Oxygen scavenging polymers in rigid polyethylene terephthalate beverage and food containers

Abstract

Multilayer plastic containers for food and beverage packaging which incorporate oxygen scavenging resins which selectively oxidize upon activation without giving off odorous fragments.

What is claimed is:  
     
         1 . A non-odorous oxygen scavenging polymer composition comprising: (1) monomers derived from cyclic hydrocarbon moieties having at least one cyclic allylic or cyclic benzylic hydrogen and (2) a transition metal oxidation catalyst.  
     
     
         2 . The composition of  claim 1 , wherein the composition comprises condensation polymers selected from the group consisting of polyesters, polyamides, polycarbonate, polyurethane, polyureas and polyether.  
     
     
         3 . The composition of  claim 1 , wherein the cyclic allylic monomers are selected from the group consisting of structure (I), structure (II) and structure (III):  
       
         
           
           
               
               
           
         
         with K, L, T 1 , T 2 , T 3 , and 14 being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and wherein, when either K or L is —H, at least one of T 1 , T 2 , T 3  and T 4  is —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12 and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Q being selected from the group consisting of —(C t H 2t−2 ) with t being an integer in the range from 1 to 4;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         4 . The composition of  claim 1 , wherein the cyclic benzylic monomers are selected from the group consisting of structure (IV), structure (V), structure (VI), structure (VII), structure (VIII), and structure (IX)  
       
         
           
           
               
               
           
         
         where X and Y are selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2  and —(CH 2 ) m —(C═O)—R, with n being an integer in the range from 1 to 12, and with m being an integer in the range from 0 to 12 and with R 1  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         with T 1 , T 2 , T 3 , and T 4  being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and at least one of T 1 , T 2 , T 3  and T 4  being —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O, and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12, and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Z being selected from the group consisting of —(C t H 2t−2 )—, —O—, —NR 2 —, —S—, with t being an integer in the range from 1 to 4 and R 2  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         5 . The composition of  claim 2 , the composition being thermoplastic.  
     
     
         6 . The composition of  claim 2 , the composition being thermoset.  
     
     
         7 . The composition of  claim 2 , the composition being a multilayered structure with other layers being an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexanedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         8 . The composition of  claim 2 , the composition being a multilayered structure with other layers being polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         9 . The composition of  claim 2 , the composition being a multilayered structure with other layers being bisphenol A carbonate.  
     
     
         10 . The composition of  claim 2 , the composition being a multilayered structure with other layers being vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         11 . The composition of  claim 2 , the composition being blended with an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexandedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         12 . The composition of  claim 2 , the composition being blended with polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         13 . The composition of  claim 2 , the composition being blended with bisphenol A polycarbonate.  
     
     
         14 . The composition of  claim 2 , the composition being a blend comprising vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         15 . The composition of  claim 2 , the composition being laminated or adhering onto a substrate selected from the group consisting of paper, foil, high temperature film, metallized film, polyamide films, ethylene vinyl alcohol film, silica coated film, nylon/EVOH/nylon, oriented polypropylene, polyester film, polyethylene, polypropylene, polyester, oriented polyethylene terephthalate and cellophane.  
     
     
         16 . The composition of  claim 1 , wherein the composition comprises a vinyl polymer selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer and mixtures thereof.  
     
     
         17 . A rigid container for food or beverage, the container being molded from a resin comprising a non-odorous oxygen scavenging polymer composition, the composition comprising (1) monomers derived from cyclic hydrocarbon moieties having at least one cyclic allylic or cyclic benzylic hydrogen and (2) a transition metal oxidation catalyst.  
     
     
         18 . The rigid container of  claim 17 , wherein the composition comprises condensation polymers selected from the group consisting of polyesters, polyamides, polycarbonate, polyurethane, polyureas, polysulfones and polyether.  
     
     
         19 . The rigid container of  claim 17 , wherein the cyclic allylic monomers are selected from the group consisting of structure (I), structure (II) and structure (III):  
       
         
           
           
               
               
           
         
         with K, L, T 1 , T 2 , T 3 , and T 4  being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and wherein, when either K or L is —H, at least one of T 1 , T 2 , T 3  and T 4  is —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12 and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Q being selected from the group consisting of —(C t H 2t−2 ) with t being an integer in the range from 1 to 4;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         20 . The rigid container of  claim 17 , wherein the cyclic benzylic monomers are selected from the group consisting of structure (IV), structure (V), structure (VI), structure (VII), structure (VIII), and structure (IX)  
       
         
           
           
               
               
           
         
         where X and Y are selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2  and —(CH 2 ) m —(C═O)—R, with n being an integer in the range from 1 to 12 and with m being an integer in the range from 0 to 12 and with R 1  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         with T 1 , T 2 , T 3 , and T 4  being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and at least one of T 1 , T 2 , T 3  and T 4  being —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12 and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Z being selected from the group consisting of —(C t H 2t−2 )—, —O—, —NR 2 —, —S—, with t being an integer in the range from 1 to 4 and R 2  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         21 . The rigid container of  claim 18 , the composition being thermoplastic.  
     
