Low chloride compositions of olefinically functionalised siloxane oligomers based on alkoxysilanes

Abstract

The invention relates to a composition comprising olefinically functionalized siloxane oligomers derived from olefinically functionalized alkoxysilanes and optionally alkoxysilanes functionalized with saturated hydrocarbons, and also, optionally, a tetraalkoxysilane, which have not more than one olefinic radical on the silicon atom, and whose chloride content is reduced, and also to processes for preparing them and to the use thereof.

Claims

1. A process for preparing a composition comprising olefinically functionalized siloxane oligomers, the process comprising reacting: (i) an olefinically functionalized alkoxysilane of formula II,
A-Si(R.sup.2).sub.x(OR.sup.1).sub.3-x  (II) wherein A in formula II represents an olefinic radical and is a linear, branched or cyclic alkenyl- or cycloalkenyl-alkylene-functional group having in each case 2 to 16 C atoms; R.sup.2 represents a linear, branched or cyclic alkyl radical having 1 to 15 C atoms and x is 0 or 1; and each R.sup.1, independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms, (ii) in the presence of at least one of a hydrolysis and a condensation catalyst that comprises hydrogen chloride; (iii) and in the presence of water and alcohol as solvent, to produce the olefinically functionalized siloxane oligomers; and (iv) removing the hydrolysis alcohol and the solvent present; and (v) at least once during said (iv) removing or subsequently, further adding alcohol and carrying out removal; (vi) wherein the total chloride content of the composition is less than or equal to 100 mg/kg; and (vii) the weight-average molecular weight (Mw) is 410 g/mol to 580 g/mol, wherein a) in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.001 to 5.0 volume units of alcohol per volume unit of alkoxysilane, and/or b) in (v), at least once during step (iv) or subsequently, additional alcohol is added and removal is carried out 1 to 6 times.

2. The process of claim 1, further comprising reacting the olefinically functionalized alkoxysilane of formula II the presence of at least one of a hydrolysis and a condensation catalyst with (i.1) at least one alkoxysilane of formula III,
B—Si(R.sup.4).sub.y(OR.sup.3).sub.3-y  (III), wherein B represents a saturated hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms; each R.sup.3, independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms; R.sup.4 represents a linear, branched or cyclic alkyl radical having 1 to 15 C atoms; and y is 0 or 1.

3. The process of claim 1, further comprising reacting the olefinically functionalized alkoxysilane of general formula II in the presence of at least one of a hydrolysis and a condensation catalyst with (i.2) at least one tetraalkoxysilane of formula IV,
Si(OR.sup.3).sub.4  (IV), wherein: each R.sup.3, independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms.

4. The process of claim 1, wherein the alcohol is methanol, ethanol or any combination thereof.

5. The process of claim 1, wherein the composition is obtained following (v) as a liquid-phase product.

6. The process of claim 2, wherein: in the olefinically functionalized alkoxysilane of general formula II:
A-Si(R.sup.2).sub.x(OR.sup.1).sub.3-x  (II) A is selected from the group consisting of vinyl, allyl, butenyl, pentenyl, hexenyl, ethylhexenyl, heptenyl, octenyl, cyclohexenyl-C1 to C8-alkylene, and a 3′-cyclohexenyl-2-ethylene group; x is 0 or 1; and R.sup.1 are each independently a methyl, ethyl or propyl group; and in the alkoxysilane of formula III:
B—Si(R.sup.4).sub.y(OR.sup.3).sub.3-y  (III) the unsubstituted hydrocarbon radical B is selected from the group consisting of methyl, ethyl, propyl, butyl, isobutyl, n-butyl, tert-butyl, pentyl, n-pentyl, isopentyl, neopentyl, hexyl, isohexyl, neohexyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 2-methylpentyl, 3-methylpentyl, octyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, C.sub.13H.sub.27, C.sub.14H.sub.29, C.sub.15H.sub.31 and a hexadecyl group; and R.sup.3 is a methyl, ethyl or propyl group; and y is 0 or 1.

7. The process of claim 2, wherein in the olefinically functionalized alkoxysilane of the general formula II x is 0 and/or in the alkoxysilane of the formula III functionalized with a saturated hydrocarbon radical y is 0.

