Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers fo

专利摘要:
A compound of formula (I) (I) Wherein n is a number from 2 to 14; R 1 is for example C 1 -C 18 alkyl or C 5 -C 12 cycloalkyl; R 2 is for example C 2 -C 12 alkylene; A is for example acetyl, (C 1 -C 4 alkoxy) carbonyl, (C 1 -C 4 alkyl) aminocarbonyl or C 1 -C 4 alkyl; B is -OR 3 , -N (R 4 ) (R 5 ) or a group of formula (II); R 3 , R 4 and R 5 are the same or different, such as hydrogen or C 1 -C 18 alkyl, or —N (R 4 ) (R 5 ) is additionally a group of formula (III) wherein Y is —O -, -CH 2- , -CH 2 CH 2 -or> N-CH 3- ; X is -O- or -NR 6 ; R 6 is for example hydrogen or C 1 -C 18 alkyl; And R is preferably a group of formula (IV); Provided that each of the radicals B, R, R 1 and R 2 in the individual repeating units of formula (I) have the same or different meanings: (Ⅱ) (Ⅲ) (Ⅳ) The compounds are useful as light stabilizers, heat stabilizers and oxidation stabilizers for organic materials, in particular synthetic polymers.
公开号:KR20010012805A
申请号:KR1019997010768
申请日:1998-05-25
公开日:2001-02-26
发明作者:갈보제임스피터；라자리다리오；구이자르디파브리지오
申请人:시바 스폐셜티 케미칼스 홀딩 인코포레이티드；
IPC主号:

专利说明:

Block oligomers containing 1-hydrocarbyloxy-2,2,6,6 as stabilizers for organic materials containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups -tetramethyl-4-piperidyl groups as stabilizers for organic materials}
[2] Stabilizing synthetic polymers using 2,2,6,6-tetramethylpiperidine derivatives is described, for example, in US-A-4 086 204, US-A-4 331 586, US-A-4 335 242 , US-A-4 234 707, US-A-4 459 395, US-A-4 492 791, US-A-5 204 473, EP-A-53 775, EP-A-357 223, EP-A-377 324, EP-A-462 069, EP-A-782 994 and GB-A-2 301 106.
[1] The present invention relates to block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups, light stabilizers, thermal stabilizers and oxidative stability to organic materials, in particular synthetic polymers. To their use as topical agents and to such stabilized organic materials.
[390] 1 is a chromatogram according to GPC analysis of a starting material prepared in Example S-1,
[391] Figure 2 is a chromatogram according to GPC analysis of the starting material prepared in Example S-2.
[3] The present invention relates to compounds of formula (I)
[4]
[5] In the food,
[6] n is a number from 2 to 14;
[7] The radicals R ₁ are independently of each other a hydrogen or hydrocarbyl radical or -OR ₁ is oxyl;
[8] The radicals R ₂ independently of one another are C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi- (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) car Carbonyl) or C ₄ -C ₁₂ alkylene containing 1,4-piperazindiyl, -O- or> NX ₁ in between when having one of the definitions of R ₄ excluding hydrogen; Or R ₂ is a group of formula (a), (b) or (c);
[9]
[10]
[11]
[12] Where m is 2 or 3,
[13] 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
[14] The radicals X ₃ independently of one another are C ₂ -C ₁₂ alkylene;
[15] The radicals A are independently of each other C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkoxy) carbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C ₅ -C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
[16] B is -OR ₃ , -N (R ₄ ) (R ₅ ) or a group of formula (II):
[17]
[18] R ₃ , R ₄ and R ₅ are the same or different and 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 (III)
[19]
[20] C ₂ -C ₄ alkyl substituted with a group of wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ , or —N (R ₄ ) (R ₅ ) Is additionally a group of formula (III);
[21] X is -O- or> NR ₆ ;
[22] R ₆ 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 (IV)
[23]
[24] Or C ₂ -C ₄ alkyl substituted by —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2, 3 or 4 position; In addition
[25] The radicals R have the meanings defined in R ₆ independently of one another, provided that in the individual repeat units of formula (I) each of the radicals B, R, R ₁ and R ₂ have the same or different meanings.
[26] In the individual repeat units of formula (I), each of the radicals B, R, R ₁ and R ₂ preferably have the same meaning.
[27] In formula (I), radicals R and radicals May have a random distribution or a block distribution.
[28] R ₁ , preferably a hydrocarbyl radical having 1 to 18 carbon atoms, is for example C ₁ -C ₁₈ alkyl, C ₅ -C ₁₈ alkenyl, C ₅ -C ₁₈ alkynyl, unsubstituted or C ₁ -C ₄ C ₅ -C ₁₂ cycloalkyl substituted by alkyl; C ₅ -C ₁₂ cycloalkenyl unsubstituted or substituted by C ₁ -C ₄ alkyl; Bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkyl unsubstituted or substituted by C ₁ -C ₄ alkyl on phenyl.
[29] Examples of alkyl containing up to 18 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, tertiary butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl. R ₁ is preferably C ₁ -C ₁₂ alkyl, such as C ₆ -C ₁₂ alkyl, in particular heptyl or octyl. R ₆ is preferably C ₁ -C ₈ alkyl, in particular C ₁ -C ₄ alkyl. One of the preferred meanings of A is C ₁ -C ₄ alkyl.
[30] An example of C ₂ -C ₄ alkyl substituted by —OH is 2-hydroxyethyl.
[31] Examples of C ₁ -C ₈ alkoxy, preferably C ₁ -C ₄ alkoxy, especially C ₂ -C ₄ alkyl substituted by methoxy or ethoxy, are 2-methoxyethyl, 2-ethoxyethyl, 3- Methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3-octoxypropyl and 4-methoxybutyl.
[32] Examples of C ₂ -C ₄ alkyl substituted by di (C ₁ -C ₄ alkyl) amino, preferably dimethylamino or diethylamino are 2-dimethylaminoethyl, 2-diethylaminoethyl, 3-dimethylamino Propyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl.
[33] Groups of formula (III) are preferably to be.
[34] Examples of C ₂ -C ₄ alkyl substituted by a group of formula (III) are It is the flag of. group Is particularly preferred.
[35] Examples of C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl include cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl , Trimethylcyclohexyl, tert-butylcyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl. Preference is given to unsubstituted or substituted cyclohexyl.
[36] Preferred examples of bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms are 1,2,3,4-tetrahydronaphthenyl.
[37] Examples of alkenyl containing up to 18 carbon atoms are allyl, 2-metall, butenyl, hexenyl, undecenyl and octadecenyl. Preference is given to alkenyls in which the carbon atom in the 1-position is saturated.
[38] Preferred example of C ₅ -C ₁₈ alkynyl is octinyl.
[39] Examples of phenyl substituted by 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy are methylphenyl, dimethylphenyl, trimethylphenyl, tert-butylphenyl, di-tert-butylphenyl, 3,5-ditertiary Butyl-4-methylphenyl, methoxyphenyl, ethoxyphenyl and butoxyphenyl.
[40] Examples of C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl on phenyl are benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, tert-butylbenzyl and 2-phenylethyl to be. Benzyl is preferred.
[41] Examples of acyl (aliphatic, cycloaliphatic or aromatic) containing up to 12 carbon atoms are formyl, acetyl, propionyl, butyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. Preferred are C ₁ -C ₈ alkanoyl and benzoyl. Acetyl is particularly preferred.
[42] Examples of alkoxycarbonyl are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, hexoxycarbonyl, heptoxycarbonyl, octoxycarbonyl, nonyloxycarbonyl , Decyloxycarbonyl, undecyloxycarbonyl and dodecyloxycarbonyl.
[43] Particularly preferred example of (C ₅ -C ₁₂ cycloalkoxy) carbonyl is cyclohexoxycarbonyl. Preference is given to (C ₅ -C ₇ cycloalkoxy) carbonyl.
[44] Examples of (C ₁ -C ₈ alkyl) aminocarbonyl include methylaminocarbonyl, ethylaminocarbonyl, propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl, hexylaminocarbonyl, heptylaminocarbonyl and octyl Aminocarbonyl. (C ₁ -C ₄ alkyl) aminocarbonyl is preferred.
[45] Particularly preferred examples of (C ₅ -C ₁₂ cycloalkyl) aminocarbonyl are cyclohexylaminocarbonyl. Preference is given to (C ₅ -C ₇ cycloalkyl) aminocarbonyl.
[46] Particularly preferred example of (C ₇ -C ₉ phenylalkyl) aminocarbonyl is benzylaminocarbonyl.
[47] Examples of alkylene containing up to 12 carbon atoms are ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, decamethylene and dodecamethylene. R ₂ is for example C ₂ -C ₈ alkylene or C ₄ -C ₈ alkylene, in particular C ₂ -C ₆ alkylene, preferably hexamethylene.
[48] An example of C ₄ -C ₁₂ alkenylene is 3-hexenylene.
[49] An example of C ₅ -C ₇ cycloalkylene is cyclohexylene.
[50] Examples of C ₄ -C ₁₂ alkylene including 1,4-piperazindiyl in the middle to be.
[51] Examples of C ₄ -C ₁₂ alkylene comprising -O- in the middle, such as 1, 2 or 3 -O-, are 3-oxapentane-1,5-diyl, 4-oxaheptan-1,7-diyl , 3,6-dioxaoctane-1,8-diyl, 4,7-dioxadecan-1,10-diyl, 4,9-dioxadodecane-1,12-diyl, 3,6,9- Trioxoundecane-1,11-diyl and 4,7,10-trioxatridecane-1,13-diyl.
[52] Examples of C ₄ -C ₁₂ alkylene comprising> NX ₁ to be.
[53] An example of C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene) is cyclohexylenedimethylene.
[54] Examples of (C ₁ -C ₄ alkylene) di (C ₅ -C ₇ cycloalkylene) are methylenedicyclohexylene and diisopropylidenedicyclohexylene.
[55] An example of phenylenedi (C ₁ -C ₄ alkylene) is phenylenedimethylene.
[56] The variable n is preferably a number from 2 to 8, in particular from 2 to 6.
[57] R is preferably hydrogen, C ₁ -C ₁₀ alkyl, cyclohexyl or a group of formula (IV), in particular a group of formula (IV).
[58] R ₁ is preferably hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₈ alkenyl, C ₅ -C ₁₈ alkynyl, C ₅ -C ₁₂ cyclo unsubstituted or substituted by C ₁ -C ₄ alkyl Alkyl; C ₅ -C ₁₂ cycloalkenyl unsubstituted or substituted by C ₁ -C ₄ alkyl; Bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkyl unsubstituted or substituted by C ₁ -C ₄ alkyl on phenyl; Or -OR ₁ is oxyl.
[59] R ₁ is especially hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₈ cycloalkyl unsubstituted or substituted by methyl; Cyclohexenyl, α-methylbenzyl or 1,2,3,4-tetrahydronaphthenyl, such as methyl, octyl or cyclohexyl.
[60] A is preferably acetyl, (C ₁ -C ₄ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl or C ₁ -C ₄ alkyl, in particular acetyl or (C ₁ -C ₄ alkyl) aminocar Bonyl.
[61] Radical B is preferably
[62]
[63] It is the flag of.
[64] Preferred are compounds of formula (I) having the following definitions:
[65] R ₂ is C ₂ -C ₁₂ alkylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ alcycloalkylene) or phenylenedi (C ₁ -C ₄ alkylene);
[66] A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₇ cycloalkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, (C ₅ -C ₇ Cycloalkyl) aminocarbonyl, benzylaminocarbonyl, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, allyl or benzyl;
[67] C ₅ -C ₇ cycloalkyl wherein R ₃ , R ₄ and R ₅ are the same or different and are hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₁₂ alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted by C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl or C ₂ -C ₃ alkyl substituted by —OH, C ₁ -C ₄ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2 or 3 position; Or -N (R ₄ ) (R ₅ ) is additionally a group of formula (III); In addition
[68] R ₆ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl, a group of formula (IV) or C ₂ -substituted by -OH, C ₁ -C ₄ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2 or 3 position; C ₃ alkyl.
[69] And R ₂ is C ₂ -C ₈ alkylene;
[70] A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, cyclohexoxycarbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, cyclohexylaminocarbonyl, benzylaminocarbonyl, C ₁ -C ₄ alkyl, cyclohexyl, allyl or benzyl;
[71] Cyclohexyl wherein R ₃ , R ₄ and R ₅ are the same or different and are hydrogen, C ₁ -C ₈ alkyl, unsubstituted or substituted by methyl; C ₃ -C ₈ alkenyl, phenyl unsubstituted or substituted by methyl; Benzyl, tetrahydrofurfuryl or C ₂ -C ₃ alkyl substituted by —OH, C ₁ -C ₄ alkoxy, dimethylamino, diethylamino or 4-morpholinyl at the 2 or 3 position; Or -N (R ₄ ) (R ₅ ) is additionally 4-morpholinyl; In addition
[72] R ₆ is hydrogen, C ₁ -C ₈ alkyl, cyclohexyl unsubstituted or substituted by methyl; Benzyl, tetrahydrofurfuryl, C ₂ -C ₃ substituted by —OH, C ₁ -C ₄ alkoxy, dimethylamino, diethylamino or 4-morpholinyl at the group of formula (IV) or at the 2 or 3 position; Preference is given to compounds of the formula (I) which are alkyl.
[73] And n is a number from 2 to 6;
[74] R is a group of formula (IV);
[75] R ₂ is C ₂ -C ₆ alkylene;
[76] A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, C ₁ -C ₄ alkyl or allyl;
[77] B is —N (R ₄ ) (R ₅ ) or a group of formula (II);
[78] R ₄ and R ₅ are the same or different and hydrogen, C ₁ -C ₈ alkyl, 2-hydroxyethyl or 2-methoxyethyl or -N (R ₄ ) (R ₅ ) is additionally 4-morpholine Nil;
[79] X is> NR ₆ ; In addition
[80] Preference is also given to compounds of the formula (I) in which R ₆ is C ₁ -C ₄ alkyl.
[81] And n is a number from 2 to 6;
[82] R is a group of formula (IV);
[83] R ₁ is methyl, octyl or cyclohexyl;
[84] R ₂ is C ₂ -C ₆ alkylene;
[85] A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl or C ₁ -C ₄ alkyl;
[86] B is -N (R ₄ ) (R ₅ ) or a group of formula (II);
[87] R ₄ and R ₅ are the same or different and are C ₁ -C ₈ alkyl or —N (R ₄ ) (R ₅ ) is additionally 4-morpholinyl;
[88] X is> NR ₆ ; In addition
[89] Preference is also given to compounds of the formula (I) in which R ₆ is C ₁ -C ₄ alkyl.
[90] Particularly preferably,
[91] n is a number from 2 to 6;
[92] R is a group of formula (IV);
[93] R ₁ is methyl, octyl or cyclohexyl;
[94] R ₂ is C ₂ -C ₆ alkylene;
[95] A is C ₁ -C ₈ acyl or (C ₁ -C ₈ alkoxy) carbonyl;
[96] B is a group of formula (II) above;
[97] X is> NR ₆ ; In addition
[98] Preference is also given to compounds of the formula (I) in which R ₆ is C ₁ -C ₄ alkyl.
[99] Polydispersity represents the molecular weight distribution of the polymerizable compound. In the present invention, polydispersity is weight average And number average It is the ratio of the molecular weight. A ratio equal to 1 indicates that the compound is monodisperse and has only one molecular weight and no molecular weight distribution. Narrow molecular weight distribution is polydisperse It is characterized by approaching this one.
[100] In general, the compounds of the present invention are polydisperse It is not limited by.
[101] Compounds according to formula (I) are polydisperse The 1 (where n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14) may be a monodisperse compound or a polydisperse compound having a molecular weight distribution. Such polydisperse compounds correspond to mixtures containing three or more different monodisperse compounds of formula (I), which may vary by variable n. Polydispersity of the mixture Is for example 1.1 to 1.7, 1.1 to 1.65, 1.1 to 1.6, 1.1 to 1.55 or 1.1 to 1.5. N in the mixture is preferably 2, 4 and 6.
[102] Polydispersity Examples are for example 1.2 to 1.65, 1.2 to 1.6, 1.2 to 1.55 or 1.2 to 1.5.
[103] The compound of the present invention can be produced by the following method.
[104] Method 1): using a starting material which already contains a group of formula (IV).
[105] (Ⅳ)
[106] Method 2): A method in which a block oligomer of formula (I-0) is used as a starting material and a group of formula (IV-O) present in the block oligomer is transferred to a group of formula (IV).
[107]
[108]
[109] In the formula, n, A, and R ₂ have the same meanings as above, and R ^* and B ^* are as defined below.
[110] The mixture described above,
[111] 1) reacting a compound of formula (α) with a compound of formula (β) in a stoichiometric ratio to obtain a compound of formula (γ);
[112] 2) A compound of formula (γ) is reacted with a compound of formula (β) in a molar ratio of 1: 2 to 1: 3, preferably 1: 2 to 1: 2.5, in particular 1: 2, Of a mixture of three or more different monodisperse compounds, wherein n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 or 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, preferably 2, 3, 4, 5, 6, 7, 8, 9 or 10, more preferably 2, 3, 4, 5, 6 , 7 or 8, in particular 2, 4 and 6);
[113] 3) The mixture obtained in 2) may be prepared according to the method 1) of reacting the compound of formula (ε) or the compound of formula (ζ) in a stoichiometric ratio to obtain a desired mixture. ) To 3) can be carried out in an organic solvent in the presence of an inorganic base, provided that the compound of formula (ζ) is used in reaction 3), the reaction 3) can be carried out without an inorganic base:
[114]
[115]
[116]
[117]
[118] A'-X '
[119] A "-NCO
[120] Wherein the radicals R, R ₁ , R ₂ and B are as defined above;
[121] X 'is a leaving group such as halogen, in particular chlorine;
[122] A ′ is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkoxy) carbonyl, C ₁ -C ₈ alkyl, unsubstituted or 1, 2 or 3 C C ₅ -C ₁₂ cycloalkyl substituted by _1- C ₄ alkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN; In addition
[123] A ″ is C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₉ phenylalkyl.
[124] If A is C ₁ -C ₈ acyl, reaction 3) can be carried out using the corresponding acid anhydride as a reagent instead of the compound of formula (ε).
[125] If A is a methyl group, the compound of formula (I) reacts a mixture of formaldehyde / formic acid with the corresponding compound of formula (δ) as described in US-A-5 130 429 or US-A-3 898 303 Can be obtained.
[126] Examples of suitable organic solvents are toluene, xylene, trimethylbenzene, isopropylbenzene, diisopropylbenzene and especially water insoluble organic ketones such as methyl isobutyl ketone. Xylene is preferred.
[127] Examples of inorganic bases are sodium hydride, potassium hydride, sodium carbonate and potassium carbonate. Sodium hydride is preferred. If the radical B in the formula (α) is a group of the formula (II), wherein X is oxygen, it is suitable to use sodium carbonate or potassium carbonate as the inorganic base in reactions 1) and 2).
[128] The reaction 1) can be carried out at a temperature of 40 ° C to 70 ° C, preferably 50 ° C to 60 ° C.
[129] Reaction 2) can be carried out at a temperature of 110 ° C to 180 ° C, preferably 140 ° C to 160 ° C.
[130] If the reactants of formula (ε) are used in reaction 3), the reaction 3) can be carried out in a closed vessel, if necessary, for example at 60 ° C to 180 ° C, preferably 146 to 160 ° C.
[131] When the reactant of formula (ζ) is used in reaction 3), the reaction 3) can be carried out, for example, at a temperature of 0 ° C to 60 ° C, preferably 0 ° C to 25 ° C.
[132] Possible byproducts are compounds of the formulas (Id) and (Ie):
[133]
[134]
[135] Each of these compounds is present in the mixture, for example in an amount of up to 30 mol%, preferably up to 20 mol%, more preferably up to 10 mol% or up to 8 mol% relative to the total mixture.
[136] Compounds of formula (α) can be prepared by reacting cyanuric chloride with compound B-H in stoichiometric proportions in the presence of an organic solvent and an inorganic base.
[137] In order to prepare the compound of the formula (α), it is suitable to use the same solvent and the same inorganic base as those listed above in the reactions 1) to 3).
[138] In general, starting materials used in the process are known. If they are not commercially available, they can be prepared similarly to known methods.
[139] In order to prepare starting materials of formula (α) as well as starting materials of formula (α), wherein B is a group of formula (II), it is suitable to use compounds of formula (S-1):
[140]
[141] Compounds of formula (SI) are hydroperoxides, preferably tert-butyl, for example 1-oxy-2,2,6,6-tetramethyl-4-piperidone in the presence of a peroxide decomposition catalyst such as MoO _{3 in a} hydrocarbon solvent. It can be prepared by reacting with hydroperoxide. The meaning of R ₁ depends on the hydrocarbon solvent used. For example, if R ₁ is cyclohexyl, the hydrocarbon solvent used is cyclohexane. In general, the preparation of compounds of formula (SI) may be prepared analogously to the process described in US-A-4 921 962, which is incorporated herein by reference.
[142] Compounds of formula (S-I) can be prepared by coupling 1-oxyl-2,2,6,6-tetramethyl-4-piperidone with hydrocarbon radicals. The principle of this reaction is for example R.L. Kinney group, J. Am. Chem. Soc., 1978, 100, 7902-7915 (Reaction of alkyl idoides with tri-n-butyltin hydride) or described in D.W. Grattan group, Polym. Degrad. and Stability 1979, 69 (Photolysis of a solution of di-tert-butyl peroxide and cyclohexane). Directed reactions are described, for example, in US-A-5 021 577 (Examples 5 and 16) as well as US-A-5 204 473 (Examples 7 to 10) and using the appropriate starting materials to formula (SI) Can be applied to prepare a compound.
[143] If R ₁ is methyl, the preparation of the compound of formula (SI) is prepared in the presence of 1-oxyl-2,2,6,6- in the presence of iron sulfate heptahydrate in dimethyl sulfoxide as described in US-A-5 374 729. The reaction can be carried out by reacting tetramethyl-4-piperidone with hydrogen peroxide.
[144] The preparation of 1-oxyl-2,2,6,6-tetramethyl-4-piperidone is described, for example, in Nature 196, 472-474, Chemical Abstracts 58: 56264 and Beilstein EIII / IV 21 3279.
[145] Examples S-A and S-B below describe the preparation of the compound of formula (S-I) in more detail.
[146] Example S-A (starting material):
[147] Preparation of 1-methoxy-2,2,6,6-tetramethyl-4-piperidone
[148]
[149] Magnetically stirred 5.0 liter flasks were placed in four flasks of 1-oxyl-2,2,6,6-tetramethyl-4-piperidone (300 g, 1.76 moles), iron sulfate heptahydrate (513.7 g, 1.85 moles) and Dimethylsulfoxide (1450 g) was added. Hydrogen peroxide, 30% (279.2 g, 2.46 moles) was added over 1 hour 45 minutes. The temperature was maintained at 29-32 ° C. The contents were further stirred at 25-30 ° C. for 30 minutes and then cooled down to 10 ° C. Water (1250 ml) was added and the mixture was extracted with four portions of 750 ml of ethyl acetate. The combined extracts were washed with 2 x 1.0 L of H ₂ O followed by 1 x 500 ml of saturated NaCl and then dried over anhydrous MgSO ₄ . Ethyl acetate was evaporated off and the product was distilled (82-84 ° C./0.33×10 ⁻² bars) to yield 254 g of pale yellow oil (yield: 78% of theory; IR-spectrum: ketone carbonyl, 1710 cm ⁻¹ ) It was.
[150] Example S-B (starting material):
[151] Preparation of 1-cyclohexyloxy-2,2,6,6-tetramethyl-4-piperidone
[152]
[153] Cyclohexane (215 ml, 2.0 mol), tert-butyl hydroperoxide (70% aqueous) (77.1 g, 0.6 mol), molybdenum trioxide (1.44 g, 0.01 mol) and 1-oxyl-2,2,6,6- A mixture of tetramethyl-4-piperidone (34 g, 0.2 mol) was charged to a 500 ml flask equipped with a Barrett trap. The mixture was stirred at reflux (80 ° C.) for 2 hours until no more water was collected. The mixture was then filtered by gravity and placed in a pressure bottle and molybdenum trioxide (1.44 g, 0.01 mol) was added. The mixture was then stirred and heated to 105 ° C. (2.34 bar) and held for 5 hours until the color changed from dark orange to pale yellow. This mixture was filtered and the clear solution washed with 10% sodium sulfite (100 ml) followed by water (2 × 50 ml). The resulting clear solution was dried over sodium sulfate and then concentrated to give 50 g of the desired material as a clear yellow oil (weight spectrum: m / e = 253).
[154] More specifically, the starting material of the formula (α) in which B is a group of the formula (II) corresponds to the formula (α-1):
[155]
[156] If X is a group of> NR ₆ , these compounds can be prepared according to the following Scheme 1:
[157]
[158] Reaction a) of Scheme 1 can be carried out similarly to the method described, for example, in EP-A-309 402 (especially Examples 45 and 46) and reaction b) of Scheme 1 is US-A-4 086 204. It can be carried out similarly to the method described in.
[159] Compounds of formula (α-1) wherein X is oxygen can be prepared, for example, according to Scheme 2 below.
[160]
[161] In the formula, L is an alkaline metal such as lithium, sodium or potassium, for example. The reaction can be carried out using an appropriate molar ratio of reactants at a temperature of -20 ° C to 70 ° C, preferably 0 ° C to 60 ° C, in an inert organic solvent such as toluene, xylene or trimethylbenzene.
[162] Compounds of formula (S-II) can be prepared by treating a suitable 4-hydroxypiperidine derivative, for example, with an alkaline alcoholate or an alkali metal at reflux temperature in an inert organic solvent such as toluene, xylene or trimethylbenzene and simultaneously reacting It can be obtained by distilling off the alcohol formed. The preparation of 4-hydroxypiperidine derivatives can be carried out analogously to the method described in EP-A-309 402 (especially Example 12).
[163] Starting materials of formula (β) wherein R is a group of formula (IV) can be prepared according to Scheme 3:
[164]
[165] The reaction can be carried out analogously to the process described in EP-A-309 402 (especially Example 45). Compounds of formula (β-1) are known and most of them are commercially available. Some compounds of formula (β-1) are described in WO-A-95 / 21157, US-A-4 316 837 and US-A-4 743 688.
[166] Polydispersity The compound of general formula (I) which is 1 can be prepared by forming the compound stepwise. Representative examples of this process are:
[167] The intermediate of formula (δ), where n is 2, is
[168]
[169] And by reacting a compound of formula (γ) with a compound of formula (β) at a molar ratio of 1:10 to 1:50, preferably from 1:20 to 1:40, especially from 1:20 to 1:35. It can manufacture. This reaction can be carried out in an organic solvent in the presence of an inorganic base. Solvents and / or excess reactants of formula (β) may be removed by distillation under suitable conditions. Examples of organic solvents are toluene, xylene, trimethylbenzene, isopropylbenzene and diisopropylbenzene. Xylene is preferred. Examples of inorganic bases are sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate. Sodium hydroxide is preferred. The reaction is carried out at a temperature of, for example, 110 ° C to 180 ° C, preferably 140 ° C to 160 ° C.
[170] The obtained intermediate is then reacted with an acylating agent or alkylating agent according to the conditions of reaction 3) described above.
[171] Compounds of formula (I) that do not have a specific polydispersity can be prepared, for example, by reacting a compound of formula (α) with an excess of 10 mole% or less of a compound of formula (β) that does not inhibit molecular formation. The product obtained can then be reacted with a compound of formula (ε) or (ζ) as described above.
[172] Preferred embodiments of the present invention are directed to a product obtainable according to process 2) by transferring a group of formula (IV-O) present in a block oligomer corresponding to formula (IO) to a group of formula (IV) It is about:
[173] (IV-O)
[174] (IO)
[175] (Ⅳ)
[176] In the above, R ₁ is a hydrocarbyl radical or -OR ₁ is oxyl;
[177] The transition is carried out by reacting a block oligomer corresponding to formula (I-O) with a hydroperoxide in a hydrocarbon solvent in the presence of a peroxide decomposition catalyst;
[178] n is a number from 2 to 14;
[179] The radicals R ₂ are each independently C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl Or C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, —O— or> NX ₁ in the middle when having one of the following definitions of R ₄ ; or
[180] R ₂ is a group of formula (a), (b) or (c);
[181] (a)
[182] (b)
[183] (c)
[184] m is 2 or 3;
[185] X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2, or 3 C ₁ -C ₄ alkyl; Also
[186] The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene;
[187] The radicals A are independently of each other C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkyl) carbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C ₅ -C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
[188] The radical B ^* is —OR ₃ , —N (R ₄ ) (R ₅ ) or a group of formula (II-O);
[189]
[190] R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of formula (III) ;
[191] (Ⅲ)
[192] Wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ;
[193] R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
[194] X ^* is -O- or> NR ₆ ^* ;
[195] R ₆ ^* is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (IV-O) or substituted at the 2,3 or 4 position by -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) C ₂ -C ₄ alkyl;
[196] The radicals R ^* are each independently one of the definitions given for R ₆ ^* ; In addition
[197] However, each of the radicals B ^*, R ^* and R ₂ in the individual recurring units of the formula (IO) has a same or a different meaning.
[198] Preferred embodiments of the present invention,
[199] R ₂ is C ₂ -C ₁₂ alkylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or has one of the definitions of R ₄ given below In the middle is C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, -O- or> NX ₁ ; or
[200] R ₂ is a group of formula (b);
[201] R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; Phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; In addition
[202] R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
[203] R ₆ ^* is C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Or to a product obtainable according to the method 2) characterized in that it is a group of formula (IV-O).
[204] Preferred embodiments of the present invention,
[205] R ₂ is C ₂ -C ₁₀ alkylene, cyclohexylene, cyclohexylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedicyclohexylene or phenylenedi (C ₁ -C ₄ alkyl Ren);
[206] R _3, R ₄ and R ₅ are the same or different substituted by C ₁ -C ₁₂ alkyl, unsubstituted or one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₇ cycloalkyl; Phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; And -N (R ₄ ) (R ₅ ) is additionally a group of formula (III); In addition
[207] R ₆ ^* is C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Or to a product obtainable according to the method 2) characterized in that it is a group of formula (IV-O).
[208] Preferred embodiments of the present invention,
[209] R ₂ is C ₂ -C ₆ alkylene;
[210] B ^* is -N (R ₄ ) (R ₅ ) or a group of formula (II-O);
[211] R ₄ and R ₅ are the same or differently C ₁ -C ₈ alkyl; or
[212] -N (R ₄ ) (R ₅ ) is additionally 4-morpholinyl;
[213] X ^* is> NR ₆ ^* ;
[214] It relates to a product obtainable according to the above method 2) characterized in that R ₆ ^* is C ₁ -C ₈ alkyl.
[215] R ^* is preferably a group of formula (IV-O) and B ^* is preferably a group of formula (II-O), wherein X ^* is a group of the formula> N- (C ₁ -C ₄ alkyl).
[216] The transfer of a group of formula (IV-O) to a group of formula (IV) can be carried out analogously to the method described in US Pat. No. 4,921,962, e.g., incorporated herein by reference.
[217] The meaning of R ₁ depends on the hydrocarbon solvent used. R ₁ is preferably a hydrocarbyl radical having 5 to 18 carbon atoms.
[218] R ₁ is in particular C ₅ -C ₁₈ alkyl, C ₅ -C ₁₈ alkenyl, C ₅ -C ₁₈ alkynyl, unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₅ -C ₁₂ cycloalkenyl unsubstituted or substituted with C ₁ -C ₄ alkyl; Bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by C ₁ -C ₄ alkyl; In addition
[219] Hydrocarbon solvents in accordance with the R ₁ C ₅ -C ₁₈ alkanes, C ₅ -C ₁₈ alkene, C ₅ -C ₁₈ alkynyl, unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkane; C ₅ -C ₁₂ cycloalkene unsubstituted or substituted with C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkanes which are bicyclic or tricyclic hydrocarbons having 6 to 10 carbon atoms or unsubstituted or substituted on the phenyl by C ₁ -C ₄ alkyl.
