SILIRANE-FUNCTIONALISED COMPOUNDS, IN PARTICULAR ORGANOSILICON COMPOUNDS, FOR PREPARING SILOXANES

Abstract

A silirane-functionalized compound, a process for preparing the same, and a process for preparing siloxanes using a silirane-functionalized compound are described herein.

Claims

1-14. (canceled)

15. A silirane-functionalized compound consisting of a substrate to which at least two silirane groups of the formula (I) ##STR00022## are covalently bonded, where in formula (I) the index n adopts a value of 0 or 1, and where the radical IV is a divalent C.sub.1-C.sub.20 hydrocarbon radical, and where the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon 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′R″ in which the radicals R′,R″ 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.

16. The silirane-functionalized compounds as claimed in claim 15, 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.

17. The silirane-functionalized compounds as claimed in claim 16, 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.

18. The silirane-functionalized compounds as claimed in claim 15, characterized in that they are silirane-functionalized organosilicon compounds selected from the group consisting of (a) compounds of the general formula (II)
SiR′.sub.nR.sub.4-n  (II), in which the index n adopts the value of 2, 3 or 4, and the radicals R 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 radicals R′ are a silirane group of the formula (II′) ##STR00023## in which the index n adopts the value of 0 or 1; in which the radical R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical; and in which the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) (hydrogen), (ii) C.sub.1-C.sub.20 hydrocarbon 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′R″, in which the radicals R′,R″ 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; or (b) compounds 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) 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 (III′) ##STR00024## in which the index n adopts the value of 0 or 1; in which the radical IV is a divalent C.sub.1-C.sub.20 hydrocarbon radical; and in which the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon 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′R″, in which the radicals R′,R″ 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.

19. The silirane-functionalized compounds as claimed in claim 18, where (a) in formula (II) the index n adopts the value of 4 and in formula (II′) the radicals R.sup.1 and R.sup.2 are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.6 alkyl radical, (iii) phenyl radical, (iv) —SiMe.sub.3, and (v) —N(SiMe.sub.3).sub.2; and (b) in formula (III) the radicals R′ independently of one another are selected from the group consisting of (i) hydrogen, (ii) chlorine, (iii) C.sub.1-C.sub.6-alkyl, (iv) C.sub.1-C.sub.6 alkylene, (v) phenyl, and (vi) C.sub.1-C.sub.6 alkoxy and in formula (III′) the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.6 alkyl radical, (iii) phenyl radical, (iv) —SiMe.sub.3, and (v) —N(SiMe.sub.3).sub.2.

20. The silirane-functionalized compounds as claimed in claim 19, where (a) in formula (II) the radicals R′ are identical, in formula (II′) the radical IV is a divalent C.sub.1-C.sub.3 hydrocarbon radical and the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of methyl, ethyl, tert-butyl, sec-butyl, cyclohexyl, —SiMe.sub.3, and —N(SiMe.sub.3).sub.2; and (b) in formula (III) the radicals R′ independently of one another are selected from the group consisting of methyl, methoxy, ethyl, ethoxy, propyl, propoxy, phenyl and chlorine and in formula (III′) the radical R.sup.a is a divalent C.sub.1-C.sub.3 hydrocarbon radical and the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of methyl, ethyl, tert-butyl, sec-butyl, cyclohexyl, —SiMe.sub.3, and —N(SiMe.sub.3).sub.2.

21. A process for preparing silirane-functionalized compounds, comprising the steps of (a) providing a silirane of the general formula (IV) ##STR00025## in which the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon 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.1R.sup.2, in which the radicals R.sup.1R.sup.2 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 in which the radicals R.sup.3, R.sup.4, R.sup.5, R.sup.6 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon radical, and (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; (b) reacting the silirane from (a) with a substrate that has at least two covalently bonded carbon-carbon double bonds, of the formula —R.sup.a.sub.n—CR═CR.sup.2, in which R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical and the index n adopts the values of 0 or 1, and in which the radicals R independently of one another are selected from the group consisting of (i) hydrogen and (ii) C.sub.1-C.sub.6 hydrocarbon radical.

