Stabilized Polyolefin Compositions Comprising Benzofuranones and Hindered Phenolic Antioxidants

Abstract

Polyolefin compositions comprising i) a polyolefin, ii) one or more phosphorus-containing benzofuranone compounds and iii) one or more hindered phenolic antioxidants are provided excellent protection against discoloration and enhanced thermal stability during melt processing as exhibited by improved retention of molecular weight and maintenance of polymer molecular architecture.

1 - 23 . (canceled) 
     
     
         24 . A composition comprising
 i) a polyolefin,   ii) one or more benzofuranone compounds comprising a compound of at least one of formula: (I-p1), (I-o1) or (I-m1):   
       
         
           
           
               
               
           
         
       
       wherein in formula (I-m1) X is P or P═O and in formulas (I-p1) and (I-o1) X is P;
 Y p , Y o  and Y m  independently is oxygen or a covalent bond, 
 when Y p , Y o  or Y m  is oxygen, 
 R 1p  represents one of subformulae II-p, II-o or II-m 
 
       
         
           
           
               
               
           
         
         R 1o  represents one of subformulae II-o or II-m, 
         R 1m  represents subformula II-m, or 
         R 1p  together with R 2p , R 1o  together with R 2o  or R 1m  together with R 2m  represent one of subformulae III, IV or V 
       
       
         
           
           
               
               
           
         
       
       or
 R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, 
 R 2p  represents one of subformulae II-p, II-o or II-m, 
 R 2o  represents one of subformulae II-o or II-m, 
 R 2m  represents subformula II-m, or 
 R 2p  together with R 1p , R 2o  together with R 1o  or R 2m  together with R 1m  represent one of subformulae III, IV or V, or 
 R 2p , R 2o  or R 2m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, or 
 when Y p , Y o  or Y m  is a covalent bond, 
 R 1p  represents one of subformulae II-p, II-o or II-m, 
 R 1o  represents one of subformulae II-o or II-m, 
 R 1m  represents subformula II-m, or 
 R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, 
 R 2p , R 2o  or R 2m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, or halogen; 
 R 4 , R 5 , R 6  and R 7  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R p2 , R p3 , R p5  and R p6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R o1 , R o2 , R o5  and R o6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R m1 , R m3 , R m5  and R m6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R a1 , R a2 , R a3  and R a4  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R b1 , R b2 , R b3 , R b4 , R b5  and R b6  are each independently hydrogen or C 1 -C 8 -alkyl and 
 R c1 , R c2 , R c3  and R c4  are each independently hydrogen or C 1 -C 8 -alkyl; and 
 iii) one or more hindered phenolic antioxidants. 
 
     
     
         25 . The composition according to  claim 24 , wherein the polyolefin comprises polypropylene. 
     
     
         26 . The composition according to  claim 24 , wherein the polyolefin comprises polyethylene. 
     
     
         27 . The composition according to  claim 24 , wherein the one or more hindered phenolic antioxidants are selected from the group consisting of tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tri s-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, N,N′-hexamethylenebis(3,5-di-tert-butyl-4-hydroxyhydrocinnamamide), 1,3,5-tri s-(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-tri one, 2,2′-methylenebis (4-methyl-6-tert-butyl phenol)monoacrylate and alpha-tocopherol. 
     
     
         28 . The composition according to  claim 24 , wherein the one or more hindered phenolic antioxidants are selected from the group consisting of tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, 1,2-bis(3,5-di-tert-butyl-4-hydroxyhydrocinnamoyl)hydrazine, alpha-tocopherol, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] and octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. 
     
     
         29 . The composition according to  claim 24 , wherein the one or more hindered phenolic antioxidants comprises at least one of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] or octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate. 
     
     
         30 . The composition according to  claim 24 , further comprising one or more organophosphorus stabilizers. 
     
     
         31 . The composition according to  claim 24 , further comprising one or more organophosphorus stabilizers selected from the group consisting of tris-nonylphenyl phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 2,2′,2″-nitrilo[triethyltris(3,3′5,5′-tetra-tert-butyl-1,1′-biphenyl-2,2′-diyl) phosphite], bis(2,4-di-α-cumylphenyl) pentaerythrtitol diphosphite and tris(2,4-di-tert-butylphenyl) phosphite. 
     