8. The process of claim 2, wherein water is added of greater than or equal to 0.60 to 1.48 mol of water per mole of silicon atoms in the alkoxysilanes of at least one of formula II and formula III.

9. The process of claim 2, further comprising at least partial hydrolysis and condensation of the alkoxysilane of at least one of formula II and formula Ill in the presence of an acidic catalyst; and, optionally removing the alcohol.

10. The process of claim 9, wherein the acidic catalyst is hydrogen chloride.

11. The process of claim 1, wherein in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.0.5 to 2.5 volume units of alcohol per volume unit of alkoxysilane.

12. The process of claim 2, wherein the olefinically functionalized alkoxysilane of formula II is selected from the group consisting of vinyltriethoxysilane, allyltriethoxysilane, butenyltriethoxysilane, pentenyltriethoxysilane, hexenyltriethoxysilane, ethylhexenyltriethoxysilane, heptenyltriethoxysilane, octenyltriethoxysilane, cyclohexenyl-C1 to C8-alkylenetriethoxysilane, cyclohexenyl-2-ethylenetriethoxysilane, 3′-cyclohexenyl-2-ethylenetriethoxysilane, cyclohexadienyl-C1 to C8-alkylenetriethoxysilane, cyclohexadienyl-2-ethylenetriethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, butenyltrimethoxysilane, pentenyltrimethoxysilane, hexenyltrimethoxysilane, ethylhexenyltrimethoxysilane, heptenyltrimethoxysilane, octenyltrimethoxysilane, cyclohexenyl-C1 to C8-alkylenetrimethoxy silane, cyclohexenyl-2-ethylenetrimethoxysilane, 3′-cyclohexenyl-2-ethylenetrimethoxysilane, cyclohexadienyl-C1 to C8-alkylenetrimethoxysilane and cyclohexadienyl-2-ethylenetrimethoxysilane; and in each case independently the alkoxysilane of formula III is selected from the group consisting of methyltriethoxysilane, ethyltriethoxysilane, n-propyltriethoxysilane, isopropyltriethoxysilane, butyltriethoxysilane, n-butyltriethoxysilane, isobutyltriethoxysilane, hexyltriethoxysilane, n-hexyltriethoxysilane, isohexyltriethoxysilane, heptyltriethoxysilane, octyltriethoxysilane, n-octyltriethoxysilane, isooctyltriethoxysilane, undecyltriethoxysilane, decyltriethoxysilane, nonadecyltriethoxysilane, dodecyltriethoxysilane, C.sub.13H.sub.27-triethoxysilane, C.sub.14H.sub.29-triethoxysilane or C.sub.15H.sub.31-triethoxysilane, hexadecyltriethoxysilane, methyltrimethoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, isopropyltrimethoxysilane, butyltrimethoxysilane, n-butyltrimethoxysilane, isobutyltrimethoxysilane, hexyltrimethoxysilane, n-hexyltrimethoxysilane, isohexyltrimethoxysilane, heptyltrimethoxysilane, octyltrimethoxysilane, n-octyltrimethoxysilane, isooctyltrimethoxysilane, undecyltrimethoxysilane, decyltrimethoxysilane, nonadecyltrimethoxysilane, dodecyltrimethoxysilane, C.sub.13H.sub.27-trimethoxysilane, C.sub.14H.sub.29-trimethoxysilane or C.sub.15H.sub.31-trimethoxysilane and hexadecyltrimethoxysilane.

13. The process of claim 1, wherein the hydrolysis alcohol and the solvent are removed by distillation.

14. The process of claim 3, further comprising at least partial hydrolysis and condensation of the alkoxysilane of at least one of formula II and formula IV in the presence of an acidic catalyst; and, optionally removing the alcohol.

15. The process of claim 12, wherein in (iii) the reaction takes place in the presence of water and an alcohol in an amount of 0.1 to 2.0 volume units of alcohol per volume unit of alkoxysilane.