22. A process for preparing a silirane-functionalized compound according to claim 18, comprising the steps of (a) providing a silirane of the general formula (IV) ##STR00026## in which the radicals R.sup.1 and R.sup.2 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon 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.1R.sup.2, in which the radicals R.sup.1R.sup.2 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 in which the radicals R.sup.3, R.sup.4, R.sup.5, R.sup.6 independently of one another are selected from the group consisting of (i) hydrogen, (ii) C.sub.1-C.sub.20 hydrocarbon radical, and (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; (b) reacting the silirane from (a) with a substrate selected from the group consisting of (i) olefinically functionalized silanes of the general formula (V)
SiR.sup.7.sub.nR.sub.4-n  (V), in which the index n adopts the values of 2, 3 or 4; and in which the radicals R 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 radicals R.sup.7 independently of one another are selected from radicals —R.sup.a.sub.n—CR═CR.sup.2, in which R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical and the index n adopts the values of 0 or 1 and the radicals R independently of one another are selected from the group consisting of (i) hydrogen and (ii) C.sub.1-C.sub.6 hydrocarbon radical; or (ii) olefinically functionalized siloxanes of the general formula (VI)
(SiO.sub.4/2).sub.a(R.sup.xSiO.sub.3/2).sub.b(R.sup.7SiO.sub.3/2).sub.b′(R.sup.x.sub.2SiO.sub.2/2).sub.c(R.sup.xR.sup.7SiO.sub.2/2).sub.c′(R.sup.7.sub.2SiO.sub.2/2).sub.c″(R.sup.x.sub.3SiO.sub.1/2).sub.d(R.sup.7R.sup.x.sub.2SiO.sub.1/2).sub.d′(R.sup.7.sub.2R.sup.xSiO.sub.1/2).sub.d″(R.sup.7.sub.3SiO.sub.1/2).sub.d′″  (VI), in which the radicals R.sup.7 independently of one another are selected from radicals —R.sup.a.sub.n—CR═CR.sup.2, in which R.sup.a is a divalent C.sub.1-C.sub.20 hydrocarbon radical and the index n adopts the values of 0 or 1 and the radicals R independently of one another are selected from the group consisting of (i) hydrogen and (ii) C.sub.1-C.sub.6 hydrocarbon radical; and 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; or (c) allyl- and/or vinyl-terminated polyethers composed of propylene and/or ethylene oxide units.

23. A mixture comprising a) at least one silirane-functionalized compound as claimed in claim 15; 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) —OH, (ii) —C.sub.xH.sub.2x—OH, in which x is an integer in the range of 1-20, (iii) —C.sub.xH.sub.2x—NH.sub.2, in which x is an integer in the range of 1-20, and (iv) —SH.

24. The mixture as claimed in claim 23, where the compound A is selected from functionalized siloxanes of the general formula (VII)
(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′″  (VII), where 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 where the radicals R′ independently of one another are selected from the group consisting of (i) —OH, (ii) —C.sub.xH.sub.2x—OH, in which x is an integer in the range of 1-20, (iii) —C.sub.xH.sub.2x—NH.sub.2, in which x is an integer in the range of 1-20, and (iv) —SH; and where 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.

25. A process for preparing siloxanes, comprising the following steps: (i) providing a mixture as claimed in claim 23, and (ii) reacting the mixture at a temperature in the range from 25° C. to 250° C.

26. The process as claimed in claim 25, where the molar ratio of silirane groups to functional groups in the siloxane is in a range of 4:1-1:4.

27. The process as claimed in claim 25, where additionally a catalyst is added.

Description

EXAMPLES

[0104] All syntheses were carried out under Schlenk conditions in baked glass apparatus. The inert gas used was argon or nitrogen. 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 solvents were dried and distilled before use. All silicone oils were dried over Al.sub.2O.sub.3 and 3 Å molecular sieve and degassed before use. 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.

