MIXTURE OF POLYMERIC ALKYL SILICATES

Abstract

An organosilicon compound includes a mixture of polymeric alkyl silicates. The polymeric alkyl silicates include at least 90% by weight a mixture of polymeric alkyl silicates of the formula (I) [SiO.sub.4/2].sub.a [(R.sup.xO)SiO.sub.3/2].sub.b [(R.sup.yO)SiO.sub.3/2].sub.b [(R.sup.xO).sub.2SiO.sub.2/2].sub.c [(R.sup.xO)(R.sup.yO)SiO.sub.2/2].sub.c [(R.sup.yO).sub.2SiO.sub.2/2].sub.c [(R.sup.xO).sub.3SiO.sub.1/2].sub.d [(R.sup.xO).sub.2(R.sup.yO)SiO.sub.1/2].sub.d [(R.sup.xO)(R.sup.yO).sub.2SiO.sub.1/2].sub.d [(R.sup.yO).sub.3SiO.sub.1/2].sub.d [O.sub.1/2R.sup.zO.sub.1/2].sub.e [O.sub.1/2R.sup.zOH].sub.e [O.sub.1/2R.sup.zOR.sup.X].sub.e [O.sub.1/2R.sup.zOR.sup.y*].sub.e (I). Polymeric alkyl silicates of a formula II are excluded.

Claims

1-15. (canceled)

16. An organosilicon compound comprising a mixture of polymeric alkyl silicates, comprising at least 90% by weight of a mixture of polymeric alkyl silicates of the formula (I) ##STR00021## wherein the indices a, b, b, c, c, c, d, d, d, d, e, e and e independently of one another indicate a number in the range from 0 to 5000, where the index e is a number in the range of 2 to 5000, with the proviso that the sum of all indices is at least 5; the radicals R.sup.x are each independently selected from radicals that satisfy at least one of the following conditions: (a) R.sup.x is a radical of the formula CHR.sup.p.sub.2 or CR.sup.p.sub.3, wherein R.sup.p is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, (b) R.sup.x is a substituted or unsubstituted, C.sub.5-C.sub.20 hydrocarbon radical that is doubly branched at the ?-carbon atom, (c) R.sup.x is an unsubstituted or alkyl-substituted cyclopentyl, cyclohexyl or cycloheptyl radical having a total of not more than 9 carbon atoms; the radicals R.sup.y are each independently a hydrogen atom, a methyl, ethyl, n-propyl or n-butyl radical, preferably a methyl or ethyl radical; in which the radicals OR.sup.y may be partially replaced by Si-bonded H atoms; R.sup.y* is a methyl, ethyl, n-propyl or n-butyl radical, preferably a methyl or ethyl radical; the radicals R.sup.z are each independently a divalent unsubstituted or substituted radical bonded via carbon or a divalent radical bonded via silicon, in which individual carbon or Si atoms may be replaced by oxygen atoms; with the proviso that the units [O.sub.1/2R.sup.zO.sub.1/2] are bonded to two units independently selected from the group of units comprising [SiO.sub.4/2], [(R.sup.xO)SiO.sub.3/2], [(R.sup.yO)SiO.sub.3/2], [(R.sup.xO).sub.2SiO.sub.2/2], [(R.sup.xO)(R.sup.yO)SiO.sub.2/2], [(R.sup.yO).sub.2SiO.sub.2/2], [(R.sup.xO).sub.3SiO.sub.1/2], [(R.sup.xO).sub.2(R.sup.yO)SiO.sub.1/2], [(R.sup.xO)(R.sup.yO).sub.2SiO.sub.1/2] and [(R.sup.yO).sub.3SiO.sub.1/2]; with the proviso that the units [O.sub.1/2R.sup.ZOH], [O.sub.1/2R.sup.ZOR.sup.X] and [O.sub.1/2R.sup.zOR.sup.y*] are bonded to one unit independently selected from the group of units comprising [SiO.sub.4/2], [(R.sup.xO)SiO.sub.3/2], [(R.sup.yO)SiO.sub.3/2], [(R.sup.xO).sub.2SiO.sub.2/2], [(R.sup.xO)(R.sup.yO)SiO.sub.2/2], [(R.sup.xO).sub.2SiO.sub.2/2]; with the proviso that the molar proportion of all radicals R.sup.y in the polymeric alkyl silicate is at most 50 mol %, based on the molar amount of the sum of all radicals R.sup.x, R.sup.y and R.sup.y*, wherein the molar fraction for the radical OR.sup.y equal to hydrogen is at most 33 mol %, based on the molar amount of the sum of all radicals OR.sup.x and OR.sup.y; and with the proviso that the following polymeric alkyl silicates, consisting exclusively of compounds of formula II, are excluded: ##STR00022## wherein Z is a radical of formula Si(ORD).sub.3 or a radical of formula CR.sup.c.sub.3, R.sup.a is each independently a divalent unsubstituted or substituted carbon-bonded radical or a divalent silicon-bonded radical, R.sup.b is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 4 to 40 carbon atoms which is branched at the ?-carbon atom or is doubly branched at the ?-carbon atom, R.sup.c is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, X is a halogen atom, an oxygen-bonded unsubstituted or substituted C.sub.1- to C.sub.40-hydrocarbon radical, wherein individual carbon atoms may be replaced by oxygen atoms, a radical of formula OSi(OR.sup.b).sub.3 or a radical of formula OSiR.sup.n.sub.3, R.sup.n is each independently a monovalent unsubstituted or substituted C.sub.1- to C.sub.40-hydrocarbon radical and m is an integer of at least 2 and at most 1000.