16. The process of claim 1, further comprising reacting the olefinically functionalized alkoxysilane of formula II the presence of at least one of a hydrolysis and a condensation catalyst with at least one of: (i.1) at least one alkoxysilane of formula III,
B—Si(R.sup.4).sub.y(OR.sup.3).sub.3-y  (III), wherein B represents a saturated hydrocarbon radical and is a linear, branched or cyclic alkyl radical having 1 to 16 C atoms; each R.sup.3, independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms; R.sup.4 represents a linear, branched or cyclic alkyl radical having 1 to 15 C atoms; and y is 0 or 1; and (i.2) at least one tetraalkoxysilane of formula IV,
Si(OR.sup.3).sub.4  (IV), wherein: each R.sup.3, independently, represents a linear, branched or cyclic alkyl radical having 1 to 4 C atoms.

17. The process of claim 16, wherein greater than or equal to 1% of the silicon atoms in the olefinically functionalized siloxane oligomer, in relation to the sum total of silicon atoms in the siloxane oligomer, are obtained as a T structure, and/or the amount of silicon atoms in monomeric alkoxysilanes represented by at least one of formula II, formula III and formula IV, or the hydrolysis product thereof, is less than or equal to 3% in relation to the total silicon atoms in the composition.

18. The process of claim 1, wherein the hydrolysis catalyst or the condensation catalyst comprises hydrogen chloride.

Description

EXAMPLES

(1) Determination of Molecular Weight:

(2) Molar masses of the molecular weight and also the molar mass distribution can be determined by means of gel permeation chromatography (GPC). The GPC analysis method is described exhaustively in references including “Modern Size-Exclusion Liquid Chromatography”, Andre Striegel et al., Wiley & Sons, 2nd edn. 2009. To calibrate the method for siloxane analyses it is possible as standard to use, for example, divinyltetramethoxydisiloxane or divinyltetraethoxydisiloxane. Percentages in relation to the olefinic siloxane oligomers in the present document correspond to a datum in area percent, which can be determined from GPC analyses.

(3) MZ-Analysetechnik columns used: Columns: 50×8.0 mm, MZ-Gel SDplus (styrene/divinylbenzene copolymer with high degree of crosslinking, spherical particle shape), porosity 50 A (angstroms, Å), 5 μm (micrometers) (preliminary column), 300×8.0 mm, MZ-Gel SDplus, porosity 50 A (angstroms, Å), 5 μm, 300×8.0 mm, MZ-Gelplus, porosity 100 A (angstroms, Å), 5 μm, 300×8.0 mm, MZ-Gel SDplus, porosity 500 A (angstroms, Å), 5 μm; eluent and pump flow rate: methyl ethyl ketone (MEK) at 1 ml/min, standard substance: internal standard—1 g/l ethylbenzene in 1% strength sample solution. The instrument is calibrated beforehand against the respective substance (monomer, dimer, trisiloxane, etc.). Instrument from Agilent: 1100 Series isotactic pump G1310A, 1100 Series column oven G1316A, 1100 Series RID detector G1362A, manual injector G1328A, vacuum degasser G1322A, GPC software (PSS WinGPC Unity).

(4) Determination of Chlorine Content and Total Chloride:

(5) The silane is digested with oxygen in a bomb calorimeter and then hydrolysed with acetic acid and hydrofluoric acid. The chloride content of the resulting solution is determined by titration with a well-defined silver nitrate solution.

(6) Determination of Chlorine Content and Hydrolysable Chloride:

(7) After hydrolysis with acetic acid, a determination is made of the chloride content by titration with a well-defined silver nitrate solution.

(8) Determination of SiO2 Content—Crucible Method:

(9) The SiO2 content is determined by acid digestion with concentrated sulphuric acid and subsequent evaporation, by fluorination.

(10) GC Analysis:

(11) As part of the GC standard analysis well known to the skilled person, the monomer content is determined by appropriate calibration and optionally internal standard.

(12) .sup.29Si NMR Spectrometry:

(13) Furthermore, the monomer content, and also M, D and T structures, can be determined using .sup.29Si NMR spectrometry, which is likewise well known to the skilled person.

(14) Determination of Dynamic Viscosity:

(15) The dynamic viscosity was determined in accordance with DIN 53015.

