MIXTURES CONTAINING PHOSPHORUS COMPOUNDS AND USE THEREOF

Abstract

Compositions and mixtures along with processes for preparing and uses for the same.

Claims

1-11. (canceled)

12. Mixtures (M), comprising: a compound (X) of polyethers of the general formula (I)
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals; wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals; wherein p is an integer from 4 to 110; a compound (Y) of phosphorus compounds of the general formula (II)
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3-(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals; wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals; wherein m is equal to 0 or 1, preferably 1; wherein n is equal to 0, 1 or 2; wherein m+n is equal to 1 or 2, preferably 1; and optionally a compound (Z) being an amount of water.

13. The mixtures (M) of claim 12, wherein the compound (X) of polyethers are those of the formula
R.sup.1(OCH.sub.2CH.sub.2).sub.q(OCHCH.sub.3CH.sub.2).sub.r(OCH.sub.2CH.sub.2).sub.sOR.sup.1  (III); wherein R.sup.1 has one of the aforementioned definitions; wherein q is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15; wherein s is 0 or an integer from 1 to 30, preferably 0 or an integer from 1 to 15, and wherein r is an integer from 4 to 50, preferably an integer from 4 to 35.

14. The mixtures (M) of claim 12, wherein the compound (Y) of phosphorus are alkylphosphonic acids having 4 to 18 carbon atoms.

15. The mixtures (M) of claim 12, wherein the mixtures comprise compound (Y) of phosphorus in amounts of 10 to 50 parts by weight.

16. The mixtures (M) of claim 12, wherein the mixtures comprise the water (Z) in amounts of 0.5 to 3.0 mol, based on 1 mole of the compound (Y) of phosphorus.

17. Process for preparing mixtures (M), comprising: providing a compound (X) of polyethers of the general formula (I), a compound (Y) of phosphorus compounds of the formula (II) and optionally a compound (Z) being an amount of water, wherein the general formula (I) is
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals, wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals, and wherein p is an integer from 4 to 110, wherein the formula (II) is
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3-(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein m is equal to 0 or 1, preferably 1, wherein n is equal to 0, 1 or 2, wherein m+n is equal to 1 or 2, preferably 1; and mixing the individual constituents together.

18. A process for preparing crosslinkable compositions based on organosilicon compounds, comprising: providing (A) of organopolysiloxanes of the formula (V)
(R.sup.7O).sub.3-aSiR.sup.3.sub.aO(SiR.sup.4.sub.2O).sub.xSiR.sup.3.sub.a(OR.sup.7).sub.3-a  (V), wherein R.sup.4 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.7 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.3 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein a may be identical or different and is 0 or 1, preferably 1, wherein x is an integer from 30 to 2000; providing (B) mixtures (M), wherein the mixtures (M) comprise a compound (X) of polyethers of the general formula (I), a compound (Y) of phosphorus compounds of the formula (II) and optionally a compound (Z) being an amount of water, wherein the general formula (I) is
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals, wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals, wherein p is an integer from 4 to 110, wherein the formula (II) is
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein m is equal to 0 or 1, preferably 1, wherein n is equal to 0, 1 or 2, wherein m+n is equal to 1 or 2, preferably 1; and mixing the individual constituents together.

19. The process of claim 18, wherein the crosslinkable compositions obtained are mouldings.

20. Compositions, comprising: (A) organopolysiloxanes of the formula (V), (B) mixtures (M), and optionally (C) silanes of the formula (VI) and/or partial hydrolysates thereof, optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) additives; wherein the mixtures (M) comprise a compound (X) of polyethers of the general formula (I), a compound (Y) of phosphorus compounds of the formula (II) and optionally a compound (Z) being an amount of water; wherein the general formula (I) is
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals, wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals, wherein p is an integer from 4 to 110; wherein the general formula (II) is
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein m is equal to 0 or 1, preferably 1, wherein n is equal to 0, 1 or 2, wherein m+n is equal to 1 or 2, preferably 1; and wherein the formula (V) is
(R.sup.7O).sub.3-aSiR.sup.3.sub.aO(SiR.sup.4.sub.2O).sub.xSiR.sup.3.sub.a(OR.sup.7).sub.3-a  (V), wherein R.sup.4 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.7 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.3 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein a may be identical or different and is 0 or 1, preferably 1, and wherein x is an integer from 30 to 2000.

