Stabilizer combination for the rotomolding process

Abstract

A process for the production of polyolefin hollow articles comprises charging the polyolefin with a stabilizer combination comprising (a) at least one compound from the group of the organic phosphites or phosphonites, (b) one or more compounds selected from the group consisting of i.) hydroxylamine derivatives and ii.) amine oxide derivatives and (c) at least one compound from the group of the hindered amine stabilizers, filling this mixture into a mold, heating this mold in an oven to above 280° C., such that the stabilized polyolefin fuses, rotating the mold around at least 2 axes, the plastic spreading to the walls, and cooling the mold while still rotating, opening it and taking the resultant hollow article out.

What is claimed is  
     
         1 . A process for the production of polyolefin hollow articles, which comprises 
 charging the polyolefin with a stabilizer combination, comprising 
 (a) at least one compound from the group of the organic phosphites and phosphonites,  
 (b) one or more compounds selected from the group consisting of 
 i.) hydroxylamine derivatives and  
 ii.) amine oxide derivatives and  
 
 (c) at least one compound from the group of the hindered amine stabilizers,  
   filling this mixture into a mold, heating this mold in an oven to above 280° C., such that the stabilized polyolefin fuses,    rotating the mold around at least 2 axes, the plastic material spreading to the walls,    cooling the mold while still rotating,    opening it, and    taking the resultant hollow article out.    
     
     
         2 . A process according to  claim 1  wherein the organic phosphites and phosphonites of component (a) are selected from the group consisting of formulae (1), (2), (3), (4), (5), (6) and (7)  
       
         
           
           
               
               
           
         
       
       in which the indices are integral and 
 n is 2, 3 or 4; p is 1 or 2; q is 2 or 3; r is 4 to 12; y is 1, 2 or 3; and z is 1 to 6;  
 A 1 , if n is 2, is C 2 -C 18  alkylene; C 2 -C 12  alkylene interrupted by oxygen, sulfur or —NR 4 —; a radical of the formula  
                     
  or phenylene;  
 A 1 , if n is 3, is a radical of the formula —C r H 2r-1 —;  
 A 1 , if n is 4, is  
                     
 A 2  is as defined for A 1  if n is 2;  
 B is a direct bond, —CH 2 —, —CHR 4 —, —CR 1 R 4 —, sulfur, C 5 -C 7  cycloalkylidene, or cyclohexylidene which is substituted by from 1 to 4 C 1 -C 4  alkyl radicals in position 3, 4 and/or 5;  
 D 1 , if p is 1, is C 1 -C 4 alkyl and, if p is 2, is —CH 2 OCH 2 —;  
 D 2 , if p is 1, is C 1 -C 4  alkyl;  
 E, if y is 1, is C 1 -C 18  alkyl, —OR 1  or halogen;  
 E, if y is 2, is —O—A 2 —O—,  
 E, if y is 3, is a radical of the formula R 4 C(CH 2 O—) 3  or N(CH 2 CH 2 O—) 3 ;  
 Q is the radical of an at least z-valent alcohol or phenol, this radical being attached via the oxygen atom to the phosphorus atom;  
 R 1 , R 2  and R 3  independently of one another are C 1 -C 18  alkyl which is unsubstituted or substituted by halogen, —COOR 4 , —CN or —CONR 4 R 4 ; C 2 -C 18  alkyl interrupted by oxygen, sulfur or —NR 4 —; C 7 -C 9  phenylalkyl; C 5 -C 12  cycloalkyl, phenyl or naphthyl; naphthyl or phenyl substituted by halogen, 1 to 3 alkyl radicals or alkoxy radicals having a total of 1 to 18 carbon atoms or by C 7 -C 9  phenylalkyl; or a radical of the formula  
                     
  in which m is an integer from the range 3 to 6;  
 R 4  is hydrogen, C 1 -C 8  alkyl, C 5 -C 12  cycloalkyl or C 7 -C 9  phenylalkyl,  
 R 5  and R 6  independently of one another are hydrogen, C 1 -C 8  alkyl or C 5 -C 6  cycloalkyl,  
 R 7  and R 8 , if q is 2, independently of one another are C 1 -C 4  alkyl or together are a 2,3-dehydropentamethylene radical; and  
 R 7  and R 8 , if q is 3, are methyl;  
 R 14  is hydrogen, C 1 -C 9  alkyl or cyclohexyl,  
 R 15  is hydrogen or methyl and, if two or more radicals R 14  and R 15  are present, these radicals are identical or different,  
 X and Y are each a direct bond or oxygen,  
 Z is a direct bond, methylene, —C(R 16 ) 2 — or sulfur, and  
 R 16  is C 1 -C 8  alkyl.  
 
     
     
         3 . A process according to  claim 1  wherein the organic phosphites and phosphonites of component (a) are selected from the group consisting of tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite and formulae (A), (B), (C), (D), (E), (F), (G), (H), (J), (K) and (L)  
       
         
           
           
               
               
           
         
       
     
     
         4 . A process according to  claim 1  wherein the hydroxylamine derivatives of component (i) are of the formula (II)  
       
         
           
           
               
               
           
         
       
       wherein 
 T 1  is straight or branched chain alkyl of 1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9 carbon atoms, or said aralkyl substituted by one or two alkyl of 1 to 12 carbon atoms or by one or two halogen atoms;  
 T 2  is hydrogen, or independently has the same meaning as T 1 .  
 
