SILIRANE COMPOUNDS AS STABLE SILYLENE PRECURSORS AND THEIR USE IN THE CATALYST-FREE PREPARATION OF SILOXANES

Abstract

A silirane-functionalized compound that consists of a substrate to which a least two silirane groups of the formula (1) are covalently bonded, a mixture containing the silirane-functionalized compounds, and a process for preparing siloxanes using the mixture are described herein.

Claims

1-12. (canceled)

13. Silirane-functionalized compounds consisting of a substrate on which at least two silirane groups of the formula (I) ##STR00024## are covalently bonded, where in formula (I) the index n adopts a value of 0 or 1; and where the radical R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical; and where the radical R.sup.1 is selected from the group consisting of (i) C.sub.1-C.sub.20 hydrocarbon radical, (ii) C.sub.1-C.sub.20 hydrocarbonoxy radical, (iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are selected from the group consisting of C.sub.1-C.sub.6 hydrocarbon radical, (iv) amine radical —NR.sup.x.sub.2, in which the radicals R.sup.x independently of one another are selected from the group consisting of (iv.i) hydrogen, (iv.ii) C.sub.1-C.sub.20 hydrocarbon radical, and (iv.iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical, and (v) imine radical —N═CR.sup.1R.sup.2, in which the radicals R.sup.1,R.sup.2 independently of one another are selected from the group consisting of (v.i) hydrogen, (v.ii) C.sub.1-C.sub.20 hydrocarbon radical and (v.iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical; and where the radicals R.sup.2,R.sup.3,R.sup.4,R.sup.5 independently of one another are selected from the group consisting of (i) hydrogen, (ii) halogen, and (iii) C.sub.1-C.sub.20 hydrocarbon radical, in which the radicals R.sup.2 and R.sup.4 may also be part of a cyclic radical, where the compound of the formula ##STR00025## in which Bbt is 2,6-[CH(SiMe.sub.3).sub.2]-4-[C(SiMe.sub.3).sub.3]—C.sub.2H.sub.6 is excluded.

14. The silirane-functionalized compounds as claimed in claim 13, characterized in that the substrate is selected from the group consisting of organosilicon compounds, hydrocarbons, silicas, glass, sand, stone, metals, semimetals, metal oxides, mixed metal oxides, and carbon-based oligomers and polymers.

15. The silirane-functionalized compounds as claimed in claim 14, characterized in that the substrate is selected from the group consisting of silanes, siloxanes, precipitated silica, fumed silica, glass, hydrocarbons, polyolefins, acrylates, polyacrylates, polyvinyl acetates, polyurethanes and polyethers composed of propylene oxide and/or ethylene oxide units.

16. The silirane-functionalized compounds as claimed in claim 13, characterized in that they are silirane-functionalized organosilicon compounds selected from the group consisting of compounds of the general formula (II)
(SiO.sub.4/2).sub.a(R.sup.xSiO.sub.3/2).sub.b(R′SiO.sub.3/2).sub.b′(R.sup.x.sub.2SiO.sub.2/2).sub.c(R.sup.xR′SiO.sub.2/2).sub.c′(R′.sub.2SiO.sub.2/2).sub.c″(R.sup.x.sub.3SiO.sub.1/2).sub.d(R′R.sup.x.sub.2SiO.sub.1/2).sub.d′(R′.sub.2R.sup.xSiO.sub.1/2).sub.d″(R′.sub.3SiO.sub.1/2).sub.d″′  (II), in which the radicals R.sup.x independently of one another are selected from the group consisting of (i) hydrogen, (ii) halogen, (iii) unsubstituted or substituted C.sub.1-C.sub.20 hydrocarbon radical and (iv) unsubstituted or substituted C.sub.1-C.sub.20 hydrocarbonoxy radical; and in which the indices a, b, b′, c, c′, c″, d, d′, d″, d″′ indicate the number of the respective siloxane unit in the compound and independently of one another are an integer in the range from 0 to 100 000, with the proviso that the sum of a, b, b′, c, c′, c″, d, d′, d″, d′″ together adopts a value of at least 2 and at least one of the indices b′, c′, d′ is ≥2 or at least one of the indices c″, d″ or d″′ is other than 0; and the radicals R′ are a silirane group of the formula (IIa) ##STR00026## in which the index n adopts a value of 0 or 1; and in which the radical R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical; and where the radical R.sup.1 is selected from the group consisting of (i) C.sub.1-C.sub.20 hydrocarbon radical, (ii) C.sub.1-C.sub.20 hydrocarbonoxy radical, (iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical, (iv) amine radical —NR.sup.x.sub.2, in which the radicals R.sup.x independently of one another are selected from the group consisting of (iv.i) hydrogen, (iv.ii) C.sub.1-C.sub.20 hydrocarbon radical, and (iv.iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical, and (v) imine radical —N═CR.sup.1R.sup.2, in which the radicals R.sup.1,R.sup.2 independently of one another are selected from the group consisting of (v.i) hydrogen, (v.ii) C.sub.1-C.sub.20 hydrocarbon radical and (v.iii) silyl radical —SiR.sup.aR.sup.bR.sup.c, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical; and where the radicals R.sup.2,R.sup.3,R.sup.4,R.sup.5 independently of one another are selected from the group consisting of (i) hydrogen, (ii) halogen, and (iii) C.sub.1-C.sub.20 hydrocarbon radical, in which the radicals R.sup.2 and R.sup.4 may also be part of a cyclic radical.