     
         32 . The composition according to  claim 24 , wherein the one or more benzofuranone compounds are present from about 20 ppm to about 1000 ppm by weight, based on the weight of the polyolefin. 
     
     
         33 . The composition according to  claim 24 , wherein the one or more hindered phenolic antioxidants are present from about 20 ppm to about 1500 ppm by weight, based on the weight of the polyolefin. 
     
     
         34 . The composition according to  claim 24 , wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more hindered phenolic antioxidants is from about 0.05 to about 1.0. 
     
     
         35 . The composition according to  claim 24 , wherein at least one of Y p , Y o  or Y m  is oxygen. 
     
     
         36 . The composition according to  claim 24 , wherein at least one of Y p , Y o  or Y m  is a covalent bond. 
     
     
         37 . The composition according to  claim 24 , wherein when at least one of Y p , Y o  or Y m  is oxygen,
 R 1p  represents one of subformulae II-p, II-o or II-m,   R 1o  represents one of subformulae II-o or II-m,   R 1m  represents subformula II-m, or   R 1p  together with R 2p , R 1o , together with R 2o  or R 1m  together with R 2m  represent one of subformulae III, IV or V, or   R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -Cis-alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom,   R 2p  represents one of subformulae II-p, II-o or II-m,   R 2o  represents one of subformulae II-o or II-m,   R 2m  represents subformula II-m, or   R 2p  together with R 1p , R 2o  together with R 1o  or R 2m  together with R 1m  represent one of subformulae III, IV or V, or   R 2p , R 2o  or R 2m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom;   
       when Y p , Y o  or Y m  is a covalent bond,
 R 1p  represents one of subformulae II-p, II-o or II-m, 
 R 1o  represents one of subformulae II-o or II-m, 
 R 1m  represents subformula II-m, or 
 R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 18 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, 
 R 2p , R 2o  and R 2m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, or halogen; 
 R 4  and R 6  are hydrogen, 
 R 5  and R 7  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R p2  and R p6  are each independently hydrogen or C 1 -alkyl, 
 R p3  and R p5  are each independently hydrogen or C 1 -C 4 -alkyl, 
 R o1  and R o6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R o2  is hydrogen or C 1 -alkyl, R o5  is hydrogen or C 1 -C 4 -alkyl, 
 R m1  is hydrogen or C 1 -alkyl, 
 R m3  and R m5  are each independently hydrogen or C 1 -C 4 -alkyl, 
 R m6  is hydrogen or C 1 -C 8 -alkyl, 
 R a1 , R a2 , R a3  and R a4  are each independently hydrogen or C 1 -C 4 -alkyl, 
 R b1 , R b2 , R b3 , R b4 , R b5  and R b6  are each independently hydrogen or C 1 -C 4 -alkyl and 
 R c1 , R c2 , R c3  and R c4  are each independently hydrogen or C 1 -C 4 -alkyl. 
 
     
     
         38 . The composition according to  claim 24 , wherein when Y p , Y o  or Y m  is oxygen,
 R 1p  represents one of subformulae II-p, II-o or II-m,   R 1o  represents one of subformulae II-o or II-m,   R 1m  represents subformula II-m, or   R 1p  together with R 2p , R 1o , together with R 2o  or R 1m  together with R 2m  represent one of subformulae III, IV or V, or   R 1p , R 1o  or R 1m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 18 -alkyl or C 3 -C 16 -cycloalkyl and   R 2p  represents one of subformulae II-p, II-o or II-m, R 2o  represents one of subformulae II-o or II-m, R 2m  represents subformula II-m, or   R 2p  together with R 1p , together with R 1o  or R 2m  together with R 1m  represent one of subformulae III, IV or V, or   R 2p , R 2o  or R 2m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 18 -alkyl or C 3 -C 16 -cycloalkyl;   
       when Y″, Y o  and Y m  represent a covalent bond,
 R 1p  represents one of subformulae II-p, II-o or II-m, 
 R 1o  represents one of subformulae II-o or II-m, 
 R 1m  represents subformula II-m, or 
 R 1p , R 1o  and R 1m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 18 -alkyl or C 3 -C 16 -cycloalkyl and 
 R 2p , R 2o  and R 2m  are C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl or fluoro. 
 
     
     
         39 . The composition according to  claim 24 , wherein when Y p  or Y o  is oxygen, R 1p , R 1p , R 1o  or R 2o  does not represent subformula II-m; when Y p  or Y o  represents a covalent bond, R 1p  or R 1o  does not represent subformula II-m. 
     