     
         22 . The rigid container of  claim 18 , the composition being thermoset.  
     
     
         23 . The rigid container of  claim 18 , the composition being made by coextrusion, blow molding or lamination with an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexanedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         24 . The rigid container of  claim 18 , the composition being made by coextrusion, blow molding or lamination with polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         25 . The rigid container of  claim 18 , the composition being made by coextrusion, blow molding or lamination with bisphenol A polycarbonate.  
     
     
         26 . The rigid container of  claim 18 , the composition being made by coextrusion, blow molding or lamination with vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         27 . The rigid container of  claim 18 , the composition being blended with an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexandedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         28 . The rigid container of  claim 18 , the composition being blended with polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         29 . The rigid container of  claim 18 , the composition being blended with bisphenol A carbonate.  
     
     
         30 . The rigid container of  claim 18 , the composition being blended with vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         31 . The rigid container of  claim 18 , the composition being laminated or adhering onto a substrate selected from the group consisting of paper, foil, high temperature film, metallized film, polyamide films, ethylene vinyl alcohol film, silica coated film, nylon/EVOH/nylon, oriented polypropylene, polyester film, oriented polyethylene terephthalate, polypropylene, polyester, and cellophane.  
     
     
         32 . The rigid container of  claim 18 , wherein the composition comprises a vinyl polymer selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer and mixtures thereof.  
     
     
         33 . The rigid container according to  claim 17 , wherein the composition is a single layer.  
     
     
         34 . The rigid container according to  claim 17 , wherein the composition is multilayered.  
     
     
         35 . The rigid container according to  claim 34 , wherein the composition comprises an outer air contact layer and an inner oxygen scavenging layer.  
     
     
         36 . The rigid container according to  claim 35 , wherein the outer air contact layer comprises an oxygen barrier resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate and a mixture of polyethylene terephthalate and polyethylene naphthalate.  
     
     
         37 . The rigid container according to  claim 35 , wherein the composition further comprises at least one of an inner food contact layer, a tie layer, and a tinted ultraviolet protection layer.  
     
     
         38 . The rigid container according to  claim 37 , wherein the inner food contact layer comprises an oxygen barrier resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate and a mixture of polyethylene terephthalate and polyethylene naphthalate.  
     
     
         39 . The rigid container of  claim 17 , wherein oxygen scavenging by the non-odorous oxygen scavenging polymer composition is initiated by moisture or actinic radiation.  
     
     
         40 . The rigid container of  claim 17 , wherein the transition metal catalyst is a metal salt.  
     
     
         41 . The rigid container of  claim 40 , wherein the metal in the metal salt is cobalt.  
     
     
         42 . The rigid container of  claim 41 , wherein the metal salt is selected from the group consisting of cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt oleate and cobalt stearate.  
     
     
         43 . The rigid container of  claim 17 , wherein the non-odorous oxygen scavenging composition further comprises at least one triggering material to enhance initiation of oxygen scavenging.  
     
     
         44 . The rigid container of  claim 43 , wherein the triggering material is a photoinitiator.  
     
     
         45 . The rigid container of  claim 44 , wherein the photoinitiator has an ultraviolet absorption window above 320 nm.  
     
     
         46 . The rigid container of  claim 44 , wherein the container further comprises a tinted ultraviolet protection layer located between the layer comprising the non-odorous oxygen scavenging composition and the inside of the rigid container.  
     
     
         47 . The rigid container of  claim 46 , wherein the tinted layer is the food contact layer.  
     
     
         48 . The rigid container of  claim 46 , wherein the resin comprises condensation polymers selected from the group consisting of polyesters, polyamides, polyurethane, polyureas, polysulfones, polycarbonates and polyether.  
     
     
         49 . The rigid container of  claim 46 , wherein the cyclic allylic monomers are selected from the group consisting of structure (I), structure (II) and structure (III):  
       
         
           
           
               
               
           
         
         with K, L, T 1 , T 2 , T 3 , and T 4  being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and wherein, when either K or L is —H, at least one of T 1 , T 2 , T 3  and T 4  is —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12 and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Q being selected from the group consisting of —(C t H 2t−2 ) with t being an integer in the range from 1 to 4;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         50 . The rigid container of  claim 46 , wherein the cyclic benzylic monomers are selected from the group consisting of structure (IV), structure (V), structure (VI), structure (VII), structure (VIII), and structure (IX):  
       
         
           
           
               