17. A mixture of polymeric alkyl silicates of the formula (I) ##STR00023## wherein the indices a, b, b, c, c, c, d, d, d, d, e, e and e independently of one another indicate a number in the range from 0 to 5000, where the index e is a number in the range of 2 to 5000, with the proviso that the sum of all indices is at least 5; the radicals R.sup.x are each independently selected from radicals that satisfy at least one of the following conditions: (a) R.sup.x is a radical of the formula CHR.sup.p.sub.2 or CR.sup.p.sub.3, wherein R.sup.p is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, (b) R.sup.x is a substituted or unsubstituted, C.sub.5-C.sub.20 hydrocarbon radical that is doubly branched at the ?-carbon atom, (c) R.sup.x is an unsubstituted or alkyl-substituted cyclopentyl, cyclohexyl or cycloheptyl radical having a total of not more than 9 carbon atoms; the radicals R.sup.y are each independently a hydrogen atom, a methyl, ethyl, n-propyl or n-butyl radical, preferably a methyl or ethyl radical; in which the radicals OR.sup.y may be partially replaced by Si-bonded H atoms; R.sup.y* is a methyl, ethyl, n-propyl or n-butyl radical, preferably a methyl or ethyl radical; the radicals R.sup.z are each independently a divalent unsubstituted or substituted radical bonded via carbon or a divalent radical bonded via silicon, in which individual carbon or Si atoms may be replaced by oxygen atoms; with the proviso that the units [O.sub.1/2R.sup.zO.sub.1/2] are bonded to two units independently selected from the group of units comprising [SiO.sub.4/2], [(R.sup.xO)SiO.sub.3/2], [(R.sup.yO)SiO.sub.3/2], [(R.sup.xO).sub.2SiO.sub.2/2], [(R.sup.xO)(R.sup.yO)SiO.sub.2/2], [(R.sup.yO).sub.2SiO.sub.2/2], [(R.sup.xO).sub.3SiO.sub.1/2], [(R.sup.xO).sub.2(R.sup.yO)SiO.sub.1/2], [(R.sup.xO)(R.sup.yO).sub.2SiO.sub.1/2] and [(R.sup.yO).sub.3SiO.sub.1/2]; with the proviso that the units [O.sub.1/2R.sup.ZOH], [O.sub.1/2R.sup.ZOR.sup.X] and [O.sub.1/2R.sup.zOR.sup.y*] are bonded to one unit independently selected from the group of units comprising [SiO.sub.4/2], [(R.sup.xO)SiO.sub.3/2], [(R.sup.yO)SiO.sub.3/2], [(R.sup.xO).sub.2SiO.sub.2/2], [(R.sup.xO)(R.sup.yO)SiO.sub.2/2], [(R.sup.yO).sub.2SiO.sub.2/2]; with the proviso that the molar proportion of all radicals R.sup.y in the polymeric alkyl silicate is at most 50 mol %, based on the molar amount of the sum of all radicals R.sup.x, R.sup.y and R.sup.y*, wherein the molar fraction for the radical OR.sup.y equal to hydrogen is at most 33 mol %, based on the molar amount of the sum of all radicals OR.sup.x and OR.sup.y; and with the proviso that the following polymeric alkyl silicates, consisting exclusively of compounds of formula II, are excluded: ##STR00024## where Z is a radical of formula Si(ORD).sub.3 or a radical of formula CR.sup.c.sub.3, R.sup.a is each independently a divalent unsubstituted or substituted carbon-bonded radical or a divalent silicon-bonded radical, R.sup.b is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 4 to 40 carbon atoms which is branched at the ?-carbon atom or is doubly branched at the ?-carbon atom, R.sup.c is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 1 to 50 carbon atoms, X is a halogen atom, an oxygen-bonded unsubstituted or substituted C.sub.1- to C.sub.40-hydrocarbon radical, wherein individual carbon atoms may be replaced by oxygen atoms, a radical of formula OSi(OR.sup.b).sub.3 or a radical of formula OSiR.sup.n.sub.3, R.sup.n is each independently a monovalent unsubstituted or substituted C.sub.1- to C.sub.40-hydrocarbon radical and m is an integer of at least 2 and at most 1000.

18. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein the polymeric alkyl silicates do not contain SiC-bonded radicals.

19. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein the polymeric alkyl silicates comprise at least 2 structural elements selected from the group of formulae 1 to 10 ##STR00025## ##STR00026## with the proviso that the sum of the number of structural units of the formulae 1+2+3+5+6 is less than 60%, based in each case on the sum of the number of all structural units, and with the proviso that if a structural unit of formula 4 is present where R.sup.x has the definition of CR.sup.p.sub.3, at least one further structural unit selected from the group of formulae 1, 2, 3, 5, 6, 9 and 10 is present.

20. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein R.sup.x is a radical of the formula CHR.sup.p.sub.2 or CR.sup.p.sub.3, wherein R.sup.p is each independently a monovalent unsubstituted or substituted hydrocarbon radical having 1 to 10 carbon atoms.

21. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein the radicals R.sup.x are selected from the group consisting of tert-butyl, 2-butyl radical, 3-methyl-2-butyl, 3-methyl-2-pentyl, 3-pentyl radical, 2-hexyl radical, 3-hexyl radical, 2-heptyl radical, 2-octyl radical, 1-phenylethyl radical, 1-phenyl-1-propyl radical, 1,1-dimethylpropyl radical and mixtures thereof.

22. The mixture of polymeric alkyl silicates as claimed claim 16, wherein the radicals R.sup.z are each independently a divalent hydrocarbon radical having 3 to 200 carbon atoms, wherein the carbon atoms may be replaced by oxygen atoms or by siloxanyl radicals of the formula (R.sup.3.sub.2SiO).sub.OSiR.sup.3.sub.2, wherein R.sup.3 is each independently a C.sub.1- to C.sub.20-hydrocarbon radical, and o is an integer from 0 to 100.

23. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein the radicals R.sup.z are selected from the group consisting of 1,3-propylene radical, 1,4-butylene radical, 1,2-cyclohexylidene radical, 1,3-cyclohexylidene radical, 1,4-cyclohexylidene radical, 1,2-phenylene radical, 1,3-phenylene radical and 1,4-phenylene radical and radicals of the formulae
CR.sup.4.sub.2CR.sup.4.sub.2(OCR.sup.4.sub.2CR.sup.4.sub.2).sub.p,
CR.sup.4.sub.2(CR.sup.4.sub.2).sub.q(OCR.sup.4.sub.2(CR.sup.4.sub.2).sub.q).sub.p,
-(Me.sub.2SiO).sub.o-Me.sub.2Si,
CH.sub.2CH.sub.2CH.sub.2-(Me.sub.2SiO).sub.o-Me.sub.2SiCH.sub.2CH.sub.2CH.sub.2,
CH.sub.2CH.sub.2-(Me.sub.2SiO).sub.o-Me.sub.2SiCH.sub.2CH.sub.2 and
CH.sub.2-(Me.sub.2SiO).sub.o-Me.sub.2SiCH.sub.2, where Me is a methyl radical, R.sub.4 may be the same or different and is a hydrogen atom or a C.sub.1- to C.sub.18-hydrocarbon radical, o is an integer from 0 to 100, p is an integer from 0 to 100, and q is an integer from 1 to 100.