[0105] Nuclear magnetic resonance spectroscopy (.sup.1H, .sup.29Si) was carried out using a Bruker Avance III 500 MHz.

[0106] Mass spectrometry was carried out by means of CI-TOF at 150 eV using a Finnigan MAT90.

[0107] Shore A hardnesses were carried out using a Sauter HBA 100-0 and Zwick/Roell 3130 (measuring time 3 seconds; values reported are averages from 5 measurements).

[0108] Rheological investigations were carried out using an Anton Paar MCR 302 under inert gas.

[0109] Preparation of the Silirane Starting Compounds

##STR00009##

[0110] Synthesis of di-tert-butyldibromosilane

[0111] A 1 L three-neck flask with reflux condenser is charged with 582 mL (989 mmol, 2 equivalents) of tert-butyllithium (1.6 M in pentane). A dropping funnel is used to add 50.0 mL (495 mmol, 1 equivalent) of trichlorosilane slowly to the solution. The solution here is to gently boil and reflux. The reaction mixture is additionally stirred for an hour and then the solvent is removed under reduced pressure. The residue is purified by recondensation (10.sup.−3 mbar) with cold trap. Di-tert-butylchlorosilane (71.6 g, 81%) is obtained as a colorless liquid.

[0112] A 500 mL three-neck flask with reflux condenser is charged with 6.58 g (173 mmol, 0.4 equivalent) of lithium aluminum hydride in 50 mL of diethyl ether and heated to 40° C. 77.50 g of di-tert-butylchlorosilane are dissolved in 300 mL of diethyl ether in a dropping funnel and added slowly dropwise to the suspension. Following complete addition, the mixture is stirred for a further 16 hours at room temperature. The solvent is subsequently removed under reduced pressure. The residue is purified by recondensation (10.sup.−3 mbar) with cold trap. This gives 59.4 g (411.8 mmol, 95%) of di-tert-butylsilane as a colorless liquid.

[0113] A 500 mL three-neck flask is charged with 41.10 g (285 mmol, 1 equivalent) of di-tert-butylsilane in 200 mL of n-hexane and cooled to −20° C. 29.2 mL (569 mmol, 2 equivalents) of bromine are added dropwise via a dropping funnel to the solution. The HBr formed is captured using wash bottles and neutralized. The reaction mixture is stirred for a further 2 hours, in the course of which it is slowly thawed to room temperature. The solvent is subsequently removed under reduced pressure and the residue is purified by recondensation (60° C., 10.sup.−2 mbar). The tBu.sub.2SiBr.sub.2 obtained is crystallized from dry MeCN at −20° C. before further use, to give a high-purity compound. This gives 78.6 g (260 mmol, 91%) of di-tert-butyldibromosilane as a colorless solid.

[0114] NMR: tBu.sub.2SiHCl:

[0115] .sup.1H-NMR: (300 K, 500 MHz, C.sub.6D.sub.6) δ=0.99 (s, 18H, tBu), 4.33 (s, 1H, Si—H).

[0116] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=27.2.

[0117] NMR: tBu.sub.2SiH.sub.2:

[0118] .sup.1H-NMR: (297 K, 300 MHz, C.sub.6D.sub.6) δ=1.04 (s, 18H, tBu), 3.66 (s, 2H, Si—H).

[0119] .sup.13C-NMR: (300 K, 125 MHz, C.sub.6D.sub.6) δ=17.8 (Si—C—), 28.9 (tBu-Me).

[0120] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=1.58.

[0121] NMR: tBu.sub.2SiBr.sub.2:

[0122] .sup.1H-NMR: (296 K, 300 MHz, C.sub.6D.sub.6) δ=1.05 (s, 18H, tBu).

[0123] .sup.13C-NMR: (300 K, 125 MHz, C.sub.6D.sub.6) δ=26.0 (Si—C—), 27.2 (tBu-Me)

[0124] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=45.6.

