Viscosity breaking process for olefin polymers

Abstract

Disclosed is a method for viscosity breaking of a polypropylene polymer, a polypropylene copolymer or a polypropylene polymer blend, which process comprises adding a chain transfer agent and an initiator to a polypropylene polymer, polypropylene copolymer or polypropylene polymer blend and heating the resultant composition. The chain transfer agent has a Cs value of greater than or equal to about 0.04 as measured in ethylene polymerization at 130° C. The initiator is for example an organic or inorganic peroxide, a carbon based radical generator, a bis azo compound, a stable nitroxyl compound, a sterically hindered NO-acyl compound or a sterically hindered alkoxyamine compound.

1 . A method for viscosity breaking of a polypropylene polymer, a propylene copolymer or a polypropylene polymer blend, 
 which method comprises    adding a chain transfer agent and an initiator to the polypropylene polymer, propylene copolymer or polypropylene polymer blend and heating the resultant composition,    wherein the chain transfer agent has a Cs value of greater than or equal to about 0.04 as measured in ethylene polymerization at 130° C.    
   
   
       2 . A method according to  claim 1  wherein the chain transfer agent is selected from the group consisting of thiols, disulfides, phosphorus acid ester, phosphines, organic iodides, organic chlorides, propionic acid esters, adehydes or tertiary amines.  
   
   
       3 . A method according to  claim 1  where the chain transfer agent is a thiol, a disulfide or a tertiary amine.  
   
   
       4 . A method according to  claim 1  where the chain transfer agent is a thiol or a disulfide of the formulae  
       R—S-A  or  R—S—S—R  
     where 
 R is an mono, di, tri or tetravalent hydrocarbyl group attached to the sulfur atom with a carbon atom and  
 A is hydrogen or —SO 3   − B +  where B +  is an organic or inorganic cation.  
 
   
   
       5 . A method according to  claim 1  where the chain transfer agent is a thiol or a disulfide of the formulae  
       R—S-A  or  R—S—S—R  
     where 
 R is C 8 -C 22 alkyl, hydroxy-C 2 -C 8 alkyl, mercapto-C 2 -C 8 alkyl, mercapto-C 8 -C 20 alkyl interrupted by one or more —NH— groups, mercapto-C 8 -C 20 alkyl interrupted by one or more —OCO— groups, mercapto-C 8 -C 18 alkyl substituted by one or more hydroxyl groups, C 6 -C 10 aryl or is C 6 -C 10 aryl substituted by one or more substituents selected from the group consisting of C 1 -C 4 alkyl, 4-thiophenyl, 3-methyl-4-thiophenyl and C 6 -C 10 aryl-C 1 -C 4 alkyl.  
 
   
   
       6 . A method according to  claim 1  where the initiator is an organic or inorganic peroxide, a carbon based radical generator, a bis azo compound, a stable nitroxyl compound, a sterically hindered NO-acyl compound or is a sterically hindered alkoxyamine compound.  
   
   
       7 . A method according to  claim 1  where the initiator is an organic or an inorganic peroxide which is 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,3,6,6,9,9-pentamethyl-3-(ethyl acetate)-1,2,4,5-tetraoxy cyclononane, t-butyl hydroperoxide, hydrogen peroxide, dicumyl peroxide, t-butyl peroxy isopropyl carbonate, di-t-butyl peroxide, p-chlorobenzoyl peroxide, dibenzoyl diperoxide, t-butyl cumyl peroxide; t-butyl hydroxyethyl peroxide, di-t-amyl peroxide and 2,5-dimethylhexene-2,5-diperisononanoate, acetylcyclohexanesulphonyl peroxide, diisopropyl peroxydicarbonate, tert-amyl perneodecanoate, tert-butyl-perneodecanoate, tert-butylperpivalate, tert-amylperpivalate, bis(2,4-dichlorobenzoyl)peroxide, diisononanoyl peroxide, didecanoyl peroxide, dioctanoyl peroxide, dilauroyl peroxide, bis(2-methylbenzoyl)peroxide, disuccinoyl peroxide, diacetyl peroxide, dibenzoyl peroxide, tert-butyl per-2-ethylhexanoate, bis(4-chlorobenzoyl)peroxide, tert-butyl perisobutyrate, tert-butyl permaleate, 1,1-bis(tert-butylperoxy)-3,5,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, tert-butyl peroxyisopropyl carbonate, tert-butyl perisononaoate, 2,5-dimethylhexane 2,5-dibenzoate, tert-butyl peracetate, tert-amyl perbenzoate, tert-butyl perbenzoate, 2,2-bis(tert-butylperoxy)butane, 2,2-bis(tert-butylperoxy)propane, dicumyl peroxide, 2,5-dimethylhexane 2,5-di-tert-butylperoxid, 3-tert-butylperoxy-3-phenyl phthalide, di-tert-amyl peroxide, α,α′-bis(tert-butylperoxyisopropyl)benzene, 3,5-bis(tert-butylperoxy)-3,5-dimethyl-1,2-dioxolane, di-tert-butyl peroxide, 2,5-dimethylhexyne 2,5-di-tert-butyl peroxide, 3,3,6,6,9,9-hexamethyl-1,2,4,5-tetraoxacyclononane, p-menthane hydroperoxide, pinane hydroperoxide, diisopropylbenzene mono-α-hydroperoxide, cumene hydroperoxide or tert-butyl hydroperoxide.  
   