     
     
         5 . A process according to  claim 4  wherein T 1  and T 2  are independently benzyl, ethyl, octyl, lauryl, dodecyl, tetradecyl, hexadecyl, heptadecyl or octadecyl.  
     
     
         6 . A process according to  claim 1  wherein the hydroxylamine derivatives of component (i) are selected from the group consisting of N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-didodecylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-tetradecylhydroxylamine, N-hexadecyl-N-heptadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, and N,N-di(hydrogenated tallow)hydroxylamine.  
     
     
         7 . A process according to  claim 1  wherein component (i) is an N,N-di(alkyl)hydroxylamine produced by the direct oxidation of N,N-di(hydrogenated tallow)amine.  
     
     
         8 . A process according to  claim 1  wherein the amine oxide derivatives of component (ii) are of the formula (III)  
       
         
           
           
               
               
           
         
       
       wherein 
 G 1  and G 2  are independently a straight or branched chain alkyl of 6 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms;  
 G 3  is a straight or branched chain alkyl of 1 to 36 carbon atoms, aryl of 6 to 12 carbon atoms, aralkyl of 7 to 36 carbon atoms, alkaryl of 7 to 36 carbon atoms, cycloalkyl of 5 to 36 carbon atoms, alkcycloalkyl of 6 to 36 carbon atoms or cycloalkylalkyl of 6 to 36 carbon atoms; with the proviso that at least one of G 1 , G 2  and G 3  contains a β carbon-hydrogen bond; and 
 wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be interuppted by one to sixteen —O—, —S—, —SO—, —SO 2 —, —COO—, —OCO—, —CO—, —NG 4 —, —CONG 4 — and —NG 4 CO— groups, or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups may be substituted by one to sixteen groups selected from —OG 4 , —SG 4 , — COOG 4 , —OCOG 4 , —COG 4 , —N(G 4 ) 2 , —CON(G 4 ) 2 , —NG 4 COG 4  and 5- and 6-membered rings containing the —C(CH 3 )(CH 2 R x )NL(CH 2 R x )(CH 3 )C— group or wherein said alkyl, aralkyl, alkaryl, cycloalkyl, alkcycloalkyl and cycloalkylalkyl groups are both interuppted and substituted by the groups mentioned above; and 
 wherein  
 G 4  is independently hydrogen or alkyl of 1 to 8 carbon atoms;  
 R x  is hydrogen or methyl;  
 L is a C 1-30  straight or branched chain alkyl moiety, a —C(O)R moiety wherein R is a C 1-30  straight or branched chain alkyl group, or a —OR moiety wherein R is a C 1-30  straight or branched chain alkyl group; and  
 
 wherein said aryl groups may be substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof.  
 
 
     
     
         9 . A process according to  claim 8  wherein wherein G 1  and G 2  are independently straight or branched chain alkyl groups of 6 to 22 carbon atoms and G 3  is a straight or branched chain alkyl of 1 to 22 carbon atoms.  
     
     
         10 . A process according to  claim 8  in which G 3  is methyl.  
     
     
         11 . A process according to  claim 8  wherein G 1  and G 2  are each independently a straight or branched chain alkyl of 12 to 22 carbon atoms and wherein G 3  is methyl.  
     
     
         12 . A process according to  claim 8  wherein G 1 , G 2  and G 3  are each independently a straight or branched chain alkyl of 12 to 22 carbon atoms.  
     
     
         13 . A process according to  claim 8  wherein the amine oxide derivatives of component (ii) are selected from the group consisting of didecyl methyl amine oxide, tridecyl amine oxide, tridodecyl amine oxide and trihexadecyl amine oxide.  
     
     
         14 . A process according to  claim 8  wherein at least one of G 1 , G 2  and G 3  comprises at least one moiety of the group consisting of —O—, —S—, —SO—, —COO—, —CO— and —CONG 4 —.  
     
     
         15 . A process according to  claim 1  wherein the amine oxide derivatives are poly(amine oxides).  
     
     
         16 . A process according to  claim 15  wherein the poly(amine oxides) comprise at least one moiety of the group consisting of —O—, —S—, —SO—, —COO—, —CO— and —CONG 4 —.  
     
     
         17 . A process according to  claim 8  wherein one or more of G 1 , G 2  and G 3  is substituted by one to sixteen groups of formulae (IV) and (V),  
       
         
           
           
               
               
           
         
       
     
     
         18 . A process according to  claim 1  wherein the hindered amine stabilizers of component (c) contain at least one group of the formula (VI)  
       
         
           
           
               
               
           
         
       
       in which R x  is hydrogen or methyl.  
     
     
         19 . A process according to  claim 18  wherein the hindered amine stabilizers are selected from the group consisting of formulae (H1), (H2), (H3), (H4), (H5), (H6), (H7), (H8), (H9), (H10), (H11), (H12), (H13), (H14), (H15), (H16) and (H17)  
       
         
           
           
               
               
           
         
       
     
     
         20 . A process according to  claim 1 , wherein the temperature reaches the range from about 200° C. to 400° C.