[220] R ₁ is also preferably heptyl, octyl, cyclohexyl, methylcyclohexyl, cyclooctyl, cyclohexenyl, α-methylbenzyl or 1,2,3,4-tetrahydronaphthenyl and the hydrocarbon solvent is R ₁ According to the definition of heptane, octane, cyclohexane, methylcyclohexane, cyclooctane, cyclohexene, ethylbenzene or tetralin.
[221] According to a more preferred embodiment of the invention, R ₁ is cyclohexyl or octyl and the hydrocarbon solvent is cyclohexane or octane according to the definition of R ₁ . If -OR ₁ is oxyl, it is advantageous that the hydrocarbon solvent is an inert organic solvent, preferably toluene or 1,2-dichloroethane.
[222] The peroxide decomposition catalyst is for example metal carbonyl, metal oxide, metal acetylacetate or metal alkoxide, wherein the metal is selected from group (IVb), (Vb), (VIb), (VIIb) and (VIII) of the periodic table, Preferred are vanadium (III) acetylacetonate, cobalt carbonyl, chromium oxide (VI), isopropoxide titanium (IV), titanium tetrabutoxide, molybdenum hexacarbonyl, molybdenum trioxide and the like. Most preferred catalyst is MoO ₃ .
[223] Suitable hydroperoxides include tertiary butyl hydroperoxide, tertiary amyl hydroperoxide, tertiary hexyl hydroperoxide, tertiary octyl hydroperoxide, ethylbenzene hydroperoxide, tetralin hydroperoxide or cumene (= isopropylbenzene) hydro Peroxide. Most preferred hydroperoxide is tert-butyl hydroperoxide.
[224] 2 to 8 moles, preferably 3 to 6 moles of hydroperoxide, 0.001 to 0.1 mole, preferably per mole of sterically hindered amine residue of formula (IV-O) present in the block oligomer corresponding to formula (IO) 0.005 to 0.05 moles of peroxide cracking catalyst and 5 to 30 moles, preferably 10 to 20 moles of hydrocarbon solvent are added:
[225] (IV-O)
[226] The hindered amine moiety of formula (IV-O)
[227] The transition to the group may be performed at 75 ° C to 160 ° C, preferably at 100 ° C to 150 ° C.
[228] The hindered amine moiety of formula (IV-O) is first reacted with an aqueous hydroperoxide in the presence of a peroxide decomposition catalyst in an inert organic solvent (similar to the method described in US-A-4 691 015) for a relatively short time. The initial reaction product obtained at is the corresponding N-oxyl intermediate (-OR ₁ = oxyl) which can be highly colored and separated.
[229] If the organic solvent is a hydrocarbon with an unstable hydrogen atom, then a sufficient molar amount of hydroperoxide remains above the amount needed to convert the amine to the corresponding N-oxyl derivative and the reaction mixture is at a moderate temperature (preferably between 100 ° C. and When heated for an additional time at 150 ° C., an additional reaction occurs between the N-oxyl compound (prepared from the first amine or used as the initial starting intermediate in the process) and the hydrocarbon solvent to produce the corresponding N-hydrocarbyloxy derivative. Create
[230] The original reaction mixture is colorless but becomes highly colored as the N-oxyl intermediate is formed. This color disappears when the N-oxyl compound is converted to a colorless N-hydrocarbyloxy product. The process therefore essentially has inherent color indicators that indicate the degree of reaction. The reaction mixture became colorless, indicating that the colored N-oxyl intermediate was completely converted to the N-hydrocarbyloxy product.
[231] Embodiments of the present invention are obtained by being capable of obtaining a product having a group of formula (IV-1) by hydrogenating the product obtainable by process 2) wherein -OR ₁ in formula (IV) is oxyl. It can be a product:
[232]
[233] The hydrogenation reaction can be carried out according to a known method in organic solvents such as methanol or ethanol in the presence of a hydrogenation catalyst, preferably palladium on carbon or PtO ₂ , for example according to the method described in US Pat. have.
[234] The block oligomer starting materials corresponding to formula (IO) described in US Patent Application No. 08/994977 and European Patent Application No. 97810989.0 are polydisperse. Is 1 and n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14, or a monodisperse compound having a molecular weight distribution. Preferably, the block oligomer starting materials have different variables n such that the mixtures have different polydispersities. For example, 1.1 to 1.65, 1.1 to 1.6, 1.1 to 1.55 or 1.1 to 1.5; or at least three different monodispersions corresponding to values of 1.2 to 1.7, such as 1.2 to 1.65, 1.2 to 1.6, 1.2 to 1.55 or 1.2 to 1.5. It is a polydisperse compound which means the mixture containing a compound (IO).
[235] Polydispersity of 1 to 1.7 Polydisperse block oligomer starting materials corresponding to formula (IO) with can be prepared as follows:
[236] 1 ^* ) reacting a compound of formula (α *) with a compound of formula (β *) in a stoichiometric ratio to yield a compound of formula (γ *);
[237]
[238]
[239]
[240] 2 ^* ) reacting the compound of formula (γ *) with a compound of formula (β *) in a molar ratio of 1: 2 to 1: 3, preferably 1: 2, where n is 2, 3, 4, 5, 6 Obtaining a mixture of three or more different monodisperse compounds of formula (δ *), which are 7, 8, 9, 10, 11, 12, 13 or 14, in particular 2, 4 and 6;
[241]
[242] 3 ^* ) 2 ^* ) is reacted in a stoichiometric ratio with a compound of formula (ε) or a compound of formula (ζ) to give the desired mixture;
[243]
[244] In the food,
[245] R ^* , R ₂ and B ^* are as defined in formula (IO) above;
[246] X 'is a leaving group, for example halogen, in particular chlorine;
[247] A ′ is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkoxy) carbonyl, C ₁ -C ₈ alkyl, unsubstituted or 1, 2 or 3 C C ₅ -C ₁₂ cycloalkyl substituted by _1- C ₄ alkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN; In addition
[248] A ″ is C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₇ -C ₉ phenylalkyl;
[249] Reactions 1 ^*) to 3 ^*) and is carried out in an organic solvent under the presence of inorganic base, at the stage when the reaction 3 ^*) using the compound of the formula (ζ), said reaction 3 ^*) it can be carried out without the inorganic base.
[250] The explanations given under method 1) in reactions 1) to 3) may also apply to reactions 1 ^* ) to 3 ^* ).
[251] Particularly preferred block oligomer starting materials corresponding to formula (IO) are from 1.1 to 1.7 It is a polydisperse compound which has. Such polydisperse compounds include, for example, three or more monodisperse compounds that differ in the number of repeating units, such as compounds of formula (SM-1a), compounds of formula (SM-1b) and compounds of formula (SM-1c) Wherein the molar ratio of the compound of formula (SM-1a) to the compound of (SM-1b) to the compound of (SM-1c) is from 2: 2: 1.5 to 2: 0.5: 0.05, preferably 2: 1.5 : 1 to 2: 0.5: 0.08, especially 2: 1: 0.5 to 2: 0.5: 0.08:
[252]
[253]
[254]
[255] In formula, A, B ^*, R ^* and R ₂ are as defined above.
[256] When the above-mentioned mixture containing a compound of formula (SM-1a), a compound of formula (SM-1b) and a compound of formula (SM-1c) is used as a starting material according to method 2), the following formula (Ia), A mixture containing the compounds of (Ib) and (Ic) is obtained, which is another embodiment of the invention:
[257]
[258]
[259]
[260] In the above formula,
[261] R ₁ is hydrogen or hydrocarbyl radical or -OR ₁ is oxyl;
[262] R ₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or is given below In the case having one of the definitions of R ₄ is C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, —O— or> NX ₁ in the middle; or
[263] R ₂ is a group of formula (a), (b) or (c);
[264] (a)
[265] (b)
[266] (c)
[267] m is 2 or 3;
[268] X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2, or 3 C ₁ -C ₄ alkyl; Also
[269] The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene;
[270] The radical A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ phenylalkyl) aminocarbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C _5- C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
[271] The radical B is —OR ₃ , —N (R ₄ ) (R ₅ ) or a group of formula (II):
[272] (Ⅱ)
[273] R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of formula (III) ;
[274] (Ⅲ)
[275] Wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ;
[276] R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
[277] X is -O- or> NR ₆ ;
[278] R ₆ is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (IV), or
[279] (Ⅳ)
[280] Or C ₂ -C ₄ alkyl substituted by —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2,3 or 4 position; In addition
[281] R is one of the definitions given in R ₆ .
[282] The compounds of formulas (Ia), (Ib) and (Ic) differ in the number of repeating units, and the molar ratio of compounds (Ia) to (Ib) to (Ic) is 2: 2: 1.5 to 2: 0.5 : 0.05, preferably 2: 1.5: 1 to 2: 0.5: 0.8, in particular 2: 1: 0.5 to 2: 0.5: 0.08.
[283] Preference is given to mixtures having the following definitions:
[284] R is a group of formula (IV)
[285] (Ⅳ)
[286] R ₁ is octyl or cyclohexyl;
[287] R ₂ is C ₂ -C ₆ alkylene;
[288] A is C ₁ -C ₈ acyl or (C ₁ -C ₄ alkyl) aminocarbonyl;
[289] B is a group of formula (II);
[290] (Ⅱ)
[291] X is> NR ₆ ; In addition
[292] R ₆ is C ₁ -C ₄ alkyl.
[293] Groups of formula (IV-O) present in block oligomer starting materials (mixtures containing compounds of formulas (SM-1a), (SM-1b) and (SM-1c))
[294] (IV-O)
[295] Formula (IV)
[296] (IV)
[297] After transition to the group of, the ratio of compound (1a) to (1b) to (1c) corresponds to the ratio shown in the initial compound of formula (SM-1a) to (SM-1b) to (SM-1c), This is because the main chains of these compounds are not affected during the reaction.
[298] In the mixtures according to the invention, the radicals R ₁ can serve as linking groups between two or more block oligomers of formulas (Ia), (Ib) and / or (Ic). In this case, the bridge of formula (L-1)
[299] (L-1)
[300] Is formed between the indicated block oligomers.
[301] The meaning of R ₁ ^* can be deduced from the meaning of R ₁ . The only difference between these two radicals is that R ₁ ^* has 1 or 2 additional atoms. Accordingly, as cyclohexyl corresponds to R ₁ is a cyclohexane diyl or cyclohexane tree falls on R ₁ ^* R ₁ ^* corresponding to as yet octyl R ₁ is as an octane-diyl or octane tree.
[302] The mixtures described above as well as the products of the present invention are very effective in improving the light, heat and oxidation resistance of organic materials, in particular synthetic polymers and copolymers. In particular, low pigment interactions and very good colors have been observed in polypropylene, especially polypropylene fibers in the presence of flame retardants, as well as in low density polyethylene (LDPE) films for agricultural use. It is particularly important that the product of the invention is itself a flame retardant.
[303] Examples of organic materials that can be stabilized are:
[304] 1. Polymers of monoolefins and diolpins such as polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as cycloolefins (eg Polymers of 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).
[305] 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:
[306] a) radical polymerization reaction (normally under high pressure and high temperature)
[307] b) Catalytic polymerization using catalysts which normally comprise at least one of Group 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 (eg, active magnesium chloride, titanium (III) chloride, alumina or silicon oxide). Such catalysts may be soluble or insoluble in the polymerization medium. The catalyst can be used independently in the polymerization or additional active agents can be used, such as metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, wherein the metal is an element of the periodic tables Ia, IIa and / or IIIa. have. The active agent 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).
[308] 2. 1) Mixtures of the polymers mentioned hereinafter such as polypropylene and polyisobutylene, mixtures of polypropylene and polyethylene (eg PP / HDPE, PP / LDPE) and mixtures of various types of polyethylene (eg LDPE / HDPE).
[309] 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 low density polyethylene (LDPE) and mixtures thereof, 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 copolymer, ethylene / alkyl acrylate copolymer, ethylene / alkyl methacrylate copolymer, ethylene / vinyl acetate copolymer and carbon monoxide and their copolymers or ethylene / acrylic acid copolymers and salts thereof ( Ionomers), as well as ethylene and propylene and dienes (eg hexadiene, dicyclopentadiene or ethylidene-norbornene) Body; 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 other polymers such as polyamides and mixtures thereof.
[310] 4. Hydrocarbon resins (eg C ₅ -C ₉ ) comprising a mixture of polyalkylene and starch and a hydrogenation variant (eg pressure sensitive adhesive).
[311] 5. Polystyrene, poly (p-methylstyrene), poly (α-methylstyrene).
[312] 6. Copolymers of styrene or α-methylstyrene with diene or acrylic derivatives such as styrene / butadiene, styrene / acrylonitrile, styrene / methacrylate alkyl, styrene / butadiene / alkyl acrylate, styrene / butadiene / alkyl methacrylate, styrene Maleic anhydride, styrene / acrylonitrile / methyl acrylate; High impact strength mixtures of styrene copolymers and other polymers such as polyacrylates, diene polymers or ethylene / propylene / diene trimers; And block copolymers of styrene (eg, styrene / butadiene / styrene, styrene / isoprene / styrene, styrene / ethylene / butylene / styrene or styrene / ethylene / propylene / styrene).
[313] 7. Graft copolymers of styrene or α-methylstyrene, such as styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene-acrylonitrile copolymers; Acrylonitrile (or methacrylonitrile) and styrene on polybutadiene; Styrene, acrylonitrile and methyl methacrylate on polybutadiene; Styrene and maleic anhydride on polybutadiene; Styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; Styrene and maleimide on polybutadiene; Styrene on polybutadiene and methacrylic acid or alkyl acrylates; Styrene and acrylonitrile on ethylene / propylene / diene trimers; Styrene and acrylonitrile on polyalkyl acrylate or polyalkyl methacrylate, styrene and acrylonitrile on acrylate / butadiene copolymers, as well as copolymers listed under 6) and mixtures thereof, such as ABS, MBS, ASA Or copolymerization mixtures known as AES polymers.
[314] 8. Halogen-containing polymers such as polychloroprene, chlorinated rubber, chlorinated and brominated copolymers of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfurized polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homogeneous And copolymers, in particular polymers of halogen-containing vinyl compounds such as polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as their copolymers (eg vinyl chloride / vinyl) Lidene chloride, vinyl chloride / vinyl acetate or vinylidene chloride / vinyl acetate copolymer).
