Gas barrier enhancing additives and methods

Abstract

Polyesters compositions comprising gas barrier enhancing additives and containers comprising such polyester compositions are provided herein. Also provided are methods for preparing polyester containers comprising said gas barrier enhancing additives. The polyester containers of the present invention exhibit decreased permeability to gases thereby providing improved shelf-life.

1 . A polyester container having enhanced gas barrier properties comprising a polyester composition comprising a polyester and a gas barrier enhancing additive, wherein the gas barrier enhancing additive is a compound having the chemical structure of Formula I: 
       
         
           
           
               
               
           
         
         wherein i, ii, iii, iv, v, n, n′, n″, n′″, and m are 0 or 1; 
         wherein p is an integer from 0 to 50; 
         wherein Z is a carbon or nitrogen atom; 
         wherein A, A′, A″, A′″, and A e  are selected from the group consisting of hydrogen, hydroxyl, primary amine, secondary amine, and unsubstituted or substituted C 1 -C 20  hydrocarbyl, wherein the C 1 -C 20  hydrocarbyl is mono-, di-, tri-, or tetravalent; 
         wherein each Y, independent of one another, comprises a compound having the chemical structure of Formula II: 
       
       
         
           
           
               
               
           
         
         wherein t, t 1 , x, x 1 , x 2 , y, and z, independent of one another, are a single bond or a double bond; wherein t′, x′, y′, and z′, independent of one another, are 0 or 1; wherein x″, y″, and w′, independent of one another, are 0, 1 or 2; 
         wherein when one or more of ii, iii, iv, and v are 1, A, A′ (or A e ), A″, and A′″, respectively and independent of one other, is singly or doubly bonded to atom a, c, or f in structure Y, or singly bonded to atom b, d, e, or g in structure Y; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom b in structure Y, x′ is 0, and x is a single bond; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom c in structure Y, y″ is 1 and y is a single bond, or y″ is 0 and y is a double bond; wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is doubly bonded to atom c in structure Y, y″ is 0 and y is a single bond; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom d in structure Y, y′ is 0 and y is a single bond; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom a in structure Y, x″ is 1 and both x and x 1  are single bonds, or x″ is 0 and one of x and x 1  is a double bond; wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is doubly bonded to atom a in structure Y, x″ is 0 and both x and x 1  are single bonds; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom e in structure Y, z′ is 0 and z is a single bond; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom f in structure Y, w′ is 1 and both z and t are single bonds, or w′ is 0 and one of z and t is a double bond; wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is doubly bonded to atom f in structure Y, w′ is 0 and both z and t are single bonds; 
         wherein when one or more of A, A′, A″, A′″, and A e , independent of one another, is singly bonded to atom g in structure Y, t′ is 0 and both t and t 1  are single bonds; 
         wherein when x is a double bond, x 1  is a single bond; wherein when x 1  is a double bond, x and x 2  are single bonds; wherein when x 2  is a double bond, x 1  and t 1  are single bonds; wherein when t is a double bond, t 1  and z are single bonds; wherein when z is a double bond, t is a single bond; wherein when t 1  is a double bond, t and x 2  are single bonds; wherein when x is a double bond, x′ is 0; wherein when x or x 1  is a double bond, x″ is 1 if one or more of A, A′, A″, A′″, or A e , independent of one another, is not singly bonded to atom a in structure Y; wherein when y is a double bond, y′ is 0 and y″ is 1 if one or more of A, A′, A″, A′″, or A e , independent of one another, is not singly bonded to atom c in structure Y; wherein when t or t′ is a double bond, t′ is 0; wherein when z and t are single bonds, w′ is 2 if one or more of A, A′, A″, A′″, or A e , independent of one another, is not singly bonded to atom f in structure Y; wherein when z or t is a double bond, w′ is 1 if one or more of A, A′, A″, A′″, or A e , independent of one another, is not singly bonded to atom f in structure Y; wherein when z is a double bond, z′ is 0; wherein when x, y, or z, independent of one another, is a single bond and one or more of A, A′, A″, A′″, or A e , independent of one another, is not singly bonded to atoms b, d, or e, respectively, in structure Y, x′, y′, or z′, independent of one another, is 1; 
         wherein R 1 , R 3 , R 5 , and R 7 , independent of one another, comprise a hydrogen, arylamino, alkoxy, aryloxy, alkenyl, alkynyl, or a straight, chained, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or acyl group; 
         wherein R 2 , R 4 , and R 6 , independent of one another, may be moieties attached by a single or double bond; 
         wherein when R 2 , R 4 , or R 6  is a moiety attached by a single bond, R 2 , R 4 , and R 6 , independent of one another, comprise a hydrogen, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, alkenyl, alkynyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, anhydride, oximo, hydrazino, carbamyl, phosphonic acid, phosphonato, or a straight, chained, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or acyl group; 
         wherein when R 2 , R 4 , or R 6  is a moiety attached by a double bond, R 2 , R 4 , or R 6 , independent of one another, comprise oxygen, sulfur, CR 8 R 9 , SO 2 , NR 10 ; wherein R 8  and R 9 , independent of one another, comprise a hydrogen, hydroxyl, amino, amido, alkylamino, arylamino, alkoxy, aryloxy, nitro, acyl, alkenyl, alkynyl, cyano, sulfo, sulfato, mercapto, imino, sulfonyl, sulfenyl, sulfinyl, sulfamoyl, phosphonyl, phosphinyl, phosphoryl, phosphino, thioester, thioether, anhydride, oximo, hydrazino, carbamyl, phosphonic acid, phosphonato, or a straight, chained, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or acyl group; and R 10  comprises a hydrogen, arylamino, alkoxy, aryloxy, alkenyl, alkynyl, or a straight, chained, branched, or cyclic alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or acyl group; 
         wherein when x″ is 2, both R 4  moieties may be the same or different; wherein when y″ is 2, both R 2  moieties may be the same or different; and wherein when w′ is 2, both R 6  moieties may be the same or different. 
       
