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Title:
DETECTION OF DEGRADATION PRODUCTS OF A POLYMER OR POLYMER COMPOSITION
Document Type and Number:
WIPO Patent Application WO/2022/148735
Kind Code:
A1
Abstract:
The present invention relates to a use of a sensor compound according to formula (I) for making detectable the degradation, in particular the degree of degradation, of a polymer or a polymer composition comprising said polymer, a method for said use as well as a polymer composition comprising said sensor compound and a method for detecting the degradation, in particular the degree of degradation, of a polymer comprising monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups or a polymer composition comprising said polymer by using said sensor compound.

Inventors:
BINDER WOLFGANG (DE)
FUNTAN ALEXANDER (DE)
MICHAEL PHILIPP (DE)
ROST SIMON (DE)
OMEIS JÜRGEN (DE)
PRZYBYLA CHRISTIAN (DE)
Application Number:
PCT/EP2022/050046
Publication Date:
July 14, 2022
Filing Date:
January 04, 2022
Export Citation:
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Assignee:
ALTANA AG (DE)
International Classes:
C08K5/18; C08K5/23
Foreign References:
DE102017117478A12019-02-07
Other References:
MOHR GERHARD J. ET AL: "Reversible chemical reactions as the basis for optical sensors used to detect amines, alcohols and humidity", vol. 9, no. 9, 1 January 1999 (1999-01-01), GB, pages 2259 - 2264, XP055815089, ISSN: 0959-9428, Retrieved from the Internet DOI: 10.1039/a901961h
KIRCHNER NICOLE ET AL: "Functional liquid crystal films selectively recognize amine vapours and simultaneously change their colour", no. 14, 1 January 2006 (2006-01-01), pages 1512, XP055815475, ISSN: 1359-7345, Retrieved from the Internet DOI: 10.1039/b517768e
MOHR GERHARD J ET AL: "Effect of the polymer matrix on the response of optical sensors for dissolved aliphatic amines based on the chromoreactand ETH T 4001", ANALYTICA CHIMICA ACTA, 1 January 2000 (2000-01-01), pages 181 - 187, XP055815483, Retrieved from the Internet [retrieved on 20210618], DOI: 10.1016/S0003-2670(00)00794-7
G.J. MOHR ET AL., J. MATER. CHEM., vol. 9, 1999, pages 2259 - 2264
N. KIRCHNER ET AL., CHEM. COMMUN., 2006, pages 1512 - 1514
G.J. MOHR ET AL., ANALYTICA CHIMICA ACTA, vol. 414, 2000, pages 181 - 187
Attorney, Agent or Firm:
ALTANA IP DEPARTMENT (DE)
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Claims:
CLAIMS

1. Use of a sensor compound according to formula (I)

Ar1-[(X=X)n-Ar2]m-C(=0)EWG (I) wherein n represents an integer from 0 to 1, m represents an integer from 1 to 4,

Ar1 represents an optionally substituted C6-20 aryl or C3-9 heteroaryl group,

Ar2 represent an optionally substituted C6-20 aryl or C3-9 heteroaryl group,

X represents CH or N and

EWG represents an electron-withdrawing group, for making detectable the degradation, in particular the degree of degradation, of a polymer or a polymer composition comprising said polymer.

2. Use of a sensor compound according to claim 1, wherein the sensor compound is a compound of formula (II) wherein m, X and EWG are as defined in claim 1 and

EDG is an electron-donating group, preferably an electron-donating group in ortho- and/or para- position to the -X=X- group.

3. Use of a sensor compound according to any one of claims 1 and 2, wherein the sensor compound is a compound of formula (III) wherein m, EDG and EWG are as defined in claims 1 and 2.

4. Use of a sensor compound according to any one of claims 1 to 3, wherein the sensor compound is 4-trifluoracetyl-4’-(dihexylamino)stilbene or 1-[4-(2-{4-[2-(4- dihexylaminophenyl)-vinyl]-phenyl}-vinyl)-phenyl]-2,2,2,-trifluoroethanone.

5. Use of a sensor compound according to any one of claims 1 to 4, wherein the polymer comprises monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups, preferably wherein the polymer is a polyester-based or a polyamide polymer, more preferably wherein the polymer is a polyester-imide-based polymer, a polyester-terephthalate- based polymer, unsaturated or saturated polyester amide polymer or unsaturated or saturated polyester imide polymer, even more preferably an unsaturated or saturated polyester imide polymer.

