Polyester based cobalt concentrates for oxygen scavenging compositions

Abstract

A solid concentrate is provided having a combination of a transition metal present in an amount ranging from 1,000 to 40,000 ppm (weight by metal) and a polyester polymer present in an amount of at least 40 wt. % based on the weight of the concentrate. Concentrates made with highly modified polyester polymers are easy to compound with transition metals forming less brittle polymer upon melt extrusion. Bottle preforms and oxygen scavenging bottles can be made from these concentrates by combining solid polyester particles, solid polyamide particles, and solid these concentrate particles c into an melt processing zone, forming a melt, and forming an article directly from the melt. The b* color and the L* color and the haze levels of the preforms are improved over the preforms made with liquid carriers instead of solid concentrates. The particles are also advantageously simultaneously dried in a drying zone under conditions effective to at least partially remove moisture from the blend to thereby further improve the b* color and L* color.

1 . A process for the manufacture of a preform comprising: 
 combining 
 (i) solid polyester particles comprising a polyester polymer;  
 (ii) solid polyamide particles comprising a polyamide polymer; and  
 (iii) solid concentrate particles comprising: 
 (A) a transition metal provided in an oxidation state other than zero and in an amount of 1,000 ppm to 40,000 ppm (by metal), based upon the weight of the concentrate: and  
 (B) polyester polymers in an amount of at least 40 wt. %, based on the weight of the concentrate, wherein at least a portion of the polyester polymers comprise highly modified polyester polymers containing 
 (a) polycarboxylic acid modifier residues in an amount ranging from 20 mole % to 60 mole %; and/or  
 (b) hydroxyl modifier residues in an amount ranging from 20 mole % to 60 mole %  
 
 
 based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer  
   into a melt processing zone, forming a melt, and forming a preform directly from the melt.    
   
   
       2 . The process of  claim 1 , wherein the transition metal content ranges from 1,000 ppm to 20,000 ppm.  
   
   
       3 . The process of  claim 2 , wherein the transition metal content ranges from 2,000 ppm to 10,000 ppm.  
   
   
       4 . The process of  claim 3 , wherein the transition metal content ranges from 3,000 ppm to 8,000 ppm.  
   
   
       5 . The process of  claim 1 , wherein the transition metal comprises cobalt, copper, rhodium, platinum, rhenium, ruthenium, palladium, tungsten, osmium, cadmium, silver, tantalum, hafnium, vanadium, titanium, chromium, nickel, zinc, or manganese.  
   
   
       6 . The process of  claim 1 , wherein the transition metal is provided as a compound comprising a carboxylate, oxide, borate, carbonate, chloride, sioxide, hydroxide, nitrate, phosphate, sulfate, silicate, or mixtures thereof.  
   
   
       7 . The process of  claim 6 , wherein the carboxylate comprises neodecanoates, octanoates, acetates, lactates, naphthalates, malates, stearates, acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, or ethylene glycolates.  
   
   
       8 . The process of  claim 5 , wherein the transition metal comprises cobalt.  
   
   
       9 . The process of  claim 8 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       10 . The process of  claim 9  wherein the transition metal is present in an amount ranging from 2,000 ppm to 8,000 ppm (by metal) based on the weight of the concentrate.  
   
   
       11 . The process of  claim 1 , wherein the portion of highly modified polyester polymers is at least 75 wt. % based on the total weight of all polyester polymers present in the concentrate.  
   
   
       12 . The process of  claim 1 , wherein the polyester polymer contained in the polyester particles and/or the highly modified polyester polymers contained in the concentrate particles comprise repeating units of terephthalic acid residues, isophthalic acid residues, naphthalienic acid residues, or mixtures thereof.  
   
   
       13 . The process of  claim 1 , wherein said highly modified polyester polymers are obtained by copolymerizing polycarboxylic acid compounds with a hydroxyl compound and a hydroxyl modifier, such that the polymer contains hydroxyl modifier residues in an amount of at least 25 mole %, based on the moles of hydroxyl compound residues present in the polymer.  
   
