Abstract
The invention relates to the identification of polymer materials on the basis of the fluorescence decay time of the intrinsic fluorescence of the polymer materials for definite sorting in a completely separated manner. The invention further relates to marking with fluorescent dyes, which, Because of the specific fluorescence decay times of the fluorescent dyes, can further increase the sorting reliability by means of redundancy and can be used to identify particular batches.
Claims
1. Use of the individual fluorescence decay times of the intrinsic fluorescence (autofluorescence) of polymers for their detection, preferably for their detection for sorting in a completely separated manner for recycling.
2. Use of perylenetetracarboxylicbisimides of the general formula 4 ##STR00005## for flouresence coding of macro-molecular substances for their clear identification via the fluorescence decay time, which is characteristic for every marker-polymer-combination (see FIGS. 7 to 15), wherein the moieties R.sup.1 to R.sup.18 can be identical or different from each other and can mean independently from each other hydrogen or linear alkyl moieties with at least one and at most 37 C-atoms, in which 1 up to 10 CH.sub.2-units independently of each other can be each replaced by carbonylgroups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CHCH-groups, in which a CH-unit can also be replaced by a Nitrogen atom, acetylenic CC-Groups 1,2-1,3- or 1,4-substituted phenyl moieties, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine moieties, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene moieties, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-, or 2,7-disubstituted naphtaline moieties, in which one or two CH-groups may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene moieties, in which one or two CH-groups may be replaced by nitrogen atoms. Up to 12 single hydrogen atoms of the CH.sub.2-groups can be independently of each other replaced also on same C-atoms by the halogens fluorine, chlorine, bromine or iodine or the cyano-group or a linear alkylchain with up to 18 C-atoms, in which one up to six CH.sub.2-units can be independently being replaced by carbonylgroups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CHCH-groups, in which a CH-unit can also be replaced by a Nitrogen atom, acetylenic CC-groups, 1,2-1,3- or 1,4-substituted phenyl moieties, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine moieties, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene moieties, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-, or 2,7-disubstituted naphtaline moieties, in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene moieties, in which one or two carbon atoms may be replaced by nitrogen atoms. Up to 12 single hydrogen atoms of the CH.sub.2-groups of the alkyl moieties can each be independently of each other replaced also on same C-atoms by the halogens fluorine, chlorine, bromine or iodine or cyano-groups or linear alkylchains with up to 18 C-atoms, in which one up to six CH.sub.2-units can be independently of each other being replaced by carbonylgroups, oxygen atoms, sulfur atoms, selenium atoms, tellurium atoms, cis- or trans-CHCH-groups, in which a CH-unit can be replaced by a Nitrogen atom, acetylenic CC-Groups 1,2-1,3- or 1,4-substituted phenyl moieties, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-disubstituted pyridine moieties, 2,3-, 2,4-, 2,5- or 3,4-disubstituted thiophene moieties, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6-, or 2,7-disubstituted naphtaline moieties, in which one or two carbon atoms may be replaced by nitrogen atoms, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-disubstituted anthracene moieties, in which one or two carbon atoms may be replaced by nitrogen atoms. Instead of carrying substituents the free valences of the methine groups or the quaternary C-atom respectively can by pairwise connected to form rings like cyclohexanerings. The moieties R.sup.1 to R.sup.9 can furthermore independently of each other mean halogen atoms F, Cl, Br, I.
3. Use of terrylenetetracarboxylicbisimides of the gene formula 5 ##STR00006## for fluorescence coding via the fluorescence decay time, which is characteristic for every marker-polymer-combination (see FIGS. 7 to 15), wherein the moieties R.sup.1 to R.sup.14 have the meaning according to claim 2.
4. Use of perylenetetracarboxylic derivatives of the general formula 6 ##STR00007## for fluorescence coding via the fluorescence decay time, which is characteristic for every marker-polymer-combination (see FIGS. 7 to 15), wherein the moieties R.sup.1 to R.sup.12 have the meaning according to claim 2.
5. Method characterized in that the perylene derivatives according to claim 2 in small concentration are brought into polymer materials and are detected via their fluorescence decay time which is characteristic for every marker-polymer-combination (see FIGS. 7 to 15); preferable concentrations lie between 1 ppb and 100 ppm, most preferably are concentrations between 1 and 100 ppb.
