive' and & does not exhibit significant flame retardant properties, the combination of phosphinates and representative sterically hindered N-alkoxyamines provides effective flame retardancy. Table 2 Properties of the polypropylene homopolymer test rod containing the flame retardant composition of the present invention after 7 days of leaching in deionized water and UL94 V (1.6 _) results. Example No. Weight loss after leaching [%] Sample thickness variation [mm] - Total burning time [sec] Combustion drips ignite cotton a) UL94 rating (1.6 mm) Example 3 of the invention i *, 丄 0.15 0.05 61 5 (5) V-2 〇 test number (the number of 5 tests), according to the UL94 test standard 'self-ignition test stick dripping combustion dripping ignited cotton under the test rod 0 from Table 2 As a result of the experiment, it is concluded that the representative polymer composition of the present invention is characterized by excellent leaching water resistance. It has been observed that after the leaching test, there is substantially no change in the weight of the scallops and the thickness of the sample. Inventive Example 3 shows that the UL94 rating can be maintained during the leaching test. 154949.doc

Claims (1)

201202325 VII. Patent application scope: 1 · A composition comprising: a) a salt of phosphinic acid represented by the following structural formula: S ίϊ 0 R1—P—OH (I) HO-P—R—P— 〇H (||) R2 or heart^ wherein one of R and R2 represents hydrogen or a Ci_C8 yard; or both scales 1 and R2 represent C-C8 alkyl; and R3 represents C^-Cw alkylene a heterophenyl group 2c2_Cig alkyl, a phenyl group, a (c丨-C4 alkyl) 丨_3 phenyl group, or a phenyl _c丨_C4 alkyl group; b) selected from the following composition Group of tetraalkylhexahydropyridine or tetraalkylhexahydropyrazine derivatives: 2,2,6,6-tetraalkylhexahydropyridine_丨_oxide, hydroxy 2,2,6,6· Tetraalkylhexahydropyridine, 1-alkoxy-2,2,6,6-tetraalkylhexanitrogen. ratio. 1,1·醯oxy-2,2,6,6-hexahydropyridine, hydroxy-2,2,6,6-tetraalkylhexahydropyrazine, alkoxy 2,2,6,6 • Tetraalkylhexahydropyrazine, and 1-decyloxy-2,2,6,6-hexahydropyrazine; and c) polymer matrix. 2. The composition of claim 1, wherein the salt of the phosphinic acid (1) is represented by the formula: (Π. 154949.doc 201202325 wherein one of R1 and R2 represents hydrogen or a Cl-C8 alkyl group; or both of the ruthenium and R2 represents a CVC8 alkyl group; Μ represents (Ci-C4 alkyl) 4N, (C丨-C4 alkyl) 3, (C2-C4; ^ OH) 4N, (c2-c4 alkyl 0H) 3NH, (C2-C4 alkyl 〇 h) 2N (CH3) 2, (C2-C4 burned 〇H)2NHCH3, (c6h5)4n, (C6H5)3NH, (C6H5CH3)4N, (C6H5CH3)3NH, NH4, melamine, ruthenium, metal or alkaline earth metal ions, or aluminum, zinc, iron or ruthenium; m a value of 1-3 and indicating the amount of positive charge on the ;; and η is a value of 1·3 and represents the amount of the phosphinic acid anion corresponding to the river. 3. The composition of claim 2, wherein the component 3) The salt of the phosphonic acid (1) is represented by the following formula: 4. The composition of claim 1 which comprises a) an aluminum salt of phosphinic acid (I) as represented by the formula: b) is selected from the group consisting of the following four groups: the four-burning six-bite derivative: 154949.doc 201202325 2,2,6,6-four-burning hexafluoride ratio bite-1-oxide, 1-base group- 2,2,6,6-tetrasyl hexahydrogen ratio bite, 1-alkoxy-2,2,6,6-tetraalkyl hexahydro σ ratio and l-decyloxy-2,2 6,6-hexahydrogen. Ratio σ; and c) thermoplastic polymer matrix. 