   
       8 . A method according to  claim 1  where the initiator is an azo compound which is 2,2′-azobisisobutyronitrile, 2,2′-azobis(2-methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis(1-cyclohexanecarbonitrile), 2,2′-azobis(isobutyramide)dihydrate, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile, dimethyl 2,2′-azobisisobutyrate, 2-(carbamoylazo)isobutyronitrile, 2,2′-azobis(2,4,4-trimethylpentane), 2,2′-azobis(2-methylpropane), 2,2′-azobis(N,N′-dimethyleneisobutyramidine) as free base or hydrochloride, 2,2′-azobis(2-amidinopropane) as free base or hydrochloride, 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)ethyl]propionamide} or 2,2′-azobis{2-methyl-N-[1,1-bis(hydroxymethyl)-2-hydroxyethyl]propionamide}.  
   
   
       9 . A method according to  claim 1  where the initiator is a stable nitroxyl compound which is of the formula  
     
       
         
         
             
             
         
       
       or which contains one or more groups of the formula  
       
         
           
           
               
               
           
         
       
       where each R is methyl or ethyl and T is a group required to complete a 5- or 6-membered ring.  
     
   
   
       10 . A method according to  claim 1  where the initiator is a stable nitroxyl compound which is bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, 4-hydroxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-ethoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-propoxy-1-oxyl-2,2,6,6-tetramethylpiperidine, 4-acetamido-1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidine, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-one, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl acetate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 2-ethylhexanoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl stearate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl benzoate, 1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl 4-t-butyl-benzoate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)n-butylmalonate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)phthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)isophthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)terephthalate, bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)hexahydroterephthalate, N,N′-bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)adipamide, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)caprolactam, N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)dodecylsuccinimide, 2,4,6-tris-[N-butyl-N-(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl)]-s-triazine, 4,4′-ethylenebis(1-oxyl-2,2,6,6-tetramethylpiperazin-3-one), 2-oxyl-1,1,3,3-tetramethyl-2-isobenzazole, 1-oxyl-2,2,5,5-tetramethylpyrrolidine or N,N-bis-(1,1,3,3-tetramethylbutyl)nitroxide.  
   
   
       11 . A method according to  claim 1  where the initiator is a sterically hindered NO-acyl compound that contains one or more of the moieties of the formula  
     
       
         
         
             
             
         
       
     
   
   
       12 . A method according to  claim 1  where the initiator is a sterically hindered alkoxyamine compound contains one or more moieties of the formula  
     
       
         
         
             
             
         
       
       where R is C 1 -C 20 alkyl, OH-substituted C 1 -C 20 alkyl or C 5 -C 12 cycloalkyl.  
     
   
   
       13 . A method according to  claim 1  where the chain transfer agent and the initiator are present from about 10 ppm to about 2000 ppm by weight, based on the weight of the polypropylene polymer, propylene copolymer or polypropylene polymer blend.  
   
   
       14 . A method according to  claim 1  where the weight:weight ratio of initiator to chain transfer agent is between about 1:10 to about 10:1.  
   
   
       15 . A method according to  claim 1  where the heating takes place in an extruder.  
   
   
       16 . A method according to  claim 1  where the heating takes place between about 160° C. and about 280° C.  
   
   
       17 . A polymer composition comprising 
 a polypropylene polymer, a polypropylene copolymer or a polypropylene blend,    a chain transfer agent and    an initiator,    wherein the chain transfer agent has a Cs value of greater than or equal to about 0.04 as measured in ethylene polymerization at 130° C.