Fluorescent siloxane elastomer, method for synthesis of the same and the use

Abstract

The invention relates to a fluorescent siloxane elastomer, to a method for producing same, and to the use. The fluorescent siloxane elastomer contains the following structural elements in the network structure thereof: (I) and (II) or (III), wherein: R1 and R2 are the same or different and mean, independently of each other, a methyl, phenyl, vinyl substituent or an H atom; X means a saturated or unsaturated hydrocarbon group having 2 to 6 C atoms; A is an oxygen, nitrogen, or sulfur atom; R3 is a fluorescent dye substituent from the families of the BODIPY or BODIPY and coumarin or BODIPY and naphthalimide or coumarin and naphthalimide fluorophores. The polysiloxanes according to the invention cause a shift in the emission range out of the UV light or expansion of the emission range into the range of visible light having wavelengths of up to 800 nm, and therefore the polysiloxanes are especially suited for detectors having the maximum efficiency thereof in the range. In the combination of the optical, electrical, mechanical, and thermal properties of the polysiloxanes, the polysiloxanes differ substantially from polysiloxanes according to the prior art. The polysiloxanes form the basis for a material that meets the high requirements for high-voltage devices and can be used in particular for monitoring the aging process of insulating means in high-voltage systems. Partial electrical discharges can be reliably optically detected and localized by means of the polysiloxanes.

Claims

1. A fluorescent siloxane elastomer that contains, in its network structure, the following structural elements: ##STR00008## where: R1 and R2 are identical or different, and independently of one another respectively denote a methyl, phenyl, vinyl substituent or an H atom; X denotes a saturated or unsaturated hydrocarbon group with 2 to 6 C atoms; A represents an oxygen atom, or a sulfur atom; R3 is a fluorescent dye substituent from BODIPY fluorophores.

2. The fluorescent siloxane elastomer according to claim 1, wherein the fluorescent-dye substituent R3 has the general formula ##STR00009## in which: R4, R5 may be identical or different and denote a hydrogen atom, a fluorine atom or a trifluoromethyl radical, R6 represents a CH.sub.3 or C.sub.2H.sub.5 group; R7 denotes a CH.sub.3, C.sub.2H.sub.5, 4-dimethylaminostyryl, 3,5-ditrifluoromethylstyryl or 4-dimethylaminonaphthylvinyl radical.

3. The fluorescent siloxane elastomer according to claim 1, wherein the BODIPY fluorophores together with coumarin fluorophores form the fluorescent dye substituents.

4. The fluorescent siloxane elastomer according to claim 3, wherein the coumarin fluorphores have the general formula ##STR00010## in which: R4 denotes an H atom or an OCH.sub.3, NHCH.sub.3, N(CH.sub.3).sub.2, NH(C.sub.2H.sub.5) or N(C.sub.2H.sub.5).sub.2 radical; R5 is an H atom or F atom or a CH.sub.3, CF.sub.3 radical; R6, R7 may be identical or different and represent an H atom or a CH.sub.3 radical, R8 represents a COO, CONH, CON(CH.sub.2CHCH.sub.2) or SO.sub.2NH, SO.sub.2N(CH.sub.2CHCH.sub.2) group.

5. The fluorescent siloxane elastomer according to claim 1, wherein the BODIPY fluorophores together with naphthalimide fluorophores form the fluorescent dye substituents.

6. The fluorescent siloxane elastomer according to claim 5, wherein the naphthalimide fluorophores have the general formula ##STR00011## in which: R4 denotes a CH.sub.3, C.sub.2H.sub.5, C.sub.3H.sub.7, phenyl, mesityl or a (2,6-diisopropyl)phenyl group; R5 represents an H atom or a CH.sub.3, OCH.sub.3, or O(C.sub.6H.sub.5) radical.

7. The fluorescent siloxane elastomer according to claim 1, wherein the refractive index lies in the range of 1.40 to 1.60 and/or in that after the curing it is a transparent or translucent elastomer.

8. The fluorescent siloxane elastomer according to claim 1, wherein it has absorption and emission maxima in the wavelength range of 300 nm to 800 nm.

9. The fluorescent siloxane elastomer according to claim 1, wherein the fluorescent siloxane elastomer is temperature-resistant up to 150 C. and/or is aging-resistant in the electrical field of a high-voltage device for voltages from 1 kV to 500 kV.

10. The fluorescent siloxane elastomer according to claim 1, wherein the fluorescent siloxane elastomer has a dye concentration of 5 ppm to 500 ppm.

11. The fluorescent siloxane elastomer according to claim 1, wherein the fluorescent siloxane elastomer contains a filler.

12. The fluorescent siloxane elastomer according to claim 11, wherein the filler is fumed silica or titanium dioxide or aluminum oxide or zirconium oxide.