5. The composition of claim 1, which comprises at least one tetraalkylhexahydropyridine derivative selected from the group consisting of b): 2,2,6,6-tetrasyl Hydrogen ° ratio °-1-oxide: OH a), 1-light base of the formula - 2,2,6,6 - four dazzling "base six rat ratio bite R. R. (Ill b), the following formula 1 - alkoxy-2,2,6,6-tetrahydrogenated six rats. Than bite. mi · 6 4 R R R '1R And 1-methoxy-2,2,6,6-hexahydropyridine of the formula: \m/ I54949.doc 201202325 One of its centralizations represents hydrogen or an N-substituent and the other represents a 〇-substituent or a c-substituent; or both Ra and Rb represent hydrogen, deuterium-substituted Or a C-substituent; R represents a CrCM alkyl group, a Cs-C6 cycloalkyl group or a C2-C2G alkyl group having an additional substituent, a C5-C6 cycloalkyl group or a c2-C2g dilute group; And Ri-R4 each represents a Ci-C<t-dition group; and R5 and R.6 independently of each other represent hydrogen or are selected from the group consisting of Ci-C4-alkyl, (: 丨-(:3 alkylphenyl and a substituent of the group consisting of phenyl groups; and R5 and R_6 together represent a pendant oxy group. 6. The composition of claim 5 which comprises at least one tetraalkylhexahydropyridine derivative III a, III b, III c Or III d as component b), wherein one of Ra and Rb represents hydrogen or an N-substituent and the other represents a 〇-substituent or a c-substituent; or both Ra and Rb represent hydrogen, hydrazine a substituent or a C-substituent; R represents a C^-Cs alkyl group, a C5-C6 cycloalkyl group or a c2-c8 alkyl group having an additional substituent, a C5_C6 cycloalkyl group 4c2_C8 alkenyl group; and Ac represents a Cl_C8 carboxylic acid. Sulfhydryl; and each of R1-R4 is a fluorenyl group And Rs and each represents hydrogen. 7. The composition of claim 5, which comprises at least one tetraalkylhexahydropyridine Ho 111a, ΙΠ b, III c or III d as component b), 154949.doc 201202325 Wherein one of Ra and Rb represents hydrogen or an N-substituent and the other represents a hydrazine substituent or a (^ substituent; or both and Rb represent a hydrazine substituent or a c substituent; C丨-Cs alkyl, C5_C6 cycloalkyl or hydroxy substituted 匕 alkyl, C5-C6 cycloalkyl or c2_c8 alkenyl; Ac represents (: 丨-(: 8 carboxylic acid sulfhydryl; and H4 Each of which is a sulfhydryl group; and each of the ruthenium 5 and 116 represents hydrogen. 8. The composition of claim 5, which comprises at least one tetraalkyl hexahydropyridine derivative III c or III d selected from the group consisting of Component b): 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-octadecylamino hexahydro 11-pyridine, bis(1-octyloxy) sebacate 2,2,6,6-tetramethylhexahydropyridin-4-yl) ester, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydro- 0 ratio Buty-4-yl) butylamino]-6-(2-hydroxyethylamino-s-triazine, bis(1-cyclohexyloxy) adipate _2,2,6,6-tetradecylpiperidine _4_yl)S, 2,4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydropyrane ratio) Buty-4-yl) butylamino]-6-chloro-homo-trim, 1-(2-hydroxy-2-mercaptopropoxy)·4_hydroxy-2,2,6,6_four Thiol hexahydro 0-bite, 1-(2-hydroxy-2-methylpropoxy)_4·sideoxy-2,2,6,6-tetradecyl hexene 154949.doc ς 201202325 Hydrogen 0 bite , 1-(2-propionyl-2-methylpropoxy)-4-octadecyloxy-2,2,6,6-tetramethylhexahydrogenate bite, azelaic acid double (1 -(2-hydroxy-2-methylpropoxy)_2,2,6,6-tetradecyl hexahydrate 0-bite-4-yl)S, adipic acid bis(1-(2-hydroxy-) 2-mercaptopropoxy)_2,2,6,6-tetradecylhexahydropyridin-4-yl)ester, 2.4-bis{N-[l-(2-hydroxy-2-methylpropoxy) ) 2,2,6,6-tetramethylhexahydrogen ratio -4-yl]-N-butylamino}_6-(2-transethylethylamino)_homo-triterpene, 2.4 - bis[(cyclohexyloxy-2,2,6,6-tetradecylhexahydropyranyl)-butyl-4-yl]butylamino]-6-chloro-ho-triazine with ν,Ν - the reaction product of bis(3-aminopropyl)ethylenediamine), 2.4-bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydro) Butylamino]-6-(2-hydroxyethylamino-s-triazine, oligomeric compound, which is 4,4,-hexamethylenebis(amino-2) , 2,6,6-tetramethylhexahydropyridine) with 2-gas-4,6-bis(dibutylamine-based mono-triazine-terminated 2,4-digas-6-[( Condensation product of 1-cyclohexyloxy-2,2,6,6-tetramethylhexahydro t|pyridyl-cardiyl)butylamino]-ho-triazine, compound of the formula: 154949.doc • 6 - 201202325 〇 and compounds of the formula: VW where η is from 1 to 15. 