17. The silirane-functionalized compounds as claimed in claim 16, where in formula (II) the indices a, b, b′, c, c′, c″, d, d″ and d″′ adopt a value of 0 and the index d′ adopts a value of 2; and where in formula (IIa) the index n adopts a value of 1, and the radical R.sup.a is a C.sub.1-C.sub.3 alkylene radical, and the radical R.sup.1 is selected from the group consisting of (i) C.sub.1-C.sub.6 hydrocarbon radical and (ii) amine radical —N(SiR.sup.aR.sup.bR.sup.c).sub.2, in which the radicals R.sup.a,R.sup.b,R.sup.c independently of one another are a C.sub.1-C.sub.6 hydrocarbon radical, and the radicals R.sup.2,R.sup.3,R.sup.4,R.sup.5 independently of one another are selected from the group consisting of (i) hydrogen and (ii) C.sub.1-C.sub.6 alkyl radical, in which the radicals R.sup.2 and R.sup.4 may also be part of a cyclic radical.

18. The silirane-functionalized compounds as claimed in claim 17, where in formula (IIa) the radical R.sup.a is an ethylene radical; and the radical R.sup.1 is selected from the group consisting of (i) C.sub.1-C.sub.6 alkyl radical and (ii) —N(SiMe.sub.3).sub.2; and the radicals R.sup.2,R.sup.3,R.sup.4,R.sup.5 independently of one another are selected from the group consisting of (i) hydrogen and (ii) C.sub.1-C.sub.6 alkyl radical, in which the radicals R.sup.2 and R.sup.4 may also be part of a hexenyl radical.

19. The silirane-functionalized compounds as claimed in claim 16, which is selected from the following compounds ##STR00027## SV1, SV2 and SV3.

20. A mixture comprising a) at least one silirane-functionalized compound as claimed in any of claims 1-7; and b) at least one compound A which has in each case at least two radicals R′, where the radicals R′ independently of one another are selected from the group consisting of (i) —Si—H, (ii) —OH, (iii) —C.sub.xH.sub.2x—OH, in which x is an integer in the range of 1-20, (iv) —C.sub.xH.sub.2x—NH.sub.2, in which x is an integer in the range of 1-20, (v) —SH, and (vi) —R.sup.a.sub.n—CR═CR.sub.2, in which R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical and the index n adopts a value of 0 or 1 and the radicals R independently of one another are selected from the group consisting of (vi.i) hydrogen and (vi.ii) C.sub.1-C.sub.6 hydrocarbon radical.