13. The fluorescent siloxane elastomer according to claim 1, wherein it has an elongation to break of up to 400%.

14. A method for synthesis of a fluorescent siloxane elastomer according to claim 1, comprising: Functionalization of the fluorescent dye with an unsaturated hydrocarbon group for a hydrosilylation reaction in a polar solvent at elevated temperature and under a nitrogen atmosphere at normal pressure or an elevated pressure, Reaction of the functionalized dye with an H-siloxane in a nonpolar solvent in the presence of platinum or rhodium as the hydrosilylation catalyst at room temperature or an elevated temperature, Removal of the catalyst by means of a sorbent and of the solvent under reduced pressure, Mixing of an addition-crosslinking, two-component siloxane mixture with the functionalized H-siloxane at room temperature, Curing of the siloxane mixture at an application-specific temperature of up to 200 C.

15. The method according to claim 14, wherein the polar solvent is acetonitrile or an alcohol and the nonpolar solvent is toluene or another aromatic hydrocarbon, an aliphatic or a chlorinated hydrocarbon, a cyclic ether or a vinylsiloxane.

16. The method according to claim 14, wherein the sorbent is a copolymer of divinylbenzene and vinylimidazole.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The invention will be explained in more detail in the following on the basis of examples, each in conjunction with drawings. There are denoted or shown by:

(2) Example 1: Allylation of the BODIPY fluorescent dye M5

(3) FIG. 1 Chromatograms of the reaction of M5 with allyl bromide

(4) FIG. 2 HPLC chromatogram of the dye M5-allyl after workup

(5) Example 2: Covalent binding of the dye M5-allyl to an H-siloxane

(6) FIG. 3 GPC graph of the covalent binding of the dye M5-allyl to an H-siloxane

(7) Example 3: Synthesis of a fluorescent polysiloxane with a refractive index of 1.43 and covalently bound dye M5

(8) FIG. 4 Fluorescence spectra of the dye M5, covalently bound in a polysiloxane matrix, at a concentration of 50 ppm M5-allyl

(9) FIG. 5 Fluorescence spectra of the dye M5, covalently bound in a polysiloxane matrix, at a concentration of 100 ppm M5-allyl

(10) FIG. 6 Fluorescence spectra of the dye M5, covalently bound in a polysiloxane matrix, at a concentration of 200 ppm M5-allyl

(11) Example 4: Synthesis of the coumarin dye F4

(12) Example 5: Covalent addition of the dye F4 to an H-siloxane

(13) FIG. 7 GPC graph of the covalent binding of the dye F4-allyl to an H-siloxane

(14) Example 6: Synthesis of a fluorescent polysiloxane with a refractive index of 1.43 and covalently bound dye F4

(15) FIG. 8 Fluorescence spectra of the dye F4, covalently bound in a polysiloxane matrix

(16) Example 7: Synthesis of a fluorescent polysiloxane with a refractive index of 1.43 and covalently bound dyes F4 and M5

(17) FIG. 9 Fluorescence spectra of the dye combination F4+M5, covalently bound in a polysiloxane matrix

(18) FIG. 10 Fluorescence absorption and emission spectra of the dyes F4 and M5 in comparison with the partial-discharge emission spectrum

(19) Example 8: Synthesis of fluorescent polysiloxanes with a refractive index of 1.54 and covalently bound dye M5

(20) FIG. 11 Fluorescence spectra of the dye M5, covalently bound in a high-refractive-index polysiloxane matrix

(21) FIG. 12 Fluorescence spectra of the dye M5, covalently bound in a high-refractive-index polysiloxane matrix, dye concentration 80 ppm

(22) FIG. 13 Fluorescence spectra of the dye M5, covalently bound in a high-refractive-index polysiloxane matrix, dye concentration 120 ppm

(23) Example 9: Synthesis of the naphthalimide dye F6

(24) FIG. 14 Excerpt of the .sup.1H-NMR spectrum in CDCl.sub.3 of F6 before reaction with an excess of 1,1,3,3-tetramethyldisilane

(25) FIG. 15 Excerpt of the .sup.1H-NMR spectrum in CDCl.sub.3 of F6 after reaction with an excess of 1,1,3,3-tetramethyldisilane

(26) Example 10: Determination of mechanical properties

(27) Example 11: Determination of electrical properties

EXAMPLES

Example 1

Allylation of the BODIPY Fluorescent dye M5

(28) The fluorescent dye M5 used (Hecht M. et al., Chemistry Open 2 (2013), pp. 25-38, DOI: 10.1002/open.201200039) has the following structure:

(29) ##STR00005##

(30) Systematic name according to IUPAC: 8-(4-hydroxyphenyl)-1,3,5,7-tetramethyl-2,6-diethyl-4,4-difluoro-4-bora-3a,4a-diaza-s-indacene