6. Method of making detectable the degradation, in particular the degree of degradation, of a polymer or a polymer composition comprising said polymer by applying a sensor compound as defined in any one of claims 1 to 4 to a polymer or polymer composition. 7. A polymer composition comprising a polymer comprising monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups, wherein the polymer is a polyester-based or a polyamide polymer, a UV-VIS or fluorescence detectable sensor compound, optionally, a further polymer additive.

8. The polymer composition according to claim 7, wherein the polymer is a polyester- imide-based polymer, a polyester-terephthalate-based polymer, unsaturated or saturated polyester amide polymer or unsaturated or saturated polyester imide polymer.

9. The polymer composition according to claim 7 or 8 wherein the polymer is an unsaturated or saturated polyester imide polymer.

10. The polymer composition according to any one of claims 7 to 9, wherein the UV-VIS or fluorescence detectable sensor compound is capable of reacting with alcohol and/or amine and/or thiol degradation products from the polymer to form a modified UV-VIS or fluorescence detectable sensor compound which has a UV-VIS or fluorescence spectrum different from the UV-VIS or fluorescence detectable sensor compound.

11. The polymer composition according to any one of claims 7 to 10, wherein the UV-VIS or fluorescence detectable sensor compound is defined according to any one of claims 1 to 4.

12. The polymer composition according to any one of claims 7 to 11, wherein the further polymer additive is selected from the group consisting of polymerization inhibitors, paint driers, curing agents, curing accelerators, initiators and any mixture thereof.

13. Method for detecting the degradation, in particular degree of degradation, of a polymer or a polymer composition comprising said polymer by providing a polymer composition according to any one of claims 7 to 12, measuring the UV-VIS or fluorescence spectra of the polymer composition at different time intervals A and B and correlating the difference in the UV-VIS or fluorescence spectra A and B of the polymer composition corresponding to the different time intervals A and B to the degree of degradation of the polymer or polymer composition. 14. Method according to claim 13, wherein the sensor compound is capable of reacting with alcohol and/or amine and/or thiol degradation products from the polymer to form a modified UV-VIS or fluorescence detectable sensor compound which has a UV-VIS or fluorescence spectrum different from the UV-VIS or fluorescence detectable sensor compound.

Description:
DETECTION OF DEGRADATION PRODUCTS OF A POLYMER OR POLYMER

COMPOSITION

Technical Field

The present invention relates to the use of a sensor compound according to formula (I) for making detectable the degradation, in particular the degree of degradation, of a polymer or a polymer composition comprising said polymer, a method for said use as well as a polymer composition comprising said sensor compound and a method for detecting the degradation, in particular the degree of degradation, of a polymer comprising monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups or a polymer composition comprising said polymer by using said sensor compound.

Technical Background

Polymer compositions are widely used as coatings in high performance applications, due to their affordable price, lightweight and processability. During their use, the polymer coatings can be affected by oxygen, light, heat and/or other reactive species which can compromise the structure of the polymer and affect their mechanical performance, appearance and lifetimes. The compromise of the polymers in form of degradation may significantly vary with their application.

In D102017117478 a sensor material is described that can be used to make temperature change in a material (e.g. a polymer matrix) visible through a change of color. The sensor material is directly connected to a solid carrier material.

G.J. Mohr et al, in J. Mater. Chem., 1999, 9, 2259-2264, describe the use of optical sensors to detect certain chemical species, such as hydrazine or glucose. Chromogenic and fluorogenic reactands are used as optical sensor material.

N. Kirchner et al, in Chem. Commun., 2006, 1512-1514, describe the use of functional liquid crystal films to detect the presence of gaseous amines. G.J. Mohr et al, in Analytica Chimica Acta 414 (2000), 181-187, describe the optical sensing of dissolved aliphatic amines through the use of certain chromo reactands. Here the presence of aliphatic amines changes the optical absorption behavior of the optical sensor material.

The state of the art analyses the degradation of polymers, in particular the degree of degradation, of polymers by complex, time and material intensive methods such as by NMR analysis or mass spectrometry or mechanical test methods.

An indicator for making detectable the degradation of polymeric compositions in an easy, time efficient and affordable manner in particular during the use of the polymer composition would be highly desirable to the industry. In particular, an indicator showing the degree of degradation of polymeric compositions in an easy, time efficient and affordable manner would be even more desirable to the industry to thereby provide information about the remaining lifetime of the polymer composition during application.

The present invention provides a sensor compound and polymer compositions comprising said sensor compound meeting these needs of the industry.

Description of the Figures

Figure 1 - Emission spectra of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040 (solid) and FT 1040 without dye (dashed)) stored in gaseous neopentylglycole atmosphere atmosphere at 180°C (A ma x = 447 nm).

