Aqueous sol gel composition as a storage-stable precursor for zinc powder paints

Abstract

An aqueous sol gel composition is useful as a storage-stable, solvent-free precursor for zinc powder paints. The composition is based on the reaction of at least the components (i) a glycidyloxypropyl alkoxysilane of the general formula (I) XSi(OR).sub.3 (I), where X represents a 3-glycidyloxypropyl group and R represents a methyl or ethyl group, (ii) an aqueous silica sol with an average particle size ranging from 5 to 150 nm and a solids content of 45 to 55 wt. %, (iii) at least one acid selected from nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, and acetic acid, and (iv) a his-amino silane of the general formula (II) (R.sup.1O).sub.3Si(CH.sub.2).sub.3(NH)(CH.sub.2).sub.3Si(OR.sup.1).sub.3 (II), where R.sup.1 is a methyl or ethyl group, and optionally (v) at least one additional alkoxysilane of the general formula (III) Y.sub.nSi(OR.sup.3).sub.4-n (I), where Y represents a propyl-, butyl-, octyl-, 3-mercaptopropyl-, 3-ureidopropyl-, or 3-isocyanatopropyl group, R.sup.3 represents a methyl or ethyl group, and n equals 0 or 1, wherein it is assumed that a mass ratio of (ii) to (i) ranges from 0.55 to 0.75 and a mass ratio of (ii) to (iv) ranges from 0.35 to 0.55. The composition also contains at least one particulate filler from precipitated silica acid, pyrogenic silica acid, crystalline silica, kaolin, feldspar, talcum, zinc oxide, iron(III) oxide, aluminum oxide, and titanium dioxide in a proportion of 5 to 70 wt. %, based on the composition.

Claims

1: An aqueous sol-gel composition as a storage-stable, solvent-free precursor for zinc dust paints, based on the reaction of at least following components: (i) a glycidyloxypropylalkoxysilane of the formula (I)
XSi(OR).sub.3(I) in which X is a 3-glycidyloxypropyl group and R is a methyl or ethyl group, (ii) an aqueous silica sol having an average particle size of 5 to 150 nm and a solids content of 20% to 60% by weight, (iii) at least one acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, and acetic acid, (iv) a bisaminoalkoxysilane of the formula (II)
(R.sup.1O).sub.3Si(CH.sub.2).sub.3(NH)(CH.sub.2).sub.3Si(OR.sup.1).sub.3(II) in which R.sup.1 represents a methyl or ethyl group, and optionally, (v) at least one further alkoxysilane of the formula (III)
Y.sub.nSi(OR.sup.3).sub.4-n(III) in which Y represents a propyl, butyl, octyl, 3-mercaptopropyl, 3-ureidopropyl or 3-isocyanatopropyl group, R.sup.3 is a methyl or ethyl group and n is 0 or 1, wherein an initial mass ratio of component (ii) to component (i) of 0.55 to 0.75 and an initial mass ratio of component (ii) to component (iv) of 0.35 to 0.55 are used, and containing (vi) at least one particulate filler selected from the group consisting of precipitated silica, fumed silica, crystalline silica, kaolin, feldspar, talc, zinc oxide, iron(III) oxide, aluminum oxide, and titanium dioxide, having a content of 5% to 70% by weight, based on the composition, wherein the aqueous sol-gel composition has a content of alcohol of <3% by weight, based on the overall composition, and a pH of 3.0 to 6.5.

2: The composition according to claim 1, wherein the mass ratio of component (ii) to component (i) is 0.60 to 0.70 and mass ratio of component (ii) to component (iv) is 0.40 to 0.50.

3: The composition according to claim 1, wherein the aqueous silica sol as component (ii) has a pH of 8.5 to 10.5.

4: The composition according to claim 1, wherein the aqueous silica sol as component (ii) comprises amorphous silica particles having an average diameter of 5 to 150 nm.

5: The composition according to claim 1, wherein a content of methanol and/or ethanol is of <3% by weight, based on the overall composition.

6: The composition according to claim 5, wherein the content of methanol and/or ethanol is of 0.5% to 2.5% by weight, based on the overall composition.

7: A process for producing the aqueous sol-gel composition according to claim 1, comprising: initially charging water and the acid as per component (iii), under an inert gas atmosphere and while stirring, metering in the aqueous silica sol as per component (ii) and then the glycidyloxypropylalkoxysilane of the formula (I) as per component (i), heating while stirring, and subsequently metering in the bisaminoalkoxysilane of the formula (II) as per component (iv), and once or more than once metering in the acid as per component (iii) and optionally metering in the at least one further alkoxysilane of the formula (III) as per component (v) while stirring, allowing reaction to continue for a further period, then removing an alcohol of hydrolysis that has formed thereof by distillation, optionally adding water, cooling to room temperature and then filtering a reaction product thus obtained and stirring the at least one particulate filler as per component (vi) into a filtrate thus obtained, and optionally establishing a pH of 3.0 to 6.5 with addition of the acid as per component (iii).