24. The mixture of polymeric alkyl silicates as claimed in claim 16, wherein the indices a, b, b, c, c, c, d, d, d, d, e, e and e are each independently a number in the range from 0 to 500, wherein the index e is a number in the range from 2 to 500, with the proviso that the sum of all indices is at least 5.

25. A process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in claim 16, by reacting silanes (1), selected from the group of tetrachlorosilane (1a), tetraalkoxysilane (1b), partial hydrolysates of tetrachlorosilane, partial hydrolysates of tetraalkoxysilane and mixtures thereof, optionally with the addition of solvents (7), with monohydroxy compounds (2) of formula ##STR00027## optionally with the addition of primary alcohols (3) of the formula ##STR00028## and/or optionally with the addition of water (4), and with dihydroxy compounds (5) of formula ##STR00029## or salts thereof, optionally in the presence of catalysts (6), simultaneously in one step or successively in two steps, preferably successively in two steps, with the proviso that if SiCl.sub.4 (1a) is reacted with monohydroxy compounds (2) of the formula HOR.sup.x, in which R.sup.X is a radical of the formula CR.sup.p.sub.3, at least one further compound selected from the group consisting of monohydroxy compounds (2) of the formula HOR.sup.x, in which R.sup.X has the definition stated therefor in claim 1, but is not a radical of the formula CR.sup.p.sub.3, primary alcohols (3) of the formula HOR.sup.y, water (4) and mixtures thereof are added to the reaction mixture, and with the proviso that monohydroxy compounds (2) and primary alcohols (3) are used in amounts of 1.0 to 3.0 mol per mole of silane (1), and dihydroxy compounds (5) are used in amounts of 0.7 to 1.5 mol per mole of silane (1).

26. The process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in claim 25, wherein silanes (1), selected from the group of tetrachlorosilane (1a), tetraalkoxysilane (1b), partial hydrolysates of tetrachlorosilane, partial hydrolysates of tetraalkoxysilane and mixtures thereof, optionally with the addition of solvents (7), are reacted with secondary alcohols (2a) or tertiary alcohols (2b) of the formula ##STR00030## wherein R.sup.x is a radical of the formula CHR.sup.p.sub.2 or CR.sup.p.sub.3, optionally with the addition of primary alcohols (3) of the formula ##STR00031## and/or optionally with the addition of water (4), and with dihydroxy compounds (5) of formula ##STR00032## or salts thereof, optionally in the presence of catalysts (6), simultaneously in one step or successively in two steps, with the proviso that if SiCl.sub.4 (1a) is reacted with a tertiary alcohol (2b) HOR.sup.x, wherein R.sup.X is a radical of the formula CR.sup.p.sub.3, at least one further compound selected from the group consisting of secondary alcohols (2a) HOR.sup.x, where R.sup.x is a radical of the formula CHR.sup.p.sub.2, primary alcohols (3) HOR.sup.y, water (4) and mixtures thereof are added to the reaction mixture, and with the proviso that alcohols of the formulae HOR.sup.x and HOR.sup.y are used in amounts of 1.0 to 3.0 mol per mole of silane (1), and dihydroxy compounds (5) are used in amounts of 0.7 to 1.5 mol per mole of silane (1).

27. The process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in claim 26, wherein in a first step, silanes (1), selected from the group of tetrachlorosilane (1a), tetraalkoxysilanes (1b), partial hydrolysates of tetrachlorosilane, partial hydrolysates of tetraalkoxysilane and mixtures thereof, optionally with the addition of solvents (7), with secondary alcohols (2a) or tertiary alcohols (2b) of the formula ##STR00033## wherein R.sup.x is a radical of the formula CHR.sup.p.sub.2 or CR.sup.p.sub.3, optionally with the addition of primary alcohols (3) of the formula ##STR00034## and/or optionally with the addition of water (4), and in a second step, the reaction mixtures obtained from the first step are reacted with dihydroxy compounds (5) of formula ##STR00035## or salts thereof, optionally in the presence of catalysts (6) and optionally with the addition of solvents (7), with the proviso that if SiCl.sub.4 (1a) is reacted with a tertiary alcohol (2b) HOR.sup.x, wherein R.sup.X is a radical of the formula CR.sup.p.sub.3, at least one further compound selected from the group consisting of secondary alcohols (2a) HOR.sup.x, where R.sup.y is a radical of the formula CHR.sup.p.sub.2, primary alcohols (3) HOR.sup.y, water (4) and mixtures thereof are added to the reaction mixture, and with the proviso that alcohols of the formulae HOR.sup.x and HOR.sup.y are used in amounts of 1.0 to 3.0 mol per mole of silane (1), and dihydroxy compounds (5) are used in amounts of 0.7 to 1.5 mol per mole of silane (1).