6. Method characterized in that for fluorescence stimulation according to claim 1 pulsed light sources are used; preferred light sources are semiconductor light sources like laser diodes and light diodes, preferably comprising gallium nitride, or also gas discharge lamps.
7. Method characterized in that the detection according to claim 1 is performed using phase-sensitive detectors.
8. Use of the fluorescence decay time according to claim 1 for detecting of polymer materials characterized in that for stimulating the fluorescence periodic pulsed light sources are used and that the fluorescence signal is accumulated and averaged.
9. Use of the fluorescence decay time according to claim 2 for coding of polymer materials characterized in that for stimulating fluorescence periodic pulsed light sources are used and that the fluorescence signal is accumulated and averaged.
10. Use of the fluorescent decay time according to claim 1 for detection of polymer materials for a sorted separation in a completely separated manner for the purpose of recycling; preferred polymeric materials are thermoplastics, and among these in particular preferred polyoxymehtylene (POM), polystyrene (PS), polyamide (PA), polyethylene terephthalate (PET), polycarbonates (PC), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyEtherKetone (PEK) or also aramides, kapton, polysulfone.
11. Use of the fluorescent decay time according to claim 2 for coding of polymer materials for a sorted separation in a completely separated manner for the purpose of recycling; preferred polymeric materials are thermoplastics, And under these in particular preferred polyoxymehtylene (POM), Polystyrene (PS), polyamide (PA), Polyethylene terephthalate (PET), Polycarbonates (PC), polyethylene (PE), polypropylene (PP), Polyvinyl chloride (PVC), PolyEtherKetone (PEK) or also aramides, kapton, Polysulfone.
12. Use of the fluorescence decay time according to claim 2 for coding of polymer materials for their recognition of objects for their clear identification, also in the sense of product counterfeiting.
Description
REFERENCE SIGNS
[0038] FIG. 1. Fluorescence spectra of polymer materials and the optical stimulation at 356 mm. Delrin: Dashed line, Luran; Dotted line. Ultramid: Solid line
[0039] FIG. 2. Fluorescence decay behavior of Luran. Dotted line: time dependent intensity curve of the stimulation lamp. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0040] FIG. 3. Fluorescence decay behavior of Delrin. Dotted line: time dependent intensity curve of the stimulation lamp. solid, Noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing Curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0041] FIG. 4. Fluorescence decay behavior of Ultramid. Dotted line: time dependent intensity curve of the stimulation lamp. Solid, Noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing Curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0042] FIG. 5. Overview of the time-dependent intensity curve off the stimulation lamp parent open dotted line, left her in close. And from left to right the deconvoluted functions of Delrin (solid line), Ultramid (Dotted line) and Luran (dashed line).
[0043] Figure next spring from left to right: UVNISabsorption(each on the left) and fluorescence spectra (each on the right) of perylene ester 1 (buttons), the peryleneimide 2 (solid) and of terryleneimide 3 (best) in chloroform.
[0044] FIG. 7. Fluorescence decay behavior of the ester 1 in Luren; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0045] FIG. 8. Fluorescence decay behavior of the ester 1 in Delrin; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0046] FIG. 9. Fluorescence decay behavior of the ester 1 in Ultramid; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0047] FIG. 10. Fluorescence decay behavior of S-13 (2) in Luran; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0048] FIG. 11. Fluorescence decay behavior of S-13 (2) in Delrin; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0049] FIG. 12. Fluorescence decay behavior of S-13 (2) in Ultramid; fluorescence stimulation at 490 mm, detection at 573 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0050] FIG. 13. Fluorescence decay behavior of the terrylene (3) in Luran; fluorescence stimulation at 490 mm, detection at 667 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0051] FIG. 11. Fluorescence decay behavior of terrylene (3) in Delrin; fluorescence stimulation at 490 mm, detection at 667 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
[0052] FIG. 12. Fluorescence decay behavior of terrylene (3) in Ultramid; fluorescence stimulation at 490 mm, detection at 667 nm. Dotted line: time-dependent intensity curve of the stimulation lamb. Solid, noisy curve: Time curve of the intrinsic fluorescence with deconvoluted function as Balancing curve (mostly covered by the Measured curve). On the right side: Detail of the fluorescence decay curve and balancing function with logarithmic scale.