8: The process according to claim 7, wherein the metering in of components (ii) and (i) is followed by stirring over a period of 30 to 90 minutes and heating to a temperature in the range from 50 to 70 C.

9: The process according to claim 7, wherein the metering in of components (iv) and optionally (v) is followed by stirring over a period of 30 to 300 minutes and the reaction is continued at a temperature in the range from 50 to 70 C.

10: The process according to claim 7, wherein the alcohol of hydrolysis formed in the reaction, methanol and/or ethanol are removed under reduced pressure and wherein the amount of alcohol removed is optionally replaced by a corresponding amount of water.

11: The process according to claim 7, wherein the reaction product is cooled to room temperature and then filtered through a paint filter.

12: The process according to claim 7, wherein at least one particulate filler, selected from the group consisting of precipitated silica, fumed silica, crystalline silica, kaolin, feldspar, talc, zinc oxide, iron(III) oxide, aluminum oxide, and titanium dioxide, is dispersed into said reaction product or into the filtrate and establishes a filler content of 5% to 70% by weight, based on the composition.

13: An aqueous sol-gel composition obtainable according to claim 7.

14: A method of producing an anticorrosion composition or an additive in anticorrosion compositions, varnishes, or paints, the method comprising: dispersing zinc particles into the aqueous, storage-stable sol-gel composition according to claim 1, wherein the zinc particles have an average particle size of 3 m to 90 m and serve as catalyst for hardening of the dispersion.

15: A method of producing zinc dust paint, comprising: adding zinc powder to the aqueous sol-gel composition according to claim 1.

16: A method of formulation of zinc dust paint, the method comprising: adding zinc powder, and zinc chloride and/or magnesium chloride to the aqueous sol-gel composition according to claim 1 and.

17: The composition according to claim 4, wherein the amorphous silica particles present therein have an average diameter of 15 nm to 80 nm.

Description

EXAMPLES

[0084] Starting materials and abbreviations used:

TABLE-US-00001 Trade name Description Manufacturer Dynasylan GLYMO 3-glycidyloxypropyltrimethoxysilane (GLYMO) Evonik Degussa Dynasylan 1122 bis(triethoxysilylpropyl)amine (Bis-AMEO) Evonik Degussa Dynasylan AMEO 3-aminopropyltriethoxysilane (AMEO) Evonik Degussa Dynasylan PTMO propyltrimethoxysilane (PTMO) Evonik Degussa Dynasylan MTMO 3-mercaptopropyltrimethoxysilane Evonik Degussa Dynasylan 2201 EQ 3-ureidopropyltriethoxysilane in methanol Evonik Degussa Si 264 3-isocyanatopropyltriethoxysilane Evonik Degussa Dynasylan A tetraethoxysilane Evonik Degussa Koestrosol 3550 silica sol, 35 nm Chemische Werke Bad Kstritz HP 1535 silica sol, 15 nm Silco International, USA SI 5540 silica sol, 130 nm Silco International, USA

[0085] pH Determination:

[0086] The pH of the reaction mixtures was determined by means of a pH paper (Special indicator pH 2.5-4.5, Merck; pH-Fix 0.0-6.0, Machery-Nagel)

[0087] Determination of the Dry Residue (Solids Content):

[0088] The solids content (also referred to as dry residue) of the aqueous silane systems was determined as follows: 1 g of the sample was weighed into a small porcelain dish and dried to constant weight in a drying cabinet at 105 C.

[0089] Determination of the SiO.sub.2 Content:

[0090] To 1.0 to 5.0 g of the sample in a 400 ml beaker were added a Kjeldahl tablet and 20 ml of sulfuric acid, and the mixture was first heated gradually. During this period, the beaker was covered with a watchglass. The temperature was increased until the sulfuric acid fumed significantly and all the organic constituents had been destroyed and the solution remained clear and light-coloured. The cold digestion solution was diluted to about 200 ml with distilled water and boiled briefly (allowing water to flow under the acid at the edge of the beaker). The residue was filtered through a white band filter and washed with hot water until the wash water indicated a pH of >4 (pH paper). The filter was dried in a platinum crucible, converted to ash and calcined in a muffle furnace at 800 C. for 1 hour. After weighing, the residue was fumed off with hydrofluoric acid, the crucible was heated until red-hot by means of a fan burner and optionally calcined once again at 800 C., cooled down and then weighed. The difference between the two weighings corresponded to the content of SiO.sub.2.