21. The mixture as claimed in claim 20, where the compound A is selected from functionalized siloxanes of the general formula (III)
(SiO.sub.4/2).sub.a(R.sup.xSiO.sub.3/2).sub.b(R′SiO.sub.3/2).sub.b′(R.sup.x.sub.2SiO.sub.2/2).sub.c(R.sup.xR′SiO.sub.2/2).sub.c′(R′.sub.2SiO.sub.2/2).sub.c″(R.sup.x.sub.3SiO.sub.1/2).sub.d(R′R.sup.x.sub.2SiO.sub.1/2).sub.d′(R′.sub.2R.sup.xSiO.sub.1/2).sub.d″(R′.sub.3SiO.sub.1/2).sub.d″′  (III), in which the radicals R.sup.x independently of one another are selected from the group consisting of (i) halogen, and (ii) unsubstituted or substituted C.sub.1-C.sub.20 hydrocarbon radical; and in which the radicals R′ independently of one another are selected from the group consisting of (i) hydrogen, (ii) —OH, (iii) —C.sub.xH.sub.2x—OH, in which x is an integer in the range of 1-20, (iv) —C.sub.xH.sub.2x—NH.sub.2, in which x is an integer in the range of 1-20, (v) —SH, and (vi) —R.sup.a.sub.n—CR═CR.sub.2, in which R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical and the index n adopts a value of 0 or 1 and the radicals R independently of one another are selected from the group consisting of (vi.i) hydrogen and (vi.ii) C.sub.1-C.sub.6 hydrocarbon radical; and in which the indices a, b, b′, c, c′, c″, d, d′, d″, d″′ indicate the number of the respective siloxane unit in the compound and independently of one another are an integer in the range from 0 to 100 000, with the proviso that the sum of a, b, b′, c, c′, c″, d, d′, d″, d″′ together adopts a value of at least 2 and at least one of the indices b′, c′, d′ is ≥2 or at least one of the indices c″, d″ or d′″ is other than 0.

22. A process for preparing siloxanes, comprising the following steps: (i) providing a mixture as claimed in claim 21, and (ii) reacting the mixture by thermal, photochemical or catalytic activation.

23. The process as claimed in claim 22, where the activation takes place thermally and the temperature is in a range from 60° C. to 200° C.

24. The process as claimed in claim 22, where the molar ratio of silirane groups to functional groups in the siloxane is in a range of 4:1-1:4.

Description

EXAMPLES

[0039] All syntheses were carried out under Schlenk conditions in baked glass apparatus. Argon or nitrogen was used as inert gas. Chemicals used (vinylsilanes, vinylsiloxanes, silicone oils, etc.) were acquired from WACKER Chemie AG, from ABCR or from Sigma-Aldrich. Cis-2-butene (2.0) and trans-2-butene (2.0) were acquired from Linde AG. All of the solvents were dried and distilled before being used. All of the silicone oils were dried over Al.sub.2O.sub.3 and 3 Å molecular sieve and degassed before being used. The molecular weights are reported as average values and are based on manufacturer figures. The polysiloxanes used are random copolymers. All of the chemicals used were stored under inert gas. Lithium with 2.5% sodium fraction was obtained by melting elemental lithium (Sigma-Aldrich, 99%, trace metal basis) and sodium (Sigma-Aldrich, 99.8%, sodium basis) at 200° C. in a nickel crucible under an argon atmosphere. Before being used, the Li/Na alloy was cut into extremely small pieces in order to increase the surface area. Al.sub.2O.sub.3 (neutral) and activated carbon were dried under a high vacuum at 150° C. for 72 hours.

[0040] Magnetic resonance spectroscopy (.sup.1H, .sup.29Si) was carried out using a Bruker Avance III 500 MHz.

[0041] Mass spectrometry was carried out using LIFDI-MS 700 with an ion source from Linden CMS.

[0042] Elemental analyses were carried out by the microanalytical laboratory of the Faculty of Chemistry at Munich Technical University using a Vario EL from Elementar.