(31) Synthesis

(32) In a 10-mL microwave pressure vessel with septum, 70 mg (0.177 mmol) of the dye M5 in 8 mL n-propanol was introduced first then 8.5 mg (0.212 mmol) NaOH was added with stirring. The reaction mixture was stirred at room temperature until complete dissolution. A zero sample (10 L reaction solution) was withdrawn, diluted with 990 L acetonitrile and investigated with HPLC. Thereupon 25.6 mg (18 L, 0.212 mmol) allyl bromide was added then the vessel was tightly sealed and heated to 95 C. To follow the reaction, 10-L samples of reaction solution were withdrawn after 1.5 h and after 3.5 h respectively, diluted with acetonitrile as above and investigated with HPLC. FIG. 1 shows the chromatograms obtained. The degree of conversion determined by means of HPLC (at 520 nm) was 98%.

(33) Analytics

(34) Tracking of the degree of conversion was carried out on a Waters-HPLC alliance 2625 system with diode array detector and a Gemini C18 column (Phenomenex GmbH) at 35 C.

(35) Acetonitrile/water with a gradient from 20:80 to 95:05 was used as eluent. The determination of the degree of conversion was carried out by means of the peak-area integration method at 520 nm.

(36) Workup of the Reaction Solution

(37) The reaction was ended after 4 h, the reaction solution was filtered over a glass frit and washed several times with n-propanol. Then the filtrate was evaporated to dryness on the rotary evaporator. The solid residue was taken up in 15 mL of a mixture of tert-butyl methyl ether and cyclohexane then transferred into a separating funnel.

(38) The organic phase was then washed three times in succession with respectively 10% KOH, 5% NaHCO.sub.3 and distilled water and then was dried overnight over sodium sulfate.

(39) The dried organic phase was filtered off from the sodium sulfate and the filtrate was evaporated to dryness on the rotary evaporator. The residue was dried to constant weight in the circulating-air oven then weighed. The yield was 69.5 mg, or 90% of theory. The purity of the worked-up product was retested with the HPLC (FIG. 2). The fine purification of the product was then carried out on a preparative chromatography system (Waters Inc., USA) with an XTerra-C18 column (21 mm dia.150 mm) with acetonitrile/water as the mobile phase and photodiode array-detector.

Example 2

Covalent Binding of the Dye M5-Allyl to an H-Siloxane

(40) Synthesis

(41) In a 10-mL two-necked flask equipped with reflux condenser, water bath and magnetic stirrer, 1.25 g HMS-501 (ABCR GmbH) in 1.5 mL toluene was dissolved with stirring. Then 4 mg of the dye M5-allyl (M=436.8 g/mol) from Example 1 was dissolved at room temperature with stirring and 50 L reaction solution, diluted with 1 mL THF, was withdrawn as the zero sample for the GPC investigation. HMS-501 is a low molecular weight H-siloxane (M=1000 g/mol), consisting of approximately 50 mol % methyl hydride siloxane and 50 mol % dimethylsiloxane basic units, which is not visible in the GPC chromatogram with THF as the mobile phase. Therefore the zero sample in FIG. 3 exhibits only the signal of the dye M5-allyl at an elution volume of 24.3 mL. Instead of toluene, it is also possible to use another aromatic hydrocarbon, a cyclic ether, a chloroalkane or a vinylsiloxane or even an aliphatic hydrocarbon as the solvent.

(42) The reaction solution was then purged for 7 minutes with nitrogen and sealed with a septum as well as an N.sub.2 balloon. Then 10 L of the diluted platinum catalyst SIP 6831.2 (ABCR GmbH, dilution 1:10 with xylene) was added via the septum and the reaction temperature was raised to 50 C. For tracking of the conversion, 50 L of reaction solution was withdrawn every hour, diluted with 1 mL THF and investigated with the GPC. The chromatograms obtained are presented in FIG. 3. It is also possible to use rhodium as the catalyst.

(43) After 3 h of reaction time at 50 C., the reaction temperature was raised to 80 C. and stirring was continued at this temperature for a further 3 h. The GPC chromatograms in FIG. 3 show that, after this time, the dye M5-allyl is covalently bound almost completely to the H-siloxane. The covalently modified H-siloxane is now visible at a broader peak between 22 mL and 16 mL elution volume, whereas the dye peak at 23 mL is still present only in traces.

(44) Analytics

(45) For tracking of the reaction, a GPC system (Knauer GmbH, Berlin, Germany) with UV and RI detectors and 3 PL gel 3007.5 mm GPC columns (Polymer Laboratories Ltd., Great Britain) with exclusion limits of 100 , 500 and Mixed-B was used. THF with a flow velocity of 1 mL/min was used as the mobile phase.