Synthesis of cis-1,1-di-tert-butyl-2,3-dimethylsilirane and trans-1,1-di-tert-butyl-2,3-dimethylsilirane

[0125] ##STR00010##

[0126] A thick-wall 500 mL Schlenk tube with screw lid (Teflon seal) is charged with 30.0 g (99.3 mmol, 1.0 equivalent) of di-tert-butyldibromosilane, which is dissolved in 17.5 g (198.6 mmol, 2 equivalents) of tetrahydrofuran. For stirring, a fairly large magnetic stirring rod with Teflon coating is selected. Added to the solution are 100 mg (0.45 mmol, 0.005 equivalent) of 3,5-di-tert-butyl-4-hydroxytoluene in order to suppress radical reactions. The flask is subsequently weighed. The solution is cooled to −78° C. in a dry ice-isopropanol cooling bath, and the argon present in the flask is removed by brief application of reduced pressure. By injection of around 1.8 bar of cis-2-butene into the reaction flask, 111.4 g (1.9 mol, 20.0 equivalents) of cis-2-butene are incorporated by condensation. The amount of cis-2-butene added is determined gravimetrically. The flask is then repressurized with argon and the screw closure is opened. In a countercurrent of argon, 5.51 g of finely cut lithium (2.5% Na, 794.4 mmol, 8.0 equivalents) are added. The flask is firmly closed again and the contents are thawed to room temperature with vigorous stirring over a period of 16 hours. This is followed by vigorous stirring at room temperature for a further 48 hours. Subsequent reaction monitoring may be carried out using .sup.29Si-NMR, for example. If conversion is complete, the cis-2-butene is slowly discharged from the flask until the flask is no longer under pressure. The tetrahydrofuran is removed under reduced pressure. The residue is extracted with 5 times 100 mL of pentane in order to remove the lithium bromide formed. The pentane is removed again under reduced pressure, and the oily residue is purified by flash distillation (40° C., 10.sup.−2 mbar). The product is captured in this case in the collecting flask by nitrogen cooling. Distillation gives 14.4 g (72.6 mmol, 73%) of cis-1,1-di-tert-butyl-2,3-dimethylsilirane as a clear, colorless oil.

[0127] NMR: cis-tBu.sub.2Si(CHMe).sub.2

[0128] .sup.1H-NMR: (300 K, 500 MHz, C6D6) δ=1.06 (s, 9H, tBu), 1.04-1.10 (m, 2H, —Si—CH—), 1.17 (s, 9H, tBu), 1.40-1.41 (m, 6H, —CH-Me).

[0129] .sup.13C-NMR: (300 K, 125 MHz, C6D6) δ=10.0 (Si—CH—), 10.3 (Si—CH—), 18.6 (—CH-Me), 20.9 (—CH-Me), 30.0 (tBu-Me), 31.6 (tBu-Me).

[0130] .sup.29Si-NMR: (300 K, 100 MHz, C6D6) δ=−53.2.

[0131] CI-MS: 197.3 [M].sup.+.

[0132] trans-1,1-Di-tert-butyl-2,3-dimethylsilirane is synthesized analogously according to synthesis example 1, but in this case using trans-2-butene. The use of a cis/trans mixture is also possible, as in the subsequent reaction the two isomers are indistinguishable in terms of their reactivity.

[0133] NMR: trans-tBu.sub.2Si(CHMe).sub.2

[0134] .sup.1H-NMR: (297 K, 300 MHz, C.sub.6D.sub.6) δ=1.06 (s, 2H, —Si—CH—), 1.09 (s, 18H, tBu), 1.54-1.47 (m, 6H, —CHMe).

[0135] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=−43.9.

