Oxygen Scavenging Compositions and Packaging Comprising Said Compositions
The instant invention concerns a composition comprising a base polymer, at least one compound of the formula E-(L-E) x wherein: E is formula (I) or formula (II) and L is a linking group; and at least one transition metal in a positive oxidation state. The invention also concerns packages containing walls comprising such compositions, methods of forming such packages, and methods of packaging an oxygen-sensitive item within such a package.
1 . A composition comprising:
(a) at least one base polymer;
(b) at least one non-polymeric oxidizable organic component present in an amount of about 0.10 to 10 weight present of the composition and the component comprising at least one compound of the formula E-(L-E) x wherein:
E is
L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C(═O)R 22 ) t —NH, —NH—R 25 —NH(C(═O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C(═O) s —O— where L is attached to a carbon atom of Ar in structure (I) or where R 12 or R 13 of structure (II) is L;
x is 0, 1, or 2;
Ar is aryl or heteroaryl;
R 1 , R 2 , and R 11 are each independently, H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O;
R 3 , R 4 , R 14 , and R 15 are each H;
R 5 to R 10 and R 16 , and R 17 are each, independently, H or C 1 -C 3 alkyl;
R 12 and R 13 are each, independently, H, C 1 -C 6 alkyl, C 6 -C 20 aryl, C 1 -C 6 alkoxy, or L;
R 18 is C 2 -C 6 alkyl;
R 19 and R 20 are each, independently, H, C 1 -C 6 alkyl, or C 6 -C 20 aryl;
R 21 and R 24 are each, independently, C 1 -C 6 alkyl;
R 22 , R 23 , R 25 and R 26 are each, independently, C 1 -C 6 alkyl or C 6 -C 20 aryl;
n and p are independently 0 or an integer from 1 to 5;
q is 0 or an integer from 1 to 4;
s and z are, independently 1, 2, or 3;
t and u are, independently 1 or 2; and
(c) at least one transition metal in a positive oxidation state, the metal being present in the composition in an amount of 10 to 400 ppm.
2 . The composition of claim 1 having the formula
3 . The composition of claim 2 where n and p are each 0, 1, or 2 and R 1 and R 2 are each independently H, C 1 -C 4 alkyl, hydroxy, C 1 -C 3 alkoxy, or carbohydrate.
4 . The composition of claim 3 wherein R 1 and R 2 are each independently H, methyl, ethyl, hydroxy, methoxy, ethoxy, or glucose.
5 . The composition of claim 3 where R 5 to R 10 are H.
6 . The composition of claim 5 where R 1 and R 2 are each H.
7 . The composition of claim 1 having the formula:
8 . The composition of claim 1 having the formula:
9 . The composition of claim 8 where R 16 and R 17 are H.
10 . The composition of claim 8 where each R 1 , is independently H, C 1 -C 4 alkyl, hydroxy, or C 1 -C 3 alkoxy, or carbohydrate.
11 . The composition of claim 10 where each R 11 is independently H, methyl, ethyl, hydroxy, methoxy, or ethoxy.
12 . The compound of claim 1 having the formula:
13 . The composition of claim 1 wherein the at least one transition metal is cobalt.
14 . The composition of claim 13 wherein the at least one transition metal further comprises zinc.
15 . The composition of claim 1 wherein the base polymer comprises a polyester polymer.
16 . The composition of claim 15 wherein the polyester polymer is polyethylene terephthalate.
17 . The composition of claim 1 wherein the oxidizable organic component is present in an amount of about 1 to about 10 weight percent based on the weight of the composition.
18 . The composition of claim 1 wherein the oxidizable organic component is present in an amount of about 1 to about 5 weight percent based on the weight of the composition.
19 . The composition of claim 1 wherein the oxidizable organic component is present in an amount of about 1 to about 3 weight percent based on the weight of the composition.
20 . The composition of claim 1 wherein the concentration of transition metal is 30 to 150 ppm.
21 . An oxygen scavenging material suitable for use in a barrier wall whose oxidative decomposition products comprise one or more aldehydes that are toxicologically innocuous.