               
           
         
         where X and Y are selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2  and —(CH 2 ) m —(C═O)—R, with n being an integer in the range from 1 to 12 and with m being an integer in the range from 0 to 12 and with R 1  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         with T 1 , T 2 , T 3 , and T 4  being selected from the group consisting of —C q H 2q+1  with q being an integer in the range from 0 to 12 and at least one of T 1 , T 2 , T 3  and T 4  being —H;  
         and with X and Y being selected from the group consisting of —(CH 2 ) n —OH, —(CH 2 ) n —NH 2 , —(CH 2 ) n NC═O and —(CH 2 ) m —(C═O)-A with n being an integer in the range from 1 to 12 and m being an integer in the range from 0 to 12 and A being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides; and Z being selected from the group consisting of —(C t H 2t−2 )—, —O—, —NR 2 —, —S—, with t being an integer in the range from 1 to 4 and R 2  being selected from the group consisting of —OH, —OCH 3 , —OC 2 H 5 , —OC 3 H 7  and halides;  
         and with G being selected from —(C═O)— and —(C n H 2n+1 )— with n being an integer from 0 to 12.  
       
     
     
         51 . The rigid container of  claim 48 , the composition being thermoplastic.  
     
     
         52 . The rigid container of  claim 48 , the composition being thermoset.  
     
     
         53 . The rigid container of  claim 48 , the composition being in a multilayer structure with other layers, at least one of the other layers comprising an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexanedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         54 . The rigid container of  claim 48 , the composition being in a multilayer structure with other layers, at least one of the other layers comprising polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         55 . The rigid container of  claim 48 , the composition being in a multilayer structure with other layers, at least one of the other layers comprising bisphenol A carbonate.  
     
     
         56 . The rigid container of  claim 48 , the composition being in a multilayer structure with other layers, at least one of the other layers comprising vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         57 . The rigid container of  claim 48 , the composition being blended with an aromatic polyester or copolyester selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene isophthalate, polycyclohexandedimethanol terephthalate, polybutylene naphthalate, polycyclohexanedimethanol naphthalate, and copolymers and blends thereof.  
     
     
         58 . The rigid container of  claim 48 , the composition being blended with polyamides or copolyamides selected from the group consisting of Nylon 6, Nylon 66, Nylon 610 and mixtures thereof.  
     
     
         59 . The rigid container of  claim 48 , the composition being blended with bisphenol A carbonate.  
     
     
         60 . The rigid container of  claim 48 , the composition being blended with vinylic polymers or copolymers selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer, acrylate polymer, acrylate copolymer, vinyl chloride polymer, vinyl chloride copolymer, divinyl chloride polymer, divinyl chloride copolymer, fluorinated vinyl polymer, fluorinated vinyl copolymer and mixtures thereof.  
     
     
         61 . The rigid container of  claim 48 , the composition being laminated or adhering onto a substrate selected from the group consisting of paper, foil, high temperature film, metallized film, polyamide films, ethylene vinyl alcohol film, silica coated film, nylon/EVOH/nylon, oriented polypropylene, polyester film, polyethylene, polypropylene, oriented polyethylene terephthalate, and cellophane.  
     
     
         62 . The rigid container of  claim 48 , wherein the composition comprises a vinyl polymer selected from the group consisting of ethylene polymer, ethylene copolymer, propylene polymer, propylene copolymer, styrene polymer, styrene copolymer and mixtures thereof.  
     
     
         63 . The rigid container according to  claim 48 , wherein the composition comprises an outer air contact layer and an inner oxygen scavenging layer.  
     
     
         64 . The rigid container according to  claim 63 , wherein the outer air contact layer comprises an oxygen barrier resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate and a mixture of polyethylene terephthalate and polyethylene naphthalate.  
     
     
         65 . The rigid container according to  claim 48 , wherein the composition further comprises at least one of an inner food contact layer, a tie layer, and a tinted ultraviolet protection layer.  
     
     
         66 . The rigid container according to  claim 65 , wherein the inner food contact layer comprises an oxygen barrier resin selected from the group consisting of polyethylene terephthalate, polyethylene naphthalate and a mixture of polyethylene terephthalate and polyethylene naphthalate.  
     
     
         67 . The rigid container of  claim 48 , wherein the transition metal catalyst is a metal salt.  
     
     
         68 . The rigid container of  claim 67 , wherein the metal in the metal salt is cobalt.  
     
     
         69 . The rigid container of  claim 68 , wherein the metal salt is selected from the group consisting of cobalt neodecanoate, cobalt 2-ethylhexanoate, cobalt oleate and cobalt stearate.  
     
     
         70 . The rigid container of  claim 69 , wherein the triggering material is a photoinitiator.  
     
     
         71 . The rigid container of claim  70 , wherein the photoinitiator has an ultraviolet absorption window above 320 nm.  
     
     
         72 . The rigid container of  claim 17 , wherein the rigid container is suitable for packaging oxygen sensitive drinks for extended freshness and shelf life.  
     
     
         73 . The rigid container of claim  72 , wherein the oxygen sensitive drink is beer.