[0091] Evaluation: D100/E=% by weight of SiO.sub.2

[0092] D=difference in weight before and after hydrofluoric acid fuming in mg

[0093] 100=conversion to %

[0094] E=starting weight in mg

[0095] Determination of the Free Methanol and Ethanol Content:

[0096] The alcohol determination was conducted by means of GC:

[0097] Column: RTX 200 (60 m)

[0098] Temperature program: 90-10-25-240-0

[0099] Detector: FID

[0100] Injection volume: 1.0 l

[0101] Internal standard: 2-butanol

Example 1

[0102] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 954.9 g of water and 2.16 g of formic acid (HCOOH=85% by weight), 392 g of HP 1535 and then 210.8 g of GLYMO were metered in (pH after the addition=3.0), and the mixture was heated to 65 C. and stirred for 1 hour. 11.79 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering apparatus. It was still necessary to add a total of 2.58 g of formic acid (HCOOH=85% by weight) in order to reach pH 4.0. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 291.96 g of alcohol/water mixture were removed by distillation at about 160 mbar. 12.23 g of water and 1.04 g of formic acid (HCOOH=85% by weight) were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 1359.80 g.

[0103] A pale yellow milky/cloudy liquid having a pH of 4.2 was obtained.

[0104] The product is storage-stable for at least 6 months.

[0105] Dry residue: 25.8% by weight

[0106] SiO.sub.2 content: 15.6% by weight

[0107] Free methanol: 1.5% by weight

[0108] Free ethanol: 0.7% by weight

Example 2

[0109] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 501.8 g of water and 1.5 g of formic acid (HCOOH=85% by weight). 171.6 g of HP 5540 and then 105.7 g of GLYMO were metered in (pH after the addition=2.0), and the mixture was heated to 65 C. and stirred for 1 hour. 5.88 g of formic acid (HCOOH=85% by weight) were added, and 44.45 g of Dynasyan 1122 were metered in via the metering apparatus. It was still necessary to add 0.98 g of formic acid (HCOOH=85% by weight) in order to reach pH 3.8. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 159.4 g of alcohol/water mixture were removed by distillation at about 120 mbar. 24.57 g of water and 0.92 g of formic acid (HCOOH=85% by weight) were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 661.44 g.

[0110] A milky/cloudy liquid having a pH of 4.0 was obtained.

[0111] The product is storage-stable for at least 6 months.

[0112] Dry residue: 25.8% by weight

[0113] SiO.sub.2 content: 15.5% by weight

[0114] Free methanol: 1.1% by weight

[0115] Free ethanol: 0.5% by weight

Example 3

[0116] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1150.7 g of water and 2.0 g of formic acid (HCOOH=85% by weight). 196 g of HP 1535 and then 210 g of GLYMO were metered in (pH after the addition=2.5) and the mixture was heated to 65 C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering apparatus. It was still necessary to add 2.6 g of formic acid (HCOOH=85% by weight) in order to reach pH 4.0. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 321.52 g of alcohol/water mixture were removed by distillation at about 230 mbar. 42.85 g of water and 1.0 g of formic acid (HCOOH=85% by weight) were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 1329.12 g.

[0117] A milky/cloudy liquid having a pH of 4.3 was obtained.

[0118] The product is storage-stable for at least 6 months.

[0119] Dry residue: 20.7% by weight

[0120] SiO.sub.2 content: 10.7% by weight

[0121] Free methanol: 1.1% by weight

[0122] Free ethanol: 0.6% by weight

Example 4

[0123] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 758.8 g of water and 2.13 g of formic acid (HCOOH=85% by weight). 588 g of HP 1535 and then 210 g of GLYMO were metered in (pH after the addition=2.5), and the mixture was heated to 65 C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of Dynasyan 1122 were metered in via the metering apparatus. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 306.17 g of alcohol/water mixture were removed by distillation at about 300 mbar. 25.15 g of water were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter.

[0124] The final weight of the residue was 1346.94 g.

[0125] A milky/cloudy liquid having a pH of 4.2 was obtained.

[0126] The product is storage-stable for at least 6 months.

[0127] Dry residue: 30.8% by weight

[0128] SiO.sub.2 content: 20.5% by weight

[0129] Free methanol: 1.3% by weight

[0130] Free ethanol: 0.6% by weight

Example 5

[0131] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 831.9 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 514.5 g of HP 5540 and then 210 g of GLYMO were metered in (pH after the addition=2.0), and the mixture was heated to 65 C. and stirred for 1 hour. 11.74 g of formic acid (HCOOH=85% by weight) were added, and 90 g of Dynasyan 1122 were metered in via the metering apparatus. It was still necessary to add a total of 177 g of formic acid (HCOOH=85% by weight) in order to reach pH 4.0. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 314.63 g of alcohol/water mixture were removed by distillation at about 180 mbar. 38.02 g of water were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 1334.02 g.

[0132] A milky/cloudy liquid having a pH of 4.3 was obtained.

[0133] The product is storage-stable for at least 6 months.