1. Syntheses

(16) 1.1 VTMO Oligomer with Alcohol Metering—V082

(17) Procedure: A 2 l apparatus is charged with 401.2 g of VTMO (vinyltrimethoxysilane), which is diluted with a fraction of methanol. Subsequently a mixture of methanol, double-distilled water and hydrochloric acid (37%) is metered in at 25° C. under ambient pressure with stirring. There is an exothermic reaction. Should the temperature rise above 45° C., metering is interrupted. The overall reaction time runs to 5 hours, beginning with the metering of the H.sub.2O/HCl/methanol mixture. After the reaction, the alcohol is distilled on a rotary evaporator at up to 90° C. and 100 mbar. When the 100 mbar are reached, this pressure is maintained for 15 minutes, after which the apparatus is let down. The liquid phase obtained is a VTMO-siloxane oligomer composition and is identified as “liquid phase 1”. At this point, sampling takes place. Liquid phase 1 is mixed further with 256.91 g of methanol and stirred at 25° C. for 30 minutes. The methanol is subsequently distilled on a rotary evaporator at up to 90° C. and 100 mbar. When the 100 mbar are reached, this pressure is maintained for 15 minutes, after which the apparatus is let down. The liquid phase obtained is a VTMO-siloxane oligomer composition based on VTMO, and is called “liquid phase 2”.

(18) TABLE-US-00001 TABLE 1 Raw materials V082 Compound Initial mass Methanol (dilution) 83.5 g Methanol (metering) 173.2 g  Hydrochloric acid 0.43 g Double-distilled water 39.7 g
1.2 VTEO-Siloxane Oligomer with Alcohol Metering—V083

(19) Procedure: A 2 l apparatus is charged with 400.0 g of VTEO. Subsequently a mixture of ethanol, double-distilled water and hydrochloric acid (37%) is metered in at 35° C. under ambient pressure with stirring. There is an exothermic reaction. Should the temperature rise above 60° C., metering is interrupted. The total reaction time runs to 5 hours, beginning at 77° C., after complete addition of the H.sub.2O/EtOH/HCl mixture. After the reaction, the alcohol is distilled on a rotary evaporator at up to 100° C. and 100 mbar. When the 100 mbar have been reached, they are maintained for 15 minutes, after which the system is let down. The liquid phase obtained is a VTEO-siloxane oligomer composition and is called “liquid phase 1”. Sampling takes place. Liquid phase 1 is mixed further with 190.46 g of ethanol and stirred at 35° C. for 30 minutes. Ethanol distillation takes place subsequently on a rotary evaporator at up to 100° C. and 100 mbar. When the 100 mbar are reached, this pressure is maintained for 15 minutes, after which the apparatus is let down. The liquid phase obtained is a VTEO-siloxane oligomer composition and is called “liquid phase 2”.

(20) TABLE-US-00002 TABLE 2 Raw materials V083 Compound Initial mass Ethanol 190.50 Water 30.64 Hydrochloric acid 0.24
1.3 VTEO/PTEO-Siloxane Oligomer with Alcohol Metering—V084

(21) Procedure: A 2 l apparatus is charged with 211.7 g of vinyltriethoxysilane (VTEO) and 216.5 g of propyltriethoxysilane (PTEO). Subsequently a mixture of ethanol, double-distilled water and hydrochloric acid (37%) is metered in at 35° C. under ambient pressure with stirring. There is an exothermic reaction. Should the temperature rise above 60° C., metering is interrupted. The total reaction time runs to 5 hours, beginning at 79° C., after complete addition of the H.sub.2O/EtOH/HCl mixture. After the reaction, the alcohol is distilled on a rotary evaporator at up to 100° C. and 100 mbar. When the 100 mbar have been reached, they are maintained for 15 minutes, after which the system is let down. The liquid phase obtained is a VTEO/PTEO-siloxane oligomer composition and is referred to as “liquid phase 1”. Sampling takes place. Liquid phase 1 is further mixed with 189.50 g of ethanol and stirred at 25° C. for 30 minutes. Ethanol distillation takes place subsequently on a rotary evaporator at up to 100° C. and 100 mbar. When the 100 mbar are reached, this pressure is maintained for 15 minutes, after which the apparatus is let down. The liquid phase obtained is a VTEO/PTEO-siloxane oligomer composition and is called “liquid phase 2”.