[315] 9. Polymers derived from α, β-unsaturated acids and derivatives thereof such as polyacrylates and polymethacrylates; Polymethyl methacrylate, polyacrylamide and polyacrylonitrile (impact modified with butyl acrylate).
[316] 10. 9) Copolymers of the units mentioned below with one another or with other unsaturated units such as acrylonitrile / butadiene copolymers, acrylonitrile / alkyl acrylate copolymers, acrylonitrile / alkoxyalkyl acrylates or acrylics Ronitrile / vinyl halide copolymer or acrylonitrile / alkyl methacrylate / butadiene trimer.
[317] 11. Polymers derived from unsaturated alcohols and amines or acyl derivatives or acetals thereof such as polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl Phthalate or polyallyl melamine; As well as their copolymers with the olefins mentioned in 1) above.
[318] 12. Homopolymers and copolymers of cyclic ethers such as polypropylene oxide, polyethylene oxide, polyalkylene glycols or copolymers of these with bisglycidyl ethers.
[319] 13. polyacetals such as polyoxymethylene and polyoxymethylene comprising ethylene oxide as co-unit; Polyacetals modified with thermoplastic polyurethanes, acrylates or MBS.
[320] 14. Polyphenylene oxides and sulfides, and mixtures of styrene polymers or polyamides with polyphenylene oxides.
[321] 15. Polyurethanes derived from hydroxy-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other hand, as well as their precursors.
[322] 16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and / or aminocarboxylic acids or the corresponding lactams such as polyamide 4, polyamide 6, polyamide 6/6, 6/10, 6/9, 6 Aromatic polyamides disclosed from / 12, 4/6, 12/12, polyamide 11, polyamide 12, m-xylene diamine and adipic acid; Polyamides prepared from hexamethylenediamine and isophthalic acid and / or terephthalic acid with or without elastomer as modifier, such as poly-2,4,4-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthal amides; And block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; Or block copolymers of the aforementioned polyamides with polyethers (eg, polyethylene glycol, polypropylene glycol or polytetramethylene glycol); As well as polyamides or copolyamides modified with EPDM or ABS; And polyamides condensed during the process (RIM polyamide system).
[323] 17. Polyureas, polyimides, polyamide-imides, polyetherimides, polyesterimides, polyhydantoins and polybenzimidazoles.
[324] 18. Polyesters of dicarboxylic acids and diols and / or hydroxycarboxylic acids or their lactones such as polyethylene terephthalate, polybutylene terephthalate, poly-1,4-dimethylolcyclohexane terephthalate and polyhydroxybenzoate As well as block copolyether esters derived from hydroxy-terminated polyethers; Also polyesters modified with polycarbonate or MBS.
[325] 19. Polycarbonates and polyester carbonates.
[326] 20. Polysulfones, polyether sulfones and polyether ketones.
[327] 21. Crosslinked polymers derived from aldehydes on the one hand and phenol, urea and melamine on the other hand such as phenol / formaldehyde resins, urea / formaldehyde resins and melamine / formaldehyde resins.
[328] 22. Dry and undry alkyd resins.
[329] 23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents and their halogen-containing modifiers which are inflammable.
[330] 24. Crosslinkable acrylic resins derived from substituted acrylates such as epoxy acrylates, urethane acrylates or polyester acrylates.
[331] 25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
[332] 26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heteroatomic rings or aromatic glycidyl compounds such as bisphenol A and bisphenol F crosslinked with conventional curing agents such as anhydrides or amines, with or without accelerators. Product of diglycidyl ether.
[333] 27. natural polymers such as cellulose, rubber, gelatin and chemically modified cognate derivatives thereof such as cellulose acetate, cellulose propionate and cellulose ethers such as cellulose butyrate or methyl cellulose; As well as rosin and their derivatives.
[334] 28. Mixtures of the foregoing polymers (composites) 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 / acrylate, POM / thermoplastic PUR, PC / thermoplastic PUR, POM / acrylate, POM / MBS, PPO / HIPS, PPO / PA 6.6 and copolymers, PA / HDPE, PA / PP, PA / PPO, PBT / PC / ABS or PBT / PET / PC.
[335] 29. Natural and synthetic organic substances which are pure monomer compounds or mixtures of these compounds such as mineral oils, animal and vegetable fats, oils and waxes, or synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and various weight ratios Oils, fats and waxes based on mixtures of mineral oils with synthetic esters, such as materials used in spinning compositions, as well as aqueous emulsions of such materials.
[336] 30. Aqueous emulsions of natural or synthetic rubber, such as natural latexes or latises of carboxylated styrene / butadiene copolymers.
[337] The invention also relates to a composition comprising an organic material susceptible to degradation resulting from light, heat or oxidation and a product or mixture according to the invention.
[338] The organic material is preferably a synthetic polymer, more preferably one selected from the group above. Polyolefins are preferred, with polyethylene and polypropylene being particularly preferred.
[339] Still another embodiment of the present invention relates to a method for stabilizing an organic material against degradation caused by light, heat or oxidation, comprising incorporating the product or mixture according to the invention into the organic material.
[340] The products and mixtures may be used in various proportions depending on the nature of the material to be stabilized, the purpose of use and the presence of other additives.
[341] Generally it is suitable, for example, to use from 0.01 to 5% by weight, preferably from 0.05 to 2% by weight, in particular from 0.05 to 1% by weight, relative to the weight of the material to be stabilized.
[342] The products and mixtures according to the invention can be added to the polymerizable material, for example before, during or after the crosslinking or polymerization of the material. It may also be incorporated into the polymerizable material in pure form or encapsulated in waxes, oils or polymers.
[343] Generally, other products and mixtures of the present invention are polymerizable by various processes, such as dry mixing in powder form or wet mixing in solution or suspension or in the form of a masterbatch containing the product and mixture in a concentration of 2.5 to 25% by weight. Can be incorporated into materials: In this process the polymer can be used in the form of a powder, powder, solution, suspension or lactic.
[344] Materials stabilized with these products and mixtures can be used in the manufacture of moldings, films, tapes, monofilaments, fibers, surface coatings, and the like.
[345] If desired, other known additives for synthetic polymers such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers, corrosion inhibitors and metal reaction inhibitors may be added to the organic materials containing the products and mixtures.
[346] Specific examples of such known additives are as follows:
[347] 1. Antioxidant
[348] 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-di-cyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl ) -4,6-dimethylphenol, 2,6-di-octadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, Nonylphenol branched straight or branched such as 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methyl-undec-1'-yl) -phenol, 2, 4-dimethyl-6- (1'-methyl-heptadec-1'-yl) -phenol, 2,4-dimethyl-6- (1'-methyltridec-1'-yl) -phenol and mixtures thereof .
[349] 1.2. Alkylthiomethylphenols such as 2,4-di-octylthiomethyl-6-tert-butylphenol, 2,4-di-octylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6- Ethylphenol, 2,6-di-dodecylthiomethyl-4-nonylphenol.
[350] 1.3. Hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butyl-hydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl 4-octadecyloxyphenol, 2,6-di-tert-butyl-hydroquinone, 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.
[351] 1.4. Tocopherols such as α-tocophenol, β-tocophenol, γ-tocophenol, δ-tocophenol and mixtures thereof (vitamin E)
[352] 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.
[353] 1.6. Alkylidene bisphenols 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-methyl-phenyl) -3 -n-dodecylmercaptobutane, 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.
[354] 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.
[355] 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.
[356] 1.9. Aromatic hydroxybenzyl compounds, for example 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 .
[357] 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.
[358] 1.11. Benzyl phosphonate, for example 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.
[359] 1.12. Acylaminophenols such as 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamate.
[360] 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.
[361] 1.14. Esters of mono- or polyhydric alcohols with β- (5-tertbutyl-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 Ester with -2,6,7-trioxabicyclo- [2.2.2] octane.
[362] 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.
[363] 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-trioxabi Esters with cyclo- [2.2.2] octane
[364] 1.17. β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, for example N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpropionic acid) hexamethylenediamide , N, N'-bis (3,5-di-tert-butyl-4-hydroxyphenylpyrropiionyl) trimethylenediamide, N, N'-bis (3,5-di-tert-butyl-4-hydroxy Hydroxy-phenylpropionyl) hydrazide, N, N'-bis [2- (3- [3,5-di-tert-butyl-4-hydroxyphenyl] propionyloxy) ethyl] oxamide (supplied by Uniroyal Naugard ^R XL-1).
[365] 1.18. Ascorbic acid (vitamin C)
[366] 1.19. Amine antioxidants such as N, N'-di-isopropyl-p-phenylenediamine, N, N'-di-secondarybutyl-p-phenylenediamine, N, N ''-bis (1,4-dimethyl Pentyl) -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-phenylenedia N'min, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4- (p-toluenesulfamoyl) -diphenylamine, N, N'-dimethyl-N, N '-Di-secondarybutyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N- (4-tert-octyl Phenyl) -1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamines such as p, p'-di-tert-octyldiphenylamine, 4-n-butyl Minophenol, 4-butyrylaminophenol, 4-nonanylamino-phenol, 4-dodecane oilaminophenol, 4-octadecane oilaminophenol, bis (4-methoxyphenyl) amine, 2,6-di- Tert-butyl-4-dimethylaminomethylphenol, 2,4'-di-aminodiphenylmethane, 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, mono- and dialkylated nonyldiphenylamine Mixtures, mixtures of mono- and dialkylated dodecyldiphenylamines, mixtures of mono- and dialkylated isopropyl / isohexylphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-di-hydro- 3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, mono Mixture of 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-tetramethylpiperiide -4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
[367] 2. UV absorbers and light stabilizers
[368] 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'-tert-butyl-2'-hydroxy-5 '-(2-octyloxycarbonylethyl) Phenyl) -5-chloro-benzotriazole, 2- (3'-tert-butyl-5 '-[2- (2-ethylhexyloxy) -carbonylethyl] -2'-hydroxyphenyl) -5- Chloro-benzot Riazole, 2- (3'-tert-butyl-2'-hydroxy-5 '-(2-methoxycarbonylethyl) phenyl) -5-chloro-benzotriazole, 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) Phenylbenzotriazole, 2,2'-methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-benzotriazol-2-ylphenol]; polyethylene glycol 300 and 2- [3 Transesterification product of '-tert-butyl-5'-(2-methoxycarbonylethyl) -2'-hydroxy-phenyl] -2H-benzotriazole; R is 3'-tert-butyl-4'-hydride [R-CH ₂ CH ₂ -COO (CH ₂ ) ₂ ] ₂ , 2- [2'-hydroxy-3 '-(α, which is hydroxy-5'-2H-benzotriazol- ₂ -ylphenyl , α-dimethylbenzyl) -5 '-(1,1,3,3-tetramethylbutyl) -petyl] benzotriazole; 2- [2'-hydroxy-3 '-(1,1,3,3-tetramethylbutyl) -5'-(α, α-dimethylbenzyl) -phenyl] benzotriazole.
[369] 2.2. 2-hydroxybenzophenones such as 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'- Trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives.
[370] 2.3. Esters of unsubstituted or substituted benzoic acid, for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis (4-tert-butyl-benzoyl) resorci Nol, 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.
[371] 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-methoxy-cinnamate, butyl α-cyano-β-methyl-p-methoxy-cinnamate, methyl α-carbomethoxy-p-methoxy-cinnamate and N- ( β-carbomethoxy-β-cyanovinyl) -2-methylindolin.
[372] 2.5. 2,2'-thio-bis [4- (1,1,3,5) with nickel compounds, for example with additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, where appropriate 3-tetramethylbutyl) phenol] (such as 1: 1 or 1: 2 complex), nickel dibutyl dithiocarbamate, 4-hydroxy-3,5-di-tert-butyl benzyl phosphonic acid monoalkyl Nickel salts of esters (e.g. methyl esters or ethyl esters), nickel complexes of ketoximes (e.g. 2-hydroxy-4-methylphenyl undecylketoxim), 1-phenyl-4-lauro with additional ligands where appropriate Nickel Complex of Il-5-hydroxy Pyrazole.
[373] 2.6. Sterically hindered amines such as 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-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) seva Kate, Bis (1,2,2,6,6-pentamethyl-4-piperidyl) n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl malonate, 1- (2-hydroxy Oxyethyl) -2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid condensation product, N, N'-bis (2,2,6,6-tetramethyl-4-piperi Linear or cyclic condensation products of di) hexahexamethylenediamine with 4-tert-octylamino-2,6-dichloro-1,3,5-triazine, tris (2,2,6,6-tetramethyl-4-piperi Diyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butane-tetracarboxylate, 1,1 '-(1,2 Ethanediyl) bis (3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethyl Ferridine, 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, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethylpiperidyl ) Succinate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5- Condensation product of triazine, 2-chloro-4,6-bis (4-n-butylamino-2,2,6,6-tetramethylpiperidyl) -1,3,5-triazine and 1,2- Straight or cyclic condensation products of bis (3-aminopropylamino) ethane, 2-chloro-4,6-di- (4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl) Condensation products of -1,3,5-triazine with 1,2-bis (3-aminopropylamino) ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3, 8-Tria Jaspiro [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, 4-hexadecyloxy and 4-stearyloxy-2, Mixture of 2,6,6-tetramethylpiperidine, N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) hexamethyrendiamine and 4-cyclohexylamine- Condensation products of 2,6-di-chloro-1,3,5-triazine, 1,2-bis (3-aminopropylamino) ethane and 2,4,6-trichloro-1,3,5- Condensation products of triazines, as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); 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-oxospyro [4,5] decane and epichlorohydrin, 1,1-bis (1 , 2,2,6,6-pentamethyl-4-piperidyloxy carbonyl) -2- (4-methoxyphenyl) ethene, N, N'-bis-formyl-N, N'-bis ( 2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine, 4-methoxy-methylene-maleic acid and 1,2,2,6,6-pentamethyl-4-hydroxy piperi Dine reaction product, with poly- [methylpropyl-3-oxy-4- (2,2,6,6-tetramethyl-4-piperidyl)]-siloxane, maleic anhydride α-olefin-copolymer Reaction product of 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