28. The process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in claim 25, wherein the catalysts (6) used are nitrogen bases selected from the group consisting of pyridine, ammonia, urea, ethylenediamine, triethylamine, tributylamine and mixtures thereof.

29. The process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in claim 25, wherein solvents (7) are used in the second process step.

30. The process for preparing the mixture of polymeric alkyl silicates of the formula (I) as claimed in any of claim 16, by reacting compounds of the formula Si(H).sub.l(OR.sup.X).sub.k(OR.sup.y).sub.j and/or partial hydrolysates thereof, where the index l is 1, 2, 3 or 4, preferably 1 or 2, and the indices k and j are each independently 0, 1, 2 or 3, with the proviso that the sum of l+k+j equals 4, with dihydroxy compounds (5) of the formula ##STR00036## optionally in the presence of a catalyst (6) and optionally with the addition of solvents (7) with elimination of hydrogen.

Description

EXAMPLES 1 TO 12 AND COMPARATIVE EXAMPLE

Measurement Methods

[0187] 1) The viscosity was measured at 25? C. using a Stabinger SVM3000 rotational viscometer from Anton Paar. [0188] 2) The mass-average molar mass M.sub.w and also the number-average molar masses M.sub.n can be determined by size exclusion chromatography (SEC) against polydimethylsiloxane standards, in toluene, at 35? C., flow rate 0.7 ml/min and detection by RI (refractive index detector) on a MesoPore-OligoPore column set (Agilent, Germany) with an injection volume of 10 ?l. [0189] 3) The conversion of the examples listed below were checked by means of nuclear magnetic resonance spectroscopy (29Si NMR; Bruker Avance III HD 500 (29Si: 99.4 MHz) spectrometer with BBO 500 MHz S2 probe head; inverse gated pulse sequence (NS=3000). 150 mg of the samples were taken up in 500 ?l of a 4*10-2 molar solution of Cr(acac).sub.3 in CD.sub.2Cl.sub.2. When using secondary alcohols, mixtures of chloroalkoxysilanes comprising Si(Cl).sub.3(OR), Si(Cl).sub.2(OR).sub.2, Si(Cl)(OR).sub.3 and Si(OR).sub.4 are formed. An average empirical formula can be calculated from the signal intensities by multiplying the relative signal intensities of the individual chloroalkoxysilanes by the Cl/Si or OR/Si ratio present in the respective chloroalkoxysilanes and averaging over the four species, as demonstrated in the examples 1-4 below. [0190] 4) To identify individual molecules and the structural motifs they contain, the material from example 6 was analyzed using MALDI-TOF. MALDI-TOF measurements were carried out with a Bruker Autoflex Speed MALDI-TOF/TOF mass spectrometer. The measurement was linear in the positive mode with a Nd:YAG laser at 355 nm. The mass range detected for the positive mode was m/z 500-5000. The calibration in this mass range was carried out with polyethylene glycol.

[0191] THAP (2,4,6-trihydroxyacetophenone, 5 mg/mL dissolved in 70% acetonitrile, 30% water, 0.1% formic acid) was used as matrix and mixed with 5 mg of the sample. NaI (5 mg/mL) and KI (5 mg/mL) dissolved in methanol were added for ionization. The sample was applied using the thin-film technique. See the structural motifs from MALDI-TOF studies on the product of Example 6.

