Tagging materials for polymers, methods, and articles made thereby

• US RE41,616 E1
• Filed: 12/17/2003
• Issued: 08/31/2010
• Est. Priority Date: 07/11/2001
• Status: Expired due to Term

• Current Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Original Assignee: Sabic Innovative Plastics IP BV (Government of Saudi Arabia)
• Inventors: Hubbard, Steven Frederick, Thomas, Verghese, Potyrailo, Radislav Alexandrovich, Schottland, Philippe
• Primary Examiner(s): Boykin; Terressa M
• Application Number:
  US10/738,702
• Time in Patent Office: 2,449 Days
• Field of Search: 428/412, 428/421, 436/56, 525/342, 528/190, 528/193, 528/196, 528/271, 528/272
• US Class Current: 528/196
• CPC Class Codes: B29B 2017/0279 Optical identification, e.g. cameras or spectroscopy
• CPC Class Codes: G01N 21/6428 Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" in vivo A61B5/00; immunoassay G01N33/53
• CPC Class Codes: Y02W 30/622 Separating plastics from other materials
• CPC Class Codes: Y10T 428/31507 Of polycarbonate
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 436/13 Tracers or tags

Abstract

A polymer comprising a tagging material is provided wherein the tagging material comprises at least one organic fluorophore dye, or at least one inorganic fluorophore, or at least one organometallic fluorophore, or at least one semi-conducting luminescent nanoparticle, or combination thereof, wherein the tagging material has a temperature stability of at least about 350° C. and is present in a sufficient quantity such that the tagging material is detectible via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 nanometers. Further embodiments of the present invention include a method for identifying a polymer and an article comprising a polymer wherein the polymer contains the aforementioned tagging material.

Claims

1. A method for identifying a polycarbonate polymer, comprising providing in the a polycarbonate polymer at least one and a tagging material wherein the tagging material comprises at least one organic fluorophore dye, or at least one inorganic fluorophore, or at least one organometallic fluorophore, or at least one semi-conducting luminescent nanoparticle, or a combination thereof, wherein the tagging material has a temperature stability of at least about 350°

C. and is present in a sufficient quantity such that the tagging material is detectible via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 546 nanometers, and wherein the tagging material is uniformly dispersed throughout the polycarbonate polymer or dispersed in a portion of the polycarbonate polymer by means of an extruder or injection molder during melt polymerization of the polycarbonate polymer whereby a sample of the polymer composition can be identified or distinguished from samples of other polymers containing no or different tagging materials, and identifying the polymer based on the detected tagging material.

2. The method in accordance with claim 1, wherein the tagging material has a temperature stability of at least about 375°

C.

3. The method in accordance with claim 1, wherein the tagging material has a temperature stability of at least about 400°

C.

4. The method in accordance with claim 1, wherein the tagging material has an excitation wavelength in a range between about 200 nanometers and about 1000 546 nanometers.

5. The method in accordance with claim 4, wherein the tagging material has an excitation wavelength in a range between about 250 nanometers and about 950 546 nanometers.

6. The method in accordance with claim 1, wherein the at least one tagging material comprises a fluorophore dye comprises comprising perylenes.

7. The method in accordance with claim 6, wherein the at least one fluorophore dye comprises anthra[2,1,9-def:

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy, or combinations thereof anthra[2,1,9-def;

6,5,10-d′

,e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy.

8. The method in accordance with claim 1, wherein at least one the tagging material comprises fluorophore dye comprises comprising a lanthanide complex.

9. The method in accordance with claim 1, wherein the fluorophore is an anti-stokes shift dye.

10. The method in accordance with claim 1, wherein at least one the tagging material comprises semi-conducting luminescent nanoparticle comprises comprising CdS, ZnS, Cd₃P₂, PbS, or combinations thereof.

11. The method in accordance with claim 1, wherein at least one the tagging material comprises a semi-conducting luminescent nanoparticle comprises rare earth aluminates comprising strontium aluminates doped with Europium and Dysprosium.

12. The method in accordance with claim 1, wherein the tagging material is present in a range between about 10⁻

18 and about 2 percent by weight of the total polymer.

13. The method in accordance with claim 12, wherein the tagging material is present in a range between about 10⁻

15 and about 0.5 percent by weight of the total polymer.

14. The method in accordance with claim 13, wherein the tagging material is present in a range between about 10⁻

12 and about 0.05 percent by weight of the total polymer.