(46) Workup of the Reaction Product

(47) For removal of the catalyst and of dye residues, the reaction mixture was diluted with 1.5 mL toluene and filtered through a 6-mL SPE column packed with 200 mg Spheropor H sorbent (Polymerics GmbH, Berlin, Germany) and post-rinsed 2 times with 1.5 mL toluene. The filtrates were then freed from toluene at 60 C. and 21 mbar vacuum on the rotary evaporator. 1.0528 g of yellow-fluorescing H-siloxane was obtained as an orange liquid. This siloxane was labeled as H-siloxane-M5.

Example 3

Synthesis of a Fluorescent Polysiloxane with a Refractive Index of 1.43 and Covalently Bound Dye M5

(48) For the synthesis, the addition-crosslinking 2-component siloxane system MED 6210 (Nusil Technology LLC, Carpinteria, Calif., USA) according to Table 1 was weighed in and homogenized.

(49) TABLE-US-00001 TABLE 1 Test specimens of MED 6210, covalently modified with M5 MED MED M5 concentration in No. 6210 A 6210 B H-siloxane-M5 the matrix 1 2 g 1.935 g 0.062 g 50 ppm 2 2 g 1.875 g 0.125 g 100 ppm 3 2 g 1.750 g 0.250 g 200 ppm

(50) The homogenized mixtures were then deaerated in the vacuum drying chamber and cured between two polycarbonate plates with 1-mm spacers in the circulating-air oven for 2 h at 120 C. to obtain transparent, pink-colored plate-shaped test specimens with a geometry of 50 mm50 mm1 mm.

(51) The test specimens obtained in this way were excited with monochromatic wavelengths of 450 nm to 540 nm in the fluorescence spectrometer (Varian Inc., USA, Equlip model) and the respective fluorescence spectrum was recorded. The fluorescence emission spectra of samples 1 to 3 are presented in FIG. 4, FIG. 5 and FIG. 6. The fluorescence spectra show that the covalently bound dye M5 in the MED 6210 polysiloxane matrix absorbs in the wavelength range from 450 nm to 540 nm, and in the wavelength range from 530 nm to 650 nm emits an intense fluorescence inversely proportional to the concentration of the dye in the matrix.

(52) The determination of the fluorescence quantum yield of this fluorescent polysiloxane unexpectedly yielded the same value of .sub.F=0.92 as for the non-covalently bound dye M5 in diethyl ether. The binding of the dye to the polysiloxane chain did not reduced its emission intensity.

(53) Furthermore, an extraction experiment (72 h with CH.sub.2Cl.sub.2) showed that the bound dye is resistant to migration. This means that the optical properties of this polymer can advantageously be stably preserved over the long term.

Example 4

Synthesis of the Coumarin Dye F4

(54) The synthesized fluorescent dye F4 has the following structure:

(55) ##STR00006##

(56) 400 mg 7-diethylamino-3-thiophen-2-yl-chromen-2-one (FEW Chemicals GmbH, Germany) was introduced first into a single-necked flask and dissolved in 20 mL chloroform. Then 2 mL chlorosulfonic acid was added dropwise at 0 C. and the reaction solution was heated slowly to room temperature within 30 minutes. After 2 hours, ice water was added to the red reaction solution. The reddish precipitate was removed by suction, washed with 50 mL each of saturated sodium hydrogen carbonate solution, water (2 times) and methanol (2 times) and then dried in vacuum.

(57) In a single-necked flask, 0.109 g diallylamine hydrochloride was introduced first and dissolved in a mixture of 6 mL acetonitrile, 4 mL chloroform and 3 mL triethylamine. To this solution, 236 mg of the reddish sulfochloride was added with stirring, then the mixture was stirred for 16 hours at 50 C. Then the solvent was removed under reduced pressure and the raw product was taken up in 50 mL dichloromethane. The green solution was washed with 50 mL each of saturated sodium hydrogen carbonate solution (2 times), 10% citric acid (2 times) and saturated aqueous sodium chloride solution then dried over magnesium sulfate. The residue was then purified by column chromatography on silica gel 60 and the product was eluted with a mixture of dichloromethane and cyclohexane (3:1). After the solvent mixture was removed in vacuum, 197 mg of F4 was obtained.

(58) .sup.1H NMR (400 MHz): [ppm]=7.99 (s, 1H), 7.52 (d, J=1.2 Hz, 2H), 7.36 (d, J=8.9 Hz, 1H), 6.65 (dd, J=8.7, 2.7 Hz, 1H), 6.54 (d, J=2.5 Hz, 1H), 5.70 (tdd, J=16.6, 10.1, 6.4 Hz, 2H), 5.19 (ddd, J=17.1, 1.2 Hz, 4H), 5.17 (ddd, J=10.7, 1.2 Hz, 4H), 3.85 (d, J=6.3 Hz, 4H), 3.45 (q, J=7.2 Hz, 4H), 1.24 (t, J=7.1 Hz, 6H).