Figure 2 - Emission spectra of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040 (solid) and FT 1040 without dye (dashed)) stored in gaseous neopentylglycole atmosphere atmosphere at 180°C (A ma x = 410 nm).

Figure 3 - Emission spectra of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution (1.5 mmol/mL) C (A max = 526 nm).

Figure 4 - UV-VIS absorbence of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution. Figure 5 - Emission spectra of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution C (A max = 479 nm). Figure 6 - UV-VIS absorbence of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT 1040) exposed to n-butylamin solution. Figure 7 - Emission spectra of Stil-3 (0.25 mg/g) embedded in a PS/DVB exposed to n- butylamin solution (1.5 mmol/mL). Figure 8 - UV-VIS absorbence of Stil-3 in a PS/DVB polymer exposed to n-butylamin solution (1.5 mmol/mL). Figure 9 - Emission spectra of Stil-4 (0.25 mg/g) embedded in a PS/DVB polymer exposed to n-butylamin solution. Figure 10 - UV-VIS absorbance of Stil-4 (0.25 mg/g) embedded in a PS/DVB polymer exposed to n-butylamin solution (1.5 mmol/mL).

Detailed Description of the Invention

The present invention relates to the use of a sensor compound according to formula (I)

Ar 1 -[(X=X)n-Ar 2 ] m -C(=0)EWG (I) wherein n represents an integer from 0 to 1, m represents an integer from 1 to 4,

Ar 1 represents an optionally substituted C 6-20 aryl or C 3-9 heteroaryl group,

Ar 2 represent an optionally substituted C 6-20 aryl or C 3-9 heteroaryl group,

X represents CH or N and

EWG represents an electron-withdrawing group, for making detectable the degradation, in particular the degree of degradation, of a polymer or a polymer composition comprising said polymer.

The degradation of the polymer may be due to oxygen, light, heat and/or other reactive species, preferably due to oxygen and/or heat, more preferably due to heat.

Upon degradation, the polymer may release alcohol and/or amine and/or thiol degradation products, preferably alcohol and/or amine degradation product, even more preferably alcohol degradation products. Even more preferably, the alcohol degradation product may be a primary and/or secondary alcohol degradation product from the polymer, the amine degradation product may be a primary and/or secondary amine degradation product from the polymer and the thiol degradation product may be a primary and/or secondary thiol degradation product from the polymer.

The alcohol and/or amine and/or thiol degradation products is/are the result(s) from the reaction of the polymer with oxygen, light, heat and/or other reactive species. The alcohol and/or amine and/or thiol degradation products may be the result of radical oxidation and/or chemical cleavage, such as for example radical cleave, of the polymer or polymer composition. The amount of alcohol and/or amine and/or thiol degradation products from the polymer depends on the polymer and on the degree of degradation.

The sensor compound of the present invention may preferably be UV-VIS or fluorescence active, preferably fluorescence active. The sensor compound of the present invention may preferably react with the alcohol and/or amine and/or thiol degradation products from the polymer or polymer composition to provide a modified sensor compound. The modified sensor compound may preferably be UV-VIS or fluorescence active, preferably fluorescence active.

The alcohol and/or amine and/or thiol degradation products from the polymer or polymer composition are able to react with the carbonyl function of the sensor compound according to the present invention. The alcohol and/or amine and/or thiol degradation products are able to form acetal or hemiacetal functional groups in case of alcohol degradation products, aminal or hemiaminal functional groups in case of amine degradation products and thioacetal or thiohemiacetal in case of thiol degradation products.

Due to the reaction of the alcohol and/or amine and/or thiol degradation products with the carbonyl function of the sensor compound of the present invention, the optical properties, preferably the UV-VIS and fluorescence properties, of the polymer or polymer composition change. The change of the optical properties, preferably the UV-VIS and fluorescence properties, of the polymer or polymer composition indicates a degradation, in particular the degree of degradation, of the polymer or polymer composition. In a preferred embodiment, the degradation is made detectable by UV-VIS or fluorescence, preferably fluorescence, spectroscopy.

The modified senor compound, which reacted with the alcohol and/or amine and/or thiol degradation products, may result in a UV-VIS or fluorescence spectrum, preferably a fluorescence spectrum, which is different from the UV-VIS or fluorescence spectrum, preferably fluorescence spectrum, of the sensor compound of the present invention.

The group -X=X- can be independently selected as a single diastereomer, such as the E or Z diastereomer, or a mixture of diastereomers, such as a mixture of E and Z diastereomers. Preferably, the group -X=X- is in the form of the E diastereomer.