21. The process of claim 20, compositions obtained are mouldings.

22. Process for preparing the compositions, comprising: providing (A) organopolysiloxanes of the formula (V), (B) mixtures (M), and optionally (C) silanes of the formula (VI) and/or partial hydrolysates thereof, optionally (D) curing accelerators, optionally (E) plasticizers, optionally (F) fillers and optionally (G) additives, wherein the mixtures (M) comprise a compound (X) of polyethers of the general formula (I), a compound (Y) of phosphorus compounds of the formula (II) and optionally a compound (Z) being an amount of water; wherein the general formula (I) is
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals, wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals, wherein p is an integer from 4 to 110; wherein the general formula (II) is
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3-(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein m is equal to 0 or 1, preferably 1, wherein n is equal to 0, 1 or 2, wherein m+n is equal to 1 or 2, preferably 1; and wherein the formula (V) is
(R.sup.7O).sub.3-aSiR.sup.3.sub.aO(SiR.sup.4.sub.2O).sub.xSiR.sup.3.sub.a(OR.sup.7).sub.3-a  (V), wherein R.sup.4 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.7 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein R.sup.3 may be identical or different and denotes monovalent, optionally substituted hydrocarbon radicals, wherein a may be identical or different and is 0 or 1, preferably 1, wherein x is an integer from 30 to 2000; and mixing the individual constituents.

23. The process of claim 22, compositions obtained are mouldings.

24. A process for preparing organosilicon compounds comprising organyloxy groups; comprising: wherein in a 1st step an organosilicon compound (a) comprising at least one silanol group is reacted with a compound (b) comprising at least two organyloxy groups, in the presence of catalysts (c), which are selected from lithium alkoxylates, lithium hydroxide, amidines or guanidines; wherein in a 2nd step, after reaction of the hydroxyl groups of the component (a) with the compounds (b) comprising organyloxy groups has taken place, the mixture (M) according to the invention is added, wherein the mixtures (M) comprise a compound (X) of polyethers of the general formula (I), a compound (Y) of phosphorus compounds of the formula (II) and optionally a compound (Z) being an amount of water; wherein the general formula (I) is
R.sup.1—(O—R.sup.2).sub.p—O—R.sup.1  (I), wherein R.sup.1 may be identical or different and denotes a hydrogen atom or hydrocarbon radicals, wherein R.sup.2 may be identical or different and denotes divalent, optionally substituted hydrocarbon radicals, wherein p is an integer from 4 to 110; wherein the general formula (II) is
O═PR.sup.5.sub.m(OR.sup.6).sub.n(OH).sub.3-(m+n)  (II), wherein R.sup.5 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein R.sup.6 may be identical or different and denotes optionally substituted hydrocarbon radicals, wherein m is equal to 0 or 1, preferably 1, wherein n is equal to 0, 1 or 2, and wherein m+n is equal to 1 or 2, preferably 1.

Description

EXAMPLE 1

[0231] 100 g of OPS 75 were mixed with 75 g of PPG 425 and heated to 105° C. under reduced pressure of 20 mbar and maintained at this temperature for one hour. Here, the ethanol and water distil off.

[0232] A clear solution was obtained which starts to crystallize at 28° C. and is solid at room temperature.

[0233] The results can be found in Table 1.

EXAMPLE 2

[0234] 100 g of OPS 75 were mixed with 75 g of PPG 1000 and heated to 105° C. under reduced pressure of 20 mbar and maintained at this temperature for one hour. Here, the ethanol and water distil off.

[0235] A clear solution was obtained which starts to crystallize at 25° C. and is solid at room temperature. Therefore, no viscosity could be measured at 25° C.

[0236] The results can be found in Table 1.

EXAMPLES 4 TO 7

[0237] The procedure described in example 1 was repeated with the amounts of feedstocks stated in Table 1.

[0238] In examples 4 and 7, after completion of the distillation phase, the mixture was cooled to 80° C. and the amounts of deionized water specified in Table 1 were added. In order to obtain homogeneous solutions, stirring was continued for a further hour in these cases. Clear solutions were obtained with the viscosities and temperatures of onset of crystallization stated in Table 1.