(59) Quantum yield of F4 (10.sup.5 M) in Momentive RTV 655: .sub.eX (421)=0.89.

Example 5

Covalent Addition of the Dye F4 to an H-Siloxane

(60) Synthesis

(61) By analogy with Example 2, 1.25 g HMS-501 (ABCR GmbH, Germany) was dissolved in 4 mL toluene in a 10-mL two-necked flask equipped with reflux condenser, magnetic stirrer and water bath, and 4 mg (8.72.Math.10.sup.6 mol) of the coumarin dye F4 (M=458.59 g/mol) was added. The dye dissolved gradually with stirring at 50 C. After dissolution, 30 L of the reaction mixture was withdrawn as zero sample, diluted with 450 L THF and investigated with the GPC. The reaction apparatus was then purged for 7 minutes with nitrogen and sealed with a septum as well as an N.sub.2 balloon. Then 10 L of the diluted platinum catalyst (SIP 6831.2 of ABCR GmbH, Germany, dilution 1:10 with xylene) was added via the septum and the reaction was started at 50 C. For tracking of the conversion, 4 samples of 30 L were withdrawn within a reaction time of 3.5 h, diluted as above and investigated with the GPC. The GPC chromatograms obtained are presented in FIG. 7. The comparison of the different graphs shows that the reaction is largely completed after 3.5 h.

(62) Surprisingly, no crosslinking of the H-siloxane was observed during the reaction, despite two reactive allyl substituents.

(63) Workup of the Reaction Product

(64) For removal of the catalyst and of the unreacted dye residues, the reaction mixture was filtered through a 6-mL SPE column containing 200 mg Spheropor H sorbent (Polymerics GmbH, Berlin, Germany) and post-rinsed 2 times with 1.5 mL toluene. The filtrates were united and freed from toluene at 60 C. and 21 mbar vacuum on the rotary evaporator. 1.0151 g of fluorescent H-siloxane was obtained as green liquid. This H-siloxane was labeled as H-siloxane-F4.

Example 6

Synthesis of a Fluorescent Polysiloxane with a Refractive Index of 1.43 and Covalently Bound Dye F4

(65) For the synthesis, the addition-crosslinking 2-component siloxane MED 6210 (Nusil Technology LLC, Carpinteria, Calif., USA) according to Table 2 was weighed in and homogenized.

(66) TABLE-US-00002 TABLE 2 Test specimens of MED 6210, covalently modified with F4 MED MED F4 concentration in No. 6210 A 6210 B H-siloxane-F4 the matrix 4 1.5 g 1.404 g 0.096 g 102 ppm

(67) Then the mixture was deaerated in the vacuum drying chamber and cured between two polycarbonate plates with spacers of 1 mm to obtain a transparent, green-colored plate with a geometry of 40 mm40 mm1 mm. Curing took place for 2 h at 120 C.

(68) The plate obtained in this way was excited with monochromatic light of wavelengths of 380 nm to 460 nm in the fluorescence spectrometer (Varian Inc., USA, Equlip model) and the respective fluorescence emission spectrum was recorded. The fluorescence emission spectrum of sample 4 is presented in FIG. 8. The fluorescence spectra in FIG. 8 show that the covalently bound dye F4 in the MED 6210 polysiloxane matrix can be advantageously excited in the UV range with wavelengths of 380 nm to 460 nm and in the visible range between 470 nm and 600 nm emits an intense fluorescent light.

Example 7

Synthesis of a Fluorescent Polysiloxane with a Refractive Index of 1.43 and Covalently Bound Dyes F4 and M5

(69) For the synthesis, the addition-crosslinking 2-component siloxane MED 6210 (Nusil Technology LLC, Carpinteria, Calif., USA) with a refractive index of 1.43 according to Table 3 was weighed in and homogenized.

(70) TABLE-US-00003 TABLE 3 Test specimens of MED 6210, covalently modified with F4 and M5 MED MED No. 6210 A 6210 B H-siloxane-F4 H-siloxane-M5 5 2 g 1.913 g 0.025 g 0.062 g (50 ppm)

(71) Then the mixture was deaerated in the vacuum drying chamber and cured between two polycarbonate plates with spacers of 1 mm for 2 h at 120 C. to obtain a transparent, green-yellow-fluorescing plate with a geometry of 40 mm40 mm1 mm. The plate obtained in this way was excited with monochromatic light of wavelengths of 360 nm to 540 nm in the fluorescence spectrometer and the respective response was recorded as the fluorescence emission spectrum. The fluorescence emission spectra of sample 5 are presented in FIG. 9. FIG. 10 shows the fluorescence absorption and emission spectra of the dyes F4 and M5 in comparison with a partial-discharge emission spectrum.