9. The composition of claim 1 which comprises: a) a salt of phosphinic acid as represented by structural formula (I) or (II): wherein one of R1 and R2 represents hydrogen or Cl-(:8 An alkyl group; or both Ri and R2 represent a Ci-Cg alkyl group; and R represents an alkylene group, a heterophenyl group 2c2_Cig alkyl group, a phenyl group, a (c "C4 alkyl group" U phenyl group, Or phenyl-Ci_C4 alkylene; 154949.doc 201202325 b) at least one tetraalkylhexahydropyridine derivative In c*md selected from the group consisting of: 1% hexyloxy-2, 2, 6, 6-tetradecyl-4-octadecylamine hexahydropyridinium, bis(1-octyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl) ), 2.4-bis[(1-cyclohexyloxy-2,2,6,6-tetradecylhexahydropyridin-4-yl)butylamino]-6-(2-hydroxyethylamine) Base-homo-triazine, bis(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydropyridin-4-yl) acetonate, 2.4-bis[(1-cyclohexyloxy) Base 2,2,6,6-tetradecylhexahydron-pyridinyl-4-yl)butylamino]-6-gas·homo-trisyl, iU-pyridyl-2-mercaptopropoxy Base>4_hydroxy-2,2,6,6·tetramethylhexahydropyridinium, κ(2- Benzyl-2-mercaptopropoxy)_4_sideoxy-2,2,6,6-tetradecyl hexahydropyrene, iU-hydroxy-2-mercaptopropoxy)_4·18醯Baseoxy-2,2,6,6-tetramethylhexahydropyridine, bis(1-(2-hydroxy-2-methylpropoxy)-2,2,6,6-tetraindole Hexa-oxygen. bis- 4 -yl) 5, adipic acid bis(1-(2-hydroxy-2-mercaptopropoxy)-2,2,6,6-tetradecyl six gas ratio β Determining -4 -yl)5, 2.4-bis{Ν-[1-(2.hydroxy-2-indolylpropoxy)_2,2,6,6-tetradecylhexa-argon. ]]butylamino}-6-(2-hydroxyethylamino)-average-three 154949.doc 201202325 〇 Qin, 2.4- bis[(1-cyclohexyloxy·2,2,6,6- Reaction product of tetramethylhexahydropyridine-4-yl)butylamino]-6-chloro-ho-triazine with ν, Ν,-bis(3-aminopropyl)ethylenediamine, 2.4- Bis[(1-cyclohexyloxy-2,2,6,6-tetramethylhexahydrobipyridin-4-yl)butylamino]-6-(2-pyridylethylamino-) - triterpenoid, an oligomeric compound which is a 4,4'-hexaindolyl bis(amino-2,2,6,6-tetramethylhexahydrobiphenyl) and 2-chloro-4,6 - bis(dibutylamino)·-triazine-terminated 2,4-dichloro·6-[(1-cyclohexyl) a condensation product of a oxy 2,2,6,6-tetramethylhexahydropyridinyl-4-yl)butylamino]-iso-triazine, a compound of the formula: And compounds of the formula: 154949.doc 201202325 ό Wherein η is from 1 to 15; and c) the thermoplastic polymer' is selected from the group consisting of polyolefin terpolymers and copolymers of olefins with each other or with vinyl monomers. 10. The composition of claim 1 which is used as a flame retardant. 11. A mixture comprising: a) a salt of phosphinic acid as represented by the following structural formula: , Ν ί / R - Ρ - ΟΗ (I) HO-P-R3-p-〇h (, ι) or R1 ' 'R2 wherein one of R1 and H2 represents hydrogen or a Ci_c8 alkyl group; or both the ruler and the ruler 2 represent an alkyl group; and r3 represents a C-Cic alkyl group and a heterophenyl group ( : 2-(:1()alkyl, phenyl, (CrC4 alkyl) η phenyl, or phenyl _Cl_c4 alkyl; b) free radicals of the following composition of the four alkyl hexahydro D Specific biting derivatives: 2,2,6,6-tetraalkylhexahydropyridine-1-oxide, 丨_hydroxy_2 2,6,6_four 154949.doc •10- 201202325 burnt hexahydrogen D-, 1-alkoxy-2,2,6,6-tetraalkyl hexahydrogen ratio. 1- and 1-oxooxy-2,2,6,6-hexahydrogen ratio bite. A method of imparting flame retardancy to a polymer matrix, the method comprising adding a mixture of claim 11 to the polymer matrix of component c). 154949.doc -11 - 201202325 IV. Designated representative map: (1) The representative representative of the case is: (none) (2) The symbolic symbol of the representative figure is simple: 5. If there is a chemical formula in this case, please reveal the best display. Chemical formula of the invention: Ο , II R1—P—OH (I) 丨2 R2 〇〇(N) II 3 II HO-P-RP—OH I, 12 R1 R2 154949.doc -2-