The term aryl is understood as an organic residue with an aromatic hydrocarbon backbone. Usually, an aryl can be a C 6 aryl, i.e. phenyl, or C10 aryl, i.e. naphthyl. Preferably, the aryl is a C 6 aryl, i.e. phenyl.

The term heteroaryl is understood as an organic residue with a heteroaromatic backbone. Heteroaryl is thus the general term for a group derived from heteroaromatic hydrocarbons by deprivation of a hydrogen atom bound to the ring. An heteroaryl group may comprise 1 to 3, preferably 1 to 2, more preferably 1 heteroatom being independently selected from nitrogen, oxygen or sulfur. Preferably, the heteroaryl group is independently selected from the group consisting of furan, thiophene, pyrrole, thiazole, oxazole, pyridine or pyrazine .

The expression optionally substituted is understood in that the reference group, i.e. the aryl or heteroaryl group it refers to, can be substituted or cannot be substituted with a substituent. Substituted means that the reference group can be substituted for example with 1, 2, 3, 4 or maximum 5 substituents, preferably 1 to 3 substituents, more preferably 1 to 2 substituents, even more preferably 1 substituent.

In a preferred embodiment, the optional substitution is in ortho- and/or para-position, preferably in para-position, to the group -X=X- of the aryl or heteroaryl group. In a preferred embodiment, the substituent(s) may independently be selected from the group consisting of halo groups, such as Cl, Br or F, alkyl groups, such as linear or branched C1-5, preferably C1-3, alkyl groups, alkenyl groups, such as linear or branched C1-5, preferably C1-3, alkenyl groups, aryl groups, such as Ce-io, preferably Ce , aryl groups, heteroaryl groups, such as C3-9, preferably C4-5, heteroaryl groups or as defined herein-above, alkoxy groups, such as C1-5, preferably C1-5, alkoxy groups, nitro groups and -N(R 1 R 2 ), wherein R 1 and R 2 are independently selected from linear or branched C1-15, preferably C2-10, more preferably C3-8 alkyl groups, alkenyl groups, such as linear or branched C1-15, preferably C2-10, more preferably C3-8 alkenyl groups, more preferably -N(R 1 R 2 ), wherein R 1 and R 2 are independently selected from linear C1-15, preferably CMO, more preferably C3-8 alkyl groups.

In a preferred embodiment, Ar 1 is an optionally substituted Ce-io aryl group, more preferably an optionally substituted C 6 aryl group.

In a preferred embodiment, Ar 2 is an optionally substituted Ce-io aryl group, more preferably an optionally substituted C 6 aryl group.

In a preferred embodiment, n represents 1.

In a preferred embodiment, m represents an integer from 1 to 3, more preferably represents an integer from 1 to 2, even more preferably represents 1.

In a preferred embodiment, X represents CH.

The abbreviation EWG is understood as an electron withdrawing group. An electron withdrawing group draws electrons away from the center at which it is substituted. An electron withdrawing group may be a nitrile group, a mono-, di-, tri- or oligohaloalkyl group, such as a C1-3 mono-, di-, tri- or oligohaloalkyl group, a Ce-io mono-, di-, tri- or oligohaloaryl group or a tosyl group. In a preferred embodiment, EWG may be a C1-3 mono-, di-, tri- or oligofluoroalkyl group, more preferably -CF3, -CF2H, -CFH2, more preferably -CF3.

The sensor compound may preferably be a compound of formula (II) wherein m, X and EWG are as defined hereinabove and

EDG is an electron-donating group, preferably an electron-donating group in ortho- and/or para-position, preferably in para-position to the -X=X- group.

The abbreviation EDG is understood as an electron donating group. An electron donating group pushes electrons to the center at which it is substituted. An electron donating group may comprise alkyl groups, such as a linear or branched CMO, preferably C alkyl group, alkoxy groups, such as linear or branched C1-5 alkoxy groups or mono- or bis-alkyl amino groups, such as linear or branched mono C1-15 alkyl amino groups or linear or branched C1-15, preferably C2-10, more preferably C3-8 bis-alkyl amino groups, such as -N(R 1 R 2 ), wherein R 1 and R 2 are independently selected from linear C1-15, preferably C2-10, more preferably C3-8 alkyl groups. More preferably, the electron donating group relates to -N(R 1 R 2 ), wherein R 1 and R 2 are independently selected from linear C1-15, preferably C2-10, more preferably C3-8 alkyl groups.

The C(=0)EWG group may preferably be in ortho- and/or para-position, preferably in para- position to the -X=X- group.

The sensor may preferably be a compound of formula (III) wherein m, EDG and EWG are as defined hereinabove.