(72) Surprisingly, the fluorescence emission spectra in FIG. 9 show that the covalently bound dyes F4 and M5 in the polysiloxane matrix add together very well and do not quench one another in their spectral properties. The material exhibits an expanded absorption range from 360 nm to 540 nm and a likewise expanded emission range, which extends from 450 nm to 650 nm. Consequently, the material according to the invention has advantageous properties of effectively absorbing partial-discharge wavelengths and of emitting in the sensitivity range of wavelengths matching APD detectors (FIG. 10).

Example 8

Synthesis of Fluorescent Polysiloxanes with a Refractive Index of 1.54 and Covalently Bound Dye M5

(73) For the synthesis, the 2-component siloxane system OE 6636 (Dow Corning Corp., USA) with a refractive index of 1.54 according to Table 4 was combined and homogenized with the H-siloxane-M5.

(74) TABLE-US-00004 TABLE 4 Test specimens of OE 6636, covalently modified with M5 M5 concentration in No. OE 6636 A OE 6636 B H-siloxane-M5 the matrix 6 1 g 1.88 g 0.12 g 40 ppm 7 1 g 1.76 g 0.24 g 80 ppm 8 1 g 1.64 g 0.36 g 120 ppm

(75) Then the mixture was deaerated in the vacuum drying chamber and cured between two polycarbonate plates with spacers of 1 mm for 2 h at 120 C. to obtain a transparent, yellow-fluorescing plate with a geometry of 40 mm40 mm1 mm. The test specimens obtained in this way were excited with monochromatic light of wavelengths of 440 nm to 540 nm in the fluorescence spectrometer and the respective response to this was recorded as the fluorescence emission spectrum. The fluorescence spectra of samples 6 to 8 are presented in FIG. 11, FIG. 12 and FIG. 13.

(76) From the fluorescence spectra, it follows that the high-refractive-index siloxane system OE 6636 modified covalently with M5 absorbs and emits in a wavelength similar to that of the low-refractive-index siloxane system MED 6210 modified with M5. The absorption range lies between 440 nm and 540 nm, and the emission range, in contrast, between 520 nm and 650 nm.

(77) Surprisingly, the combination of the H-siloxane modified covalently with M5, which is predominantly a polydimethylsiloxane, and the system OE 6636, which is predominantly a polydiphenylsiloxane, did not exhibit any cloudiness or precipitates.

Example 9

Synthesis of the Naphthalimide Dye F6

(78) 0.501 g 4-Bromo-1,8-naphthalimide (Sigma-Aldrich) was dissolved in toluene in a single-necked flask. For this purpose, a solution of 0.200 g allylamine hydrochloride in 0.61 mL triethylamine and 1 mL THF:ethanol (1:1) was added. This mixture was heated for 16 hours at 85 C. with stirring. The now yellowish solution was evaporated to dryness and the residue was purified by column chromatography on silica gel 60. The product was eluted with a 10:1 mixture of dichloromethane and ethyl acetate. After the removal of the solvent, a white solid F6a was obtained in a yield of 75% (0.428 g).

(79) 0.400 g (1.26 mmol) of the white solid F6a was dissolved in 30 mL DMF then 0.500 g phenol and 0.694 g (5.02 mmol) potassium carbonate were added. The mixture was heated to 145 C. and stirred for 1.5 hours at this temperature. After the cooling to room temperature, the solvent was removed on the rotary evaporator and the brownish residue was taken up in 100 mL chloroform. The organic phase was washed with 50 mL each of 5% sodium hydroxide solution (2 times), water (2 times) and saturated sodium chloride solution (1 time) and dried over MgSO.sub.4. The yellow residue was chromatographed on silica gel 60. It was possible to elute the product with an 8:1 mixture of dichloromethane and ethyl acetate. After removal of the solvent mixture, it was possible to obtain 94% (0.392 g) F6. The quantum yield of F6 (10.sup.5 M) in Momentive RTV 655 was .sub.eX (371)=0.75.

(80) The hydrosilylation reaction of the dye F6 was carried out in the presence of a Karstedt's platinum catalyst (platinum divinyltetramethyldisiloxane) with the H-siloxane model compound 1,1,3,3-tetramethyldisilane according to the following scheme.

(81) ##STR00007##

(82) The progress of the reaction was additionally checked by .sup.1H-NMR measurements. For this purpose, samples of the reaction solution were withdrawn at the beginning of the reaction and 24 hours after the beginning of the reaction, the solvent was evaporated and the samples were dissolved in CDCl.sub.3.

(83) The resonances of the dye F6 before (FIG. 14) and after (FIG. 15) the silylation reaction are illustrated in the segment of the .sup.1H-NMR spectrum. The disappearance of the allyl resonances and the appearance of new resonances in the aliphatic region (e.g. at 4.16 ppm) prove the covalent binding of the dye F6 to the H-siloxane.

