Stabilizer mixtures

Abstract

A stabilizer mixture containing the components (A), (B) and (C) wherein component (A) is for example a compound of the formula (A-1) wherein A 1 is hydrogen or C 1 -C 4 alkyl, A 2 is a direct bond or C 1 -C 10 alkylene, and n 1 is a number from 2 to 50; component (B) is a low molecular weight sterically hindered amine compound containing a group of the formula (I) or (II); and component (C) is a high molecular weight sterically hindered amine compound containing a group of the formula (I); with the proviso that components (A), (B) and (C) are different.

1 . A stabilizer mixture containing the components (A), (B) and (C) wherein component (A) is 
 a compound selected from the group consisting of a compound of the formula (A-1)                          wherein    A 1  is hydrogen or C 1 -C 4 alkyl,    A 2  is a direct bond or C 1 -C 10 alkylene, and    n 1  is a number from 2 to 50;    at least one compound of the formula (A-2-a) or (A-2-b)                          wherein    n 2  and n 2 * are a number from 2 to 50;    component (B) is a low molecular weight sterically hindered amine compound selected from the group consisting of compound of the formula (B-1)                          in which    E 1  is hydrogen, C 1 -C 8 alkyl, O., —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl,    m 1  is 1, 2 or 4,    if m 1  is 1, E 2  is C 1 -C 25 alkyl,    if m 1  is 2, E 2  is C 1 -C 14 alkylene or a group of the formula (b-I)                          wherein    E 3  is C 1 -C 10 alkyl or C 2 -C 10 alkenyl, E 4  is C 1 -C 10 alkylene, and    E 5  and E 6  independently of one another are C 1 -C 4 alkyl, cyclohexyl or methylcyclohexyl, and    if m 1  is 4, E 2  is C 4 -C 10 alkanetetrayl:    a compound of the formula (B-2)                          in which    two of the radicals E 7  are —COO—(C 1 -C 20 alkyl), and    two of the radicals E 7  are a group of the formula (b-II)                          with E 8  having one of the meanings of E 1 ;    a compound of the formula (B-3)                          in which    E 9  and E 10  together form C 2 -C 14 alkylene,    E 11  is hydrogen or a group -Z 1 -COO-Z 2 ,    Z 1  is C 2 -C 14 alkylene, and    Z 2  is C 1 -C 24 alkyl, and    E 12  has one of the meanings of E 1 ;    a compound of the formula (B-4)                          wherein    the radicals E 13  independently of one another have one of the meanings of E 1 ,    the radicals E 14  independently of one another are hydrogen or C 1 -C 12 alkyl, and    E 15  is C 1 -C 10 alkylene or C 3 -C 10 alkylidene;    a compound of the formula (B-5)                          wherein    the radicals E 16  independently of one another have one of the meanings of E 1 ;    a compound of the formula (B-6)                          in which    E 17  is C 1 -C 24 alkyl, and    E 18  has one of the meanings of E 1 ;    a compound of the formula (B-7)                          in which    E 19 , E 20  and E 21  independently of one another are a group of the formula (b-III)                          wherein E 22  has one of the meanings of E 1 ;    a compound of the formula (B-8)                          wherein    the radicals E 23  independently of one another have one of the meanings of E 1 ,    and E 24  is hydrogen, C 1 -C 12 alkyl or C 1 -C 12 alkoxy;    a compound of the formula (B-9)                          wherein    m 2  is 1, 2 or 3,    E 25  has one of the meanings of E 1 , and    when m 2  is 1, E 26  is a group                          when m 2  is 2, E 26  is C 2 -C 22 alkylene, and    when m 2  is 3, E 26  is a group of the formula (b-IV)                          wherein the radicals E 27  independently of one another are C 2 -C 12 alkylene, and the radicals E 28  independently of one another are C 1 -C 12 alkyl or C 5 -C 12 cycloalkyl; or    a compound of the formula (B-10)                          wherein    the radicals E 29  independently of one another have one of the meanings of E 1 , and E 30  is C 2 -C 22 alkylene, C 5 -C 7 cycloalkylene, C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), phenylene or phenylenedi(C 1 -C 4 alkylene); and    component (C) is a high molecular weight sterically hindered amine compound selected from the group consisting of the formula (C-1)                          in which    R 1 , R 3 , R 4  and R 5  independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 -alkyl-substituted C 5 -C 12 cycloalkyl, phenyl, phenyl which is substituted by —OH and/or C 1 -C 10 alkyl; C 7 -C 9 phenylalkyl, C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by —OH and/or C 1 -C 10 alkyl; or a group of the formula (c-I)                          R 2  is C 2 -C 18 alkylene, C 5 -C 7 cycloalkylene or C 1 -C 4 alkylenedi(C 5 -C 7 cycloalkylene), or the radicals R 1 , R 2  and R 3 , together with the nitrogen atoms to which they are bonded, perform a 5- to 10-membered heterocyclic ring, or    R 4  and R 5 , together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring,    R 6  is hydrogen, C 1 -C 8 alkyl, O., —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy. C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl, and b 1  is a number from 2 to 50,    with the proviso that at least one of the radicals R 1 , R 3 , R 4  and R 5  is a group of the formula (c-I);    a compound of the formula (C-2)                          wherein    R 7  and R 11  independently of one another are hydrogen or C 1 -C 12 alkyl,    R 8 , R 9  and R 10  independently of one another are C 2 -C 10 alkylene, and    X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7  and X 8  independently of one another are a group of the formula (c-II).                          in which    R 12  is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl, —OH— and/or C 1 -C 10 alkyl-substituted phenyl, C 7 -C 9 phenylalkyl. C 7 -C 9 phenylalkyl which is substituted on the phenyl radical by —OH and/or C 1 -C 10 alkyl; or a group of the formula (c-I) as defined above, and    R 13  has one of the meanings of R 6 ;    a compound of the formula (C-3)                          in which    R 14  is C 1 -C 10 alkyl, C 5 -C 12 cycloalkyl, C 1 -C 4 alkyl-substituted C 5 -C 12 cycloalkyl, phenyl or C 1 -C 10 alkyl-substituted phenyl,    R 15  is C 3 -C 10 alkylene,    R 16  has one of the meanings of R 6 , and    b 2  is a number from 2 to 50:    a compound of the formula (C-4)                          in which    R 17  and R 21  independently of one another are a direct bond or a —N(X 9 )—CO—X 10 —CO—N(X 11 )— group, where X 9  and X 11  independently of one another are hydrogen, C 1 -C 8 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula (c-I).    X 10  is a direct bond or C 1 -C 4 alkylene,    R 18  has one of the meanings of R 6 ,    R 19 , R 20 , R 23  and R 24  independently of one another are hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl or phenyl,    R 22  is hydrogen, C 1 -C 30 alkyl, C 5 -C 12 cycloalkyl, phenyl, C 7 -C 9 phenylalkyl or a group of the formula (c-I), and    b 3  is a number from 1 to 50;    a compound of the formula (C-5)                          in which    R 25 , R 26 , R 27 , R 28  and R 29  independently of one another are a direct bond or C 1 -C 10 alkylene,    R 30  has one of the meanings of R 6 , and    b 4  is a number from 1 to 50; or    a product (C-6) obtainable by reacting a product, obtained by reaction of a polyamine of the formula (C-6-1) with cyanuric chloride, with a compound of the formula (C-6-2)      H 2 N—(CH 2 ) b′     5   —NH—(CH 2 ) b″     5   —NH—(CH 2 ) b′″     5   —NH 2   (C-6-1)                      in which    b′ 5 , b″ 5  and b′″ 5  independently of one another are a number from 2 to 12,    R 31  is hydrogen, C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, phenyl or C 7 -C 9 phenylalkyl, and    R 32  has one of the meanings of R 6 .    
     