[374] 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'-ethoxananilide, 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.
[375] 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-dodecyloxyphenyl ) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-butyloxy-propoxy) phenyl ] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-octyloxy-propyloxy) phenyl] -4,6-bis (2,4-dimethyl) -1,3,5-triazine, 2- [4- (dodecyloxy / tridecyloxy-2-hydroxypropoxy) -2-hydroxy - Nil] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-hydroxy-3-dodecyloxy-propoxy ) 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- Hydroxy-4- (3-butoxy-2-hydroxy-propoxy) 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.
[376] 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 (salicyl) oxalyl dihydrazide, N, N ' -Bis (salicylic oil) thiopropionyl dihydrazide.
[377] 4. Phosphites and phosphonites such as triphenyl phosphite, diphenyl alkyl phosphite, phenyl dialkyl phosphite, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, disdis Tearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis (2,4-di-tert-butyl-6-methylphenyl) pentaerythritol depot Spite, bis (2,4,6-tris-tert-butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert-butylphenyl) 4,4'-biphenyl Lene diphosphonite, 6-isooctyloxy-2,4,8,10-te La-tert-butyl-12H-dibenz [d, g] -1,3,2-dioxaphosphosine, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenz [d, g] -1,3,2-dioxaphosphosine, bis (2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis (2,4-di-tert-butyl-6-methylphenyl Ethyl phosphite, 2,2 ', 2' '-nitrilo [triethyltris (3,3', 5,5'-tetratertbutyl-1,1'-biphenyl-2,2'-diyl) Phosphite], 2-ethylhexyl (3,3 ', 5,5'-tetra tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite.
[378] 5. Hydroxyamines such as N, N-dibenzylhydroxyamine, N, N-diethylhydroxyamine, N, N-dioctylhydroxyamine, N, N-dilaurylhydroxyamine, N , N-ditetradecylhydroxyamine, N, N-dihexadecylhydroxyamine, N, N-dioctadecylhydroxyamine, N-hexadecyl-N-octadecylhydroxyamine, N-heptadecyl- N-octadecylhydroxyamine, N, N-dialkylhydroxyamine derived from hydrogenated resin.
[379] 6. Nitrons, eg N-benzyl-alpha-phenyl-nitron, N-ethyl-alpha-methyl-nitron, N-octyl-alpha-heptyl-nitron, N-lauryl-alpha-undecyl Nitron, N-tetradecyl-alpha-tridecyl-nitron, N-hexadecyl-alpha-pentadecyl-nitron, N-octadecyl-alpha-heptadecyl-nitron, N-hexadecyl-alpha- Derived from heptadecyl-nitron, N-octadecyl-alpha-pentadecyl-nitron, N-heptadecyl-alpha-heptadecyl-nitron, N-octadecyl-alpha-hexadecyl-nitron, hydrogenated resinamine Nitron derived from N, N-dialkylhydroxyamine.
[380] 7. Thio synergists, for example dilauryl thiodipropionate or distearyl thiodipropionate.
[381] 8. Peroxide decomposing compounds, for example esters of β-thiodipropionic 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.
[382] 9. Polyamide stabilizers such as copper salts and divalent manganese salts in combination with iodides and / or phosphorus compounds.
[383] 10. Basic co-stabilizers such as 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.
[384] 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).
[385] 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.
[386] 13. Other additives, for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, flow-controlling agents, optical brighteners, fire retardants, antistatic agents and blowing agents.
[387] 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-dimethylphenyl) -5,7-di-tert-butyl-benzofuran 2-on.
[388] The weight ratio of the product or mixture according to the invention to the usual additives can be for example 1: 0.5 to 1: 5.
[389] The products or mixtures of the present invention can be used as stabilizers, in particular light stabilizers, for photographic reproduction techniques and almost all materials known in the art of other reproduction techniques as disclosed, for example, in Research Disclosure 1990, 31429 (pages 474 to 480).
[392] The invention is illustrated in more detail by the following examples. All percentages and parts are by weight or parts by weight unless otherwise noted.
[393] Examples S-1 and S-2 below are representative examples for preparing starting materials. Examples 1 to 4 are representative examples for preparing the product according to the invention.
[394] GPC (Gel Permeation Chromatography) separates molecules from the size difference of the molecules ) Or in an analytical process to obtain information about the molecular weight distribution of the polymer.
[395] This technique is known and is described, for example, in W.W. < RTI ID = 0.0 > W. W. < / RTI > By Yan et al. In "Modern Size Exclusion Liquid Chromatography."
[396] Narrow molecular weight distribution results in multiple dispersibility ( ) Is closer to one.
[397] The GPC analysis shown in Examples S-1 and S-2 below was performed with GPC chromatography ^R Perkin-Elmer LC 250 equipped with ^R Perkin-Elmer Rl detector LC 30 and ^R Perkin-Elmer oven LC 101.
[398] All analyzes were performed at 45 ° C. with three columns PLGEL 3 μm Mix E 300 mm length × 7.5 mm i.d. (Polymers Laboratories Ltd. Shropshire, U.K.).
[399] Tetrahydrofuran was used as eluent (flow rate 0.40 mL / min) and the sample was dissolved in tetrahydrofuran (2%) (% w / v).
[400] In the formulas of the following examples, n 'indicates that there are repeat units in the molecule and that the product obtained is not uniform.
[401] Example S-1: Preparation of Product of Formula
[402] 32.2 g (0.175 mol) of N-2,2,6,6-tetramethyl-4-piperidinyl) -n-butylamine solution in 30 ml of water at 3 ° C. in 32.2 g in 250 ml of xylene (0.175 mole) of the cyanuric chloride solution was added slowly and the temperature was maintained during the addition and held for an additional hour.
[403] After 2 h at room temperature, the mixture was cooled to 0 ° C. and 7.3 g (0.18 mole) aqueous sodium chloride solution in 25 ml water was added.
[404] After 1/2 hour at 0 ° C. and 2 hours at room temperature, the aqueous solution was separated off and 34.6 g (0.087 mol) of N, N′-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine was added.
[405] The mixture was heated to 50 ° C. for 1 hour and heated to 60 ° C. for 4 hours by adding 24.2 g (0.175 mol) of ground potassium carbonate.
[406] After washing with water, the organic phase was concentrated under 60-70 ° C./10 mbar and vacuum to recover 125 ml of xylene.
[407] 69 g (0.175 mol) of N, N'-bis (2,2,6,6-tetramethyl-4-piperidinyl) -1,6-hexanediamine were added and the mixture was heated to 150 ° C. for 2 hours. Heated and cooled again, and 7 g (0.175 mol) of ground sodium chloride were added.
[408] The mixture was heated to 140 ° C. for a further 4 hours and azeotropically removed water remaining in the reaction and heated at 160 ° C. for a further 4 hours.
[409] After cooling to 60 ° C., the mixture was diluted with 130 ml of xylene, filtered and washed three times with 50 ml of ethylene glycol.
[410] After concentration at 60 ° C./10 mbar and vacuum, 7.5 g (0.073 moles) of acetic anhydride were added. After 1/2 hour at room temperature, the mixture was heated to 130 ° C. for 5 hours. After cooling to room temperature, 20.2 g (0.146 mol) of ground potassium carbonate were added and the mixture was heated to 130 ° C. for 2 hours.
[411] The mixture was then cooled to 50 ° C., filtered and concentrated at 140 ° C./1 millibar under vacuum.
[412] After drying, a solid having a melting point of 128 ° to 134 ° C was obtained.
[413] (By GPC): 2712g / mol
[414] : 1.41
[415] GPC analysis is represented by the chromatogram shown in FIG.
[416] The three main single component ratios ((n '= 2) :( n' = 4) :( n '= 6)) of the multidispersing product are 2: 0.93: 0.4 in mole%.
[417] Example S-2: Preparation of Product of Formula
[418] The product was prepared according to the method described in Example S-1 using a suitable reagent.
[419] A solid having a melting point of 122 ° to 130 ° C was obtained.
[420] (By GPC): 2810g / mol
[421] : 1.42
[422] GPC analysis is shown in the chromatogram of Figure 2 below.
[423] The three major single component ratios ((n '= 2) :( n' = 4) :( n '= 6)) of the multidispersing product are 2: 0.84: 0.32 in mole%.
[424] Example 1 Preparation of a Product of Formula
[425]
[426] 7.0 g (0.0317 moles) of Example S-1 product, 60 ml of cyclohexane and 0.1 g of MoO ₃ in four magnetically stirred 200 ml flasks with ^R Dean-Stark trap. Charged. The contents were heated to reflux. 20.4 g (0.158 mol) of 70% tert-butylhydroperoxide were then charged to a fixed addition funnel and added over 30 minutes. It was further refluxed for 30 minutes. The reaction mixture was transferred to a magnetically stirred ^R Fischer-Porter pressure bottle with an additional 0.1 g of MoO ₃ . The contents are heated at 120 ° C. for 3 hours and at this temperature the red color of the nitroxyl intermediate becomes pale yellow. MoO ₃ was filtered and the filtrate was evaporated to a yellow glass. The yield was 10.1 g in quantitative analysis.
[427] ¹ H NMR: 0.84-2.5 ppm (broad, complex mixture); 3.2-3.44 ppm (s, broad, NCH ₂ ); 3.54-3.70 ppm (s, broad, NOCH); 4.76-5.4 ppm (broad, NCH).
[428] The integral ratios of 3.2, 3.54 and 4.76 ppm are 2: 1: 1.
[429] ¹³ C NMR: 81.9 ppm (NOC); 165 ppm (triazine C).
[430] Example 2: Preparation of Product of Formula
[431]
[432] 5.7 g (0.0258 moles) of Example S-1 product, 50 mL n-octane and 0.20 g MoO in four magnetically stirred 200 mL flasks with ^R Dean-Stark traps ₃ was charged. The contents were heated to reflux. Subsequently, 16.6 g (0.129 mol) of 70% tertiarybutylhydroperoxide was charged to an additional funnel and added over 30 minutes. After an additional 30 minutes of reflux, the reaction mixture was transferred to a magnetically stirred ^R Fisher-Porter pressure bottle. Then additional 0.10 g of MoO ₃ was added. The contents are heated under pressure at 125 ° C. for 3 hours and at this temperature the red color of the nitroxyl intermediate becomes pale yellow. MoO ₃ was filtered and the filtrate was evaporated to a yellow glass. The yield was 8.2 g in quantitative analysis (91% of theory).
[433] ¹ H NMR: 0.8-2.5 ppm (broad, complex mixture); 3.2-3.5 ppm (s, broad, NCH ₂ ); 3.65-3.96 ppm (broad, NOCH); 4.9-5.4 ppm (s, broad, NCH).
[434] The integral ratios of 3.2, 3.65 and 4.76 ppm are 2: 1: 1.
[435] ¹³ C NMR: 78.7 ppm, 81.9 ppm and 83.2 ppm (mixture of isomers of NOC, C ₈ H ₁₇ ); 165 ppm (triazine C).
[436] Example 3: Preparation of a Product of Formula
[437]
[438] ^In a magnetically stirred 200 ml four flask with ^R Dean-Stark trap, 7.0 g (0.0303 mol) of the product of Example S-2, 60 ml cyclohexane and 0.20 g MoO ₃ was charged. The contents were heated to reflux. Then, an additional funnel was charged with 19.5 g (0.152 mol) of 70% tert-butylhydroperoxide. The funnel contents were added over 30 minutes. Redness of the intermediate was observed. It was refluxed for 1 hour. The reaction mixture was transferred to a magnetically stirred ^R Fischer-Porter pressure bottle containing 0.10 g of MoO ₃ . The contents are heated under pressure at 125 ° C. for 2 hours, at which point the red color of the nitroxyl intermediate becomes pale yellow. MoO ₃ was filtered and the filtrate was evaporated to a yellow glass. The yield was 9.3 g (93% of theory) in quantitative analysis.
[439] ¹ H NMR: 0.80-2.2 ppm (broad, complex mixture); 3.1-3.5 ppm (s, broad, NCH ₂ ); 3.54-3.70 ppm (s, broad, NOCH); 4.90-5.4 ppm (broad, NCH).
[440] The integral ratios of 3.2, 3.54 and 4.76 ppm are 2: 1: 1.
[441] ¹³ C NMR: 81.8 ppm (NOC), 165 ppm (triazine C).
[442] Example 4: Preparation of a Product of Formula
[443]
[444] 6.2 g (0.0268 moles) of the product of Example S-2, 50 ml n in four magnetically stirred 200 ml flasks with ^R Dean-Stark trap, cooler and additional funnel -Octane and 0.10 g of MoO ₃ were charged. The contents were heated to reflux. An additional funnel was then charged with 17.3 g (0.134 moles) of 70% tert-butylhydroperoxide. The funnel contents were added over 30 minutes. Redness of the intermediate was observed. It was refluxed for 1 hour. The reaction mixture was transferred to a magnetically stirred ^R Fischer-Porter pressure bottle containing 0.10 g of MoO ₃ . The contents are heated under pressure at 125 ° C. for 2 hours, at which point the red color of the nitroxyl intermediate becomes pale yellow. MoO ₃ was filtered and the filtrate was evaporated to a yellow glass. The yield was 8.4g at quantitative analysis (88% of theory).
[445] ¹ H NMR: 0.6-2.5 ppm (broad, complex mixture); 3.1-3.5 ppm (s, broad, NCH ₂ ); 3.56-3.94 ppm (broad, NOCH); 4.9-5.4 ppm (s, broad, NCH).
[446] The integral ratio of 3.1, 3.56 and 4.9 ppm is 2: 1: 1.
[447] ¹³ C NMR: 78.5 ppm, 81.8 ppm and 83. 2 ppm (NOC, mixture of isomers of C ₈ H ₁₇ ), 165 ppm (triazine C).
[448] Example A:
[449] Polyolefin formulations - general-purpose rotary machines the additives listed below and (poly ethylene polypropylene containing propylene ^{copolymers; Akron, Ohio, USA; R} A. from Schulman, Inc. ^R poly Tropsch TPP 518-01) at 200 ℃ Colored thermoplastic olefin (TPO) pellets were prepared by mixing in a ^R Superior / MPM 1 "single screw extruder equipped with (24: 1 L / D), cooling in a water bath and pelletizing. Tumble the additives before extrusion and molding Dry blended in a dryer.
[450] additive:
[451] ^R Red 3B (pigment red 177, color index 65300) of 0.25% ^* ),
[452] 0.05% ^*) pentaerythritol tetrakis [3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate],
[453] 0.05% ^*) of tris [2,4-ditert-butylphenyl] phosphite,
[454] 0.2% ^*) 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benztriazole,
[455] 0.2 ^*) bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate,
[456] 0.1% ^*) , calcium stearate,
[457] About 10% ^*) of talc and
[458] 0.2% ^*) of Example 1, 2, 3 or 4
[459] ----------------------------
[460] ^*) Is weight percent based on polyolefin blend
[461] The resulting pellets were molded into 1.524 mm thick 2 "x 2" plaques at about 190 ° C. using an ^R BOY 30M injection molding machine.
[462] ^R Atlas Ci65 Xenon Arc Weather-O-meter with experimental plaques placed in a metal frame and subjected to intermittent light / dark cycles and water spraying at 0.55 W / m ² and 50% relative humidity at 70 ° C black panel temperature, 340 nanometers ( ^R Society of Automotive Engineers-SAE J 1960 Test Process-External Automotive Conditions).
[463] The specimens were tested at intervals of about 625 kilojoules by performing color measurements on an Applied Color Systems spectrophotometer in refractive mode in accordance with ASTM D 2244-79. Gloss measurements were performed on a ^R BYK-GARDNER Haze / Gloss Meter at 60 ° C. in accordance with ASTM D 523.
[464] The stabilized sample shows good gloss retention and good color change resistance upon UV irradiation.