22 . The material of claim 21 wherein the aldehydes comprise at least one of benzaldehyde, vanillin, 3-ethoxy-2-hydroxybenzaldehyde, 4-hydroxy-3-methylbenzaldehyde, 4-hydroxy-3,5-dimethoxybenzaldehyde, 4-hydroxybenzaldehyde-3-sulfonic acid sodium salt, (1,1′-bihenyl)-4-carboxaldehyde, 2-methoxybenzaldehyde 4-nitropheynylhydrazone, 3,4,5-triacetoxybenzaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 3-benzoxy-4-methoxybenzaldehyde, 2-formylbenzenesulfonic acid sodium salt, 4-dodecyloxyenzaldehyde, benzaldehyde-p-sulfonic acid sodium salt, 3-benzoxybenzaldehyde, 3-phenoxybenzaldehyde, 5-nitrovanillin, ethyl vanillin beta-D-glucopyranoside, 1,4-benzodioxan-6-carboxaldehyde, 3,4-didecyloxybenzaldehyde, 4-benzyloxy-3-methoxybenzaldehyde, N-ethyl-N-hydroxyethyl-2-methyl-4-aminobenzaldehyde, 2,4-dinitrobenzaldehyde, 4-methoxybenzaldehyde-3-sulfonic acid sodium salt, 4-benzyloxybenzaldehyde, 4-(4-nitrobenzyloxy)benzaldehyde, 4-octylbenzaldehyde, 2-hexyloxybenzaldehyde, 3,4-didodecyloxybenzaldehyde, 3,4-dioctyloxybenzaldehyde, 3,5,-di-tert-butyl-4-hydroxybenzaldehyde, and 3-(4-tert-butylphenoxy)benzaldehyde.
23 . The material of claim 21 wherein the aldehydes comprise benzaldehyde.
24 . A wall of a package comprising at least one layer, the layer comprising a composition, the composition comprising:
(a) at least one base polymer;
(b) at least one non-polymeric oxidizable organic component present in an amount of about 0.10 to 10 weight present of the composition and the component comprising at least one compound of the formula E-(L-E) x wherein:
E is
L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C(═O)R 22 ) t —NH, —NH—R 25 —NH(C(═O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C(═O) s —O— where L is attached to a carbon atom of Ar in structure (I) or where R 12 or R 13 of structure (II) is L;
x is 0, 1, or 2;
Ar is aryl or heteroaryl;
R 1 , R 2 , and R 11 are each independently, H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O;
R 3 , R 4 , R 14 , and R 15 are each H;
R 5 to R 10 and R 16 , and R 17 are each, independently, H or C 1 -C 3 alkyl;
R 12 and R 13 are each, independently, H, C 1 -C 6 alkyl, C 6 -C 20 aryl, C 1 -C 6 alkoxy, or L;
R 18 is C 2 -C 6 alkyl;
R 19 and R 20 are each, independently, H, C 1 -C 6 alkyl, or C 6 -C 20 aryl;
R 21 , and R 24 are each, independently, C 1 -C 6 alkyl;
R 22 , R 23 , R 25 and R 26 are each, independently, C 1 -C 6 alkyl or C 6 -C 20 aryl;
n and p are independently 0 or an integer from 1 to 5;
q is 0 or an integer from 1 to 4;
s and z are, independently 1, 2, or 3;
t and u are, independently 1 or 2; and
(c) at least one transition metal in a positive oxidation state, the metal being present in the composition in an amount of 10 to 400 ppm.
25 . A process for making an article comprising:
(a) forming a melt by combining the following ingredients in a melt processing zone:
at least one base polymer,
at least one non-polymeric oxidizable organic component present in an amount of about 0.10 to 10 weight present of the composition and the component comprising at least one compound of the formula E-(L-E) x wherein:
E is
L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C(═O)R 22 ) t —NH, —NH—R 25 —NH(C(═O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C(═O) s —O— where L is attached to a carbon atom of Ar in structure (I) or where R 12 or R 13 of structure (II) is L;
x is 0, 1, or 2;
Ar is aryl or heteroaryl;
R 1 , R 2 , and R 11 are each independently, H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C(—O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O;
R 3 , R 4 , R 14 , and R 15 are each H;
R 5 to R 10 and R 16 , and R 17 are each, independently, H or C 1 -C 3 alkyl;
R 12 and R 13 are each, independently, H, C 1 -C 6 alkyl, C 6 -C 20 aryl, C 1 -C 6 alkoxy, or L;
R 18 is C 2 -C 6 alkyl;
R 19 and R 20 are each, independently, H, C 1 -C 6 alkyl, or C 6 -C 20 aryl;
R 21 and R 24 are each, independently, C 1 -C 6 alkyl;
R 22 , R 23 , R 25 and R 26 are each, independently, C 1 -C 6 alkyl or C 6 -C 20 aryl;
n and p are independently 0 or an integer from 1 to 5;
q is 0 or an integer from 1 to 4;
s and z are, independently 1, 2, or 3;
t and u are, independently 1 or 2;
(b) forming an article from the melt.