Synthesis example 1: preparation of 1,3-bis(2-(1-(tert-butyl)-2,3-dimethylsiliran-1-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (SV1)

[0043] ##STR00011##

[0044] The bis-silirane SV1 is synthesized via a three-step reaction pathway, beginning with the starting compound divinyltetramethyldisiloxane. In the first synthesis step this compound is reacted via a hydrosilylation reaction with trichlorosilane in the presence of the Karstedt catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex). For this reaction, 100 g (740 mmol, 4.0 equivalents) of trichlorosilane are introduced into 30 mL of toluene in a 250 mL Schlenk flask and mixed with 34.4 g (180 mmol, 1.0 equivalent) of divinyltetramethyldisiloxane. Then 0.05 mL of Karstedt catalyst (2.1-2.4% Pt in xylene) is added to the reaction mixture, 10 which is stirred at room temperature for 18 hours. After the end of the reaction, the mixture is filtered through dried neutral aluminum oxide and residual solvent is removed under reduced pressure. This gives 81.3 g (96%, 177 mmol) of the product (Cl.sub.3SiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O as a clear, colorless liquid.

[0045] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.10 (s, 12H, CH.sub.3), 0.55-0.60 (in, 4H, CH.sub.2), 1.05-1.10 (in, 4H, CH.sub.2).

[0046] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=8.14 (SiO), 13.84 (SiCl.sub.3).

[0047] EA [%]: calculated: C=21.01, H=4.41. found: C=20.93, H=4.63.

[0048] The next synthesis step takes place via the substitution of the hexachlorosilane with tert-butyllithium. For this reaction, 30.0 g (65.6 mmol, 1.0 equivalent) of (Cl.sub.3SiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O are dissolved in 75 mL of pentane and the solution is cooled to −10° C. Via a dropping funnel 8.40 g (131 mmol, 2.0 equivalents) 1.7 M tert-butyllithium solution are slowly added dropwise. The reaction is then heated to 0° C. and stirred for 8 hours. Lithium chloride formed is removed by filtration and the filtrate is separated from the solvent under reduced pressure. A subsequent sublimination of the crude product under high vacuum (110° C., 10-5 mbar) affords 22.0 g (67%, 43.9 mmol) of the tetrachlorosilane (Cl.sub.2tBuSiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O as a white solid.

[0049] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=0.05 (s, 12H, Si—CH.sub.3), 0.78-0.82 (m, 4H, CH.sub.2), 1.00 (s, 18H, SiC—CH.sub.3), 1.04-1.08 (m, 4H, CH.sub.2).

[0050] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=8.22 (Si—O), 38.47 (Si-tBuCl.sub.2).

[0051] EA [%]: calculated: C=38.39, H=7.65. found: C=38.25, H=7.76.

[0052] The last step of the synthesis of the bis-silirane involves the reduction of the tetrachlorosilane by means of a lithium-sodium alloy (2.5% Na). For this reaction step, 10.0 g (20.0 mmol, 1.0 equivalent) of tetrachlorosilane (Cl.sub.2tBuSiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O are dissolved in 50 mL of THF. The reaction solution is cooled to −30° C., after which 33.6 g (600 mmol, 30.0 equivalents) of cis-butene are incorporated by condensation. In an argon countercurrent 2.10 g (300 mmol, 15.0 equivalents) of a lithium-sodium alloy (2.5% Na) are added and the reaction solution is stirred vigorously at room temperature for 7 days. When the reduction of the chlorosilane is at an end, the solvent is removed under reduced pressure and the residue is taken up in pentane. Precipitated lithium salt is removed by filtration and the filtrate is again dried under reduced pressure. This gives 7.80 g (86%, 16.7 mmol) of the bis-silirane SV1 as a yellowish oil. In view of the purity of the cis-butene gas used (purity 2.0), the trans and the 1-butene species are found alongside the cis species.

Trans Species:

[0053] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=0.12-0.14 (m, 12H, Si—CH.sub.3), 0.46-0.52 (m, 4H, Si CH.sub.2), 0.74-0.78 (m, 4H, Si—CH.sub.2), 1.12 (s, 18H, SiC—CH.sub.3), (m, 4H, Si—CH), 1.43-1.45 (m, 12H, SiCH—CH.sub.3).

[0054] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=−53.11 (CH—Si—CH), 8.01 (Si—O).

Cis Species:

[0055] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=0.14-0.16 (m, 12H, Si—CH.sub.3), 0.86-0.88 (m, 8H, CH.sub.2), 1.03 (s, 18H, SiC—CH.sub.3), 1.08-1.11 (m, 4H, Si—CH), 1.43-1.45 (m, 12H, SiCH—CH.sub.3).