   
       14 . The process of  claim 13 , wherein the amount of hydroxyl modifier residues ranges from 30 mole % to 60 mole %, based on all hydroxyl residues present in the polymer.  
   
   
       15 . The process of  claim 1 , wherein the polyester polymer contained in the polyester particles comprises: 
 (i) a polycarboxylic acid component comprising at least 92 mole % residues of terephthalic acid, derivates of terephthalic acid, or mixtures thereof, and    (ii) a hydroxyl component comprising at least 40 mole % residues of ethylene glycol; and/or    the highly modified polyester polymer contained in the concentrate particles comprises:    (i) a polycarboxylic acid component comprising at least 92 mole % residues of terephthalic acid or derivates of terephthalic acid or mixtures thereof, and    (ii) a hydroxyl component comprising at least 40 mole % residues of ethylene glycol and at least 25 mole % and up to 60 mole % residues of a hydroxyl modifier;    each based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer.    
   
   
       16 . The process of  claim 1 , wherein the hydroxyl modifier residue comprises a residue of butanediol, 1,4-cyclohexane dimethanol, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, trimethylene glycol, neopentyl glycol, or diethylene glycol or combinations thereof.  
   
   
       17 . The process of  claim 16 , wherein the hydroxyl modifier residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       18 . The process of  claim 1 , wherein the concentrate is essentially free of a polyamide polymer.  
   
   
       19 . The process of  claim 1 , wherein the It.V. of the polyester polymer contained in the polyester particles and/or the It.V. of the highly modified polyester polymer provided to make the concentrate is from 0.60 dL/g to 1.15 dL/g and is obtained without solid state polymerization.  
   
   
       20 . The process of  claim 19 , wherein the It.V. of the polyester polymer contained in the polyester particles and/or the It.V. of the highly modified polyester polymer provided to make the concentrate is at least 0.70 dL/g.  
   
   
       21 . The process of  claim 1 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       22 . The process of  claim 21 , wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       23 . The process of  claim 1 , wherein the polyester polymer contained in the polyester particles and/or the highly modified polyester polymer contained in the concentrate is semicrystalline.  
   
   
       24 . The process of  claim 1 , wherein the polyester polymer contained in the polyester particles and/or the highly modified polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       25 . The process of  claim 1 , wherein the transition metal is added into a melt phase process for making the highly modified polyester polymer.  
   
   
       26 . The process of  claim 1 , wherein the concentrate is obtained by melt compounding the highly modified polyester polymer with the transition metal.  
   
   
       27 . The process of  claim 1 , wherein the preform comprises a bottle preform having a composition comprising from 1 to 10 wt. % of an oxidizable polymer or an oxygen scavenging polymer, 30 to 300 ppm cobalt, and polyester polymer present in an amount of at least 90 wt. %, each based on the weight of the preform.  
   
   
       28 . The process of  claim 27 , wherein the preform comprises a bottle preform having a composition comprising from 50 to 200 ppm cobalt.  
   
   
       29 . The process of  claim 27 , wherein the preform comprises a bottle preform having a composition comprising from 1 to 5 wt. % of an oxidizable polymer or an oxygen scavenging polymer.  
   
   
       30 . The process of  claim 29 , wherein the preform comprises a bottle preform having a composition comprising from 50 to 200 ppm cobalt.  
   
   
       31 . The process of  claim 1 , wherein the let down ratio of the transition metal concentration in the concentrate to the transition metal concentration in the preform composition ranges from 30:1 to 200:1.  
   
   
       32 . The process of  claim 31 , wherein the let down ratio of the transition metal concentration in the concentrate to the transition metal concentration in the preform composition ranges from 30:1 to 100:1.  
   
   
       33 . The process of  claim 1 , wherein the preform comprises the transition metal present in an amount ranging from 30 ppm to 500 ppm based on the weight of the preform.  
   