Example 10

Determination of Mechanical Properties

(84) For the production of test specimens, the addition-crosslinking 2-component silicone Lumisil LR 7600 (Wacker Chemie AG, Germany) with the refractive index of 1.41 according to Table 5 was weighed in and homogenized.

(85) TABLE-US-00005 TABLE 5 Test specimens of Lumisil LR 7600, unmodified and covalently modified with F4 and M5 No. LR 7600 A LR 7600 B H-siloxane-F4 H-siloxane-M5 9 25 g 24.224 g 0.775 g (50 ppm) 10 25 g 24.687 g 0.313 g (20 ppm) 11 25 g 25.000 g

(86) Then the mixtures were deaerated in the vacuum drying chamber and cured in polycarbonate molds for 2 h at 120 C. to obtain transparent plates (2 pieces per dye variant) with the geometry of 100 mm100 mm2 mm. From the plates, respectively 10 type 5A dumbbell specimens according to DIN EN ISO 527-2 were punched out and tested in the tension test according to DIN 53505 at a crosshead speed of 250 mm/min under normal climate conditions (23 C., 50% RH). From the tension-elongation curves obtained, tensile strength and elongation at break were determined.

(87) The second plate was artificially aged in accordance with IEC 62067. The aging of the plates consisted of 20 cycles, each comprising 2 h of heating from 25 C. to 95 C., 2 h of isothermal holding at 95 C. and then 8 h of cooling to 25 C. After the aging, the mechanical properties were determined once again and compared with those before the aging (Table 6). The commercial product Powersil 600 (Wacker Chemie AG, Germany), which is used in conventional high-voltage devices, was chosen as reference material. Powersil 600 is a filled and non-transparent siloxane elastomer.

(88) TABLE-US-00006 TABLE 6 Mechanical properties (tensile strength and elongation at break ) before and after aging Sample 11 Sample 10 Sample 9 Powersil 600 Condition [MPa] [%] [MPa] [%] [MPa] [%] [MPa] [%] new 5.6 432 4.6 488 4.0 467 6.6 447 aged 4.0 377 4.0 375 4.0 341 6.3 385

(89) The comparison of the tensile strength of the fluorescent polysiloxanes (sample 9 and 10) with the unmodified polysiloxane Lumisil LR 7600 (sample 11) shows that the tensile strength in the new condition is lowered by approximately 18% and 30% respectively by the modification, but in contrast remains at the same level of approximately 4 MPa after the aging in all samples.

(90) The comparison of the elongation at break shows that fluorescent samples have, before aging, an elongation after break higher by 8% to 13% in comparison with the unmodified sample. After aging, the elongation at break of the modified sample 10 is equal within the range of error and that of the sample 9 is slightly (10%) smaller than in the unmodified sample 11.

(91) The comparison of the mechanical properties of the unmodified (sample 11) and of the modified LR 7600 (samples 9 and 10) with the mechanical properties of the conventional, non-transparent polysiloxane Powersil 600 shows surprisingly that the transparent polysiloxanes satisfy the mechanical requirements for high-voltage devices.

Example 11

Determination of Electrical Properties

(92) For the production of test specimens, the addition-crosslinking 2-component silicone Lumisil LR 7600 (Wacker Chemie AG, Germany) with the refractive index of 1.41 according to Table 5 was weighed in and homogenized. Then the mixtures were deaerated in the vacuum drying chamber and cured in polycarbonate molds for 2 h at 120 C. to obtain transparent plates. A geometry of 100 mm100 mm0.5 mm (1 piece per dye variant) was used for the measurement of the breakdown strength, and the geometry of 100 mm100 mm2 mm (2 pieces per dye variant) was used for the determination of the loss factor and of the capacitance.

(93) For the determination of the breakdown strength, the 0.5 mm thick test specimen was placed on a planar ground electrode and a ball-tip high-voltage electrode (20 mm dia.) was placed on top of the test specimen. Then the high voltage of 1 kV (a.c. voltage, 50 Hz) was applied for 1 minute in each case and raised in steps of 1 kV until breakdown. The measurements were repeated at 5 different positions of the test specimen and the mean value was evaluated.

(94) The determination of the capacitance and of the loss factor was carried out on the 2-mm-thick test specimen in a test apparatus of type 2904 (Tettex Instruments, Basel, Switzerland) for solid insulating materials. The test specimens were placed between the planar electrodes of the apparatus then covered with a glass hood, and capacitance and loss factor were determined at room temperature (23 C.) and at elevated temperature (90 C.) at a voltage of 1.5 kV (a.c. voltage, 50 Hz). The test specimens for the determination of capacitance and loss factor were aged according to the method described in Example 10 and investigated once again after aging. The measured values before and after aging are presented in Table 7 and Table 8.