[0136] CI-MS: 197.3 [M].sup.+

Example 1: Synthesis of 2,4,6,8-tetrakis(1,1-di-tert-butylsilirane-2-yl)-2,4,6,8-tetramethylcyclotetrasiloxane (D.SUB.4.V1)

[0137] ##STR00011##

[0138] In a 20 mL Schlenk tube with Teflon-coated magnetic stirring bar, 987 mg (2.86 mmol, 1.0 equivalent) of 2,4,6,8-tetramethyltetravinylcyclotetrasiloxane and 2.50 g (12.6 mmol, 4.4 equivalents) of cis-1,1-di-tert-butyl-2,3-dimethylsilirane are dissolved in 5 ml of toluene. As a catalyst, with stirring, 1 mg (4.01 μmol, 0.0014 equivalent) of silver trifluoromethanesulfonate is added. The mixture is stirred at 60° C. for 4 hours. The 2-butene gas which is formed in this process must be able to escape via a pressure relief valve. Complete conversion can be verified via 1H-NMR (vinyl protons). The solvent and the excess monosilirane are subsequently removed under reduced pressure (60° C., 10.sup.−5 mbar). This gives 2.58 g (98%) of D.sub.4V1 in the form of a viscous yellow oil. To remove the residues of catalyst, the oil is dissolved in 5 mL of pentane and filtered through Al.sub.2O.sub.3. After rinsing with 2 mL of pentane, the collected filtrate is filtered via a syringe filter. Removal of the solvent under reduced pressure gives 2.23 g (2.44 mmol, 85%) of 2,4,6,8-tetrakis(1,1-di-tert-butylsiliran-2-yl)-2,4,6,8-tetramethyl-cyclotetrasiloxane as a colorless viscous oil.

[0139] NMR: D.sub.4V1

[0140] .sup.1H-NMR: (300 K, 500 MHz, C.sub.6D6) δ=−0.16-0.02 (m, 4H, —CH—), 0.46-0.66 (m, 12H, Si-Me), 0.77-0.88 (m, 8H, —CH.sub.2—), 1.04-1.13 (m, 36H, tBu), 1.24-1.31 (m, 36H, tBu).

[0141] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=−49.8-(−49.0) (—Si-tBu.sub.2), −23.8-(−21.9) (—Si—O—).

[0142] CI-MS: 911.4[M].sup.+, 769.8 [M-SitBu.sub.2].sup.+, 628.1 [M-2SitBu.sub.2].sup.+.

Example 2: Synthesis of tetrakis((1,1-di-tert-butylsiliran-2-yl)methyl)silane (TAV1)

[0143] ##STR00012##

[0144] In a 20 mL Schlenk tube with Teflon-coated magnetic stirring bar, 661 mg (3.44 mmol, 1.0 equivalent) of tetraallylsilane and 3.00 g (15.1 mmol, 4.4 equivalents) of cis-1,1-di-tert-butyl-2,3-dimethylsilirane are dissolved in 5 ml of toluene. As a catalyst, with stirring, 1 mg (4.12 μmol, 0.0012 equivalent) of silver trifluoromethanesulfonate is added. The mixture is stirred at 60° C. for 4 hours. The 2-butene gas which is formed in this process must be able to escape via a pressure relief valve. Complete conversion can be verified via .sup.1H-NMR (vinyl protons). The solvent and the excess monosilirane are subsequently removed under reduced pressure (60° C., 10.sup.−5 mbar). This gives 2.46 g (94%) of TAV1 in the form of a viscous slightly brownish oil. To remove the residues of catalyst, the oil is dissolved in 5 mL of pentane and filtered through Al.sub.2O.sub.3. After rinsing with 2 mL of pentane, the collected filtrate is filtered via a syringe filter. Removal of the solvent under reduced pressure gives 2.15 g (2.82 mmol, 82%) of tetrakis((1,1-di-tert-butylsiliran-2-yl)methyl)silane as a colorless viscous oil.