The sensor compound may preferably be 4-trifluoracetyl-4’-(dihexylamino)stilbene or 1-[4-(2- {4-[2-(4-dihexylaminophenyl)-vinyl]-phenyl}-vinyl)-phenyl]-2 ,2,2,-trifluoroethanone.

The polymer may comprise monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups. Preferably, the polymer comprises monomers having primary and/or secondary alcohol and/or primary and/or secondary amine functional groups. More preferably, the polymer comprises monomers having primary and/or secondary alcohol functional groups.

The polymer may be a polyester-based or a polyamide polymer, more preferably the polymer may be a polyester-imide-based polymer, a polyester-terephthalate-based polymer, unsaturated or saturated polyester-amide-polymer, a polyurethan-based polymer, a polyurea- based polymer or a polyamine-based polymer, preferably a unsaturated or saturated polyester- imide-based polymer, more preferably an unsaturated or saturated polyester-imide based polymer.

The degradation product from the polyester-based or polyamid polymer may preferably be an alcohol degradation product, such as neopentylglycol, or an amine degradation product such as butylamine.

The present invention further relates to a method of making detectable the degradation, preferably the degree of degradation, of a polymer releasing alcohol and/or amine and/or thiol degradation products upon degradation or a polymer composition comprising said polymer by applying a sensor compound as defined herein-above to the polymer or polymer composition.

The embodiments and definitions as described herein-above apply mutatis mutandis to this aspect of the invention.

The present invention further relates to a polymer composition comprising a polymer comprising monomers having primary and/or secondary alcohol and/or primary and/or secondary amine and/or primary and/or secondary thiol functional groups, a UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound, optionally, a further polymer additive.

The embodiments and definitions as described herein-above apply mutatis mutandis to this aspect of the invention.

The UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound may be capable of reacting with alcohol and/or amine and/or thiol degradation products from the polymer to form a modified UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound which has a UV-VIS or fluorescence, preferably fluorescence, spectrum different from the UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound.

In a preferred embodiment, the UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound may be capable of reacting with alcohol and/or amine, preferably alcohol, degradation products from the polymer to form a modified UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound which has a UV-VIS or fluorescence, preferably fluorescence, spectrum different from the UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound.

The UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound may be selected from a 1,2-naphthoquinone-4-sonfonic acid salt -based compound, a Meisenheimer complex-based compound, a Riboflavin-based compound, or a sensor compound according to formula (I) to (III) as defined herein-above.

Preferably, the UV-VIS or fluorescence, preferably fluorescence, detectable sensor compound is defined a sensor compound according to formula (I) to (III) as defined herein-above.

The polymer may be a polyester-based or a polyamide polymer, more preferably the polymer may be a polyester-imide-based polymer, a polyester-terephthalate-based polymer, unsaturated or saturated polyester-amide-polymer, a polyurethan-based polymer, a polyurea- based polymer or a polyamine-based polymer, preferably a unsaturated or saturated polyester- imide-based polymer, more preferably a unsaturated or saturated polyester-imide-based polymer.

The polymer composition may preferably comprise the sensor molecule in amounts from 0.001 to 10 mg/g polymer, preferably in amounts from 0.01 to 5 mg/g polymer, more preferably in amounts from 0.1 to 2.5 mg/g polymer and even more preferably in amounts from 0.125 to 2.0 mg/g polymer.

The polymer composition may comprise further polymer additives being selected from the group consisting of polymerization inhibitors, paint driers, curing agents, curing accelerators, initiators, inorganic additives such as silica (in particular pyrogenic silica) and any mixture thereof.

The polymer composition may be either in uncured form or in cured form.

The present invention further relates to a method for detecting the degree of degradation of a polymer or a polymer composition comprising said polymer by providing a polymer composition as defined herein-above, measuring the fluorescence or UV-VIS, preferably fluorescence, spectra of the polymer composition at different time intervals A and B and correlating the difference in the fluorescence or UV-VIS, preferably fluorescence, spectra A and B of the polymer composition corresponding to the different time intervals A and B to the degree of degradation of the polymer or polymer composition.

Under measurement of the fluorescence or UV-VIS spectra of the polymer composition at different time intervals A and B is herein understood that the fluorescence or UV-VIS, preferably fluorescence, spectra are measured at significant different time intervals, such as at least with a difference in time of at least 1 day (24 h), preferably at least 4 days (96 h), more preferably at least 8 days (192 h), even more preferably at least 11 days (264 h) and even more preferably at least 30 days (720 h). The fluorescence or UV-VIS spectra of the polymer composition at time interval A preferably relates to the time 0, meaning before the polymer composition is applied to conditions inducing degradation, such as heat, light or oxygen, preferably heat.