TABLE-US-00001 TABLE 1 Composition and average empirical formula of the reaction product according to Examples 1, 2 and Comparative example Comparative Example 1 Example 2 example Alkoxychlorosilane Content [%] Content [%] Content [%] Si(Cl).sub.3(OR) 15.8 12.0 0.0 Si(Cl).sub.2(OR).sub.2 65.7 58.8 100 Si(Cl)(OR).sub.3 18.2 28.8 0.0 Si(OR).sub.4 0.3 0.4 0.0 Average empirical Si(Cl)1.97(O-2- Si(Cl).sub.1.82(O-2- Si(Cl).sub.2.00(O- formula Bu).sub.2.03 Pr).sub.2.18 tBu).sub.2.00

[0192] When using a mixture of different alcoholsas in Example 3mixed chloroalkoxysilanes are obtained, for example, in addition to Si(Cl).sub.3(O-2-Bu) also Si(Cl).sub.3(O-Me)analogous permutations are observed for the other chloroalkoxysilanes. To calculate the average empirical formula, the signal intensities of the respective groups (monoalkoxytrichlorosilanes, dialkoxydichlorosilanes, trialkoxychlorosilanes and tetraalkoxysilanes) are added and then offset against each other in the same way as in the example shown above. In contrast, the reaction of tetrachlorosilane with two equivalents of a tertiary alcohol (e.g. tert-butanol) results in the formation of a single compound, the dialkoxydichlorosilane.

TABLE-US-00002 TABLE 2 Composition and average empirical formula of the reaction product according to Examples 3-5. Example 3 Example 4 Example 5 Alkoxychlorosilane* Content [%] Content [%] Content [%] Si(Cl).sub.3(OR.sup.1) 3.19 Si(Cl).sub.3(OR.sup.2) 18.52 12.98 Si(Cl).sub.2(OR.sup.1).sub.2 6.50 Si(Cl).sub.2(OR.sup.1)(OR.sup.2) 21.57 5.65 1.5 Si(Cl).sub.2(OR.sup.2).sub.2 7.91 50.61 97.2 Si(Cl)(OR.sup.1).sub.3 4.01 2.0 Si(Cl)(OR.sup.1).sub.2(OR.sup.2) 19.34 Si(Cl)(OR.sup.1)(OR.sup.2).sub.2 17.24 14.66 Si(Cl)(OR.sup.2).sub.3 1.13 14.79 Si(OR.sup.1).sub.4 1.0 Si(OR.sup.1).sub.3(OR.sup.2) Si(OR.sup.1).sub.2(OR.sup.2).sub.2 0.19 0.47 Si(OR.sup.1)(OR.sup.2).sub.3 0.25 0.56 Si(OR.sup.2).sub.4 0.15 0.27 Average empirical Si(Cl).sub.1.79(OR).sub.2.21 Si(Cl).sub.1.81(OR).sub.2.19 Si(Cl).sub.1.98(OR).sub.2.02 formula (43.2% OMe) (10.58% OMe) (5.54% OMe) *OR.sup.1 describes the methoxy radical, depending on the example, OR.sup.2 describes in these examples either the 2-Bu-O or tert-butoxy radical.

General Set-Up of the Apparatus for the Alkoxylation of Tetrachlorosilane to Produce the Chloroalkoxysilanes (CAS) of Examples 1-5 and the Comparative Example

[0193] A 4 L three-necked flask is equipped with a KPG stirrer, a 1 L non-pressure equalizing dropping funnel (fitted with an olive) and an olive. The flask is connected via the olive to an empty safety wash bottle and a downstream exhaust gas scrubber filled with NaOH. The entire apparatus is carried out in a fume hood with a neutralization system and flushed with argon before filling (the argon is added via the dropping funnel) and the reaction flask is cooled to 0? C. The tetrachlorosilane is initially charged and the appropriate alcohol (or previously prepared mixtures of alcohols) are slowly added via the dropping funnel. During the addition, a constant stream of argon is passed through the system to remove the resulting hydrogen chloride gas from the gas phase. The mixture is then warmed to room temperature and stirred at this temperature for two hours.

[0194] When using tert-butanol, the solid is first dissolved in toluene (1 part by weight of tert-butanol to 2 parts by weight of toluene).

General Set-Up of the Apparatus for Reacting the Chloroalkoxysilanes (CAS) with Organic Diols According to Examples 6 to 12

[0195] A 2 L three-necked flask is equipped with a KPG stirrer, a 1 L pressure-equalizing dropping funnel (fitted with an olive), and a reflux condenser with olive. The apparatus is connected via the olive to an empty safety wash bottle and a downstream exhaust gas scrubber filled with NaOH. The entire apparatus is carried out in a fume hood with a neutralization system and flushed with argon before filling (the argon is added via the dropping funnel). The chloroalkoxysilane mixture is initially charged and diluted with toluene. A mixture of the selected diol and pyridine is slowly added via the dropping funnel (the reaction flask is first heated to the temperature given in Table 3, depending on the example). During the addition, a constant stream of argon is passed through the system to remove the resulting hydrogen chloride gas from the gas phase. After the addition is complete, the mixture is stirred at the reaction temperature for two hours at unchanged flow of argon, brought to room temperature and filtered through a pleated filter. The adhering toluene is removed on a rotary evaporator at 60? C. and 100 mbar.