[0145] NMR: TAV1

[0146] .sup.1H-NMR: (300 K, 500 MHz, C.sub.6D.sub.6) δ=0.39-0.44 (m, 4H, tBu.sub.2SiCH), 1.10-1.11 (m, 36H, tBu), 1.19-1.22 (m, 8H, Si(CH.sub.2).sub.4), 1.25-1.26 (m, 36H, tBu), 1.40-1.47 (m, 4H, tBu.sub.2SiCH.sub.2), 1.60-1.66 (m, 4H, tBu.sub.2SiCH.sub.2).

[0147] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=5.0 (Si—(CH.sub.2).sub.4—), −49.5 (—Si-tBu.sub.2).

[0148] CI-MS: 760.0[M].sup.+, 285.2 [Si.sub.2tBu.sub.4a].sup.+.

Example 3: Synthesis of poly(((1,1-di-tert-butylsiliran-2-yl)methylsiloxane)-co-dimethylsiloxane) Copolymer (VMS14V1)

[0149] ##STR00013##

[0150] In a 20 mL Schlenk tube with Teflon-coated magnetic stirring bar, 8.00 g (3.72 mmol, 1.0 equivalent) of (vinylmethylsiloxane)-dimethylsiloxane copolymer (M.sub.w=2.150 g/mol, 18% vinylmethylsiloxane) and 4.06 g (20.46 mmol, 5.5 equivalents) of cis-1,1-di-tert-butyl-2,3-dimethylsilirane are dissolved in 5 ml of toluene. As a catalyst, with stirring, 1 mg (4.09 μmol, 0.0011 equivalent) of silver trifluoromethanesulfonate is added. The mixture is stirred at 60° C. for 4 hours. The 2-butene gas which is formed in this process must be able to escape via a pressure relief valve. Complete conversion can be verified via 1H-NMR (vinyl protons). The solvent and the excess monosilirane are subsequently removed under reduced pressure (60° C., 10.sup.−5 mbar). This gives 10.31 g (96%) of VMS14V1 in the form of a viscous slightly brownish oil. To remove the residues of catalyst, the oil is dissolved in 5 mL of pentane and filtered through Al.sub.2O.sub.3. After rinsing with 2 mL of pentane, the collected filtrate is filtered via a syringe filter. Removal of the solvent under reduced pressure gives 6.23 g (2.18 mmol, 58%) of poly(((1,1-di-tert-butylsiliran-2-yl)methylsiloxane)-co-dimethylsiloxane) as a colorless viscous oil.

[0151] NMR: VMS14V1

[0152] .sup.1H-NMR: (300 K, 500 MHz, C.sub.6D.sub.6) δ=−0.18 (m, 5H, tBu.sub.2SiCH), 0.17-0.56 (m, 159H, Si-Me), 0.70-0.87 (m, 10H, tBu.sub.2SiCH.sub.2) 1.06-1.17 (m, 45H, tBu), 1.21-1.34 (m, 45H, tBu).

[0153] .sup.29Si-NMR: (300 K, 100 MHz, C.sub.6D.sub.6) δ=−21.3-22.7 (—SiMe.sub.2-O—), −23.66 (—SiMeR—O—), −49.17 (—SitBu.sub.2).

Use Example 1: Linking of Polydimethylsiloxane (Silanol Terminated, n=132) with tetrakis((1,1-di-tert-butylsiliran-2-yl)methyl)silane (TAV1)

[0154] ##STR00014##

[0155] A suitable vessel is charged with TAV1 (100 mg, 131.3 μmol, 1.0 equivalent) and silicone oil (2.58 g, 262.6 μmol, 2.0 equivalents, 9800 g/mol, Si—OH terminated) in a molar ratio of 1:1 (silirane groups:Si—OH) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 16.5.

Use Example 2: Linking of Polydimethylsiloxane (Silanol Terminated, n=132) with poly(((1,1-di-tert-butylsiliran-2-yl)methylsiloxane)-co-dimethylsiloxane) Copolymer (VMS14V1)

[0156] ##STR00015##

[0157] A suitable vessel is charged with VMS14V1 (200 mg, 69.9 μmol, 1.0 equivalent) and silicone oil (1.71 g, 174.7 μmol, 2.5 equivalents, 9800 g/mol, Si—OH terminated) in a molar ratio of 1:1 (silirane groups:Si—OH) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 9.8.