The fluorescence or UV-VIS spectra of the polymer composition at time interval B preferably relates to a time at least 1 day (24 h), preferably at least 4 days (96 h), more preferably at least 8 days (192 h), even more preferably at least 11 days (264 h) and even more preferably at least 30 days (720 h)after the polymer composition is applied to conditions inducing degradation, such as heat, light or oxygen, preferably heat.

The embodiments and definitions as described herein-above apply mutatis mutandis to this aspect of the invention.

Examples

1. Synthetic procedure for the synthesis of sensor molecules Stil-3 and Stil-4

2,2,2-Trifluoro-1-(4-vinylphenyl)ethan-1-one (1):

A two-neck flask was heated under vacuum and flushed with nitrogen three times. It was charged with Mg-turnings (1.82 g, 75.00 mmol, 1.50 eq.) and dry THF (50 ml_) was added. Afterwards 4-bromostryene (6.50 ml_, 50.00 mmol, 1.00 eq.) was added via syringe and the reaction was initiated by hand warmth. The reaction turned yellow and was allowed to cool down to room temperature and was stirred for 1 h. After addition of dry THF (5.00 ml_) the reaction mixture was cooled down to -78 °C. Ethyl trifluoroacetate (9.00 ml_, 75.00 mmol, 1.50 eq.) was added dropwise via syringe and the reaction was allowed to run for 1 h at -78 °C. After the solution was warmed up to 0 °C 1 M HCI (100.00 ml_) was slowly added and the reaction mixture was extracted with ethyl acetate (3 x 100.00 ml_). The combined organic phases were washed with brine and dried over Mg2SC>4. The solvent was removed under vacuum and the crude product was purified by column chromatography using pentane / diethyl ether (v/v = 50 : 1) and isolated as a colorless oil.

Synthesis of p-lodo-N,N-dihexylaniline (2): A mixture of p-iodoaniline (3.79 g, 17.31 mmol), 1-bromohexane (8.50 ml_, 10.00 g, 60.58 mmol, 3.50 eq.), N-ethyldiisopropylamine (10.34 ml_, 7.83 g, 60.58 mmol) and dimethylformamide (15 mL) was stirred at 110°C for 20 h. After cooling to room temperature, the reaction mixture was poured on 100 ml of distilled water and the product was extracted with chloroform (3 x 50 mL). The combined organic phase was washed with distilled water (2 x 75 mL) and dried over MgaSCL. The obtained oil was purified by flash chromatography on silica gel using hexane / ethyl acetate (19 : 1 = v/v) as the eluent, yielding 2 as a yellow liquid.

Synthesis of 4-Bromo-4’-(dihexylamino)stilbene (3):

A mixture of 2 (9.00 g, 23.40 mmol), 4-bromostyrene (3.78 ml, 5.31 g, 29.25 mmol, 1.25 eq.), palladium diacetate (57.78 mg, 0.261 mmol, 0.011 eq.), tri-o-tolylphosphine (150.84 mg, 0.495 mmol, 0.021 eq.) and triethylamine (19.26 mL, 138.06 mmol, 5.90 eq.) was dissolved in dry DMF (30.00 mL) and refluxed at 115°C under nitrogen. To the cooled solution water and chloroform were added and the aqueous layer was extracted with chloroform (3 x 50 mL). The combined organic layer was washed distilled water (3 x 75 mL), dried over MgaSCL. The crude product was purified by column chromatography on silica gel using hexane / chloroform (2 : 1 = v/v) as the eluent and afterwards was recrystallized from methanol yielding 3 as a yellow solid.

4-trifluoracetyl-4’-(dihexylamino)stilbene (Stil-3):

3 (250.0 mg g, 0.55 mmol) was dissolved in 5 ml of dry tetrahydrofuran and cooled to -78 °C using methanol / liquid nitrogen as the cooling agent. To the stirred solution was added a 1.6 M solution of butyllithium in hexane (387.5 pi, 0.65 mmol, 1.10 eq.) and stirring was continued for 30 min. Then, ethyl trifluoroacetate (70.0 pL, 0.85 mmol, 1.03 eq.) was added and the solution was stirred for another 60 min. The solution was warmed up to room temperature, 1 ml of methanol was added and, subsequently, 20 ml of diethylether. The orange solution was washed once with 3 ml of 1 M hydrochloric acid, 3 ml of a sodium bicarbonate solution and twice with 15 ml of distilled water. After drying over MgaSCL and evaporation to dryness, the orange oil was purified by flash chromatography on silica gel hexane / dichloromethane (v/v =

4 : 1) as the eluent, yielding Stil-3 as orange crystals.