(22) TABLE-US-00003 TABLE 3 Raw materials V084 Compound Initial mass Water 29.6 g Ethanol 189.5 g  HCl 0.22 g

2. Ion Exchanger—can be Integrated in the Inventive Process

Example 2.1

(23) 150 g of vinyl-/alkyl-functional siloxane co-oligomer (hydrolysable chloride content: 255 wt-ppm or mg/kg) were passed with a flow rate of 2.01 m/h over the ion exchanger Lewatit MP 62 (available from Lanxess) in the OH.sup.− form. Working up gave 140.1 g of vinyl-/alkyl-functional siloxane co-oligomer with 32 wt-ppm of hydrolysable chloride. The ethanol content of the odourless product obtained after elution was 18 wt % EtOH. EtOH was removable on a rotary evaporator.

Example 2.2

(24) 50 g of vinyl-/alkyl-functional siloxane co-oligomer (hydrolysable chloride content: 110 wt-ppm or mg/kg) were passed with a flow rate of 2.05 m/h over the ion exchanger Lewatit MP 62 (available from Lanxess) in the OH.sup.− form. Working up gave 142.8 g of vinyl-/alkyl-functional siloxane co-oligomer with 4 wt-ppm of hydrolysable chloride.

3. Analysis

(25) 3.1 General Analysis

(26) TABLE-US-00004 TABLE 4 Analytical results from V082, V083 and V084 V082 V083 V084 Experiment “Liquid “Liquid “Liquid “Liquid “Liquid “Liquid No. phase 1” phase 2” phase 1” phase 2” phase 1” phase 2” Total chloride <35 40 35 <35 115 70 [mg/kg] Hydrol. 24 4 3 <3 4 4 chloride [mg/kg] SiO.sub.2 54.7 54.9 45.4 45.4 41.6 41.6 [Mass %] Free alcohol 0.3 0.2 0.7 0.7 0.5 0.5 [mass %] Monomer 1.7 0.7 1.5 0.9 3.2 2.5 [mass %]
3.2. GPC Analyses

(27) TABLE-US-00005 TABLE 5a Results of the GPC analyses for Examples V082, V083 and V084 Mn Mw Experiment No. [g/mol] [g/mol] D V082 liquid 424.50 516.97 1.2191 phase 1 V082 liquid 425.90 513.49 1.2056 phase 2 V083 liquid 409.36 476.39 1.1638 phase 1 V083 liquid 426.97 492.92 1.1545 phase 2 V084 liquid 416.27 456.23 1.0960 phase 1 V084 liquid 423.00 464.28 1.0976 phase 2

(28) TABLE-US-00006 TABLE 5b Results of the GPC analyses for further siloxane oligomers prepared in analogy to Examples 1.1-V082, Ex. 1.2-V083 and Ex. 1.3-V084. analogous Mn Mw Mmax experiments g/mol g/mol D [g/mol] V082 liquid phase 1 474 556.3 1.17 2000 V082 liquid phase 2 482.9 561.1 1.16 2000 V083 liquid phase 1 435.4 488.2 1.12 1300 V083 liquid phase 2 447.9 503.4 1.12 1500 V084 liquid phase 1 427.2 469.7 1.09 1200 V084 liquid phase 2 427.7 475.7 1.11 1200

(29) TABLE-US-00007 TABLE 5c Anal- Disiloxane + Trisiloxane + Tetrasiloxane + Pentasiloxane + ogous <Disiloxane cyclotrisiloxane cyclotetrasiloxane cyclopentasiloxane cyclohexasiloxane >Pentasiloxane to [%] [%] [%] [%] [%] [%] V082 <0.1 8.9 25.8 23.3 14.8 17.3 liquid phase 1 V082 <0.1 8.5 25.5 23.4 15.2 27.5 liquid phase 2 V083 1.4 25.1 39.8 17.7 8.4 7.6 liquid phase 1 V083 <0.1 23.4 40.5 18.2 8.9 8.9 liquid phase 2 V084 2.5 36.5 38 14.1 5.5 3.5 liquid phase 1 V084 2 35.2 38 14.5 5.9 4.4 liquid phase 2 For key see Table 5d