   
       34 . The process of  claim 33 , wherein the preform comprises the transition metal present in an amount ranging from 50 ppm to 300 ppm based on the weight of the preform.  
   
   
       35 . The process of  claim 1 , wherein the preform further comprises zinc.  
   
   
       36 . The process of  claim 35 , wherein the zinc is present in the range of from 50 ppm to 300 ppm.  
   
   
       37 . The process of  claim 36 , wherein the zinc is present in the range of from 50 ppm to 150 ppm.  
   
   
       38 . The process of  claim 1 , wherein the oxidizable polymer comprises a polyamide polymer having repeating units with a benzylic hydrogen atom.  
   
   
       39 . The process of  claim 38 , wherein the polyamide polymer is obtained from a reactant containing a xylylene moiety.  
   
   
       40 . The process of  claim 1 , wherein the polyamide polymer has a number average molecular weight Mn of 1,000 to 45,000.  
   
   
       41 . The process of  claim 40 , wherein the polyamide polymer has a number average molecular weight Mn of at least 3,500.  
   
   
       42 . The process of  claim 41 , wherein the polyamide polymer has a number average molecular weight Mn of less than 15,000.  
   
   
       43 . The process of  claim 1 , wherein the polyester polymer particles, the concentrate particles, and the polyamide polymer particles are combined into the melt processing zone as individual streams, as particle/particle dry blends, or as combinations thereof.  
   
   
       44 . The process of  claim 1 , further comprising combining an additive comprising a colorant, acetaldehyde scavenger, reheat agent, UV absorber or inhibitor, stabilizer, thermal stabilizer, or mixtures thereof.  
   
   
       45 . The process of  claim 1 , wherein the concentrate contains a higher concentration of the transition metal than present in the preform.  
   
   
       46 . The process of  claim 1 , wherein neither the solid polyester polymer particles nor the polyester polymer used to prepare the concentrate are solid stated.  
   
   
       47 . The process of  claim 1 , further comprising forming a bottle from the preform, wherein the preform comprises 150 ppm or less of cobalt based upon the weight of the preform, and wherein the bottle has a sidewall haze of 4.0% or less.  
   
   
       48 . The process of  claim 47 , wherein the bottle has a sidewall haze of 3.5% or less.  
   
   
       49 . A process for the manufacture of a preform comprising: 
 combining 
 (i) solid polyester particles comprising a polyester polymer comprising;  
 (a) polycarboxylic acid component residues comprising at least 80 mole % residues of terephthalic acid, or derivates of terephthalic acid, or mixtures thereof;  
 (b) hydroxyl component residues comprising at least 40 mole % ethylene glycol;  
   based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer;    (ii) solid polyamide particles comprising a polyamide polymer; and    (iii) solid concentrate particles comprising: 
 (A) a transition metal provided in an oxidation state other than zero and in an amount of 1,000 ppm to 40,000 ppm, based upon the weight of the concentrate: and  
 (B) polyester polymers in an amount of at least 80 wt. %, based on the weight of the concentrate, wherein at least 50 wt % of the polyester polymers comprise highly modified polyester polymers containing 
 (a) polycarboxylic acid component residues comprising at least 80 mole % residues of terephthalic acid, or derivates of terephthalic acid, or mixtures thereof;  
 (b) hydroxyl component residues comprising at least 40 mole % ethylene glycol, with at least 20 mole % to 60 mole % of residues of a hydroxyl modifier  
 
 based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer; and 
 (C) wherein the concentrate is free of polyamide polymer;  
 
   into a melt processing zone, forming a melt, and forming a preform directly from the melt.    
   
   
       50 . The process of  claim 49 , wherein the transition metal content ranges from 1,000 ppm to 20,000 ppm.  
   
   
       51 . The process of  claim 50 , wherein the transition metal content ranges from 2,000 ppm to 10,000 ppm.  
   
   
       52 . The process of  claim 51 , wherein the transition metal comprises cobalt, copper, rhodium, platinum, rhenium, ruthenium, palladium, tungsten, osmium, cadmium, silver, tantalum, hafnium, vanadium, titanium, chromium, nickel, zinc, or manganese.  
   
