Sterilized polyetherimide/polyphenylene ether sulfone articles
A sterilized article comprising a hydrogen peroxide plasma or hydrogen peroxide vapor sterilized polymer composition, the polymer composition comprising from 20 to 80 weight % of a polyphenylene ether sulfone; and from 20 to 80 weight % of a polyetherimide. When sterilized with a hydrogen peroxide plasma, or hydrogen peroxide vapor, the articles have surprisingly improved resistance to changes in color and clarity as well as resistance to loss of mechanical properties.
1. A sterilized article comprising a sterilized polymer composition having an as molded color, treated with a member selected from hydrogen peroxide plasma, hydrogen peroxide vapor, and combinations thereof, the polymer composition comprising
a) from 80 to 20 weight % of a polyphenylene ether sulfone; the polyphenylene ether sulfone having the formula
wherein
n is 25 to 100
R is selected from C 1-8 alkyl, aryl, alkyl aryl, alkoxy, halogen, and combinations thereof,
x is 0 to 4 and
the aryl sulfone linkages are selected from 4,4′ linkages, 3,3′ linkages, 3,4′ linkages, and combinations thereof; and
b) from 20 to 80 weight % of a polyetherimide, wherein after exposure to 300 cycles of the hydrogen peroxide plasma sterilization using a mixture of hydrogen peroxide vapor and hydrogen peroxide plasma for 30 minutes at 20 to 55° C., the color of the polymer composition of the article exhibits a color shift of delta E of 10 units or less relative to the as molded color of the polymer composition before the first hydrogen peroxide plasma sterilization cycle, wherein delta E is measured in accordance with ASTM D2244-05.
2. The sterilized article of claim 1 , wherein after 300 cycles of the hydrogen peroxide plasma exposure the article has a weight loss of less than 5% of its initial weight before hydrogen peroxide plasma exposure.
3. The sterilized article of claim 1 , wherein after exposure to 150 cycles of the hydrogen peroxide plasma sterilization using a mixture of hydrogen peroxide vapor and hydrogen peroxide plasma for 30 minutes at 20 to 55° C., the color of the polymer composition exhibits a color shift of delta E of 10 units or less relative to the color of the polymer composition before the first hydrogen peroxide plasma sterilization cycle, wherein delta E is measured in accordance with ASTM D2244-05 and an article molded from the composition (i) initially also exhibits a multiaxial impact energy of greater than or equal to 45 ft-lbs (61 Joules) and (ii) after 150 cycles hydrogen peroxide plasma exposure has a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 Joules) and multiaxial impact energy is determined according to ASTM D5628-10 at 23° C.
4. The sterilized article of claim 1 , wherein the delta E of the polymer composition after the exposure to 100 cycles of hydrogen peroxide plasma sterilization is less than 5 units.
5. The sterilized article of claim 1 , wherein the delta E of the polymer composition is 10 units or less after exposure of the article to 100 to 200 sterilization cycles, wherein each cycle is from 10 to 60 minutes at 20 to 55° C.
6. The sterilized article of claim 5 , wherein the delta E of the polymer composition after the exposure of the article to 100 to 200 sterilization cycles is less than 5 units.
7. The sterilized article of claim 1 , wherein the delta E of the polymer composition after the exposure to 100 cycles of hydrogen peroxide plasma sterilization is less than a delta E of a second article comprising the same polymer composition without the polyetherimide, wherein the delta E of the second article is measured after exposure to 100 cycles of hydrogen peroxide plasma sterilization under the same conditions, relative to the color of the second article measured before the first hydrogen peroxide plasma sterilization cycle.
8. The sterilized article of claim 7 , wherein the delta E of the polymer composition is less than the delta of the second article, after each has been exposed to the same conditions, wherein the conditions include 100 to 200 sterilization cycles, wherein each cycle is from 10 to 60 minutes at 20 to 55° C.
9. The sterilized article of claim 1 , wherein at least a portion of the polymer composition has an etching, and wherein the etching is legible when observed from a distance of 0.3 meters without magnification after the exposure of the article to 100 cycles of hydrogen peroxide plasma sterilization.
10. The sterilized article of claim 9 , wherein the etching is legible when observed from a distance of 0.3 meters without magnification after exposure of the article to 100 to 200 sterilization cycles, wherein each cycle is from 10 to 60 minutes at 20 to 55° C.
11. The sterilized article of claim 1 , wherein the polymer composition comprises
from 30 to 70 weight % of the polyphenylene ether sulfone; and
from 70 to 30 weight % of the polyetherimide.
12. The sterilized article of claim 1 , wherein the polymer composition comprises
from 40 to 60 weight % of the polyphenylene ether sulfone; and
from 60 to 40 weight % of the polyetherimide.
13. The sterilized article of claim 1 , wherein the polymer composition comprises
from 20 to 40 weight % of the polyphenylene ether sulfone; and
from 80 to 60 weight % of the polyetherimide.
14. The sterilized article of claim 1 , wherein the polyetherimide comprises repeating units of the formula
wherein
R is a divalent radical of the formulae
or combinations thereof wherein Q is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y — wherein y is an integer from 1 to 5; and
T is —O— or a group of the formula —O-Z-O— wherein the divalent bonds of the —O— or the —O-Z-O— group are in the 3,3′, 3,4′, 4,3′, or the 4,4′ positions or a divalent group of formula
wherein Q 2 is selected from —O—, —S—, —C(O)—, —SO 2 —, —SO—, and —C y H 2y — wherein y is an integer from 1 to 5.