     
         2 - 3 . (canceled)  
     
     
         4 . A stabilizer mixture according to  claim 1  wherein 
 A 1  is hydrogen or methyl,    A 2  is a direct bond or C 2 -C 6 alkylene, and    n 1  is a number from 2 to 25;    n 2  and n 2 * are a number from 2 to 25.    
     
     
         5 . A stabilizer mixture according to  claim 1  wherein 
 m 1  is 1, 2 or 4,    if m 1  is 1, E 2  is C 12 -C 20 alkyl,    if m 1  is 2, E 2  is C 2 -C 10 alkylene or a group of the formula (b-I)    E 3  is C 1 -C 4 alkyl,    E 4  is C 1 -C 6 alkylene, and    E 5  and E 6  independently of one another are C 1 -C 4 alkyl, and    if m 1  is 4, E 2  is C 4 -C 8 alkanetetrayl;    two of the radicals E 7  are —COO—(C 10 -C 15 alkyl), and    two of the radicals E 7  are a group of the formula (b-II);    E 9  and E 10  together form C 9 -C 13 alkylene,    E 11  is hydrogen or a group -Z 1 -COO-Z 2 ,    Z 1  is C 2 -C 6 alkylene, and    Z 2  is C 10 -C 16 alkyl;    E 14  is hydrogen, and    E 15  is C 2 -C 6 alkylene or C 3 -C 5 alkylidene;    E 17  is C 10 -C 14 alkyl;    E 24  is C 1 -C 4 alkoxy;    m 2  is 1, 2 or 3,    when m 2  is 1, E 26  is a group                          when m 2  is 2, E 26  is C 2 -C 6 alkylene, and    when m 2  is 3, E 26  is a group of the formula (b-IV)    the radicals E 27  independently of one another are C 2 -C 6 alkylene, and    the radicals E 28  independently of one another are C 1 -C 4 alkyl or C 5 -C 8 cycloalkyl; and    E 30  is C 2 -C 8 alkylene.    
     