[0134] Dry residue: 31.0% by weight

[0135] SiO.sub.2 content: 20.7% by weight

[0136] Free methanol: 1.1% by weight

[0137] Free ethanol: 0.5% by weight

Example 6

[0138] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1003.7 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 343 g of HP 5540 and then 210 g of GLYMO were metered in (pH after the addition=3.0), and the mixture was heated to 65 C. and stirred for 1 hour. 11.88 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering apparatus. It was still necessary to add 2.32 g of formic acid (HCOOH=85% by weight) in order to reach pH 4.0. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 311.97 g of alcohol/water mixture were removed by distillation at about 200 mbar. 28.71 g of water were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 1343.39 g.

[0139] A milky/cloudy liquid having a pH of 4.2 was obtained.

[0140] The product is storage-stable for at least 6 months.

[0141] Dry residue: 25.9% by weight

[0142] SiO.sub.2 content: 15.7% by weight

[0143] Free methanol: 1.1% by weight

[0144] Free ethanol: 0.5% by weight

Example 7

[0145] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1175.1 g of water and 3.0 g of formic acid (HCOOH=85% by weight). 171.5 g of HP 5540 and then 210 g of GLYMO were metered in (pH after the addition=2.0), and the mixture was heated to 65 C. and stirred for 1 hour. 11.73 g of formic acid (HCOOH=85% by weight) were added, and 90 g of bis-AMEO were metered in via the metering apparatus. It was still necessary to add 0.91 g of formic acid (HCOOH=85% by weight) in order to reach pH 4.0. Thereafter, stirring was continued at 65 C. for another 3 hours. Finally, 336.96 g of alcohol/water mixture were removed by distillation at about 190 mbar. 58.03 g of water were added to the mixture. The residue that had been cooled down to room temperature was filtered through a paint filter. The final weight of the residue was 1314.02 g.

[0146] A cloudy pale beige liquid having a pH of 5.0 was obtained.

[0147] The product is storage-stable for at least 6 months.

[0148] Dry residue: 21.2% by weight

[0149] SiO.sub.2 content: 10.7% by weight

[0150] Free methanol: 0.9% by weight

[0151] Free ethanol: 0.5% by weight

Example 8

[0152] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1203.89 g of water and 3.00 g of formic acid (HCOOH=85% by weight). Subsequently, 135.68 g of Koestrosol 3550 were added, and 180 g of Dynasyan GLYMO were metered in via a metering apparatus. The mixture was heated to 65 C. and stirred at this temperature for 1 hour. 17.7 g of formic acid (HCOOH=85% by weight) were added, and 120 g of Dynasyan 1122 were metered in via the metering apparatus. Thereafter, stirring was continued at 65 C. for 3 hours and an additional 1.11 g of formic acid (HCOOH=85% by weight) were added. Finally, 340.64 g of alcohol/water mixture were removed by distillation at about 180 mbar. 38.80 g of demineralized water were added to the mixture.

[0153] The final weight of the residue was 1347.82 g.

[0154] Another 36.19 g of alcohol/water mixture were removed by distillation from the mixture at about 180 mbar, and 51.22 g of demineralized water were added. The cooled residue was filtered through a Seitz T-950 filter plate.

[0155] The final weight of the residue was 1347.82 g.

[0156] A milky white liquid having a pH of about 4.3 was obtained.

[0157] The product is storage-stable for at least 6 months.

[0158] Dry residue: 20.6% by weight

[0159] SiO.sub.2 content: 10.8% by weight

[0160] Free methanol: 0.4% by weight

[0161] Free ethanol: 0.7% by weight

Example 9

[0162] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1067.61 g of water and 3.00 g of formic acid (HCOOH=85% by weight). Subsequently, 271.09 g of Koestrosol 3550 were added, and 180.16 g of GLYMO were metered in via a metering apparatus. The mixture was heated to 65 C. and stirred at this temperature for 1 hour.

[0163] After the mixture had been stirred at 65 C. for 1 hour, it was adjusted to pH 3.0 with an additional 2.79 g of formic acid (HCOOH=85% by weight) and stirred at 65 C. for another 0.5 hour. Subsequently, 17.71 g of formic acid (HCOOH=85% by weight) were added, and 120.06 g of Dynasyan 1122 were metered in. Thereafter, stirring of the mixture was continued at 65 C. for 3 hours and another 3.21 g of formic acid (HCOOH=85% by weight) were added. Finally, 343.80 g of alcohol/water mixture were removed by distillation at about 160 mbar. 48.91 g of demineralized water were added to the mixture.

[0164] The cooled residue was filtered through a Seitz T-950 filter plate.

[0165] The final weight of the residue was 1308.51 g.

[0166] A milky white liquid having a pH of about 4.0 was obtained.

[0167] The product is storage-stable for at least 6 months.