15. The method of claim 1, wherein the polymer comprises a thermoplastic polymer material.

16. The method of claim 15, wherein the thermoplastic polymer material comprises polycarbonate.

17. The method of claim 1, wherein the tagging material is incorporated into the polymer by coating, admixing, blending, or copolymerization.

18. The method of claim 1, wherein the polymer is used in a storage media for data.

19. The method of claim 1, wherein the polymer contains a coloring material.

20. The method in accordance with claim 1, wherein the tagging material has a temperature stability for a time period of less than about 10 minutes.

21. The method in accordance with claim 1, wherein the tagging material has a temperature stability for a time period of less than about 1 minute.

22. The method in accordance with claim 1, wherein the tagging material has a temperature stability for a time period of less than about 20 seconds.

70. The method of claim 1, wherein the tagging material comprises a scintillation dye.

23. A method for identifying a polycarbonate, comprising providing in the polycarbonate at least one tagging material wherein the tagging material comprises a perylene, wherein the perylene has a temperature stability of at least about 350°

C., is present in a range between about 10<sup>−

18</sup> percent by weight and about 2 percent by weight of the total polycarbonate and is detectable via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 546 nanometers.

24. A polymer composition comprising

(a) a polycarbonate polymer, and

(b) a tagging material wherein the tagging material comprises at least one organic fluorophore dye, or at least one inorganic or organometallic fluorophore, or at least one semi-conducting luminescent nanoparticle, or combination thereof, wherein the tagging material has a temperature stability of at least about 350°

C. and is present in a sufficient quantity such that the tagging material is detectable via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 546 nanometers, wherein the tagging material is uniformly dispersed throughout the polycarbonate polymer or dispersed on a portion of the polycarbonate polymer by means of an extruder or injection molding during melt polymerization of the polycarbonate polymer, whereby a sample of the polymer composition can be identified or distinguished from samples of other polymers containing no or different tagging materials.

25. The polymer composition in accordance with claim 24, wherein the tagging material has a temperature stability of at least about 375°

C.

26. The polymer composition in accordance with claim 24, wherein the tagging material has a temperature stability of at least about 400°

C.

27. The polymer composition in accordance with claim 24, wherein the at least one composition comprises a fluorophore dye has having an excitation wavelength in a range between about 200 nanometers and about 1000 546 nanometers.

28. The polymer composition in accordance with claim 27, wherein the at least one fluorophore dye has an excitation wavelength in a range between about 250 nanometers and about 950 546 nanometers.

29. The polymer composition in accordance with claim 24, wherein the at least one composition a perylene as a fluorophore dye comprises perylenes .

30. The polymer composition in accordance with claim 29, wherein the at least one fluorophore dye comprises anthra[2,1,9-def:

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy, or combinations thereof

anthra[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone,

2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy.

31. The polymer composition in accordance with claim 24, wherein the at least one fluorophore dye composition comprises a lanthanide complex.

32. The polymer in accordance with claim 24, wherein the fluorophore comprises an anti-stokes shift dye.

33. The polymer composition in accordance with claim 24, wherein the at least one composition comprises a semi-conducting luminescent nanoparticles comprises comprising CdS, ZnS, Cd₃P₂, PbS, or combinations thereof.

34. The polymer composition in accordance with claim 24, wherein the at least one composition comprises a semi-conducting luminescent nanoparticles comprises comprising rare earth aluminates comprising strontium aluminates doped with Europium and Dysprosium.

35. The polymer composition in accordance with claim 24, wherein the tagging material is present in a range between about 10⁻

18 percent by weight and 2 percent by weight of the total polymer.

36. The polymer composition in accordance with claim 35, wherein the tagging material is present in a range between about 10⁻

15 percent by weight and about 0.5 percent by weight of total polymer.

37. The polymer composition in accordance with claim 36, wherein the tagging material is present in a range between about 10⁻

12 percent by weight and about 0.05 percent by weight of total polymer.

38. The polymer in accordance with claim 24, wherein the polymer comprises a thermoplastic polymer material.

39. The polymer in accordance with claim 38, wherein the thermoplastic polymer material comprises polycarbonate.

40. The polymer in accordance with claim 24, wherein the tagging material is incorporated into the polymer by coating, admixing, blending, or copolymerization.

41. The polymer composition in accordance with claim 24, wherein the polymer is used in a storage media for data.

42. The polymer composition in accordance with claim 24 comprising a coloring material.

43. The polymer composition in accordance with claim 24, wherein the tagging material has a temperature stability for a time period of less than about 10 minutes.

44. The polymer composition in accordance with claim 24, wherein the tagging material has a temperature stability for a time period of less than about 1 minute.