     
         6 . A stabilizer mixture according to  claim 1  wherein 
 R 1  and R 3  independently of one another are a group of the formula (c-I),    R 2  is C 2 -C 8 alkylene,    R 4  and R 5  independently of one another are hydrogen, C 1 -C 12 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (c-I), or the radicals R 4  and R 5 , together with the nitrogen atom to which they are bonded, form a 5- to 10-membered heterocyclic ring, and    b 1  is a number from 2 to 25;    R 7  and R 11  independently of one another are hydrogen or C 1 -C 4 alkyl,    R 8 , R 9  and R 10  independently of one another are C 2 -C 4 alkylene, and X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7  and X 8  independently of one another are a group of the formula (c-II),    R 12  is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl or a group of the formula (c-I);    R 14  is C 1 -C 4 alkyl,    R 15  is C 3 -C 6 alkylene, and    b 2  is a number from 2 to 25;    R 17  and R 21  independently of one another are a direct bond or a group —N(X 9 )—CO—X 10 —CO—N(X 11 )—,    X 9  and X 11  independently of one another are hydrogen or C 1 -C 4 alkyl,    X 10  is a direct bond,    R 19  and R 23  are C 1 -C 25 alkyl or phenyl,    R 20  and R 24  are hydrogen or C 1 -C 4 alkyl,    R 22  is C 1 -C 25 alkyl or a group of the formula (c-I), and    b 3  is a number from 1 to 25;    R 25 , R 26 , R 27 , R 28  and R 29  independently of one another are a direct bond or C 1 -C 4 alkylene, and    b 4  is a number from 1 to 25;    b′ 5 , b″ 5  and b′″ 5  independently of one another are a number from 2 to 4, and    R 31  is hydrogen, C 1 -C 4 alkyl, C 5 -C 8 cycloalkyl, phenyl or benzyl.    
     
     
         7 . A stabilizer mixture according to  claim 1  wherein 
 component (A) is a compound selected from the group consisting of formula (A-1-a), (A-2-a) and (A-2-b);                          wherein n 1  is a number from 2 to 20;                          wherein n 2  and n 2 * are a number from 2 to 20;    component (B) is a compound selected from the group consisting of formula (B-1-a), (B-1-b), (B-1-c), (B-1-d), (B-2-a), (B-3-a), (B-3-b), (B-4-a), (B-4-b), (B-5), (B-6-a), (B-7), (B-8-a), (B-9-a), (B-9-b), (B-9-c) and (B-10-a);                          wherein E 1  is hydrogen, C 1 -C 8 alkyl, O., —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl;                          in which two of the radicals E 7  are —COO—C 13 H 27  and    two of the radicals E 7  are                          and E 8  has one of the meanings of E 1 ;                          wherein E 12  has one of the meanings of E 1 ;                          wherein E 13  has one of the meanings of E 1 ;                          wherein E 16  has one of the meanings of E 1 ;                          wherein E 18  has one of the meanings of E 1 ;                          in which E 19 , E 20  and E 21  independently of one another are a group of the formula (b-II)                          wherein E 22  has one of the meanings of E 1 ;                          wherein E 23  has one of the meanings of E 1 ;                          wherein E 25  has one of the meanings of E 1 ;                          wherein E 29  has one of the meanings of E 1 ; and    component (C) is a compound selected from the group consisting of formula (C-1-a), (C-1-b), (C-1-c), (C-1-d), (C-2-a), (C-3-a), (C-4-a), (C-4-b), (C-4-c) or (C-5-a) and a product (C-6-a);                          wherein b 1  is a number from 2 to 20 and R 6  is hydrogen, C 1 -C 8 alkyl, O., —OH, —CH 2 CN, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 6 alkenyl, C 7 -C 9 phenylalkyl unsubstituted or substituted on the phenyl by 1, 2 or 3 C 1 -C 4 alkyl; or C 1 -C 8 acyl;                          wherein R 13  has one of the meanings of R 6 ,                          wherein b 2  is a number from 2 to 20 and R 16  has one of the meanings of R 6 ;                          wherein b 3  is a number from 1 to 20 and R 18  has one of the meanings of R 6 ;                          wherein b 4  is a number from 1 to 20 and R 30  has one of the meanings of R 6 ;    a product (C-6-a) obtainable by reacting a product, obtained by reaction of a polyamine of formula (C-6-1-a) with cyanuric chloride, with a compound of e formula (C-6-2-a)      H 2 N—(CH 2 ) 3 —NH—(CH 2 ) 2 —NH—(CH 2 ) 3 —NH 2   (C-6-1-a)                      in which R 32  has one of the meanings of R 6 .    
     