TABLE-US-00001 TABLE 1 OPS PPG PPG Viscosity Onset of 75 425 1000 H2O at 25° C. crystal- Example [g] [g] [g] [g] [mPas] lization 1 100 75 * +28° C. 2 100 80 * +25° C. 4 100 80 7.12 341 −10° C. 5 100 150 251 −5° C. 6 100 225 180 −25° C. 7 100 150 10.64 252 <−30° C. * not measurable due to crystallization

EXAMPLE 8

[0239] The procedure described in example 7 was repeated, with the modification that PPG 400 was used instead of PPG 425. No differences were observed in this case. In particular, the melting point was likewise less than −30° C.

EXAMPLE 9

[0240] 309 g of an α,ω-bis[(tetrahydro-1,4-oxazin-4-yl)methyldiethoxysilyl]polydimethylsiloxane having a viscosity of 80 000 mPa.Math.s, 130 g of an α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.Math.s (commercially available under the name “Weichmacher 1000” from Wacker Chemie AG, Munich, Germany), 1 g of a product consisting of 16.0 mol % of units of the formula MeSi(OEt).sub.2O.sub.1/2, 46.4 mol % of units of the formula MeSi(OEt)O.sub.2/2, 36.5 mol % of units of the formula MeSiO.sub.3/2, 0.2 mol % of units of the formula Me.sub.2Si(OEt)O.sub.1/2 and 0.9 mol % of units of the formula Me.sub.2SiO.sub.2/2, 8 g of 3-aminopropyltriethoxysilane (commercially available under the name GENIOSIL® GF 93 from Wacker Chemie AG, Munich, Germany), 2 g of vinyltriethoxysilane (commercially available under the name GENIOSIL® GF 56 from Wacker Chemie AG, Munich, Germany) and 5 g of tetraethyl silicate (commercially available under the name “Silikat TES 28” from Wacker Chemie AG, Munich, Germany) were initially charged in a planetary mixer and mixed for a period of 30 minutes. 45 g of a fumed silica having a BET specific surface area of 150 m.sup.2/g (commercially available under the name HDK® V15 from Wacker Chemie AG, Munich, Germany) were then mixed in and the mixture was completely homogenized at a pressure of 50 hPa. Lastly, 1 g of the mixture prepared in example 1 and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the name “Katalysator 41” from Wacker Chemie AG, Munich, Germany) were added and the mixture was homogenized for a further 5 minutes at a pressure of ca. 50 hPa (absolute).

[0241] The RTV1 composition thus obtained was filled into commercially available moisture-proof polyethylene cartridges and stored at room temperature for 24 h and a further sample at 70° C. for 7 days. Then, from each of these samples thus stored, slabs of 2 mm thickness were spread out and stored at 23° C. and 50% relative humidity for 7 days. Test specimens according to DIN 53504 of form S2 were punched out of the cured materials and the mechanical characteristics were measured. The results can be found in Table 2.

EXAMPLE 10

[0242] Example 9 was repeated with the modification that 1.57 g of a mixture according to example 7 were added instead of 1 g of the mixture according to example 1.

[0243] The results can be found in Table 2.

EXAMPLE 11

[0244] 880 kg of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80 000 mPa.Math.s (commercially available under the name POLYMER FD 80 from Wacker Chemie AG, Munich, Germany) were mixed with a solution of 91 g of triazabicyclo[4.4.0]dec-5-ene in 27 kg of vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL 10 from Wacker Chemie AG, Munich, Germany). After a reaction time of 45 minutes at room temperature, 255 g of the mixture according to example 1 were added and mixed homogeneously.

[0245] An α,ω-bis(vinyldimethoxysilyl)polydimethylsiloxane having a viscosity of 100 Pas was obtained without further work-up as a clear colourless product.

EXAMPLE 12

[0246] 300 g of the product prepared according to example 11 were initially charged in a planetary mixer with 130 g of an α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPa.Math.s (commercially available under the name “Weichmacher 1000” from Wacker Chemie AG, Munich, Germany), 5 g of N-(2-aminoethyl)-3-ami-nopropyltrimethoxysilane (commercially available under the name GENIOSIL® GF 91 from Wacker Chemie AG, Munich, Germany), 2 g of vinyltrimethoxysilane (commercially available under the name GENIOSIL® XL 10 from Wacker Chemie AG, Munich, Germany) and mixed for a period of 30 minutes. 45 g of a fumed silica having a BET specific surface area of 150 m.sup.2/g (commercially available under the name HDK® V15 from Wacker Chemie AG, Germany (Munich)), were then mixed in and the mixture was completely homogenized at a pressure of 50 hPa. Lastly, 1 g of a solution according to example 1 and 2 g of a reaction product of dibutyltin diacetate and tetraethoxysilane (commercially available under the name “Katalysator 41” from Wacker Chemie AG, Munich, Germany) were added and the mixture was homogenized for a further 5 minutes at a pressure of ca. 50 hPa (absolute).