1-r4-(2-(4-r2-(4-dihexylaminophenyl)-vinyl1-phenyl)-vinyl )-phenyl1-2,2,2,-trifluoroethanone

(Stil-4) A two-neck flasked was heated under vacuum and flushed with nitrogen three times. Then 3 (2.00 g, 4.52 mmol, 1.15 eq.), 1 (788.64mg, 3.94 mmol, 1.00 eq.) and dichlorobis- (triphenylphosphine)-palladium(ll) (74.66 mg, 0.10 mmol, 0.027 eq.) were dissolved in triethylamine (15.00 ml_, 108.00 mmol, 27.4 eq.) and dry DMF (16.00 ml_). The reaction mixture was stirred at 115 °C for 16 h. The solution was allowed to cool down and water (50.00 ml_) was added. The aqueous layer was extracted with DCM (3 x 50.00 ml_) and the combined organic layers were washed with distilled water (3 x 100.00 ml_). After the organic layer was dried with Mg2SC>4 the solvent was removed under vacuum and the crude product was purified by column chromatography on neutral AI 2 O 3 using hexane/ethyl acetate (v/v = 2 : 1) as the eluent, yielding Stil-4 as red crystals.

2. Formulation of a polymer composition comprising a sensor molecule

2.1. Poly(ester imide) composition according to the invention

Protocol for preparation of poly(ester imide) (PEI)-specimen

For the preparation of the poly(ester imide) PEI-specimen commercial available poly(ester imide) polymers (Dobeckan® FT 1040/120 A and Dobeckan® FT 1040/120 B) were used without addition of any further additives (except Stil-3 and Stil-4).

The poly(ester imide) polymers (Dobeckan® FT 1040/120 A and Dobeckan® FT 1040/120 B) were mixed in a ratio of 1 : 1 (wt%). The mixture was transferred into a teflon mould (25 mm x 10 mm x 2 mm) and curing was done by storing the teflon mould within a petri-dish in an pre-heated oven at 80 °C for 50 minutes, followed by 5 minutes at 140 °C. After cooling down, the specimen was removed from the mould, having a transparent, yellowish/brownish appearance.

Embedding of sensor molecule (Stil-3 and Stil-4) into the poly(ester imide) polymer

(Dobeckan® FT 1040/120 A+B)

The poly(ester imide) polymers (Dobeckan® FT 1040/120 A and Dobeckan® FT 1040/120 B) were mixed in a ratio of 1 : 1 (wt%). The required amount of dye Stil-3 or Stil-4 (dye concentrations were between 0.125 mg/g PEI resin up to 2 g/g PEI resin) was dissolved in the mixture of the poly(ester imide) polymers (Dobeckan® FT 1040/120 A+B). The mixture was transferred into teflon mould (25 mm x 10 mm x 2 mm) and curing was done by storing the teflon mould within a petri-dish in an pre-heated oven at 80 °C for 50 minutes, followed by 5 minutes at 140 °C. After cooling down, the specimen was removed from the mould, having a transparent, yellowish (Stil-3) and orange (Stil-4) appearance. For detailed information see Table 1.

Figure 1 describes the emission spectra of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040 (solid) and FT 1040 without dye (dashed)) stored in gaseous neopentylglycole atmosphere atmosphere at 180°C (A max = 447 nm). Figure 1 describes that the emission spectra for a polymer composition comprising Stil-3 reduces over the course of degradation from day 0 to day 30 and therefore shows the degradation over a certain lifetime.

Figure 2 describes the emission spectra of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040 (solid) and FT 1040 without dye (dashed)) stored in gaseous neopentylglycole atmosphere atmosphere at 180°C (A max = 410 nm). Figure 2 describes that the emission spectra for a polymer composition comprising Stil-4 reduces over the course of degradation from day 0 to day 30 and therefore shows the degradation over a certain lifetime.

Figure 3 describes the emission spectra of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution (1.5 mmol/mL) C (A max = 526 nm). Figure 3 describes that the emission spectra for a polymer composition comprising Stil-3 reduces over the course of degradation from day 0 to day 11 and therefore shows the degradation over a certain lifetime. Figure 4 describes the UV-VIS absorbence of Stil-3 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution. Figure 4 describes that the absorbance spectra for a polymer composition comprising Stil-3 increases over the course of degradation from day 0 to day 11 and therefore also shows the degradation over a certain lifetime.

Figure 5 describes the emission spectra of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution C (A ma x = 479 nm). Figure 5 describes that the emission spectra for a polymer composition comprising Stil-4 reduces over the course of degradation from day 0 to day 11 and therefore shows the degradation over a certain lifetime.