[0056] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=−49.70 (CH—Si—CH), 7.30 (Si—O).

1-Butene Species:

[0057] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=0.07-0.10 (m, 12H, Si—CH.sub.3), 0.59-0.68 (m, 4H, Si—CH.sub.2), 0.79-0.81 (m, 4H, Si—CH.sub.2), 1.08 (s, 18H, SiC—CH.sub.3), 1.18-1.19 (m, 2H, CH.sub.2Si—CH—CH.sub.2CH.sub.3), 1.19-1.20 (m, 4H, CHSi—CH.sub.2), 1.39-1.40 (m, 4H, SiCH—CH.sub.2—CH.sub.3), 1.47-1.49 (m, 6H, SiCHCH.sub.2—CH.sub.3).

[0058] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) 6=−42.34 (CH.sub.2—Si—CH), 6.89 (Si—O).

[0059] EA [%]: calculated: C=61.20, H=11.56. found: C=58.13, H=11.31.

[0060] LIFDI-MS: (THF) m/z=471.95 [M].sup.+, 415.99 [M-C.sub.4H.sub.8].sup.+, 360.01 [M-C.sub.8H.sub.16].sup.+.

[0061] Since the three stated bis-siliranes are stereoisomers, they have the same molecular mass. They are therefore indistinguishable in the mass spectrum. The same is true of the results of the elemental analysis.

Synthesis example 2: preparation of 1,3-bis(2-(7-(tert-butyl)-7-silabicyclo[4.1.0]heptan-7-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (SV2)

[0062] ##STR00012##

[0063] The tetrachlorosilane (Cl.sub.2tBuSiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O, which represents the starting compound in this synthesis is prepared by a route analogous to that in synthesis example 1. For the subsequent reduction, 1.00 g (2.00 mmol, 1.0 equivalent) of tetrachlorosilane is mixed with 3.94 g (47.9 mmol, 24.0 equivalents) of cyclohexene in 2.5 mL of THF. The reaction solution is admixed with 208 mg (29.9 mmol, 25.0 equivalents) of a lithium-sodium alloy (2.5% Na) and stirred vigorously at room temperature for 10 hours. When reduction of all the chlorosilanes is completed, the solvent and excess cyclohexene are removed under reduced pressure, and the residue is resuspended again in 5 mL of pentane. Precipitated LiCl is removed and the filtrate is dried under reduced pressure. This gives 382 mg (37%, 0.73 mmol) of the bis-silirane SV2 as a clear oil. A cis and a trans species of the bis-silirane SV2 are obtained.

Cis Species:

[0064] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.13-0.15 (m, 12H, Si—CH.sub.3), 0.90 (m, 8H, Si—CH.sub.2), 1.03 (s, 18H, SiC—CH.sub.3), 1.49-1.54 (m, 8H, SiCHCH.sub.2—CH.sub.2), 1.71-1.78 (m, 8H, SiCH—CH.sub.2), 1.98-2.05 (m, 4H, Si—CH).

[0065] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=−49.09 (Si—CH), 7.27 (Si—O).

Trans Species:

[0066] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.12-0.13 (m, 12H, Si—CH.sub.3), 0.47-0.52 (m, 4H, Si—CH.sub.2), 0.77-0.81 (m, 4H, Si—CH.sub.2), 1.15 (s, 18H, SiC—CH.sub.3), 1.64-1.67 (m, 4H, Si—CH), 1.78-1.83 (m, 8H, SiCHCH.sub.2—CH.sub.2), 1.88-1.97 (m, 8H, SiCH—CH.sub.2).

[0067] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=−53.75 (Si—CH), 7.89 (Si—O).