[0168] Dry residue: 26.0% by weight

[0169] SiO.sub.2 content: 15.8% by weight

[0170] Free methanol: 1.0% by weight

[0171] Free ethanol: 0.5% by weight

Example 10

[0172] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1112.88 g of water and 101 g of formic acid (HCOOH=85% by weight). First 225.49 g of Koestrosol K 1530 (pH after the addition=3.5), then 180 g of GLYMO were metered in, the mixture was heated to 65 C. and the mixture was stirred for 1 hour. Subsequently, 18.71 g of formic acid (HCOOH=85% by weight) were added, and 120 g of bis-AMEO were metered in via the metering apparatus. At a pH of 4.0, the mixture was stirred at 65 C. for 3 hours. Finally, 321.56 g of alcohol/water mixture were removed by distillation at about 130 mbar. 20.23 g of water were added to the mixture. The residue was cooled to RT, then filtered through a Seitz T-950 filter plate. The final weight of the residue was 1334.77 g.

[0173] A liquid having a pH of 4.0 was obtained. The product is storage-stable for at least 6 months.

[0174] Dry residue: 20.9% by weight

[0175] SiO.sub.2 content: 10.5% by weight

[0176] Free methanol: 1.2% by weight

[0177] Free ethanol: 0.8% by weight

Example 11

[0178] A 2 l stirred apparatus with metering apparatus and reflux condenser under a nitrogen atmosphere was initially charged with 1265.70 g of water and 3.05 g of formic acid (HCOOH=85% by weight). First 133.43 g of Koestrosol 3550 (pH after the addition=3.0), then 134.93 g of GLYMO were metered in, the mixture was heated to 65 C. and the mixture was stirred for 1 hour. 21.08 g of formic acid (HCOOH=85% by weight) were added, and 119.97 g of bis-AMEO were metered in via the metering apparatus. After stirring for 15 minutes, 44.99 g of PTMO were added. At a pH of 3.9, the mixture was stirred at 65 C. for 3 hours. Finally, 370.09 g of alcohol/water mixture were removed by distillation at about 130 mbar. 32.57 g of water were added to the mixture. The residue was cooled to RT, then filtered through a Seitz K-900 tilter plate. The final weight of the residue was 1340.09 g.

[0179] A milky/cloudy liquid having a pH of 3.9 was obtained. The product is storage-stable for at least 6 months.

[0180] Dry residue: 19.8% by weight

[0181] SiO.sub.2 content: 11.0% by weight

[0182] Free methanol: 1.3% by weight

[0183] Free ethanol: 1.1% by weight

Example 12

[0184] To an initial charge of 1267.5 g of water in a 21 stirred apparatus with metering apparatus and reflux condenser were added 3.0 g of HCOOH (85%). 271.0 g of Koestrosol 3550 were added dropwise within 10 minutes. Subsequently, 180 g of GLYMO were metered in within 10 minutes via the metering apparatus. The mixture was stirred at 65 C. for 1 h. Subsequently, 17.7 g of HCOOH (85%) were added and 120 g of Dynasylan 1127 were metered in within 10 minutes. The mixture was stirred at 65 C. for 3 h.

[0185] The pH was between 3.3 and 3.9. It was to be measured before and after each addition. Within the 3 h, the pH was to be checked at regular intervals.

[0186] Thereafter, about 302 g of alcohol/water mixture were distilled off at about 130-200 mbar. It was observed here whether the mixture was viscous and, if it was, the distillation was stopped. The final weight of the residue was 1558 g; demineralized water and/or acid can be added if necessary; note pH.

[0187] The product was filtered at room temperature through a Seitz T-950 filter plate.

[0188] Dry residue: 22.0% by weight

[0189] SiO.sub.2: 13.4% by weight

[0190] Free MeOH: 0.7% by weight

[0191] Free EtOH: 0.4% by weight

Example 13

[0192] To an initial charge of 1067.5 g of water in a 2 l stirred apparatus with metering apparatus and reflux condenser were added 2.0 g of H.sub.3PO.sub.4 (85%), and the mixture was then mixed rapidly with 271.0 g of Koestrosol 3550 while stirring. The metering apparatus was used to meter in 165 g of GLYMO within 10 minutes. The mixture was stirred at 65 C. for 1 h. Subsequently, 33.0 g of H.sub.3PO.sub.4 (85%) were added and 135 g of Dynasylan 1122 were metered in within 10 minutes. The mixture was stirred at 65 C. for 3 h.

[0193] The pH was between 3.3 and 3.9. It was to be measured before and after each addition. Within the 3 h, the pH was to be checked at regular intervals.

[0194] Thereafter, about 302 g of alcohol/water mixture were distilled off. It was observed here whether the mixture was viscous and, if it was, the distillation was stopped.

[0195] The final weight of the residue was 1355 g; demineralized water or aqueous acid can be added if necessary; note pH.

[0196] The product was filtered at room temperature through a Seitz T-900 filter plate.