     
         40 . The composition according to  claim 24 , wherein Y p  or Y o  is oxygen, R 1p  together with R 2p  or R 1o  together with R 2o  represent one of subformulae III, IV or V, R 2  together with R 1p  and R 2o  together with R 1o  represent one of subformulae III, IV or V, R 4 , R 5 , R 6  and R 7  are each independently hydrogen or C 1 -C 8 -alkyl, R p2 , R p3 , R p5  and R p6  are each independently hydrogen or C 1 -C 8 -alkyl, R o1 , R o2 , R o5  and R o6  are each independently hydrogen or C 1 -C 8 -alkyl, R a1 , R a2 , R a3  and R a4  are each independently hydrogen or C 1 -C 8 -alkyl, R b1 , R b2 , R b3 , R b4 , R b5  and R b6  are each independently hydrogen or C 1 -C 8 -alkyl and R c1 , R c2 , R c3  and R c4  are each independently hydrogen or C 1 -C 8 -alkyl. 
     
     
         41 . The composition according to  claim 24 , wherein the one or more benzofuranone compounds has the following structure: 
       
         
           
           
               
               
           
         
       
     
     
         42 . A shaped article comprising the composition according to  claim 24 . 
     
     
         43 . A method of preparing the shaped article according to  claim 42 , the method comprising melt blending the composition. 
     
     
         44 . An additive composition comprising:
 i) one or more benzofuranone compounds comprising a compound having at least one of formula: (I-p1), (I-o1) or (I-m1):   
       
         
           
           
               
               
           
         
       
       wherein in formula (I-m1) X is P or P═O and in formulas (I-p1) and (I-o1) X is P;
 Y p , Y o  and Y m  independently is oxygen or a covalent bond, 
 when Y p , Y o  or Y m  is oxygen, 
 R 1p  represents one of subformulae II-p, II-o or II-m 
 
       
         
           
           
               
               
           
         
         R 1o  represents one of subformulae II-o or II-m, 
         R 1m  represents subformula II-m, or 
         R 1p  together with R 2p , R 1o  together with R 2o  or R 1m  together with R 2m  represent one of subformulae III, IV or V 
       
       
         
           
           
               
               
           
         
       
       or
 R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 18 -aralkyl, C 2 -C 16 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, 
 R 2  represents one of subformulae II-p, II-o or II-m, 
 R 2o  represents one of subformulae II-o or II-m, 
 R 2m  represents subformula II-m, or 
 R 2  together with R 1p , R 2o  together with R 1o  or R 2m  together with R 1m  represent one of subformulae III, IV or V, or 
 R 2p , R 2o  or R 2m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, or 
 
       when Y p , Y o  or Y m  is a covalent bond,
 R 1p  represents one of subformulae II-p, II-o or II-m, 
 R 1o  represents one of subformulae II-o or II-m, 
 R 1m  represents subformula II-m, or 
 R 1p , R 1o  or R 1m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, C 1 -C 18 -alkyl, C 3 -C 16 -cycloalkyl, C 7 -C 13 -aralkyl, C 2 -C 18 -alkenyl, C 2 -C 30 -alkyl, which is interrupted by one or more oxygen atoms, or C 2 -C 16 -alkyl, which is interrupted by one sulfur atom, 
 R 2p , R 2o  or R 2m  is C 6 -C 10 -aryl, which is unsubstituted or substituted by C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, halogen or one phenyl, or halogen; 
 R 4 , R 5 , R 6  and R 7  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R p2 , R p3 , R p5  and R p6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R o1 , R o2 , R o5  and R o6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R m1 , R m3 , R m5  and R m6  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R a1 , R a2 , R a3  and R a4  are each independently hydrogen or C 1 -C 8 -alkyl, 
 R b1 , R b2 , R b3 , R b4 , R b5  and R b6  are each independently hydrogen or C 1 -C 8 -alkyl and 
 R c1 , R c2 , R c3  and R c4  are each independently hydrogen or C 1 -C 8 -alkyl; and 
 ii) one or more hindered phenolic antioxidants. 
 
     
     
         45 . The additive composition according to  claim 44 , wherein a weight/weight ratio of the one or more benzofuranone compounds to the one or more hindered phenolic antioxidants is from about 0.05 to about 1.0.