Synthesis example 3: preparation of 1,3-bis(2-(7-(tert-butyl)-7-silabicyclo[4.1.0]heptan-7-yl)ethyl)-1,1,3,3-tetramethyldisiloxane (SV3)

[0068] ##STR00013##

[0069] The bis-silirane SV3 is prepared via a two-step synthesis from the corresponding hexachlorosilane. In the first step 10.0 g (21.9 mmol, 1.0 equivalent) of (Cl.sub.3SiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O are introduced into 40 mL of THE and cooled to 0° C. Then a solution of 8.72 g (43.7 mmol, 2.0 equivalents) of potassium-hexamethyldisilazane (KHMDS) in 30 ml of THE is added slowly dropwise over a period of 30 minutes. The resulting suspension is stirred at room temperature for 6 hours. The solvent is then removed under reduced pressure. The residue is taken up in 40 mL of pentane, followed by filtration. Removal of the solvent again under reduced pressure gives 12.5 g (81%, 17.7 mmol) of (TMS.sub.2NCl.sub.2SiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O as a clear, yellowish liquid.

[0070] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.07 (s, 12H, OSi—CH.sub.3), 0.33 (s, 36H, NSi—CH.sub.3), 0.83-0.87 (m, 4H, OSi—CH.sub.2), 1.25-1.29 (m, 4H, NSi—CH.sub.2).

[0071] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=2.19 (Si—C.sub.12), 6.38 (Si-Mes), 8.45 (Si—O).

[0072] EA [%]: calculated: C=33.97, H=07.98, N=03.96. found: C=33.39, H=07.96, N=03.94.

[0073] The subsequent reaction step involves the reduction of a tetrachlorosilane to give the corresponding bis-silirane. For this reaction, 10.0 g (14.2 mmol, 1.0 equivalent) of (TMS.sub.2NCl.sub.2SiCH.sub.2CH.sub.2SiMe.sub.2).sub.2O are dissolved in 50 mL of THE and the reaction mixture is conditioned to −30° C. Then 23.10 g (424 mmol, 30.0 equivalents) of cis-butene are introduced into the reaction vessel by condensation, and 1.47 g (212 mmol, 15.0 equivalents) of lithium-sodium alloy (2.5% Na) are added in an argon countercurrent. The reaction mixture is warmed to room temperature and stirred for 5 days. Following the complete reduction of the chlorosilane, the solvent is removed under reduced pressure and the residue is resuspended in 30 mL of pentane. Precipitated lithium chloride is separated off and the product solution is filtered through dried neutral aluminum oxide. The filtrate is subsequently dried under reduced pressure, to give 5.46 g (57%, 8.06 mmol) of a cis/trans mixture and also the corresponding bis-silirane SV3 from the 1-butene species, as a yellowish, turbid oil.

Cis Species:

[0074] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.12-0.13 (m, 12H, OSi—CH.sub.3), 0.22 (s, 36H, NSiCH.sub.3), 0.77-0.80 (m, 8H, CH.sub.2), 1.12-1.15 (m, 4H, Si—CH), 1.19-1.21 (m, 12H, CH—CH.sub.3).

[0075] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=−50.01 (CH—Si—CH), 4.71 (N—Si-TMS), 7.81 (Si—O).

Trans Species:

[0076] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.11-0.12 (m, 12H, Si—CH.sub.3), 0.25-0.26 (m, 36H, NSiCH.sub.3), 0.47-0.52 (m, 4H, CH.sub.2), 0.81-0.85 (m, 4H, CH.sub.2), 1.17-1.18 (m, 4H, Si—CH), 1.27-1.30 (m, 12H, CH—CH.sub.3).

[0077] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=−44.90 (CH—Si—CH), 4.70 (N—Si-TMS), 7.68 (Si—O).

1-Butene Species:

[0078] .sup.1H-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=0.09-0.10 (m, 12H, Si—CH.sub.3), 0.23-0.24 (m, 36H, NSiCH.sub.3), 0.52-0.57 (m, 4H, SiCH.sub.2), 0.67-0.71 (m, 4H, SiCH.sub.2), 0.93-0.99 (m, 4H, SiCH—CH.sub.2), 1.27 (m, 2H, CH.sub.2Si—CH), 1.34-1.35 (m, 6H, SiCHCH.sub.2—CH.sub.3).

[0079] .sup.29Si-NMR: (294 K, 500 MHz, C.sub.6D.sub.6) δ=−41.12 (CH—Si—CH), 5.31 (N—Si-TMS), 7.86 (Si—O).