   
       53 . The process of  claim 49 , wherein the transition metal is provided as a compound comprising a carboxylate, oxide, borate, carbonate, chloride, sioxide, hydroxide, nitrate, phosphate, sulfate, silicate, or mixtures thereof.  
   
   
       54 . The process of  claim 53 , wherein the carboxylate comprises neodecanoates, octanoates, acetates, lactates, naphthalates, malates, stearates, acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, or ethylene glycolates.  
   
   
       55 . The process of  claim 52 , wherein the transition metal comprises cobalt.  
   
   
       56 . The process of  claim 55 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       57 . The process of  claim 49 , wherein the portion of highly modified polyester polymers is at least 75 wt. % based on the total weight of all polyester polymers present in the concentrate.  
   
   
       58 . The process of  claim 49 , wherein the highly modified polyester polymers are obtained by copolymerizing polycarboxylic acid compounds with a hydroxyl compound and a hydroxyl modifier, such that the polymer contains hydroxyl modifier residues in an amount of at least 25 mole %, based on the moles of hydroxyl compound residues present in the polymer.  
   
   
       59 . The process of  claim 58 , wherein the amount of hydroxyl modifier residues ranges from 30 mole % to 60 mole %, based on all hydroxyl residues present in the polymer.  
   
   
       60 . The process of  claim 49 , wherein the hydroxyl modifier residue comprises a residue of butanediol, 1,4-cyclohexane dimethanol, 2,4-dihydroxy-1,1,3,3-tetramethyl-cyclobutane, trimethylene glycol, neopentyl glycol, or diethylene glycol or combinations thereof.  
   
   
       61 . The process of  claim 60 , wherein the hydroxyl modifier residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       62 . The process of  claim 49 , wherein the It.V. of the polyester polymer contained in the polyester particles and/or the It.V. of the highly modified polyester polymer provided to make the concentrate is from 0.60 dL/g to 1.15 dL/g and is obtained without solid state polymerization.  
   
   
       63 . The process of  claim 62 , wherein the It.V. of the polyester polymer contained in the polyester particles and/or the It.V. of the highly modified polyester polymer provided to make the concentrate is at least 0.70 dL/g.  
   
   
       64 . The process of  claim 49 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       65 . The process of  claim 64 , wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       66 . The process of  claim 49 , wherein the polyester polymer contained in the polyester particles and/or the highly modified polyester polymer contained in the concentrate is semicrystalline.  
   
   
       67 . The process of  claim 49 , wherein the polyester polymer contained in the polyester particles and/or the highly modified polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       68 . The process of  claim 49 , wherein the transition metal is added into a melt phase process for making the highly modified polyester polymer.  
   
   
       69 . The process of  claim 49 , wherein the concentrate is obtained by melt compounding the highly modified polyester polymer with the transition metal.  
   
   
       70 . The process of  claim 49 , wherein the preform comprises a bottle preform having a composition comprising from 1 to 10 wt. % of an oxidizable polymer or an oxygen scavenging polymer, 30 to 300 ppm cobalt, and polyester polymer present in an amount of at least 90 wt. %, each based on the weight of the preform.  
   
   
       71 . The process of  claim 70 , wherein the preform comprises a bottle preform having a composition comprising from 50 to 200 ppm cobalt.  
   
   
       72 . The process of  claim 70 , wherein the preform comprises a bottle preform having a composition comprising from 1 to 5 wt. % of an oxidizable polymer or an oxygen scavenging polymer.  
   
   
       73 . The process of  claim 72 , wherein the preform comprises a bottle preform having a composition comprising from 50 to 200 ppm cobalt.  
   
   
       74 . The process of  claim 49 , wherein the let down ratio of the transition metal concentration in the concentrate to the transition metal concentration in the preform composition ranges from 30:1 to 200:1.  
   