[0197] Dry residue: 25.4% by weight

[0198] SiO.sub.2: 15.8% by weight

[0199] Free MeOH: 0.7% by weight

[0200] Free EtOH: 0.5% by weight

Example 14

[0201] To an initial charge of 887.6 g of water in a 2 l stirred apparatus with metering apparatus and reflux condenser was added 1.0 g of HNO.sub.3 (65%). 227.9 g of Koestrosol 3550 were added dropwise within 10 minutes. Subsequently, 150 g of GLYMO were metered in within 10 minutes via the metering apparatus. The mixture was stirred at 65 C. for 1 h. Subsequently, 44.7 g of HNO.sub.3 (65%) were added and 100 g of Dynasyan 1127 were metered in within 10 minutes. The mixture was stirred at 65 C. for 3 h.

[0202] The pH was between 3.3 and 3.9. It was to be measured before and after each addition. Within the 3 h, the pH was to be checked at regular intervals.

[0203] Thereafter, about 252 g of alcohol/water mixture were distilled off at about 130-200 mbar. It was observed here whether the mixture was viscous and, if it was, the distillation was stopped. The final weight of the residue was 1139.5 g; water and acid were added if necessary and the pH was measured.

[0204] The product was filtered at room temperature through a Seitz T-950 filter plate.

[0205] Dry residue: 22.8% by weight

[0206] SiO.sub.2: 15.6% by weight

[0207] Free MeOH: 0.8% by weight

[0208] Free EtOH: 0.4% by weight

[0209] Production of the Compositions (BMF) for Storage Tests

[0210] Additions used for the application examples: [0211] 4P/16 zinc powder (Everzinc, Belgium) [0212] MIOX MICRO 30 (Kaminer Montanindustrie) [0213] Bayferrox Red 130 BM (Harald-Scholz Co. & GmbH) [0214] Red Seal zinc oxide (Everzinc, Belgium) [0215] M500 crystalline silica dust (SIBELCO) [0216] MKT mica (Imerys Ceramics, France) [0217] RDI-S titanium dioxide (Huntsman) [0218] talc (Talc Extra Blanco, Minerals l Derivats S.A. Spain)

[0219] The additions in question were incorporated into a formulation from the preceding examples with a Dispermat CA 40 DSC. The viscosities were determined with a 4 mm flow cup according to DIN.

[0220] Table 1 shows the compositions (BMF) for storage tests. For production of the compositions BMF2 to 34, proceeding from the formulation from the examples in question, particulate substances FS1 to FS8 were incorporated by dispersion with addition of water.

[0221] (FS1=MIOX Micro 30, FS2=MKT MICA, FS3=Sibelco, FS4=Bayferrox Red BM 130, FS5=zinc oxide, FS6=titanium dioxide, FS7=Talc Extra Blanco, FS8=4P/16 zinc powder)

TABLE-US-00002 Ad- dition Pro- of water portion to the of the formu- formu- lation lation in % FS1 in FS2 in FS3 in FS4 in FS5 in FS6 in FS7 in FS8 in in the by wt., % by wt., % by wt., % by wt., % by wt., % by wt., % by wt., % by wt., % by wt., Formu- com- based based based based based based based based based lation position on the on the on the on the on the on the on the on the on the from in % by com- com- com- com- com- com- com- com- com- example weight position position position position position position position position position BMF1 12 100 BMF2 12 90 10 BMF3 12 69.5 23 7.5 BMF4 12 60 20 20 BMF5 12 56 7 37 BMF6 12 47 6 47 BMF7 12 56 7 37 BMF8 12 47 6 47 BMF9 12 56 7 37 BMF10 12 47 6 47 BMF11 12 56 7 37 BMF12 12 47 6 47 BMF13 12 70 23 7 BMF14 12 60 20 20 BMF15 12 50 17 33 BMF16 12 43 14 43 BMF17 12 50 17 33 BMF18 12 43 14 43 BMF19 12 50 17 33 BMF20 12 43 14 43 BMF21 12 56 7 33 BMF22 12 47 6 43 BMF23 12 50 18.8 18.8 12.4 BMF24 12 47 6 25 22 BMF25 12 50 17 20 13 BMF26 12 43 14 25 18 BMF27 12 56 7 20 17 BMF28 12 47 6 25 22 BMF29 12 32.8 50 17.2 BMF30 12 42.4 11.3 22.3 24.0 BMF31 12 56.4 11 10.6 5.5 11 5.5 BMF32 12 47 6 25 22 BMF33 12 51.0 14 25.5 9.5 BMF34 12 62 38

[0222] Table 2 shows the pH values and the viscosities of the BMFs at the start and after storage at 50 C. for 4 months.