[0080] EA [%]: calculated: C=49.63, H=10.71, N=4.13. found: C=47.34, H=10.60, N=3.98.

[0081] LIFDI-MS: (THF) m/z=675.69 [M].sup.+, 619.75 [M-C.sub.4H.sub.8].sup.+, 564.25 [M-C.sub.8H.sub.16].sup.+, 244.06 [M-C.sub.20H.sub.52N.sub.2Si.sub.4].sup.+.

Use Example 1: Crosslinkinq of Hydridomethylsiloxane-Dimethylsiloxane Copolymer with SV1

[0082] ##STR00014##

[0083] SV1 (100 mg, 212.3 μmol, 1.0 equivalent) and silicone oil (254 mg, 106.2 μmol, 0.5 equivalent, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si—H terminated)) are weighed out in a molar ratio of 1:2 (silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is taken up in 0.5 mL of pentane and stirred with a magnetic stirring bar until homogeneous mixing is ensured. The pentane is then removed again under reduced pressure. Crosslinking takes place at 140° C. under inert gas for 24 hours. The product is a slightly turbid, colorless and slightly elastic polymer which is not sticky. Owing to the short chain length of the siloxane, the material is fairly brittle and ruptures under tensile load. The polymer swells significantly in benzene and does not dissolve. No soluble constituents were detectable by NMR spectroscopy. The butene formed in the crosslinking is perceptible through the characteristic odor.

Use Example 2: Crosslinking of Hydridomethylsiloxane-Dimethylsiloxane Copolymer with SV3

[0084] ##STR00015##

[0085] SV3 (100 mg, 147.6 μmol, 1.0 equivalent) and silicone oil (233 mg, 97.4 μmol, 0.66 equivalent, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si—H terminated)) are weighed out in a molar ratio of 1:3 (silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The product is a clear, slightly yellowish and slightly elastic polymer which is not sticky. Owing to the short chain length of the siloxane, the material is fairly brittle and ruptures under tensile load. The polymer swells significantly in benzene and does not dissolve. No soluble constituents were detectable by NMR spectroscopy.

Use Example 3: Crosslinking of Hydridomethylsiloxane-Dimethylsiloxane Copolymer with SV3

[0086] ##STR00016##

[0087] SV3 (100 mg, 147.6 μmol, 1.0 equivalent) and silicone oil (78 mg, 32.5 μmol, 0.22 equivalent, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si—H terminated)) are weighed out in a molar ratio of 9:10 (silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The product is a clear, slightly yellowish and slightly elastic polymer which is not sticky. Owing to the short chain length of the siloxane, the material is fairly hard and brittle and ruptures under tensile load. The polymer swells significantly in benzene and does not dissolve. No soluble constituents were detectable by NMR spectroscopy. Because of the higher silirane fraction, the polymer is significantly more solid than in the case of use example 2.

Use Example 4: Inert Gas-Free Crosslinking of Hydridomethylsiloxane-Dimethylsiloxane Copolymer with SV3

[0088] ##STR00017##

[0089] SV3 (100 mg, 147.6 μmol, 1.0 equivalent) and silicone oil (78 mg, 32.5 μmol, 0.22 equivalent, 2.395 g/mol, (25-30% methylhydridosiloxane-dimethylsiloxane copolymer, Si—H terminated)) are weighed out in a molar ratio of 9:10 (Silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar in air until homogeneous mixing is ensured. Crosslinking takes place at 140° C. in air for 24 hours. The product is a clear, slightly yellowish and slightly elastic polymer which is not sticky. The material exhibits properties analogous to those of the described elastomer from the use example 3. Oxygen and moisture from the ambient air have no recognizable effect on the crosslinking of the polymer. The bis-silirane SV3 is therefore sufficiently stable with respect to air.

Use Example 5: Crosslinking of Hydridomethylsiloxane-Dimethylsiloxane Copolymer with SV1

[0090] ##STR00018##

[0091] SV1 (87.5 mg, 185.6 μmol, 10.0 equivalents) and silicone oil (1.03 g, 18.58 μmol, 1.0 equivalent, 55.000 g/mol, (0.5-1% methylhydridosiloxane-dimethylsiloxane copolymer, TMS terminated)) are weighed out in a molar ratio of 20:6 (Silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The product is a white, opaque and elastic polymer which is not sticky. The polymer swells significantly in benzene and does not dissolve. No soluble constituents were detectable by NMR spectroscopy.