     
         8 . (canceled)  
     
     
         9 . A stabilizer mixture according to  claim 1  wherein E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25  and E 29  are hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.  
     
     
         10 . A stabilizer mixture according to  claim 1  wherein R 6 , R 13 , R 16 , R 18 , R 30  and R 32  are hydrogen, C 1 -C 4 alkyl, C 1 -C 10 alkoxy, cyclohexyloxy, allyl, benzyl or acetyl.  
     
     
         11 . A stabilizer mixture according to  claim 7  wherein E 1 , E 8 , E 12 , E 13 , E 16 , E 18 , E 22 , E 23 , E 25 , E 29 , R 6 , R 13 , R 16 , R 18 , R 30  and R 32  are hydrogen or methyl and E 1  and R 6  additionally are C 1 -C 8 alkoxy.  
     
     
         12 . A stabilizer mixture according to  claim 7  wherein component (A) is a compound selected from the group consisting of the formula (A-1-a) wherein n 1  is a number from 2 to 20, and a compound of the formula (A-2-a) or (A-2-b) wherein n 2  and n 2 * are a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein E 1  is hydrogen and component (C) is a compound selected from the group consisting of the formula (C-1-a) wherein b 1  is a number from 2 to 20 and R 6  is hydrogen, a compound of the formula (C-1-b) wherein R 6  is hydrogen or propoxy and b 1  is a number from 2 to 20, a compound of the formula (C-1-d) wherein R 6  is hydrogen or methyl and b 1  is a number from 2 to 20, a compound of the formula (C-2-a) wherein R 13  is methyl, a compound of the formula (C-3-a) wherein R 16  is hydrogen and b 2  is a number from 2 to 20, a compound of the formula (C-4-a) wherein R 18  is hydrogen and b 3  is a number from 1 to 20, and a product (C-6-a).  
     
     
         13 . A stabilizer mixture according to  claim 7  wherein component (A) is a compound selected from the group consisting of the formula (A-1-a) wherein n 1  is a number from 2 to 20, and a compound of the formula (A-2-a) or (A-2-b) wherein n 2  and n 2 * are a number from 2 to 20, component (B) is a compound of the formula (B-1-b) wherein E 1  is hydrogen and component (C) is a compound of the formula (C-1-a) wherein b 1  is a number from 2 to 20 and R 6  is hydrogen.  
     
     
         14 . A stabilizer mixture according to  claim 7  wherein 
 component (A) is a compound of the formula (A-1-a), component (B) is a compound of the formula (B-1-b) with E 1  being hydrogen and component (C) is a compound of the formula (C-1-a) with R 6  being hydrogen; or    component (A) is a compound of the formula (A-1-a), component (B) is a compound of the formula (B-1-b) with E 1  being octyloxy and component (C) is a compound of the formula (C-1-a) with R 6  being hydrogen; or    component (A) is a compound of the formula (A-1-a), component (B) is a compound of the formula (B-3-a) with E 12  being hydrogen and component (C) is a compound of the formula (C-1-a) with R 6  being hydrogen; or    component (A) is a compound of the formula (A-1-a), component (B) is a compound of the formula (B-10-a) with E 29  being hydrogen and component (C) is a compound of the formula (C-1-a) with R 6  being hydrogen; or    component (A) is a compound of the formula (A-1-a), component (B) is a compound of the formula (B-1-b) with E 1  being methyl and component (C) is a compound of the formula (C-2-a) with R 13  being methyl.    
     
     
         15 . A composition comprising an organic material subject to degradation induced by light, heat or oxidation and a stabilizer mixture according to  claim 1 .  
     
     
         16 . A composition according to  claim 15  wherein the organic material is a synthetic polymer.  
     
     
         17 . A composition according to  claim 15  wherein the organic material is a polyolefin.  
     
     
         18 . A composition according to  claim 15  wherein the organic material is polyethylene, polypropylene, a polyethylene copolymer or a polypropylene copolymer.  
     
     
         19 . A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into the organic material a stabilizer mixture according to  claim 1 .  
     
     
         20 - 27 . (canceled)  
     
     
         28 . A stabilizer mixture according to  claim 1  wherein the product (C-6) is represented by a compound of the formula (C-6-α, (C-6-β or (C-6-γ), or a mixture of these three compounds  
       
         
           
           
               
               
           
         
         wherein the radicals R 31  and R 32  are as defined in  claim 1  and b 5  is 2 to 20.  
       
     
     
         29 . A stabilizer mixture according to  claim 1  wherein the product (C-6) is represented by the compound of the formula  
       
         
           
           
               
               
           
         
         wherein b 5  is 2 to 20.