TABLE-US-00003 Before heat storage After heat storage at 50 C. for 4 months Viscosity Viscosity DIN 4 DIN 4 pH mm/sec pH mm/sec Appearance after storage BMF1 3.3 11 3.3 11 no change BMF2 3.4 12 3.2 12 no change BMF3 6.0 22 6.2 21 sediment which can easily be stirred up again BMF4 6.1 24 6.0 24 sediment which can easily be stirred up again BMF5 3.4 30 3.3 29 sediment which can easily be stirred up again BMF6 3.4 120 3.4 120 sediment which can easily be stirred up again BMF7 6.3 17 6.2 16 sediment which can easily be stirred up again BMF8 6.5 18 6.7 19 sediment which can easily be stirred up again BMF9 3.1 19 3.0 19 sediment which can easily be stirred up again BMF10 3.3 21 3.2 22 sediment which can easily be stirred up again BMF11 3.4 25 3.4 26 sediment which can easily be stirred up again BMF12 3.2 28 3.2 28 sediment which can easily be stirred up again BMF13 6.1 18 6.0 18 sediment which can easily be stirred up again BMF14 6.1 20 6.2 20 sediment which can easily be stirred up again BMF15 3.2 30 3.1 31 sediment which can easily be stirred up again BMF16 3.1 64 3.0 60 sediment which can easily be stirred up again BMF17 6.3 14 6.2 14 sediment which can easily be stirred up again BMF18 6.3 15 6.3 16 sediment which can easily be stirred up again BMF19 3.2 14 3.2 14 sediment which can easily be stirred up again BMF20 3.4 16 3.4 16 sediment which can easily be stirred up again BMF21 3.2 20 3.3 19 sediment which can easily be stirred up again BMF22 3.3 22 3.1 22 sediment which can easily be stirred up again BMF23 6.1 16 6.1 16 sediment which can easily be stirred up again BMF24 6.2 18 6.3 18 sediment which can easily be stirred up again BMF25 6.1 14 6.1 15 sediment which can easily be stirred up again BMF26 6.0 17 6.2 18 sediment which can easily be stirred up again BMF27 6.0 18 6.1 18 sediment which can easily be stirred up again BMF28 6.1 20 6.1 20 sediment which can easily be stirred up again BMF29 6.1 15 6.1 15 sediment which can easily be stirred up again BMF30 6.0 17 6.2 18 sediment which can easily be stirred up again BMF31 6.3 21 6.1 22 sediment which can easily be stirred up again BMF32 6.2 24 6.1 24 sediment which can easily be stirred up again BMF33 5.9 16 6.1 14 sediment which can easily be stirred up again BMF34 7.3 18 gelated/hardened after one day

[0223] As can be infeed from Table 2, all inventive compostions BMF2 to BMF33 are stable after storage at 50 C. over 4 months (virtually no change in pH and viscosity) provided that the pH of the binder formulation is <7. Should the pH of a binder formulation rise to >6.5 as a result of the addition of said particulate substances (FS1 to FS7), it can be adjusted to <6.6 with one of the said acids. BMF 34 shows the catalytic effect of zinc dust for the hardening of the system.

[0224] Comparative examples from WO 2012/130544 with regard to storage stability of binder for the formulation of zinc dust paints; cf. tables 2a to 2e (figures for the formulation each in % by weight, based on the composition):

TABLE-US-00004 TABLE 2a Use example 5 from WO 2012/130544: Composition in With Example 5 itemized 100% WO 2012/130544 fillers formulation Binder 6 4.0 4.0 28.6 (from Example 30) Addition consisting of: 10.0 mixture B 75.0% mixture M 25.0% 0 Zinc oxide 0.9045 6.5 Bayferrox 130 BM 0.906 6.5 MIOX Micro 30 2.6895 19.2 Zinc dust 3.0 21.4 Sikron M500 2.5 17.8

TABLE-US-00005 TABLE 2b Modified use example 5 from WO 2012/130544, no zinc dust: Composition in Example 5 With WO 012/130544, itemized 100% no zinc dust fillers formulation Binder 6 4.0 4.0 33.3 (from Example 30) Addition consisting of: 8.0 mixture B (no Zn) 75% mixture M 25% 0 Zinc oxide 1.206 10.1 Bayferrox 130 BM 1.206 10.1 MIOX Micro 30 3.588 29.9 Zinc dust 0 Sikron M500 2.0 16.6

TABLE-US-00006 TABLE 2c Use example 7 from WO 2012/130544: Composition in With Example 7 itemized 100% WO 2012/130544 fillers formulation Binder 8 4.0 4.0 28.6 (from Example 35) Addition consisting of: 10.0 mixture B 75.0% mixture M 25.0% 0 Zinc oxide 0.9045 6.5 Bayferrox 130 BM 0.906 6.5 MIOX Micro 30 2.6895 19.2 Zinc dust 3.0 21.4 Sikron M500 2.5 17.8

TABLE-US-00007 TABLE 2d Modfied use example 7 from WO 2012/130544, no zinc dust: Composon in With Example 7, itemized 100% no zinc dust fillers formulation Binder 8 4.0 4.0 33.3 (from Example 35) Addition consisting of: 8.0 mixture B (no Zn) 75% mixture M 25% 0 Zinc oxide 1.206 10.1 Bayferrox 130 BM 1.206 10.1 MIOX Micro 30 3.588 29.9 Zinc dust 0 Sikron M500 2.0 16.6