45. The polymer composition in accordance with claim 24, wherein the tagging material has a temperature stability for a time period of less than about 20 seconds.

71. The polymer composition of claim 24, wherein the tagging material comprises a scintillation dye.

46. A polycarbonate comprising a perylene, wherein the perylene has a temperature stability of at least about 350°

C. and is present in a range between about 10<sup>−

18</sup> percent by weight and about 2 percent by weight of the total polycarbonate and is detectible via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 nanometers.

47. An article comprising a polymer composition wherein the polymer composition comprises

(a) a polycarbonate polymer, and

(b) a at least one tagging material wherein the tagging material comprises at least one organic fluorophore dye, or at least one semi-conducting luminescent nanoparticle, or combination thereof, wherein the tagging material has a temperature stability of at least about 350°

C. and is present in a sufficient quantity such that the tagging material is detectible via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 546 nanometers, wherein the tagging material is uniformly dispersed throughout the polycarbonate polymer or dispersed on a portion of the polycarbonate polymer by means of an extruder or injection molder during melt polymerization of the polycarbonate polymer, whereby a sample of the polymer composition can be identified or distinguished from samples of other polymers containing no or different tagging materials.

48. The method in accordance with claim 47, wherein the tagging material has a temperature stability of at least about 375°

C.

49. The method in accordance with claim 47, wherein the tagging material has a temperature stability of at least about 400°

C.

50. The article in accordance with claim 47, wherein the at least one fluorophore dye has an excitation wavelength in a range between about 200 nanometers and about 1000 546 nanometers.

51. The article in accordance with claim 50, wherein the at least one fluorophore dye has an excitation wavelength in a range between about 250 nanometers and about 950 546 nanometers.

52. The article in accordance with claim 47, wherein the at least one fluorophore dye comprises perylenes.

53. The article in accordance with claim 52, wherein the at least one fluorophore dye comprises anthra[2,1,9-def:

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone, 2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy, or combinations thereof

antrha[2,1,9-def;

6,5,10-d′

e′

f′

]diisoquinoline-1,3,8,10(2H,9H)-tetrone,

2,9-bis[2,6-bis(1-methylethyl)phenyl]-5,6,12,13-tetraphenoxy.

54. The article in accordance with claim 47, wherein at least one fluorophore dye comprises a lanthanide complex.

55. The article in accordance with claim 47, wherein the fluorophore is an anti-stokes shift dye.

56. The article in accordance with claim 47, wherein at least one semi-conducting luminescent nanoparticle comprises CdS, ZnS, Cd₃P₂, PbS, or combinations thereof.

57. The article in accordance with claim 47, wherein at least one semi-conducting luminescent nanoparticle comprises rare earth aluminates comprising strontium aluminates doped with Europium and Dysprosium.

58. The article in accordance with claim 47, wherein the tagging material is present in a range between about 10⁻

18 to about 2 percent by weight of the total polymer.

59. The article in accordance with claim 58, wherein the tagging material is present in a range between about 10⁻

15 to about 0.5 percent by weight of total polymer.

60. The article in accordance with claim 59, wherein the tagging material is present in a range between about 10⁻

12 to about 0.05 percent by weight of total polymer.

61. The article in accordance with claim 47, wherein the polymer comprises a thermoplastic polymer material.

62. The article in accordance with claim 61, wherein the thermoplastic polymer material comprises polycarbonate.

63. The article in accordance with claim 47, where in the tagging material is incorporated in to the polymer by coating, admixing, blending, or copolymerization.

64. The article in accordance with claim 47, wherein the polymer is used in a storage media for data.

65. The article in accordance with claim 47, wherein the polymer contains a coloring material.

66. The article in accordance with claim 47, wherein the tagging material has a temperature stability for a time period of less than about 10 minutes.

67. The article in accordance with claim 47, wherein the tagging material has a temperature stability for a time period of less than about 1 minute.

68. The article in accordance with claim 47, wherein the tagging material has a temperature stability for a time period of less than about 20 seconds.

72. The article of claim 47, wherein the tagging material comprises a scintillation dye.

69. A storage medium for data comprising a polycarbonate wherein the polycarbonate comprises a perylene wherein the perylene has a temperature stability of at least about 350°

C., is present in a range between about 10<sup>−

18</sup> percent by weight and about 2 percent by weight of the total polycarbonate, and is detectabile via a spectrofluorometer at an excitation wavelength in a range between about 100 nanometers and about 1100 nanometers.