Use Example 3: Linking of Polydimethylsiloxane (Silanol Terminated, n=132) with 2,4,6,8-tetrakis(1,1-di-tert-butylsiliran-2-yl)-2,4,6,8-tetramethylcyclotetrasiloxane (D.SUB.4.V1)

[0158] ##STR00016##

[0159] A suitable vessel is charged with D.sub.4V1 (466 mg, 509.9 μmol, 1.0 equivalent) and silicone oil (10.0 g, 1.02 mmol, 2.0 equivalents, 9800 g/mol, Si—OH terminated) in a molar ratio of 1:1 (silirane groups:Si—OH) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 9.1.

Use Example 4: Linking of Polydimethylsiloxane (Propylamine Terminated, n=15) with poly(((1,1-di-tert-butylsiliran-2-yl)methylsiloxane)-co-dimethylsiloxane) Copolymer (VMS14V1)

[0160] ##STR00017##

[0161] A suitable vessel is charged with VMS14V1 (500 mg, 174.7 μmol, 1.0 equivalent) and silicone oil (450 g, 349.4 μmol, 2.0 equivalents, 1286 g/mol, propylamine terminated) in a molar ratio of 1.25:1 (silirane groups-NH.sub.2) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 27.5.

Use Example 5: Linking of Polydimethylsiloxane (Hydroxymethyl Terminated, n=181) with 2,4,6,8-tetrakis(1,1-di-tert-butylsiliran-2-yl)-2,4,6,8-tetramethylcyclotetrasiloxane (D.SUB.4.V1)

[0162] ##STR00018##

[0163] A suitable vessel is charged with D.sub.4V1 (67.4 mg, 73.8 μmol, 1.0 equivalent) and silicone oil (2.0 g, 147.5 mmol, 2.0 equivalents, 13 540 g/mol, Si—CH.sub.2OH terminated) in a molar ratio of 1:1 (silirane groups:Si—CH.sub.2OH) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 4.1.

Use Example 6: Linking of Polydimethylsiloxane (Silanol Terminated, n=486) with poly(((1,1-di-tert-butylsiliran-2-yl)methylsiloxane)-co-dimethylsiloxane) Copolymer (ViSi30KV1)

[0164] ##STR00019##

[0165] A suitable vessel is charged with ViSi30KV1 (150 mg, 4.42 μmol, 1.0 equivalent, 33 940 g/mol) and silicone oil (2.19 g, 60.77 μmol, 13.75 equivalents, 36 000 g/mol, Si—OH terminated) in a molar ratio of 1:1 (silirane groups:Si—OH) under inert gas. The mixture is heated to 100° C. and stirred with a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at 110° C. for 24 hours under inert gas. The product is a clear, colorless and elastic polymer which is not sticky and has a Shore A hardness of 7.

Use Example 7: Linking of a Mixture of Polydimethylsiloxane (Silanol Terminated, n=132) and tetrakis((1,1-di-tert-butylsiliran-2-yl)methyl)-silane (TAV1) by Catalysis at Room Temperature

[0166] ##STR00020##

[0167] A suitable vessel is charged with TAV1 (100 mg, 131.3 μmol, 1.0 equivalent) and silicone oil (2.58 g, 262.6 μmol, 2.0 equivalents, 9800 g/mol, Si—OH terminated) in a molar ratio of 1:1 (silirane groups:Si—OH) under inert gas. Additionally added as crosslinking catalyst are 1.20 mg 1.3 μmol, 0.01 equivalent) of triphenylmethyl tetrakis(pentafluorophenyl)borate. The mixture is stirred at room temperature by means of a magnetic stirring bar until homogeneous mixing is ensured. Crosslinking takes place at room temperature (23° C.) for 1 hour under inert gas. The product is a clear, pale brown and elastic polymer which is not sticky.