26 . A method for packaging an oxygen sensitive material comprising:
(a) preparing a package having a wall comprising at least one layer, at least one of the layers comprising a composition, the composition comprising
at least one base polymer;
at least one non-polymeric oxidizable organic component present in an amount of about 0.10 to 10 weight present of the composition and the component comprising at least one compound of the formula E-(L-E) x wherein:
E is
L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C(═O)R 22 ) t —NH, —NH—R 25 —NH(C(═O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C(═O) s —O— where L is attached to a carbon atom of Ar in structure (I) or where R 12 or R 13 of structure (II) is L;
x is 0, 1, or 2;
Ar is aryl or heteroaryl;
R 1 , R 2 , and R 11 are each independently, H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O;
R 3 , R 4 , R 14 , and R 15 are each H;
R 5 to R 10 and R 16 , and R 17 are each, independently, H or C 1 -C 3 alkyl;
R 12 and R 13 are each, independently, H, C 1 -C 6 alkyl, C 6 -C 20 aryl, C 1 -C 6 alkoxy, or L;
R 18 is C 2 -C 6 alkyl;
R 19 and R 20 are each, independently, H, C 1 -C 6 alkyl, or C 6 -C 20 aryl;
R 21 and R 24 are each, independently, C 1 -C 6 alkyl;
R 22 , R 23 , R 25 and R 26 are each, independently, C 1 -C 6 alkyl or C 6 -C 20 aryl;
n and p are independently 0 or an integer from 1 to 5;
q is 0 or an integer from 1 to 4;
s and z are, independently 1, 2, or 3;
t and u are, independently 1 or 2; and
at least one transition metal in a positive oxidation state, the metal being present in the composition in an amount of 10 to 400 ppm.
(b) introducing the oxygen sensitive material into the package; and
(c) closing the package.
27 . A method for producing a packaging material having a wall with oxygen barrier properties comprising:
(a) providing polymer mixture comprising at least one base polymer containing at least one non-polymeric oxidizable organic component present in an amount of about 0.10 to 10 weight present of the composition and the component comprising at least one compound of the formula E-(L-E) x wherein:
E is
L is a linking group of the formula —(O—R 21 ) z —O—, —(NH—R 21 ) z —NH—, —(NH—C(═O)R 22 ) t —NH, —NH—R 25 —NH(C(═O)R 26 NHR 25 NH) u —, —(O—R 23 —O—R 24 —C(═O) s —O— where L is attached to a carbon atom of Ar in structure (I) or where R 12 or R 13 of structure (II) is L;
x is 0, 1, or 2;
Ar is aryl or heteroaryl;
R 1 , R 2 , and R 11 are each independently, H, C 1 -C 12 alkyl, C 1 -C 6 alkoxy, C 6 -C 20 aryloxy, hydroxy, C 2 -C 6 alkenyl, NR 19 R 20 , acetyl, nitro, glyceryl, carbohydrate, —C(═O)H, L, or two R 1 or two R 2 groups can form a group of the formula —O—R 18 —O;
R 3 , R 4 , R 14 , and R 15 are each H;
R 5 to R 10 and R 16 , and R 17 are each, independently, H or C 1 -C 3 alkyl;
R 12 and R 13 are each, independently, H, C 1 -C 6 alkyl, C 6 -C 20 aryl, C 1 -C 6 alkoxy, or L;
R 18 is C 2 -C 6 alkyl;
R 19 and R 20 are each, independently, H, C 1 -C 6 alkyl, or C 6 -C 20 aryl;
R 21 and R 24 are each, independently, C 1 -C 6 alkyl;
R 22 , R 23 , R 25 and R 26 are each, independently, C 1 -C 6 alkyl or C 6 -C 20 aryl;
n and p are independently 0 or an integer from 1 to 5;
q is 0 or an integer from 1 to 4;
s and z are, independently 1, 2, or 3;
t and u are, independently 1 or 2;
wherein the polymer mixture comprises at least one transition metal in a positive oxidation state, the metal being present in the composition in an amount of 10 to 400 ppm;
(b) forming the polymer mixture of step (a) into a wall; and
(c) forming a container which comprises the wall.