权利要求:
Claims (27)
[1" claim-type="Currently amended] A compound of formula (I)
(I)
In the food,
n is a number from 2 to 14;
The radicals R ₁ are independently of each other a hydrogen or hydrocarbyl radical or -OR ₁ is oxyl;
The radicals R ₂ independently of one another are C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi- (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) car Carbonyl) or 1,4-piperazindiyl, -O- or C ₄ -C ₁₂ alkylene containing> NX ₁ in the middle or one of the definitions of R ₄ excluding hydrogen; Or R ₂ is a group of formula (a), (b) or (c);
(a)
(b)
(c)
Where m is 2 or 3,
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
The radicals X ₃ independently of one another are C ₂ -C ₁₂ alkylene;
The radicals A are independently of each other C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkoxy) carbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C ₅ -C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
B is -OR ₃ , -N (R ₄ ) (R ₅ ) or a group of formula (II):
(Ⅱ)
R ₃ , R ₄ and R ₅ are the same or different and 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 or a group of formula (III) at the 2, 3 or 4 position C ₂ -C ₄ alkyl substituted by (III), wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ , or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
X is -O- or> NR ₆ ;
R ₆ 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 (IV)
Or C ₂ -C ₄ alkyl substituted by —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2, 3 or 4 position; In addition
The radicals R, independently of each other, have the meanings defined for R ₆ ,
Provided that each of the radicals B, R, R ₁ and R ₂ in the individual repeat units of formula (I) have the same or different meanings.
[2" claim-type="Currently amended] The compound of formula (I) according to claim 1, wherein R is a group of formula (IV).
[3" claim-type="Currently amended] The method of claim 1, wherein, R ₁ is hydrogen, C ₁ -C ₁₈ alkyl, C ₅ -C ₁₈ alkenyl, C ₅ -C ₁₈ alkynyl, unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₅ - C ₁₂ cycloalkyl; C ₅ -C ₁₂ cycloalkenyl unsubstituted or substituted by C ₁ -C ₄ alkyl; Bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkyl unsubstituted or substituted by C ₁ -C ₄ alkyl on phenyl; Or -OR ₁ is oxyl.
[4" claim-type="Currently amended] The compound of claim 1, wherein R ₁ is hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₈ cycloalkyl unsubstituted or substituted by methyl; A compound of formula (I) which is cyclohexenyl, α-methylbenzyl or 1,2,3,4-tetrahydronaphthenyl.
[5" claim-type="Currently amended] The compound of formula (I) according to claim 1, wherein R ₁ is methyl, octyl or cyclohexyl.
[6" claim-type="Currently amended] The compound of formula (I) according to claim 1, wherein A is acetyl, (C ₁ -C ₄ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl or C ₁ -C ₄ alkyl.
[7" claim-type="Currently amended] The method of claim 1,
R ₂ is C ₂ -C ₁₂ alkylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ alcycloalkylene) or phenylenedi (C ₁ -C ₄ alkylene);
A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₇ cycloalkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, (C ₅ -C ₇ Cycloalkyl) aminocarbonyl, benzylaminocarbonyl, C ₁ -C ₆ alkyl, C ₅ -C ₇ cycloalkyl, allyl or benzyl;
C ₅ -C ₇ cycloalkyl wherein R ₃ , R ₄ and R ₅ are the same or different and are hydrogen, C ₁ -C ₁₂ alkyl, unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; C ₃ -C ₁₂ alkenyl, phenyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted by C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl or C ₂ -C ₃ alkyl substituted by —OH, C ₁ -C ₄ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2 or 3 position; Or -N (R ₄ ) (R ₅ ) is additionally a group of formula (III); In addition
R ₆ is hydrogen, C ₁ -C ₁₂ alkyl, C ₅ -C ₇ cycloalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl; Benzyl unsubstituted or substituted by 1,2 or 3 C ₁ -C ₄ alkyl on phenyl; Tetrahydrofurfuryl, a group of formula (IV) or C ₂ -substituted by -OH, C ₁ -C ₄ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) at the 2 or 3 position; A compound of formula (I) wherein C ₃ alkyl.
[8" claim-type="Currently amended] The method of claim 1,
R ₂ is C ₂ -C ₈ alkylene;
A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, cyclohexoxycarbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, cyclohexylaminocarbonyl, benzylaminocarbonyl, C ₁ -C ₄ alkyl, cyclohexyl, allyl or benzyl;
Cyclohexyl wherein R ₃ , R ₄ and R ₅ are the same or different and are hydrogen, C ₁ -C ₈ alkyl, unsubstituted or substituted by methyl; C ₃ -C ₈ alkenyl, phenyl unsubstituted or substituted by methyl; Benzyl, tetrahydrofurfuryl or C ₂ -C ₃ alkyl substituted by —OH, C ₁ -C ₄ alkoxy, dimethylamino, diethylamino or 4-morpholinyl at the 2 or 3 position; Or -N (R ₄ ) (R ₅ ) is additionally 4-morpholinyl; In addition
R ₆ is hydrogen, C ₁ -C ₈ alkyl, cyclohexyl unsubstituted or substituted by methyl; Benzyl, tetrahydrofurfuryl, C ₂ -C ₃ substituted by —OH, C ₁ -C ₄ alkoxy, dimethylamino, diethylamino or 4-morpholinyl at the group of formula (IV) or at the 2 or 3 position; A compound of formula (I) which is alkyl.
[9" claim-type="Currently amended] The method of claim 1,
n is a number from 2 to 6;
R is a group of formula (IV);
R ₂ is C ₂ -C ₆ alkylene;
A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl, C ₁ -C ₄ alkyl or allyl;
B is —N (R ₄ ) (R ₅ ) or a group of formula (II);
R ₄ and R ₅ are the same or different and hydrogen, C ₁ -C ₈ alkyl, 2-hydroxyethyl or 2-methoxyethyl or -N (R ₄ ) (R ₅ ) is additionally 4-morpholine Nil;
X is> NR ₆ ; In addition
R ₆ is C ₁ -C ₄ alkyl.
[10" claim-type="Currently amended] The method of claim 1,
n is a number from 2 to 6;
R is a group of formula (IV);
R ₁ is methyl, octyl or cyclohexyl;
R ₂ is C ₂ -C ₆ alkylene;
A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₁ -C ₄ alkyl) aminocarbonyl or C ₁ -C ₄ alkyl;
B is -N (R ₄ ) (R ₅ ) or a group of formula (II);
R ₄ and R ₅ are the same or different and are C ₁ -C ₈ alkyl or —N (R ₄ ) (R ₅ ) is additionally 4-morpholinyl;
X is> NR ₆ ; In addition
R ₆ is C ₁ -C ₄ alkyl.
[11" claim-type="Currently amended] The method of claim 1,
n is a number from 2 to 6;
R is a group of formula (IV);
R ₁ is methyl, octyl or cyclohexyl;
R ₂ is C ₂ -C ₆ alkylene;
A is C ₁ -C ₈ acyl or (C ₁ -C ₈ alkoxy) carbonyl;
B is a group of formula (II) above;
X is> NR ₆ ; In addition
R ₆ is C ₁ -C ₄ alkyl.
[12" claim-type="Currently amended] A product obtainable by transferring a group of formula (IV-O) present in a block oligomer corresponding to formula (I-O) to a group of formula (IV):
(IV-O)
(IO)
(Ⅳ)
In the above, R ₁ is a hydrocarbyl radical or -OR ₁ is oxyl;
The transition is carried out by reacting a block oligomer corresponding to formula (I-O) with a hydroperoxide in a hydrocarbon solvent in the presence of a peroxide decomposition catalyst;
n is a number from 2 to 14;
The radicals R ₂ are each independently C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl Or C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, -O- or> NX ₁ in the middle when having one of the definitions of R ₄ given below; or
R ₂ is a group of formula (a), (b) or (c);
(a)
(b)
(c)
m is 2 or 3;
X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2, or 3 C ₁ -C ₄ alkyl; Also
The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene;
The radicals A are independently of each other C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ cycloalkoxy) carbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C ₅ -C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
The radical B ^* is —OR ₃ , —N (R ₄ ) (R ₅ ) or a group of formula (II-O);
(II-O)
R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of formula (III) ;
(Ⅲ)
Wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ;
R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
X ^* is -O- or> NR ₆ ^* ;
R ₆ ^* is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (IV-O) or substituted at the 2,3 or 4 position by -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III) C ₂ -C ₄ alkyl;
The radicals R ^* are each independently one of the definitions given for R ₆ ^* ; In addition
However, the formula each of the radicals B ^*, R ^* and R ₂ in the individual recurring units of (Ⅰ-O) has the same or a different meaning.
[13" claim-type="Currently amended] The method of claim 12,
R ₂ is C ₂ -C ₁₂ alkylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or has one of the definitions of R ₄ given below In the middle is C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, -O- or> NX ₁ ; or
R ₂ is a group of formula (b);
R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; Phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; In addition
R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
R ₆ ^* is C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Or a product of formula (IV-O).
[14" claim-type="Currently amended] 13. The polydispersity of claim 12, wherein the block oligomer corresponding to formula (IO) is from 1 to 1.7. Product with.
[15" claim-type="Currently amended] The method of claim 12,
R ₁ is C ₅ -C ₁₈ alkyl, C ₅ -C ₁₈ alkenyl, C ₅ -C ₁₈ alkynyl, unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₅ -C ₁₂ cycloalkenyl unsubstituted or substituted with C ₁ -C ₄ alkyl; Bicyclic or tricyclic hydrocarbyl having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by C ₁ -C ₄ alkyl; In addition
Hydrocarbon solvents in accordance with the R ₁ C ₅ -C ₁₈ alkanes, C ₅ -C ₁₈ alkene, C ₅ -C ₁₈ alkynyl, unsubstituted or substituted by C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkane; C ₅ -C ₁₂ cycloalkene unsubstituted or substituted with C ₁ -C ₄ alkyl; A product which is a bicyclic or tricyclic hydrocarbon having 6 to 10 carbon atoms or C ₇ -C ₉ phenylalkane unsubstituted or substituted on phenyl by C ₁ -C ₄ alkyl.
[16" claim-type="Currently amended] The method of claim 12,
The radical -OR ₁ is oxyl; In addition
A product wherein the hydrocarbon solvent is an inert organic solvent.
[17" claim-type="Currently amended] The product of claim 12, wherein the peroxide decomposition catalyst is a metal carbonyl, metal oxide, metal acetylacetonate or metal alkoxide, wherein the metal is selected from Group IVb, Vb, VIb, VIIb and Group VIII metals of the periodic table.
[18" claim-type="Currently amended] 13. The product of claim 12, wherein the hydroperoxide is tertiary butyl hydroperoxide and the peroxide decomposition catalyst is MoO ₃ .
[19" claim-type="Currently amended] The group of formula (IV-O) according to claim 12, which is present in a block oligomer corresponding to formula (I-O).
2 to 8 moles of hydroperoxide, 0.001 to 0.1 moles of peroxide decomposition catalyst and 5 to 30 moles of hydrocarbon solvent per mole were used.
[20" claim-type="Currently amended] A product obtainable by hydrogenating a product according to claim 12 in which -OR ₁ in formula (IV) is hydrogenated to give a block oligomer having a group of formula (IV-1):
(IV-1)
[21" claim-type="Currently amended] Mixtures containing compounds of formulas (la), (lb) and (lc)
(Ia)
(Ib)
(Ic)
In the above formula,
The compounds of formulas (Ia), (Ib) and (Ic) differ in the number of repeating units, and the molar ratio of compounds (Ia) to (Ib) to (Ic) is 2: 2: 1.5 to 2: 0.5 : 0.05; In addition
R ₁ is hydrogen or hydrocarbyl radical or -OR ₁ is oxyl;
R ₂ is C ₂ -C ₁₂ alkylene, C ₄ -C ₁₂ alkenylene, C ₅ -C ₇ cycloalkylene, C ₅ -C ₇ cycloalkylenedi (C ₁ -C ₄ alkylene), C ₁ -C ₄ alkylenedi (C ₅ -C ₇ cycloalkylene), phenylenedi (C ₁ -C ₄ alkylene) or X ₁ is C ₁ -C ₁₂ acyl or (C ₁ -C ₁₂ alkoxy) carbonyl or is given below In the case having one of the definitions of R ₄ is C ₄ -C ₁₂ alkylene comprising 1,4-piperazindiyl, —O— or> NX ₁ in the middle; or
R ₂ is a group of formula (a), (b) or (c);
(a)
(b)
(c)
m is 2 or 3;
X ₂ is C ₁ -C ₁₈ alkyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl; Phenyl unsubstituted or substituted with 1, 2, or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2, or 3 C ₁ -C ₄ alkyl; Also
The radicals X ₃ are each independently C ₂ -C ₁₂ alkylene;
The radical A is C ₁ -C ₈ acyl, (C ₁ -C ₈ alkoxy) carbonyl, (C ₅ -C ₁₂ phenylalkyl) aminocarbonyl, (C ₁ -C ₈ alkyl) aminocarbonyl, (C _5- C ₁₂ cycloalkyl) aminocarbonyl, (C ₇ -C ₉ phenylalkyl) aminocarbonyl, C ₁ -C ₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₆ alkenyl, C ₇ -C ₉ phenylalkyl unsubstituted or substituted by 1, 2 or 3 C ₁ -C ₄ alkyl on phenyl; Or -CH ₂ CN;
The radical B is —OR ₃ , —N (R ₄ ) (R ₅ ) or a group of formula (II):
(Ⅱ)
R _3, R ₄ and R ₅ are the same or different from the C ₁ -C ₁₈ alkyl, unsubstituted or substituted by one, two or three C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl; C ₃ -C ₁₈ alkenyl, phenyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl or C ₁ -C ₄ alkoxy; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl or -OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by a group of formula (III) ;
(Ⅲ)
Wherein Y is —O—, —CH ₂ —, —CH ₂ CH ₂ — or> N—CH ₃ ;
R ₃ is additionally hydrogen or —N (R ₄ ) (R ₅ ) is additionally a group of formula (III);
X is -O- or> NR ₆ ;
R ₆ is C ₁ -C ₁₈ alkyl, C ₃ -C ₁₈ alkenyl, C ₅ -C ₁₂ cycloalkyl unsubstituted or substituted with 1, 2 or 3 C ₁ -C ₄ alkyl; C ₇ -C ₉ phenylalkyl unsubstituted or substituted on phenyl by 1, 2 or 3 C ₁ -C ₄ alkyl; Tetrahydrofurfuryl, a group of formula (IV), or
(Ⅳ)
Or C ₂ -C ₄ alkyl substituted at the 2, 3 or 4 position by —OH, C ₁ -C ₈ alkoxy, di (C ₁ -C ₄ alkyl) amino or a group of formula (III); In addition
R is one of the definitions given in R ₆ .
[22" claim-type="Currently amended] The method of claim 21,
R is a group of formula (IV)
(Ⅳ)
R ₁ is octyl or cyclohexyl;
R ₂ is C ₂ -C ₆ alkylene;
A is C ₁ -C ₈ acyl or (C ₁ -C ₄ alkyl) aminocarbonyl;
B is a group of formula (II);
(Ⅱ)
X is> NR ₆ ; In addition
R ₆ is a C ₁ -C ₄ alkyl mixture.
[23" claim-type="Currently amended] A composition comprising an organic material susceptible to degradation by light, heat or oxidation and a compound according to claim 1.
[24" claim-type="Currently amended] The composition of claim 23 wherein said organic material is a synthetic polymer.
[25" claim-type="Currently amended] The composition of claim 23 wherein said organic material is polyethylene or polypropylene.
[26" claim-type="Currently amended] A composition comprising an organic material susceptible to degradation by light, heat or oxidation and a product according to claim 12.
[27" claim-type="Currently amended] A method of stabilizing an organic material from light, heat or oxidation by incorporating the product according to claim 1 into an organic material susceptible to decomposition by light, heat or oxidation.