Figure 6 describes the UV-VIS absorbence of Stil-4 (1 mg/g) embedded in an poly(ester imide) polymer (Dobeckan® FT1040) exposed to n-butylamin solution. Figure 6 describes that the emission spectra for a polymer composition comprising Stil-4 increases over the course of degradation from day 0 to day 11 and therefore shows the degradation over a certain lifetime.

2.2. Polv(styrene divinylbenzene) (PS/DVB) composition according to the present invention

Preparation of Polv(styrene divinylbenzene) PS/DVB formulation

Prior usage styrene (50 ml_) was extracted with NaOH (10 wt%) (2 x 25 ml_) and washed with distilled water (3 x 25 ml_). Afterwards the destabilization styrene was dried over Na2SC>4 and filtered into a flask. The initiator azobis(isobutyronitril) (AIBN) (1 mol% referred to styrene) was weighed in and dissolved in styrene and divinylbenzene (4 mol% referred to styrene).

The reaction mixture was transferred into a teflon mould (25 mm x 10 mm x 2 mm) and was stored in an oven at 78 °C for 3 hours. During the curing process the teflon mould was covered with a watch glass to reduce the evaporation of styrene. After 3 hours the polymer was obtained as a transparent, colorless, glass-like specimen. Embedding of dye into a Polvfstyrene divinylbenzene) PS/DVB matrix

The required amount of dye Stil-3 or Stil-4 (dye concentrations were between 0.125 mg/g PS/DVB up to 0.5 mg/g PS/DVB) was dissolved in the reaction mixture of styrene, divinylbenzene (4 mol% referred to styrene) and AIBN (1 mol% referred to styrene). The reaction solution was transferred into a teflon mould (25 mm x 10 mm x 2 mm) and was stored in an oven at 78 °C for 3 hours. During the curing process the teflon mould was covered with a watch glass to reduce the evaporation of styrene. After 3 hours the polymer was obtained as a transparent, yellow/orange, glass-like specimen. For detailed information see Table 2.

Figure 7 describes the emission spectra of Stil-3 (0.25 mg/g) embedded in a PS/DVB polymer composition exposed to n-butylamin solution (1.5 mmol/mL). Figure 7 describes that the emission spectra for a polymer composition comprising Stil-3 reduces over the course of degradation from day 0 to day 11 and therefore shows the degradation over a certain lifetime.

Figure 8 describes the UV-VIS absorbance of Stil-3 in a PS/DVB polymer composition exposed to n-butylamin solution (1.5 mmol/mL). Figure 8 describes that the absorbance spectra for a polymer composition comprising Stil-3 increases at A ma x = ??? nm over the course of degradation from day 0 to day 11 and decreases at A ma x = ??? nm over the course of degradation from day 0 to day 11 and therefore also shows the degradation over a certain lifetime.

Figure 9 describes the emission spectra of Stil-4 (0.25 mg/g) embedded in a PS/DVB polymer composition exposed to n-butylamin solution. Figure 9 describes that the emission spectra for a polymer composition comprising Stil-3 reduces at A max = 557 nm over the course of degradation from day 0 to day 11 and increases at A max = 475 nm over the course of degradation from day 0 to day 11 and therefore shows the degradation over a certain lifetime.

Figure 10 describes the UV-VIS absorbance of Stil-4 (0.25 mg/g) embedded in a PS/DVB polymer composition exposed to n-butylamin solution (1.5 mmol/mL). Figure 10 describes that the absorbance spectra for a polymer composition comprising Stil-4 increases over the course of degradation from day 0 to day 11 and therefore also shows the degradation over a certain lifetime.

3. Method of measuring the degradation of the polymer composition

UV-VIS spectra were recorded on a Perkin Elmer UV/VIS Lambda 365 spectrometer equipped with a Lambda 365 Integrating sphere. Spectra were measured at room temperature in the spectral range of 300 - 700 nm and analyzed with the software UV Express - version 4.1.0.

Fluorescence spectra were recorded on an Agilent Technologies Cary Eclipse Fluorescence Spectrophotometer and analyzed with the Cary Eclipse Scan Application 1.2 (147). The solid samples were clamped at the height of the excitation beam inside the spectrometer and were measured using excitation wavelengths of 447 nm (for Stil-3 in the poly(ester imide) polymer composition (FT 1040/120 A+B)) and 410 nm (for Stil-4 in the poly(ester imide) polymer composition (FT 1040/120 A+B)). Detector voltage was set to 500 V. Fluorescence measurements so far are the better analytic method, due to less matrix interference and better detectability of the sensor molecule.