     
     
         2 . The polyester container of  claim 1 , wherein the polyester is selected from the group consisting of PET, PET copolymer. PEN, polyethylene isophthalate, nylons, aliphatic polyesters and combinations thereof. 
     
     
         3 . The polyester container of  claim 2 , wherein the polyester is PET or a PET copolymer. 
     
     
         4 . The polyester container of  claim 1 , wherein the loading level of the gas barrier enhancing additive is in the range of about 0.1 to about 40 weight percent of the polyester composition. 
     
     
         5 . The polyester container of  claim 1 , wherein the gas barrier enhancing additive has a molecular weight greater than about 194 g/mole. 
     
     
         6 . The polyester container of  claim 1 , wherein the gas barrier enhancing additive is a purine derivative selected from the group consisting of purine dimmers, trimers and tetramers. 
     
     
         7 . The polyester container of  claim 1 , wherein the vapor pressure of the gas barrier enhancing additive at 260° C. is less than about 25 Pa. 
     
     
         8 . A method for forming a hollow plastic container comprising:
 (i) providing a polyester resin material;   (ii) heating the polyester resin material to provide a molten resin;   (iii) adding a gas barrier enhancing additive of Formula I to the molten resin;   (iv) introducing the molten resin into a mold;   (v) cooling the molten resin to form a preform;   (vi) removing the perform from the mold; and   (vi) blow molding the perform to form a hollow plastic container.   
     
     
         9 . A method for forming a hollow plastic container comprising:
 (i) providing a polyester resin material comprising a polyester and a gas barrier enhancing additive;   (ii) heating the polyester resin material to provide a molten resin;   (iii) introducing the molten resin into a mold;   (iv) cooling the molten resin to form a preform;   (v) removing the perform from the mold; and   (v) blow molding the perform to form a hollow plastic container.   
     
     
         10 . The method of  claims 9  or  10 , wherein the polyester is PET or a PET copolymer. 
     
     
         11 . The method of  claim 11 , wherein the container is a PET bottle. 
     
     
         12 . The polyester container of  claim 1 , wherein the polyester container comprises a plurality of layers. 
     
     
         13 . The polyester container of  claim 1 , wherein the polyester contain exhibits increased shelf-life from about 1.0× to about 2.0× relative to a standard polyester container. 
     
     
         14 . The polyester container of  claim 1 , wherein oxygen permeation is reduced greater than about 10% relative to a standard polyester container. 
     
     
         15 . The polyester container of  claim 1 , wherein carbon dioxide permeation is reduced greater than about 10% relative to a standard polyester container.