Analytical Example 1: (Rheological Study of the Linking of VMS14V1 and Silicone Oil (n=132, Si—OH Terminated)

[0168] ##STR00021##

[0169] The crosslinking reaction from use example 2 was carried out in multiple mixing proportions, with the mixing proportion relating to the amount-of-substance ratio of silirane groups to silanol groups. The mixing of the components and their transfer into the rheometer took place under inert gas. Crosslinking took place in the rheometer at 110° C. under nitrogen.

TABLE-US-00001 TABLE 1 crosslinking experiments conducted with VMS14V1 in a rheometer at 110° C. Silicone oil (9800 g/mol, Compound VMS14V1 Si—OH terminated) Ratio silirane/Si—OH 100 mg 1220 mg  0.7 100 mg 949 mg 0.9 100 mg 857 mg 1 100 mg 613 mg 1.4 100 mg 476 mg 1.8

[0170] The crosslinking time can be estimated by the change over time in the viscosity of the mixtures. The crosslinking time is observed to fall as the silirane fraction rises. Beyond a mixing proportion of 1:1, the mixtures are crosslinked after 16-24 hours at 110° C. The highest viscosity is achieved with a ratio of ˜1.4.

[0171] The loss factor tan(δ), which represents the ratio of loss modulus G″ to storage modulus G′, is a measure of the viscoelastic properties of a material. The lower tan(6), the less energy is lost in elastic processes. tan(δ)=0 denotes ideally elastic behavior. The tan(δ) values represented in table 2 (mean values of the last 100 measurement points) are a measure of the elastic properties and of the degree of crosslinking of the through-crosslinked mixtures. The lowest tan(δ) value is achieved with a 1:1 mixture; this points to a very high degree of crosslinking. In the case of undercrosslinked mixtures (ratio=0.7/0.9), higher loss factors are obtained.

TABLE-US-00002 TABLE 2 loss factor tan(δ) for various through-crosslinked elastomers Ratio silirane/Si—OH Loss factor tan(δ) 0.7 0.0205 0.9 0.0029 1 0.0016 1.4 0.0017 1.8 0.0020

Analytical Example 2: Investigation of the Shore A Hardness of Different Mixtures of Silirane Compound and Silicone Oils

[0172] The Shore A hardness was determined by crosslinking mixtures of silirane compound and Si—OH terminated silicone oils at 110° C. for 72 hours in order to ensure complete conversion. The Shore A hardness was measured directly after crosslinking and again 8 weeks after; no difference was found in this case.

TABLE-US-00003 TABLE 3 Shore-A hardnesses of elastomers formed from various silirane compounds and silicone oils. Mixing proportion (silirane groups/ Silirane Silicone oil functional groups Shore A compound (dimethylsiloxane) in silicone oil) hardness TAV1 9800 g/mol, Si—OH 1.0 17 terminated TAV1 9800 g/mol, Si—OH 1.1 15 terminated TAV1 9800 g/mol, Si—OH 1.3  6 terminated TAV1 9800 g/mol, Si—OH 1.5 1-2 terminated VMS14V1 9800 g/mol, Si—OH 1.0 10 terminated VMS14V1 9800 g/mol, Si—OH 1.3  5 terminated VMS14V1 9800 g/mol, Si—OH 1.5 0-1 terminated ViSi30KV1 36 000 g/mol, Si—OH 1.0  7 terminated ViSi30KV1 36 000 g/mol, Si—OH 1.3 16 terminated ViSi30KV1 36 000 g/mol, Si—OH 1.5 19 terminated ViSi30KV1 36 000 g/mol, Si—OH 2.0 27 terminated ViSi30KV1 9800 g/mol, Si—OH 1.0 28 terminated ViSi30KV1 9800 g/mol, Si—OH 1.3 33 terminated ViSi30KV1 9800 g/mol, Si—OH 1.5 24 terminated