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 1000 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 polyester polymer concentrate comprising: 
 (i) 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    (ii) 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.  
   
   
   
       2 . The concentrate of  claim 1 , wherein the transition metal content ranges from 1,000 ppm to 20,000 ppm.  
   
   
       3 . The concentrate of  claim 2 , wherein the transition metal content ranges from 2,000 ppm to 10,000 ppm.  
   
   
       4 . The concentrate of  claim 3 , wherein the transition metal content ranges from 3,000 ppm to 8,000 ppm.  
   
   
       5 . The concentrate 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 concentrate 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 concentrate 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 concentrate of  claim 5 , wherein the transition metal comprises cobalt.  
   
   
       9 . The concentrate of  claim 8 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       10 . The concentrate 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.  
   
   
       11 . The concentrate of  claim 1 , wherein the polyester polymer contained in the concentrate comprises repeating units of terephthalic acid residues, isophthalic acid residues, naphthalienic acid residues, or mixtures thereof.  
   
   
       12 . The concentrate of  claim 1 , 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.  
   
   
       13 . The concentrate of  claim 12 , wherein the amount of hydroxyl modifier residues ranges from 30 mole % to 60 mole %, based on the moles of hydroxyl compound residues present in the polymer.  
   
   
       14 . The concentrate of  claim 1 , wherein the highly modified polyester polymer 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    based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer    
   
   
       15 . The concentrate 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.  
   
   
       16 . The concentrate of  claim 15 , wherein the hydroxyl modifier residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       17 . The concentrate of  claim 1 , wherein the concentrate is essentially free of a polyamide polymer.  
   
   
       18 . The concentrate of  claim 1 , wherein the It.V. of the highly modified polyester polymer ranges from 0.70 dL/g to 1.15 dL/g and is obtained without solid state polymerization.  
   
   
       19 . The concentrate of  claim 1 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       20 . The concentrate of  claim 19 , wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       21 . The concentrate of  claim 1 , wherein the polyester polymer contained in the concentrate is semicrystalline.  
   
   
       22 . The concentrate of  claim 1 , wherein the polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       23 . The concentrate of  claim 1 , wherein the transition metal is added into a melt phase process for making the polyester polymer.  
   
   
       24 . The concentrate of  claim 1 , wherein the concentrate is obtained by melt compounding a polyester polymer with the transition metal.  
   
   
       25 . A polyester polymer concentrate comprising: 
 (i) 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:    (ii) 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, derivates of terephthalic acid, or mixtures thereof; and  
 (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  
   (iii) the concentrate is free of polyamide polymer.    
   
   
       26 . The concentrate of  claim 25 , wherein the transition metal content ranges from 1,000 ppm to 20,000 ppm.  
   
   
       27 . The concentrate of  claim 26 , wherein the transition metal content ranges from 2,000 ppm to 10,000 ppm.  
   
   
       28 . The concentrate of  claim 25 , 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.  
   
   
       29 . The concentrate of  claim 25 , 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.  
   
   
       30 . The concentrate of  claim 29 , wherein the carboxylate comprises neodecanoates, octanoates, acetates, lactates, naphthalates, malates, stearates, acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, or ethylene glycolates.  
   
   
       31 . The concentrate of  claim 28  wherein the transition metal comprises cobalt.  
   
   
       32 . The concentrate of  claim 31 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       33 . The concentrate of  claim 25 , 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.  
   
   
       34 . The concentrate of  claim 25 , 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.  
   
   
       35 . The concentrate of  claim 34 , wherein the amount of hydroxyl modifier residues ranges from 30 mole % to 60 mole %, based on the moles of hydroxyl compound residues present in the polymer.  
   
   
       36 . The concentrate of  claim 25 , 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.  
   
   
       37 . The concentrate of  claim 36 , wherein the hydroxyl modifier residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       38 . The concentrate of  claim 25 , wherein the transition metal comprises cobalt in an amount from 2,000 ppm to 10,000 ppm.  
   
   
       39 . The concentrate of  claim 25 , wherein the It.V. of the highly modified polyester polymer ranges from 0.70 dL/g to 1.15 dL/g and is obtained without solid state polymerization.  
   
   
       40 . The concentrate of  claim 25 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       41 . The concentrate of  claim 40 , wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       42 . The concentrate of  claim 25 , wherein the polyester polymer contained in the concentrate is semicrystalline.  
   
   
       43 . The concentrate of  claim 25 , wherein the polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       44 . The concentrate of  claim 25 , wherein the transition metal is added into a melt phase process for making the polyester polymer.  
   
   
       45 . The concentrate of  claim 25 , wherein the concentrate is obtained by melt compounding a polyester polymer with the transition metal.  
   
   
       46 . A polyester polymer concentrate comprising: 
 (i) cobalt 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    (ii) highly modified polyester polymers in an amount of at least 80 wt. %, based on the weight of the concentrate, containing 
 (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  
   (iii) the concentrate is free of polyamide polymer.    
   
   
       47 . A solid concentrate obtained by melt compounding a transition metal having an oxidation state other than zero and in an amount ranging from 1,000 ppm to 10,000 ppm (by metal) and a polyester polymer having an It.V. of at least 0.55 dL/g in an amount of at least 40 wt. %, each based on the weight of the concentrate.  
   
   
       48 . The concentrate of  claim 47 , wherein the transition metal content ranges from 1,500 ppm to 8,000 ppm.  
   
   
       49 . The concentrate of  claim 48 , wherein the transition metal content ranges from 2,000 ppm to 6,000 ppm.  
   