(30) TABLE-US-00008 TABLE 5d Results of the GPC analyses (fractions in area %) of the further siloxane oligomers prepared in analogy to Examples 1.1-V082, Ex. 1.2-V083 and Ex. 1.3-V084. 250- 500- 0-250 rel. 500 rel. 750 rel. 750-1000 rel. >1000 rel. MW [%] MW [%] MW [%] MW [%] MW [%] V082 1.46 48.84 32.03 12.21 5.47 liquid phase 1 V082 1.35 48.12 32.47 12.45 5.61 liquid phase 2 V083 1.85 63.56 26.44 6.65 1.5 liquid phase 1 V083 0.51 62.57 27.41 7.41 2.1 liquid phase 2 V084 2.45 66.73 25.47 4.64 0.71 liquid phase 1 V084 2 65.81 25.96 5.26 0.97 liquid phase 2

(31) TABLE-US-00009 TABLE 6 Results from NMR analyses for V082 Fractions in the siloxane oligomer compositions .sup.1H and Silane M D T Experiment .sup.13C monomer structure structure structure No. NMR [mol %] [mol %] [mol %] [mol %] V082 liquid 1.4 mol 1.1 (VTMO) 41.1 49.8 8.0 phase 1 SiOMe V082 liquid 1.3 mol 0.5 (VTMO) 40.4 50.4 8.7 phase 2 SiOMe

(32) TABLE-US-00010 TABLE 7 Results from NMR analyses for V083 Fractions in the siloxane oligomer compositions .sup.1H and Silane M D T Experiment .sup.13C monomer structure structure structure No. NMR [mol %] [mol %] [mol %] [mol %] V083 liquid 1.4 mol 1.0 (VTEO) 56.2 39.8 3.0 phase 1 SiOEt V083 liquid 1.4 mol 0.6 (VTEO) 52.7 42.6 4.1 phase 2 SiOEt

(33) TABLE-US-00011 TABLE 8 Results from NMR analyses for V084 Fractions in the siloxane oligomer compositions Silane Experiment .sup.1H and .sup.13C monomer M structure D structure T structure No. NMR [mol %] [mol %] [mol %] [mol %] V084 3.0 mol SiOEt — (VTEO) 33.4 17.6 0.9 Liquid and 0.94 mol 1.8 (PTEO) 33.9 12.4 — phase 1 propylsilyl V084 3.0 mol SiOEt — (VTEO) 33.8 16.4 1.0 Liquid and 0.94 mol 1.4 (PTEO) 35.1 12.3 — phase 2 propylsilyl

4. Comparative Examples

Comparative Example 1

(34) V078—Example 1 from EP0518057 B1—Preparation of a co-condensate of vinyltrimethoxysilane and methyltrimethoxysilane with a molar vinyl:methoxy groups ratio of around 1:3.

(35) Procedure: A 2 l four-necked apparatus with water-operated condenser and magnetic stirrer was charged with 397.6 g of vinyltrimethoxysilane (VTMO) and 244.6 g of methyltrimethoxysilane at 20° C. The mixture was admixed, using a 500 ml dropping funnel, with a solution of 49.9 g of distilled water in 332.8 g of methanol, this solution containing 2400 ppm of hydrogen chloride. After a total of 16 hours, the entire methanol together with HCl was distilled off at about 300 mbar. Thereafter the resulting oligomer mixture was distilled to a pressure of about 1 mbar and a boiling range ending at 113° C. In this way, 170 g of clear product were obtained.

(36) TABLE-US-00012 TABLE 9 Raw materials V078 Compound Supplier Initial mass VTMO Evonik Degussa GmbH 397.6 g MTMS Evonik Degussa GmbH 244.6 g Hydrochloric Merck (HCl 37%)  49.9 g acid Double-distilled water 2400 ppm Methanol ROTH 332.8 g

Comparative Example 2

(37) V081—Example 6 from EP 0518057 B1—Preparation of a condensate of vinyltrimethoxysilane with a molar vinyl:methoxy groups ratio of about 1:1.75. Procedure: A 2 l four-necked apparatus with water-operated condenser and magnetic stirrer was charged with 693.83 g of VTMO at 20° C. The mixture was admixed with a solution of 52.82 g of distilled water in 351.53 g of methanol, the solution containing 1100 ppm of hydrogen chloride. A 500 ml dropping funnel was used for this purpose. The temperature rose to about 36° C. within 26 minutes. After a total of 13 hours, the entire methanol together with hydrochloric acid was removed by distillation under about 300 mbar within 2-3 hours. The resulting oligomer mixture was thereafter distilled down to a pressure of about 1 mbar and a boiling range ending at 100° C. In this way, 240 g of clear product were obtained.