TABLE-US-00008 TABLE 2e The formulations with regard to Use Examples 5 and 7 from WO 2012/130544 were produced without zinc and stored in order to be directly comparable with Use Examples BMF 23 and BMF 31. The results from comparative storage tests show that binders according to the invention for use for production or for formulation of zinc dust paints are storage-stable for much longer periods than those according to binders from WO 2012/130544. Comparative examples from WO 2012/130544 from WO from WO from WO from WO Inventive examples 2012/130544 2012/130544 2012/130544 2012/130544 Use Use Use Example Use Example 5, Use Example Use Example 7, Example Example 5 no zinc 7 no zinc BMF 23 BMF 31 Binder 6 (from 28.6 33.3 Example 30) Binder 8 (from 28.6 33.3 Example 35) Binder for zinc 50 56.4 dust paints Zinc oxide 6.5 10.1 6.5 10.1 12.4 11 Bayferrox 130 6.5 10.1 6.5 10.1 5.5 BM MIOX Micro 19.2 29.9 19.2 29.9 18.8 30 Zinc dust 21.4 0 21.4 0 Sikron M500 17.8 16.6 17.8 16.6 10.6 Mica MKT 18.8 11 Talc 5.5 Storage stability 1 (solid) 3 (solid) 1 (solid) 3 (solid) >120 >120 at 50 C. in days

[0225] Performance Testing of the Stored BMFs

TABLE-US-00009 TABLE 3 For the application examples (EF1 to EF10), the following BMFs were used: Proportion Proportion by by weight of weight of 4/P16 BMFs BMF in the zinc powder in Application used; cf. application the application formulation Tables 2 formulation formulation EF 1 BMF1 16 84 EF 2 BMF3 72.1 27.9 EF 3 BMF4 72.0 28.0 EF 4 BMF17 72.2 27.8 EF 5 BMF18 72.2 27.8 EF 6 BMF33 32 68 EF 7 BMF31 67.8 32.8 EF 8 BMF23 64 36 EF 9 BMF29 70 30 EF 10 BMF30 36 64

[0226] The application formulations listed in Table 3 were applied to steel sheets.

[0227] Cleaning of the R-36 Steel Test Sheets Made from DC01 C290, 152760.8 mm (Rocholl)

[0228] The steel test sheets were placed into an alkaline cleaning bath (composition: 10.0 g/I S 5610, pH 11.5, 60 C., 35 sec.). After the alkaline cleaning, the metal substrates were rinsed with demineralized water. The excess water was blown off the surface with a compressed air gun. [0229] Application: Spiral applicator wet film thickness 60 m [0230] Dry film thickness: 20-30 m [0231] Cross-cut: to EN ISO 2409 [0232] Corrosion test: Neutral salt spray test (NSS) according to DIN EN ISO 9227 [0233] Abrasion resistance: Scrub test with SDL Atlas M238BB Electronic Crockmeter, contact with water for 15 sec, followed by 10 back-and-forth strokes with Wypai X60 from Kimberly Clark, assessment: 10=no change, 0=coating rubbed off completely

[0234] The Zn-containing application formulations produced according to Table 3, ater the coating operation, were dried/hardened at 20 C. for 24 hours and tested.

[0235] The test results are compiled in Table 4.

TABLE-US-00010 Results with BMFs which had Appli- Results without prior storage been stored beforehand at cation of the BMFs used 50 C. for 4 months formu- Scrub Cross- Scrub Cross- lation test cut NSS test cut NSS EF 1 5 CC0 corrosion over the 4 CC0 corrosion over the entire area after 80 entire area after 80 hours hours EF 2 6 CC1 corrosion over the 6 CC1 corrosion over the entire area after 150 entire area after 250 hours hours EF 3 6 CC1 corrosion over the 7 CC1 corrosion over the entire area after 150 entire area after 150 hours hours EF 4 6 CC1 corrosion over the 7 CC1 corrosion over the entire area after 200 entire area after 250 hours hours EF 5 6 CC1 corrosion over the 7 CC1 corrosion over the entire area after 200 entire area after 250 hours hours EF 6 5 CC1 slight corrosion over 5 CC1 slight corrosion over the area after 500 the area after 500 hours hours EF 7 8 CC1 corrosion over the 7 CC1 corrosion over the entire area after 300 entire area after 300 hours hours EF 8 10 CC1 corrosion over the 9 CC1 corrosion over the entire area after 300 entire area after 300 hours hours EF 9 9 CC1 corrosion over the 9 CC1 corrosion over the entire area after 350 entire area after 350 hours hours EF 10 8 CC1 slight corrosion over 9 CC1 slight corrosion over the area after 500 the area after 500 hours hours

[0236] As can be inferred from Table 4, the performance results before and after storage are identical. This shows that the compositions according to the invention can be utilized advantageously without any problems as storage-stable aqueous systems, or precursors for zinc dust paints, that can be handled advantageously.