Use Example 6: Crosslinking of 2,4,6,8-Tetramethylcyclotetrasiloxan (TMCTS) with SV1

[0092] ##STR00019##

[0093] SV1 (100 mg, 212.3 μmol, 1.0 equivalent) and the cyclic siloxane TMCTS (23 mg, 95.53 μmol, 0.45 equivalent, 2,4,6,8-tetramethylcyclotetrasiloxane) are weighed out in a molar ratio of 1:0.9 (silirane groups to Si—H groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas in a closed system for 24 hours. The resultant product is a solid, transparent polymer which is not sticky and has slightly elastic properties. The polymer swells significantly in benzene, without dissolving. No soluble constituents were detectable by NMR spectroscopy.

Use Example 7: Crosslinking of Short-Chain OH-Terminated Polydimethylsiloxane with SV1

[0094] ##STR00020##

[0095] SV1 (50 mg, 106.2 μmol, 1.0 equivalent) and silicone oil (1.03 g, 106.2 μmol, 1.0 equivalent, 9.750 g/mol, polydimethylsiloxane, OH-terminated) are weighed out in a molar ratio of 1:1 (silirane groups to Si—OH groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The resulting polymer is colorless, slightly turbid, not sticky, and exhibits elastic properties.

Use Example 8: Crosslinking of Short-Chain OH-Terminated Polydimethylsiloxane with SV3

[0096] ##STR00021##

[0097] SV3 (50 mg, 73.79 μmol, 1.0 equivalent) and silicone oil (721 mg, 73.79 μmol, 1.0 equivalent, 9.750 g/mol, polydimethylsiloxane, OH-terminated) are weighed out in a molar ratio of 1:1 (silirane groups to Si—OH groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The resulting product is a colorless, slightly turbid, elastic polymer. There is severe swelling of the polymer in benzene, without it dissolving. No soluble constituents were detectable by NMR spectroscopy. Alternatively molar mixing ratios of 0.5:1 (silirane groups to Si—OH groups) and 2:1 (silirane groups to Si—OH groups) are used in accordance with an analogous procedure. In the former case, colorless, clear, very soft and sticky elastomers are obtained. In the case of the superstoichiometric addition of the crosslinker, a colorless, turbid polymer is obtained which has elastic properties. The polymer obtained is softer by comparison with the 1:1 mixture.

Use Example 9: Crosslinking of Long-Chain OH-Terminated Polydimethylsilane with SV1

[0098] ##STR00022##

[0099] SV1 (34 mg, 73.8 μmol, 1.0 equivalent) and silicone oil (67 mg, 73.8 μmol, 1.0 equivalent, 36.000 g/mol, polydimethylsiloxane, OH-terminated) are weighed out in a molar ratio of 1:1 (silirane groups to Si—OH groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The result is a turbid, soft and elastic polymer. Because of the longer chains by comparison with use example 7, the polymer network is more flexible, providing a possible explanation for the lower strength of the resultant elastomer. There is severe swelling of the polymer in benzene, without being dissolved. No soluble constituents were detectable by NMR spectroscopy.

Use Example 10: Crosslinking of Long-Chain OH-Terminated Polydimethylsilane with SV3

[0100] ##STR00023##

[0101] SV3 (50 mg, 73.8 μmol, 1.0 equivalent) and silicone oil (67 mg, 73.8 μmol, 1.0 equivalent, 36.000 g/mol, polydimethylsiloxane, OH-terminated) are weighed out in a molar ratio of 1:1 (silirane groups to Si—OH groups) under inert gas into a suitable vessel. The mixture is stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 140° C. under inert gas for 24 hours. The resulting polymer is a clear, colorless, nonsticky elastomer. There is severe swelling of the polymer by addition of benzene, but without the polymer dissolving. No soluble constituents were detectable by NMR spectroscopy.