   
       50 . The concentrate of  claim 47 , 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.  
   
   
       51 . The concentrate of  claim 47 , 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.  
   
   
       52 . The concentrate of  claim 51 , wherein the carboxylate comprises neodecanoates, octanoates, acetates, lactates, naphthalates, malates, stearates, acetylacetonates, linoleates, oleates, palmitates, 2-ethylhexanoates, or ethylene glycolates.  
   
   
       53 . The concentrate of  claim 50 , wherein the transition metal comprises cobalt.  
   
   
       54 . The concentrate of  claim 53 , wherein the transition metal comprises cobalt, and at least a portion of the cobalt is present in the concentrate in the +2 oxidation state.  
   
   
       55 . The concentrate of  claim 53 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       56 . The concentrate of  claim 47 , wherein the polyester polymer is at least 75 wt. % based on the total weight of the concentrate.  
   
   
       57 . The concentrate of  claim 56 , wherein the polyester polymer is at least 98 wt. %, based on the total weight of the concentrate.  
   
   
       58 . The concentrate of  claim 57 , wherein the concentrate is essentially free of polymers other than the polyester polymer.  
   
   
       59 . The concentrate of  claim 47 , wherein the polyester polymer contained in the concentrate comprises repeating units of terephthalic acid residues, isophthalic acid residues, naphthalienic acid residues, or mixtures thereof.  
   
   
       60 . The concentrate of  claim 47 , wherein the polyester polymer 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.    based on 100 mole percent of the polycarboxylic acid residues and 100 mole percent hydroxyl residues in the polyester polymer    
   
   
       61 . The concentrate of  claim 47 , wherein the hydroxyl component 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.  
   
   
       62 . The concentrate of  claim 61 , wherein the hydroxyl residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       63 . The concentrate of  claim 47 , wherein the concentrate is essentially free of a polyamide polymer.  
   
   
       64 . The concentrate of  claim 47 , wherein the It.V. of the polyester polymer ranges from 0.70 dL/g to 1.15 dL/g and is obtained without solid state polymerization.  
   
   
       65 . The concentrate of  claim 47 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       66 . The concentrate of  claim 65 , wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       67 . The concentrate of  claim 47 , wherein the polyester polymer contained in the concentrate is semicrystalline.  
   
   
       68 . The concentrate of  claim 47 , wherein the polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       69 . A solid concentrate obtained by melt compounding a transition metal having an oxidation state other than zero and in an amount ranging from 1,000 ppm to 10,000 ppm (by metal) and a polyester polymer having an It.V. of at least 0.55 dL/g in an amount of at least 80 wt. %, each based on the weight of the concentrate, wherein the polyester polymer comprises 
 (i) a polycarboxylic acid component comprising at least 92.0 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,    based on 100 mole percent of the polycarboxylic acid component residues and 100 mole percent hydroxyl component residues in the polyester polymer, respectively.    
   
   
       70 . The concentrate of  claim 69 , wherein the transition metal comprises cobalt.  
   
   
       71 . The concentrate of  claim 70 , wherein the transition metal content ranges from 1500 ppm to 8,000 ppm.  
   
   
       72 . The concentrate of  claim 71 , wherein the transition metal content ranges from 2,000 ppm to 6,000 ppm.  
   
   
       73 . The concentrate of  claim 70 , wherein at least a portion of the cobalt is present in the concentrate in the +2 oxidation state.  
   
   
       74 . The concentrate of  claim 70 , wherein the transition metal is provided as a compound comprising cobalt neodecanoate, cobalt acetate, or mixtures thereof.  
   
   
       75 . The concentrate of  claim 70 , wherein the polyester polymer is at least 98 wt. %, based on the total weight of the concentrate.  
   
   
       76 . The concentrate of  claim 70 , wherein the hydroxyl residue comprises a residue of 1,4-cyclohexane dimethanol.  
   
   
       77 . The concentrate of  claim 70 , wherein the concentrate is essentially free of a polyamide polymer.  
   
   
       78 . The concentrate of  claim 70 , wherein the It.V. of the polyester polymer ranges from 0.70 dL/g to 1.15 dL/g obtained without solid state polymerization.  
   
   
       79 . The concentrate of  claim 70 , wherein the concentrate particles have an It.V. ranging from 0.60 dL/g to 1.15 dL/g.  
   
   
       80 . The concentrate of  claim 79  wherein the concentrate particles have an It.V. of at least 0.70 dL/g.  
   
   
       81 . The concentrate of  claim 69 , wherein the polyester polymer contained in the concentrate is semicrystalline.  
   
   
       82 . The concentrate of  claim 69 , wherein the polyester polymer contained in the concentrate is essentially amorphous and has a DSC Tg of at least 70° C.  
   
   
       83 . A solid concentrate obtained by melt compounding cobalt metal having an oxidation state other than zero and in an amount ranging from 1,000 ppm to 10,000 ppm (by metal) and a polyester polymer having an It.V. of at least 0.55 dL/g in an amount of at least 80 wt. %, each based on the weight of the concentrate, wherein the polyester polymer comprises 
 (i) a carboxylic acid component comprising at least 92.0 mole % residues of terephthalic acid, or derivates of terephthalic acid, or mixtures thereof, and    (ii) a hydroxyl component comprising at least 80 mole % residues of ethylene glycol,    based on 100 mole percent of the carboxylic acid component residues and 100 mole percent hydroxyl component residues in the polyester polymer, respectively.