[0247] The RTV1 composition thus obtained was filled into commercially available moisture-proof polyethylene cartridges and stored at room temperature for 24 h and a further sample at 70° C. for 7 days. Then, from each of these samples thus stored, slabs of 2 mm thickness were spread out and stored at 23° C. and 50% relative humidity for 7 days. Test specimens according to DIN 53504 of form S2 were punched out of the cured materials and the mechanical characteristics were measured.

[0248] The results can be found in Table 2.

EXAMPLE 13

[0249] Preparation of an Oligomeric Mixture 13a:

[0250] 240 g (3.25 mol) of an α,ω-bis(trimethylsiloxy)polydimethylsiloxane having a viscosity of 1000 mPas, 234 g (1.0 mol) of trimethoxy(2,4,4-trimethylpentyl)silane (=iOctSi(OMe).sub.3), obtainable from Wacker Chemie AG under the name SILRES® BS 1316, and 0.80 g of a solution of sodium ethoxide (21%) in ethanol are mixed and heated to 110° C. for 4 hours. After cooling the solution, the mixture is neutralized by adding 1.60 g of a solution of dimethyldichlorosilane (10%) in n-heptane. This mixture was devolatilized on a rotary evaporator at 120° C. at a reduced pressure of 50 mbar. The composition of the mixture was determined by .sup.29Si-NMR spectroscopy. The mixture comprised 1.4% by weight iOctSi(OMe).sub.3, 0.4% by weight Me.sub.2Si(OMe).sub.2 and 98.2% by weight of an oligomeric mixture of average composition of [iOctSi(OMe).sub.2O.sub.1/2].sub.0.08[iOctSi(OMe)O.sub.2/2].sub.0.15[iOctSiO.sub.3/2].sub.0.05 [Me.sub.2SiO.sub.2/2].sub.0.43[Me.sub.2Si(OMe)O.sub.1/2].sub.0.29. The molecular weights determined by gel permeation chromatography were 929 g/mol (Mw—weight average) and 635 (Mn—number average). The polydispersity (Mw/Mn) was 1.46.

[0251] A mixture of 660 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 80 000 mPas and 220 g of an α,ω-dihydroxypolydimethylsiloxane having a viscosity of 20 20 000 mPas was stirred with 30.44 g of a solution of 0.04 g of 1,5,7-triazabicyclo[4.4.0]dec-5-ene in 30.4 g of (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane at 200 revolutions/min for 5 minutes. After a reaction time of 5 minutes, this gives a mixture of 98.0% by weight a,w-bis((2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyl-diethoxysilyl)polydimethylsiloxane, 1.9% by weight (2,3,5,6-tetrahydro-1,4-oxazin-4-yl)methyltriethoxysilane and 0.1% by weight ethanol having a viscosity of 52 000 mPas.

[0252] RTV1-Sealing Compound Using the Oligomeric Mixture 13a:

[0253] 455 g of the reaction mixture thus obtained were added to 10.6 g of tetraethoxysilane hydrolysate oligomer having a content of SiO.sub.2 of 40% on total hydrolysis and condensation, available from Wacker Chemie AG, Munich, Germany, under the name “SILIKAT TES 40”, 12.6 g of an equilibration product of 6.3 g of methyltriethoxysilane hydrolysate oligomers having an average of 10 Si atoms per molecule and 6.3 g of 3-aminopropyltriethoxysilane, and the mixture stirred for a further 5 minutes at 200 revo-lutions/min. Then, 44 g of a hydrophilic fumed silica having a surface area of 150 m.sup.2/g, available from Wacker Chemie AG under the name HDK® V15A, were added and the mixture stirred initially at 200 revolutions/min for a further 5 minutes until all the fumed silica had been wetted. The mixture was then stirred at 600 revolutions/min for 10 minutes at a reduced pressure of 200 mbar. Finally, 1.58 g of a solution of 0.27 g of dioctyltin oxide in 1.31 g of an equilibration product of 0.655 g of methyltriethoxysilane hydrolysate oligomers having an average of 10 Si atoms per molecule and 0.655 g of 3-aminopropyltriethoxysilane and 2.6 g of the additive of the invention according to example 7 and 25.6 g of the oligomeric mixture 13a were added and the mixture stirred for a further 5 minutes under reduced pressure (200 mbar).