[0196] A summary of the reactants used in the examples and weights thereof for producing the chloroalkoxysilanes (CAS) are given in Table 3.

TABLE-US-00003 TABLE 3 Weights, addition rates and average empirical formulae of the reactions of tetrachlorosilane with various alcohols or mixtures. Weight Alcohol/ Duration Average of SiCl.sub.4 Weight of addition empirical Examples* [g] [g] [Hours] formula Example 1 1600 2-Butanol/1310 6.0 Si(Cl).sub.1.97(OR).sub.2.03 Example 2 600 Isopropanol/425 2.5 Si(Cl).sub.1.82(OR).sub.2.18 Example 3 401 2-Butanol/175 2.0 Si(Cl).sub.1.79(OR).sub.2.21 Methanol/76 Example 4 401 2-Butanol/314 2.0 Si(Cl).sub.1.81(OR).sub.2.19 Methanol/15 Example 5 401 Tert-butanol/341 2.0 Si(Cl).sub.1.96(OR).sub.2.04 Methanol/5 Comparative 21 Tert-butanol/19 0.5 Si(Cl).sub.2.00(OR).sub.2.00 Example *For Examples 1-4, the formation of trichloroalkoxysilanes, dichlorodialkoxysilanes, chlorotrialkoxysilanes and tetraalkoxysilanes is observed. In Examples 3 and 4, the alcohols were mixed prior to addition via the dropping funnel. In contrast, the comparative example shows only a singlet of the dichlorodialkoxysilane. Examples 2-5 were carried out in 2 L three-necked flasks and the comparative example in a 100 mL three-necked flask.

[0197] The weights for the further reactions of the chloroalkoxysilanes (CAS) with organic diols are shown in Table 4.

TABLE-US-00004 TABLE 4 Weights and reaction temperatures of the reactions of chloroalkoxysilanes with organic diols. Diol/ CAS/ Weight of Volume Weight Weight pyridine of toluene Temp. Examples [g] [g] [g] [ml] [? C.] Example 6 DPG/ Example 1/ 83.953 400 20 70.815 130.001 Example 7 DPG/ Example 1/ 83.968 430 60 70.814 129.980 Example 8 DPG/ Example 1/ 84.030 300 150 70.818 130.007 Example 9 DPG/ Example 2/ 94.900 300 20 74.147 130.007 Example 10 DPG/ Example 3/ 105.120 300 20 84.280 135.000 Example 11 DEG/ Example 4/ 96.957 350 20 68.22 150.000 Example 12 DPG/ Example 5/ 96.967 350 20 68.22 150.001 * DPG = dipropylene glycol, DEG = diethylene glycol.

[0198] The analytical data collected for the products of Examples 6 to 12 are summarized in Table 5.

TABLE-US-00005 TABLE 5 Analytical data of the products of Examples 6-12. Viscosity GPC Examples [mPa*s] M.sub.N M.sub.W PD Example 6* 16801 (5/s) 1397 829242 593.7 3637 (150/s) Example 7* 1508 (5/s) 1002 170627 170.3 877 (150/s) Example 8 151.8 800 56956 71.2 Example 9 44.3 799 8175 10.2 Example 10 42.0 642 5965 9.3 Example 11 39.4 782 7347 9.4 Example 12 41.2 754 6598 8.8 *The materials from examples 6 and 7 show thixotropic behavior. In both cases, the viscosities are given at defined shear rates (5 revolutions/s and 150 revolutions/s).

[0199] Based on MALDI-TOF investigations on the product of Example 6, the following molecules could be identified as part of the mixture:

##STR00020##

[0200] Molecules detected by MALDI-TOF. The following indices could be established for the respective compounds. The indices of the compounds A, B, C, D and F could be detected from n=1-11, and for the index E from n=0-2. For compound E, the repeat units could also be present distributed among the other DPG units.