(38) TABLE-US-00013 TABLE 10 Raw materials V081 Compound Supplier Initial mass VTMO Evonik Degussa GmbH 693.7 g Methanol 351.5 g Hydrochloric acid Merck (HCl 37%)  52.8 g 1100 ppm Double-distilled water
Analytical Results for the Comparative Experiments:

(39) TABLE-US-00014 TABLE 11 Analytical results for V078 (Comparative Example 1) Colour Experiment Total hydrolysable SiO.sub.2 VTMO number No. chlorides chloride (mass) (mass) [mg V078 [mg/kg] [mg/kg] [%] [%] Pt—Co/l] Distillate (cf. 230 16 52.4 <0.1 <5 Example 1 in EP0518057B1)

(40) TABLE-US-00015 TABLE 12 Analytical results for V081 (Comparative Example 2) Colour Experiment Total hydrolysable SiO.sub.2 VTMO number No. chloride chloride (mass) (mass) [mg V081 [mg/kg] [mg/kg] [%] [%] Pt—Co/l] Distillate (cf. 50 <3 48.6 1.7 <5 Example 6 in EP0518057B1)

(41) TABLE-US-00016 TABLE 13 Evaluation of the GPC analysis results Experiment number Mn [g/mol] Mw [g/mol] D = Mw/Mn V078 275.13 291.11 1.0581 V081 254.06 269.90 1.0624

(42) TABLE-US-00017 TABLE 14 Results from the .sup.29Si NMR analyses on the products from Comparative Experiments V078 and V081, [VS = vinylsilyl, MS = methylsilyl] Comparative Fractions in the siloxane oligomer compositions Experiment M structure D structure T structure Silane monomer No. [mol %] [mol %] [mol %] [mol %] V078 52.1 (VS) 9.1 (VS) —(VS) 0.9 (VTMO) 29.3 (MS) 8.6 (MS) —(MS) — (MTMS) V081 91.8 (VS) 6.8 (VS) —(VS) 1.2 (VTMO)

5. Performance Experiments

(43) TABLE-US-00018 TABLE 14 Product assignment for performance experiments Product from Performance experiment No. experiment No. V082 liquid phase 1 — V082 liquid phase 2 V127 V083 liquid phase 1 — V083 liquid phase 2 V128 V084 liquid phase 1 — V084 liquid phase 2 V129 V078 V116 V081 V118
5.1 Kneading Experiments

(44) The following kneading operations were operated with a temperature profile of “3 min at 140° C., from 140° C. to 170° C. in 2 min, 5 min at 170° C.” with a rotary speed of 30 rpm in a HAAKE kneading apparatus. Subsequently, each batch was processed by compression to form two plates at 190° C. under a load pressure of 20 t. In order to simplify the addition of the peroxide, silane/peroxide solutions were prepared.

(45) 5.2 Preparation of the Measurement Specimens

(46) The samples prepared were stored in a conditioning chamber at 23° C. and 50% relative humidity, after which specimens were made for tensile tests and for the determination of the water uptake capacity and determination of the melt index.