[0254] The mixture is then filled into commercially available cartridges and stored with exclusion of moisture. 24 h after preparation of the mixtures, 2 mm thick slabs were drawn out from these mixtures and dumbbell-shaped test specimens of type 2, according to ISO 37, 6th edition 2017-11, were produced therefrom after curing for 7 days at 23° C. and 50% relative humidity.

[0255] The results can be found in Table 2.

[0256] Without the additive of the invention according to example 7, a mixture analogous to example 13 no longer cured to a tack-free material after pre-storage at 70° C. for 7 days.

TABLE-US-00002 TABLE 2 Mechanical characteristics Tensile Tensile Elongation stress at strength at break 100% elongation Example Pre-storage (MPa) (%) (MPa) 9 24 h, RT 1.1 360 0.43 9 7 d, 70° C. 1.3 460 0.40 10 24 h, RT 1.5 460 0.43 10 7 d, 70° C. 1.5 520 0.39 12 24 h, RT 1.4 430 0.44 12 7 d, 70° C. 1.3 420 0.42 13 24 h, RT 2.1 260 0.73 13 7 d, 70° C. 2.0 280 0.69

[0257] The skin formation times were each in the usual range of between 15 and 25 minutes. Without the additives according to the invention, the mixtures according to examples 9, 10, 12 and 13 no longer cured to tack-free materials after pre-storage for 7 days at 70° C.

EXAMPLE 14

[0258] In a laboratory dissolver, 400 g of the α,ω-dihydroxypolydimethylsiloxane were intensively mixed with 8.5 g of phenyltrimethoxysilane and 0.25 g of a solution of 20% by mass 1,5,7-triazabicyclo[4.4.0]dec-5-ene in isooctyltriethoxysilane at an initial temperature of 25° C. for 5 minutes. The mixing shaft with dissolver gear ring, the diameter of which was ca. 5 cm, was set to 1000 revolutions per minute.

[0259] That the mixture was free of silanol groups after 30 minutes was established by means of the titanate rapid test described in EP 2 170 995 B1 on page 7. The endcap-ping reaction was thus already complete at this timepoint.

[0260] Subsequently, 0.5 g of the additive according to the invention from example 7 was mixed in over 10 min. [0261] Viscosity after 2 hours: 90.0 Pa.Math.s [0262] Viscosity after 22 hours: 85.5 Pa.Math.s

EXAMPLE 15 (NON-INVENTIVE)

[0263] Experiment 13 was repeated with the modification that no additive according to the invention was subsequently mixed in. [0264] Viscosity after 2 hours: 89.0 Pa.Math.s [0265] Viscosity after 22 hours: 48.5 Pa.Math.s

[0266] It can be seen that without the stabilizer according to the invention there is a sharp loss of viscosity.

EXAMPLE 16

[0267] In a laboratory dissolver, 400 g of the α,ω-dihydroxypolydimethylsiloxane were intensively mixed with 7 g of 4-(triethoxysilylmethyl)tetrahydro-1,4-oxazine and 0.25 g of a solution of 20% by mass 1,5,7-triazabicyclo[4.4.0]dec-5-ene in isooctyltriethoxysilane at an initial temperature of 25° C. for 5 minutes. The mixing shaft with dissolver gear ring, the diameter of which was ca. 5 cm, was set to 1000 revolutions per minute.

[0268] That the mixture was free of silanol groups after 30 minutes was established by means of the titanate rapid test described in EP 2 170 995 B1 on page 7. The endcap-ping reaction was thus already complete at this timepoint.

[0269] Subsequently, 0.5 g of the additive according to the invention from example 7 was mixed in over 10 min. [0270] Viscosity after 2 hours: 190.0 Pa.Math.s [0271] Viscosity after 22 hours: 162.5 Pa.Math.s

EXAMPLE 17 (NON-INVENTIVE)

[0272] Experiment 15 was repeated with the modification that no additive according to the invention was subsequently mixed in. [0273] Viscosity after 2 hours: 184.5 Pa.Math.s [0274] Viscosity after 22 hours: 113.0 Pa.Math.s

[0275] It can again be seen that without the additive according to the invention, there is an extreme reduction in viscosity.