   
       75 . The process of  claim 74 , wherein the let down ratio of the transition metal concentration in the concentrate to the transition metal concentration in the preform composition ranges from 30:1 to 100:1.  
   
   
       76 . The process of  claim 49 , wherein the preform comprises the transition metal present in an amount ranging from 30 ppm to 500 ppm based on the weight of the preform.  
   
   
       77 . The process of  claim 76 , wherein the preform comprises the transition metal present in an amount ranging from 50 ppm to 300 ppm based on the weight of the preform.  
   
   
       78 . The process of  claim 49 , wherein the preform further comprises zinc.  
   
   
       79 . The process of  claim 78 , wherein the zinc is present in the range of 50 ppm to 300 ppm.  
   
   
       80 . The process of  claim 79 , wherein the zinc is present in the range of 50 ppm to 150 ppm.  
   
   
       81 . The process of  claim 49 , wherein the oxidizable polymer comprises a polyamide polymer having repeating units with a benzylic hydrogen atom.  
   
   
       82 . The process of  claim 81 , wherein the polyamide polymer is obtained from a reactant containing a xylylene moiety.  
   
   
       83 . The process of  claim 49 , wherein the polyamide polymer has a number average molecular weight Mn of 1,000 to 45,000.  
   
   
       84 . The process of  claim 83 , wherein the polyamide polymer has a number average molecular weight Mn of at least 3,500.  
   
   
       85 . The process of  claim 84 , wherein the polyamide polymer has a number average molecular weight Mn of less than 15,000.  
   
   
       86 . The process of  claim 49 , wherein the polyester polymer particles, the concentrate particles, and the polyamide polymer particles are combined into the melt processing zone as individual streams, as particle/particle dry blends, or as combinations thereof.  
   
   
       87 . The process of  claim 49 , further comprising combining an additive comprising a colorant, acetaldehyde scavenger, reheat agent, UV absorber or inhibitor, stabilizer, thermal stabilizer, or mixtures thereof.  
   
   
       88 . The process of  claim 49 , wherein the concentrate contains a higher concentration of the transition metal than present in the preform.  
   
   
       89 . The process of  claim 49 , wherein the transition metal comprises cobalt neodecanoate or cobalt acetate present in an amount ranging from 2,000 ppm to 8,000 ppm (by metal) based on the weight of the concentrate.  
   
   
       90 . The process of  claim 49 , further comprising forming a bottle from the preform, wherein the preform comprises 150 ppm or less of cobalt based upon the weight of the preform, and wherein the bottle has a sidewall haze of 4.0% or less.  
   
   
       91 . The process of  claim 90 , wherein the bottle has a sidewall haze of 3.5% or less.  
   
   
       92 . A process for the manufacture of a preform comprising: 
 combining 
 (i) solid polyester particles comprising a polyester polymer comprising; 
 (a) polycarboxylic acid component residues comprising at least 92 mole % residues of terephthalic acid, or derivates of terephthalic acid, or mixtures thereof;  
 (b) hydroxyl component residues comprising at least 40 mole % ethylene glycol,  
 
 based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer; and  
 (ii) solid polyamide particles comprising a polyamide polymer; and  
 (iii) solid concentrate polymer comprising: 
 (A) a transition metal provided in an oxidation state other than zero and in an amount of 1,000 ppm to 20,000 ppm, based upon the weight of the concentrate: and  
 (B) highly modified polyester polymers in an amount of at least 80 wt. %, based on the weight of the concentrate, comprising: 
 (a) polycarboxylic acid component residues comprising at least 92 mole % residues of terephthalic acid, or derivates of terephthalic acid, or mixtures thereof;  
 (b) hydroxyl component residues comprising at least 40 mole % ethylene glycol, with at least 20 mole % to 60 mole % of residues of 1,4-cyclohexane dimethanol, diethylene glycol, or mixtures thereof  
 
 
 based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer; and 
 (C) wherein the concentrate is free of polyamide polymer;  
 
   into a melt processing zone, forming a melt, and forming a preform directly from the melt.