Oxygen scavenging terpolymers
View Patent ↗A method and system for oxygen molecule scavenging is disclosed. The system employs as a novel terpolymer as the reducing agent for oxygen molecules. The terpolymer is the polymerization product of macrocyclic poly(alkylene dicarboxylate) oligomer, unsaturated functional polymer, and epoxy-functional styrene-acrylate oligomer.
1. A terpolymer having carbon-carbon unsaturated bonds susceptible to reaction with oxygen molecules, comprising:
a polymerization product of macrocyclic poly(alkylene dicarboxylate) oligomer, unsaturated functional polymer, and epoxy-functional styrene-acrylate oligomer wherein the unsaturated functional polymer is hydroxyl-terminated polybutadiene having a number average molecular weight greater than 1400.
2. The terpolymer of claim 1 , wherein the macrocyclic poly(alkylene dicarboxylate) oligomer comprises macrocyclic poly(butylene terephthalate) or macrocyclic poly(ethylene terephthalate) or a combination of them both.
3. The terpolymer of claim 1 , wherein the epoxy-functional styrene-acrylate oligomer is the polymerization product of (i) at least one epoxy-functional acrylic monomer; and (ii) at least one styrenic monomer, wherein the polymerization product has an epoxy equivalent weight of from about 180 to about 2800, a number-average epoxy functionality (Efn) value of less than about 30, a weight-average epoxy functionality (Efw) value of up to about 140, and a number-average molecular weight (Mn) value of less than 6000.
4. The terpolymer of claim 1 , wherein the macrocyclic poly(alkylene dicarboxylate) oligomer is present in the terpolymer in a weight percent ranging from about 30 to about 60 of the terpolymer, wherein the unsaturated functional polymer is present in the terpolymer in a weight percent ranging from about 30 to about 55 of the terpolymer, and wherein the epoxy-functional styrene-acrylate oligomer is present in the terpolymer in a weight percent ranging from about 5 to about 20 of the terpolymer.
5. The terpolymer of claim 1 , wherein the macrocyclic poly(alkylene dicarboxylate) oligomer is present in the terpolymer in a weight percent ranging from about 35 to about 45 of the terpolymer, wherein the unsaturated functional polymer is present in the terpolymer in a weight percent ranging from about 35 to about 55 of the terpolymer, and wherein the epoxy-functional styrene-acrylate oligomer is present in the terpolymer in a weight percent ranging from about 5 to about 20 of the terpolymer.
6. The terpolymer of claim 1 , wherein the macrocyclic poly(alkylene dicarboxylate) oligomer is present in the terpolymer in a weight percent ranging from about 40% to about 45% of the terpolymer, wherein the unsaturated functional polymer is present in the terpolymer in a weight percent ranging from about 40% to about 55% of the terpolymer, and wherein the epoxy-functional styrene-acrylate oligomer is present in the terpolymer in a weight percent ranging from about 5% to about 10% of the terpolymer.
7. The terpolymer of claim 6 , wherein the terpolymer has a weight average molecular weight (Mw) of about 15,000, a number average molecular weight (Mn) of about 8,000, and a polydispersity of from about 1.82 to about 1.95, all as measured via Gel Permeation Chromatography (GPC) using polystyrene as a test reference.
8. The terpolymer of claim 7 , wherein the terpolymer has a melting temperature of about 210-215° C. measured by Differential Scanning Calorimetry (DSC).
9. A thermoplastic compound, comprising: (a) a thermoplastic polymer matrix; and (b) a terpolymer of claim 1 .
10. The thermoplastic compound of claim 9 , further comprising a catalyst for the terpolymer functioning as a reducing agent for oxygen molecules.
11. The thermoplastic compound of claim 9 , further comprising a functional additive selected from the group consisting of adhesion promoters; biocides, anti-fogging agents; anti-static agents; bonding, blowing and foaming agents; dispersants; fillers and extenders; fire and flame retardants and smoke suppresants; impact modifiers; initiators; lubricants; micas; pigments, colorants and dyes; plasticizers; processing aids; release agents; silanes, titanates and zirconates; slip and anti-blocking agents; stabilizers; stearates; ultraviolet light absorbers; viscosity regulators; waxes; and combinations of them.
12. The thermoplastic compound of claim 9 , wherein the terpolymer comprises from about 0.1 to about 3 percent by weight of the compound.
13. A thermoplastic article, comprising the thermoplastic compound of any of claims 9 - 12 .
14. The thermoplastic article of claim 13 , wherein the article is a bottle pre-form.
15. The thermoplastic article of claim 13 , wherein the article is a blow-molded bottle.
16. The article of claim 15 , wherein the bottle contains a perishable food or beverage susceptible to oxidation.
17. A method for scavenging for oxygen within a thermoplastic article, comprising:
(a) mixing a reducing agent for oxygen molecules into a thermoplastic compound and
(b) forming an article from the thermoplastic compound containing the reducing agent,
wherein the reducing agent is a terpolymer of claim 1 , and
wherein the terpolymer has carbon-carbon unsaturated bonds susceptible to reaction with oxygen molecules.
18. The method of claim 17 , wherein step (a) also includes mixing a catalyst into the thermoplastic compound.
19. The method of claim 17 , wherein the terpolymer reduces an oxygen molecule by reaction with a carbon-carbon unsaturated bond, thereby scavenging the oxygen molecule from the article.