(47) TABLE-US-00019 TABLE 15 Raw materials and batches for practical application Compound Batch ATH M56/15  EVA M56/156 DCUP M56/026

(48) TABLE-US-00020 TABLE 16 Peroxide mixtures for kneadings Siloxane oligomer/DCUP Initial mass Initial siloxane for performance solution batch DCUP oligomer mass experiment No. V078 9.81 g 0.19 g V116 V081 9.81 g 0.19 g V118 V082 9.81 g 0.19 g V127 V083 9.81 g 0.19 g V128 V084 9.82 g 0.19 g V129

(49) TABLE-US-00021 TABLE 17 Initial masses in the kneading experiments Initial Initial Initial Silane Experiment mass mass DCUP/silanoxane oligomer/DCUP No. EVA ATH oligomer solution solution batch V116 27.72 g 41.61 g 0.45 g V078 V118 27.72 g 41.61 g 0.44 g V081 V127 27.72 g 41.61 g 0.42 g V082 V128 27.72 g 41.61 g 0.42 g V083 V129 27.72 g 41.61 g 0.44 g V084 V153 27.72 g 41.61 g — — (blank sample)
5.3 Determinations of the Melt Index (MFR) and the Volume Flow Index (MVR)

(50) Preparation and evaluation took place in accordance with DIN ISO 1133 (Method B), the content of which is referenced in full and made part of the content of the present application. Testing apparatus: Zwick 4106 flow tester. The determination of melt index (MFR) and volume flow index (MVR) is carried out under a fixed shearing load and at defined temperature (T.sub.PT) and defined loading (m.sub.nom) on a polymeric melt through a standard nozzle. The change in travel of the die over time is ascertained, and MVR and MFR are calculated according to the formulae known to the skilled person. ˜7 g of the individual samples were comminuted and the melt index (“MFR”) was determined at a temperature of 160° C. under a load of 21.6 kg.

(51) TABLE-US-00022 TABLE 18 Results for the analysis of the melt index (MFR) and volume flow index (MVR) from V116 and V118 Experiment No. V116 V118 Siloxane oligomer from V078 V081 Experimental temperature 160° C. Preheating time 4 min Loading weight 21.6 kg MFR [g min] 3.19 3.39 MVR [cm.sup.3 min] 2.36 2.51 Density [g/cm.sup.3] 1.352 1.348

(52) TABLE-US-00023 TABLE 19 Results for the analysis of the melt index (MFR) and volume flow index (MVR) from V127, V128, V129 and V153 (blank sample) Experiment No. V153 V127 V128 V129 Siloxane oligomer — V082 V083 V084 from Experimental 160° C. temperature Preheating time 4 min Loading weight 21.6 kg MFR [g min] 2.03 3.27 3.47 3.67 MVR [cm.sup.3 min] 1.50 2.43 2.57 2.72 Density [g/cm.sup.3] 1.349 1.350 1.351 1.351
5.4 Water Uptake Capacity
5.4.1 Determination of Water Uptake Capacity

(53) Test specimens of defined geometry are stored under defined conditions (temperature, time) in a water bath. The change in weight of the samples is captured before and during storage and after the drying operations.

(54) The water uptake capacity was determined using the specimens produced, after a time period of 24 hours, by means of a triple determination, with the specimens having been stored in the water bath at 70° C. for the stated period.

(55) TABLE-US-00024 TABLE 20 Results of water uptake capacity Experiment No. Value [mg/cm] after 7 d storage V153 3.81 V116 1.55 V118 1.40 V127 1.22 V128 1.64 V129 1.64
5.5 Determination of Tensile Properties

(56) The tensile properties were determined in accordance with DIN EN ISO 527-1, 527-2, 527-3, the content of which is referenced in full and made part of the content of the present application. For this purpose, a sample rod of defined geometry is clamped into the tensile testing machine and subjected to uniaxial loading until breakage occurs (uniaxial extension at defined extension rate). The change in stress is recorded on the sample rod via the extension of the specimen, and the tensile strength and elongation at break are ascertained. Testing instrument: Zwick 4115 universal tester. Using the specimens or tensile rods (“bones”) produced, after 24 h of storage in a conditioning chamber at 23° C. and 50% relative humidity, the tensile properties (elongation at break and tensile strength) of the samples were determined in a five-fold determination, using a testing speed of 200 mm/min and a pre-tensioning force of 0.2 MPa.

(57) TABLE-US-00025 TABLE 21 Complete overview of results for tensile properties and elongations at break Product from Elongation at experiment PF experiment break Tensile strength No. No. [%] [MPa] V082 V127 73.81 8.87 V083 V128 88.01 8.14 V084 V129 55.15 8.07 V078 V116 80.37 8.66 V081 V118 85.61 9.31