15. The sterilized article of claim 1 , wherein the polyetherimide has less than 5 ppm of free bisphenol A.
16. The sterilized article of claim 1 , wherein the polyphenylene ether sulfone is a copolymer of the following structure:
wherein
n>m; and n+m is 25 to 1000,
R is selected from a C 1-8 alkyl, aryl, alkylaryl, alkoxy, halogen, and combinations thereof,
x is 0 to 4,
the aryl sulfone linkages are selected from 4,4′ linkages, 3,3′ linkages, 3,4′ linkages, and combinations thereof,
A is selected from —O—, —S—, —SO 2 —, C 6-18 aryl, C 3-12 alkyl, and combinations thereof, and
linkages of A to the aryl groups are selected from 4,4′ linkages, 3,3′ linkages, 3,4′ linkages, and combinations thereof.
17. The sterilized article of claim 16 , wherein each x is 0.
18. The sterilized article of claim 1 , wherein
the polyetherimide comprises less than 50 ppm amine end groups,
the polyphenylene ether sulfone has less than 50 ppm hydroxyl groups, and
the polyphenylene ether sulfone is methyl ether end-capped.
19. The sterilized article of claim 1 , wherein the polymer composition further comprises, based on the weight of the polymer composition, 0.1 to 20.0 weight % of a colorant selected from rutile titanium dioxide, anatase titanium dioxide, coated titanium dioxide, passivated titanium dioxide, and encapsulated titanium dioxide, wherein the titanium dioxide has a particle size of from 0.1 to 10 micrometers.
20. The sterilized article of claim 19 , wherein the polymer composition further comprises a colorant selected from carbon black, solvent red 52, solvent violet 36, solvent violet 13, pigment brown 24, pigment blue 29, pigment blue 15:4, or combinations thereof.
21. The sterilized article of claim 1 , wherein the polymer composition further comprises, based on the weight of the polymer composition, at least 0.01 weight % of a phosphorous containing stabilizer having a molecular weight of at least 300 Daltons.
22. The sterilized article of claim 21 , wherein the phosphorous stabilizer is selected from aryl phosphites and aryl phosphonates.
23. The sterilized article of claim 1 , wherein the polymer composition further comprises, based on the weight of the polymer composition, at least 0.05 weight % of a mold release agent selected from C6 to C36 alkyl carboxylic esters, C6 to C36 alkyl carboxylic acids, C6 to C36 alkyl carboxylic acid salts, C6 to C36 alkyl amides, and polyolefins.
24. The sterilized article of claim 1 , wherein the article is selected from a molded part, sheet, slab, profile, film, and fiber.
25. The sterilized article of claim 24 , wherein the article is selected from a medical device, dental device, surgical device, sterilization device, decontamination device, food handling device, food preparation device, beverage handling device, beverage preparation device, or a component thereof.
26. The sterilized article of claim 25 , wherein the article is selected from a container, a syringe body, a tray, an animal cage, an endoscope, a ureteroscope, a catheter, a clamp, a cable, a telescope, forceps, scissors, and a drill.
27. The sterilized article of claim 1 , wherein the article further comprises a biocidal additive component.
28. The sterilized article of claim 27 , wherein the biocidal additive component is selected from metals, inorganic compounds, and organic compounds.
29. The sterilized article of claim 27 , wherein the biocide is selected from germicides, antibiotics, antibacterials, antivirals, antifungals, antiprotozoals, antiyeasts, antialgals, antiparasites, and combinations thereof.
30. The sterilized article of claim 1 , wherein the tensile strength at yield of the article after 150 hydrogen peroxide plasma sterilization cycles is at least 12,000 psi (82.8 MPa).
31. A sterilized article comprising a sterilized polymer composition, having an as molded color treated with a member selected from hydrogen peroxide plasma, hydrogen peroxide vapor, and combinations thereof, the polymer composition comprising
a) from 80 to 20 weight % of a polyphenylene ether sulfone; the polyphenylene ether sulfone having the formula
wherein
n is 25 to 1000,
R is selected from C 1-8 alkyl, aryl, alkyl aryl, alkoxy, halogen, and combinations thereof,
x is 0 to 4, and
the aryl sulfone linkages are selected from 4,4′ linkages, 3,3′ linkages, 3,4′ linkages, and combinations thereof;
and
b) from 20 to 80 weight % of a polyetherimide;
wherein after exposure to 150 cycles of the hydrogen peroxide plasma sterilization using a mixture of hydrogen peroxide vapor and hydrogen peroxide plasma for 30 minutes at 20 to 55° C., the color of the polymer composition exhibits a color shift of delta E of 10 units or less relative to the as molded color of the polymer composition color before the first hydrogen peroxide plasma sterilization cycle;
wherein delta E is measured in accordance with ASTM D2244-05 and an article molded from the composition (i) initially also exhibits a multiaxial impact energy of greater than or equal to 45 ft-lbs (61 Joules) and (ii) after 150 cycles hydrogen peroxide plasma exposure has a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 Joules) and multiaxial impact energy is determined according to ASTM D5628-10 at 23° C.;
wherein at least a portion of the polymer composition has an etching, and wherein the etching is legible when observed from a distance of 0.3 meters without magnification after the exposure of the article to 100 cycles of hydrogen peroxide plasma sterilization.