(95) TABLE-US-00007 TABLE 7 Loss factor tan and capacitance C before and after aging Sample 11 Sample 10 Sample 9 Powersil 600 C tan C tan C tan C Condition tan [10.sup.4] [pF] [10.sup.4] [pF] [10.sup.4] [pF] [10.sup.4] [pF] New (23 C.) 9.1 22.9 8.7 24.6 8.8 23.7 7.3 24.6 New (90 C.) 18.3 21.0 18.6 22.7 19.3 22.1 38.3 23.1 Aged (23 C.) 8.2 23.4 8.5 23.2 8.6 23.7 4.3 25.3 Aged (90 C.) 22.0 22.2 18.7 21.4 17.7 23.7 12.9 23.4

(96) TABLE-US-00008 TABLE 8 Breakdown strength E.sub.b Breakdown strength E.sub.b [kV/mm] Condition Sample 11 Sample 10 Sample 9 Powersil 600 New (23 C.) 30.6 32.3 32.7 29.6

(97) Unexpectedly, the transparent material LR7600 (sample 11) exhibits a breakdown strength as high as than of Powersil 600. This is not changed within the range of the measurement error by the modification with the fluorescent dyes according to the invention.

(98) At 23 C., the loss factor of the unmodified polysiloxane lies at 9.110.sup.4, and it is practically not changed by the modification with the fluorescent dyes. For all Lumisil-LR-7600 samples 9, 10 and 11, the values of the loss factor at 90 C. exhibit practically no change before and after aging. This behavior shows that Lumisil LR 7600 is stable to aging and this stability is surprisingly not influenced by the modification with the fluorescent dyes according to the invention and thereby it is particularly suitable as material for high-voltage devices.

(99) The capacitance of all samples reveals no influence of the type of the material, of the modification or of the aging, and always lies in the range of 21 pF to 24 pF.

(100) The comparison of the electrical properties of the unmodified (sample 11) and of the modified LR 7600 (samples 9 and 10) with the electrical properties of the conventional, non-transparent polysiloxane Powersil 600 shows unexpectedly that the transparent polysiloxanes satisfy the electrical requirements for high-voltage devices.

(101) In the combination of their optical, electrical and mechanical properties, new areas of application are therefore opened up unexpectedly for the fluorescent polysiloxanes according to the invention and, in fact, areas of application for which an urgent need exists that heretofore it has not been possible to address satisfactorily.

(102) Polysiloxanes with covalently bound fluorescent dyes as material for optical waveguides and for high-voltage accessories are not known from the prior art. It is also not obvious for the person skilled in the art to use them for this purpose, because organic dyes in insulations of high-voltage accessories have heretofore been regarded as contamination for the person skilled in the art and may represent nuclei for the tree growth, which ultimately may end in a breakdown.

(103) Surprisingly, the measurements of the breakdown behavior on the polysiloxanes modified covalently with fluorescent dyes did not indicate any reduction of the breakdown strength of this material.

(104) As a further surprisingly positive optical effect, it turns out that the polysiloxanes according to the invention exhibit a shift of the emission range from the UV light or expansion thereof into the range of the visible light with wavelengths up to 800 nm, so that they are particularly suitable for detectors whose highest efficiency lies in this range and furthermore they permit more cost-effective manufacture thereof.

(105) Contrary to the phenomenon known to the person skilled in the art, that quenching effects can usually be observed in the case of mixing of dyes, the method according to the invention leads to fluorescent polysiloxanes with the surprisingly positive effect of enhancement of their absorption and emission properties.

(106) Furthermore, for the new polysiloxanes, their high electrical breakdown strength in a voltage range up to 500 kV has proved to be a likewise unexpected effect. This breakdown strength finds its explanation especially in the step, essential to the invention, of the method that for the synthesis of the polysiloxanes, i.e. the removal of the platinum catalyst by means of a sorbent.

(107) With the said optical and electrical properties as well as the likewise positive effects of a temperature resistance up to 150 C. and the high elongation to break of up to 400%, the polysiloxanes according to the invention differ substantially in their properties from polysiloxanes according to the prior art, and to this extent represents the basis for a material that meets the high requirements for high-voltage devices.

(108) With the shift away from nuclear and fossil energy sources, the transition to renewable energies and the associated erection of offshore wind turbines, substantially stricter requirements are being imposed, for example, on cable junction boxes, with which marine cables and also cables laid underground for transmission of the energy at extra-high-voltage levels must be equipped. A reliable monitoring is indispensable for such cable junction boxes, in order to be able to detect and locate, in timely manner, risks in the process of aging of materials, as well as defects. With the polysiloxanes according to the invention and their excellent properties, this technical problem that urgently must be solved will be addressed in an economically advantageous manner.