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同族专利:

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公开号 | 公开日

---

CN1257492A|2000-06-21|

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ES2193546T3|2003-11-01|

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CA2288322C|2008-03-25|

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TW589341B|2004-06-01|

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DE69812612T2|2003-11-06|

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WO1998054173A1|1998-12-03|

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EP0984958A1|2000-03-15|

---

KR100530091B1|2005-11-22|

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US6177491B1|2001-01-23|

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CN1214028C|2005-08-10|

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DE69812612D1|2003-04-30|

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CA2288322A1|1998-12-03|

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JP2001527578A|2001-12-25|

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JP4441711B2|2010-03-31|

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EP0984958B1|2003-03-26|

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AU8534898A|1998-12-30|

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:
1997-05-27|Priority to EP97810327

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1997-05-27|Priority to EP97810327.3

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1998-05-25|Application filed by 시바 스폐셜티 케미칼스 홀딩 인코포레이티드

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1998-05-25|Priority to PCT/EP1998/003061

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2001-02-26|Publication of KR20010012805A

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2005-11-22|Application granted

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2005-11-22|Publication of KR100530091B1

优先权:

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申请号 | 申请日 | 专利标题

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EP97810327|1997-05-27|

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EP97810327.3|1997-05-27|

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PCT/EP1998/003061|WO1998054173A1|1997-05-27|1998-05-25|Block oligomers containing 1-hydrocarbyloxy-2,2,6,6-tetramethyl-4-piperidyl groups as stabilizers for organic materials|