阅读说明：本技术 作为锌粉漆的储存稳定前体的水性溶胶-凝胶组合物 (Aqueous sol-gel composition as storage-stable precursor for zinc paint ) 是由 P.阿尔伯特 D.布林曼 J.基尔贝格 E.尤斯特 于 2018-04-24 设计创作，主要内容包括：本发明涉及作为锌粉漆的储存稳定的无溶剂前体的水性溶胶-凝胶组合物,其基于至少以下组分的反应：(i)通式(I)的缩水甘油氧基丙基烷氧基硅烷X-Si(OR)<Sub>3</Sub>(I),其中X表示3-缩水甘油氧基丙基,和R表示甲基或乙基,(ii)平均粒度为5至150 nm且固体含量为≥45至≤55重量%的水性硅溶胶,(iii)至少一种酸,其选自硝酸、硫酸、盐酸、磷酸、甲酸、乙酸,和(iv)通式(II)的双-氨基烷氧基硅烷：(R<Sup>1</Sup>O)<Sub>3</Sub>Si(CH<Sub>2</Sub>)<Sub>3</Sub>(NH)(CH<Sub>2</Sub>)<Sub>3</Sub>Si(OR<Sup>1</Sup>)<Sub>3</Sub>(II),其中R<Sup>1</Sup>表示甲基或乙基,和任选的(v)至少一种通式(III)的另外的烷氧基硅烷Y<Sub>n</Sub>-Si(OR<Sup>3</Sup>)<Sub>4-n</Sub>(I),其中Y表示丙基、丁基、辛基、3-巯基丙基,3-脲基丙基或3-异氰酸根合丙基,R<Sup>3</Sup>表示甲基或乙基基团,和n等于0或1,其中组分(ii)与组分(i)的初始质量比为0.55至0.75,和组分(ii)与组分(iv)的初始质量比为0.35至0.55,和(vi)含量为基于该组合物计5至70重量%的至少一种微粒状填料,其选自沉淀二氧化硅、热解二氧化硅、结晶二氧化硅、高岭土、长石、滑石、氧化锌、氧化铁(III)、氧化铝、二氧化钛,其中该储存稳定的水性溶胶-凝胶组合物具有基于整个组合物计＜3重量%的醇含量和3.0至6.5的pH值,本发明还涉及用于制备这类溶胶-凝胶组合物的特定方法及其用途。(The invention relates to an aqueous sol-gel composition as a storage-stable, solvent-free precursor for zinc paints, based on the reaction of at least the following components: (i) glycidoxypropylalkoxysilane of the general formula (I) X-Si (OR)3(I), in which X represents 3-glycidoxypropyl and R represents methyl or ethyl, (II) aqueous silica sol having an average particle size of from 5 to 150 nm and a solids content of from ≥ 45 to ≤ 55% by weight, (iii) at least one acid selected from nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, and (iv) bis-aminoalkoxysilane of the general formula (II): (R1O)3Si (CH2)3(NH) (CH2)3Si (OR1)3(II) wherein R1 represents methyl OR ethyl, and optionally (v) at least one further alkoxysilane Yn-Si (OR3)4-n (i) of the general formula (III) wherein Y represents propyl, butyl, octyl, 3-mercaptopropyl, 3-ureidopropyl OR 3-isocyanatopropyl, R3 represents methyl OR ethyl, and n is equal to 0 OR1, wherein the initial mass ratio of component (II) to component (i) is from 0.55 to 0.75, and the initial mass ratio of component (II) to component (iv) is from 0.35 to 0.55, and (vi) the content is from 5 to 70% by weight, based on the composition, of at least one particulate filler selected from precipitated silica, fumed silica, crystalline silica, kaolin, feldspar, talc, zinc oxide, Iron (III) oxide, aluminum oxide, titanium dioxide, wherein the storage-stable aqueous sol-gel composition has an alcohol content of < 3% by weight, based on the entire composition, and a pH value of from 3.0 to 6.5, to a specific process for preparing such sol-gel compositions, and to the use thereof.)

1. An aqueous sol-gel composition as a storage-stable solvent-free precursor for zinc paint, based on the reaction of at least the following components:

(i) Glycidoxypropylalkoxysilane of the general formula (I)

X-Si(OR) (I)

Wherein X represents 3-glycidoxypropyl group, and R represents methyl or ethyl group,

(ii) An aqueous silica sol having an average particle size of 5 to 150 nm and a solid content of not less than 20 to not more than 60% by weight,

(iii) At least one acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, and

(iv) Bis-aminoalkoxysilanes of the general formula (II)

(RO)Si(CH)(NH)(CH)Si(OR) (II)，

Wherein R1 represents a methyl or ethyl group,

And optionally

(v) At least one further alkoxysilane of the general formula (III)

Y-Si(OR) (I)

Wherein Y represents propyl, butyl, octyl, 3-mercaptopropyl, 3-ureidopropyl or 3-isocyanatopropyl, R3 represents methyl or ethyl and n is equal to 0 or1,

Wherein the initial mass ratio of component (ii) to component (i) is from 0.55 to 0.75, and the initial mass ratio of component (ii) to component (iv) is from 0.35 to 0.55, and

(vi) At least one particulate filler in an amount of from 5 to 70% by weight, based on the composition, selected from precipitated silica, pyrogenic silica, crystalline silica, kaolin, feldspar, talc, zinc oxide, iron (III) oxide, alumina, titanium dioxide,

Wherein the storage-stable aqueous sol-gel composition has an alcohol content of < 3% by weight and a pH value of from 3.0 to 6.5, based on the entire composition.

2. A composition according to claim 1, wherein,

Characterized in that the initial mass ratio of component (ii) to component (i) is from 0.60 to 0.70, and the initial mass ratio of component (ii) to component (iv) is from 0.40 to 0.50.

3. a composition according to claim 1 or 2,

Characterized in that the aqueous silica sol as component (ii) has a pH value of 8.5 to 10.5.

4. The composition according to any one of claims 1 to 3,

Characterized by an aqueous silica sol as component (ii), wherein the amorphous silica particles present therein have an average diameter of ≥ 5 to 150 nm, particularly preferably 8 to 130nm, in particular 15 to 80 nm.

5. the composition according to any one of claims 1 to 4,

Characterized in that the content of methanol and/or ethanol is < 3% by weight, based on the total composition.

6. a composition according to claim 5, wherein,

Characterized in that the content of methanol and/or ethanol is 0.5 to 2.5% by weight, based on the entire composition.

7. process for the preparation of a sol-gel composition according to any one of claims 1 to 6,

Wherein

-pre-charging water and an acid according to component (iii),

Metering in an aqueous silica sol according to component (ii) and then metering in a glycidyloxypropylalkoxysilane of the formula (I) according to component (I) under an inert gas atmosphere with stirring, heating with stirring, and

Subsequently, with stirring, the bis-aminoalkoxysilane of the formula (II) according to component (iv) and the acid according to component (III) and optionally at least one further alkoxysilane of the formula (III) according to component (v) are metered in and the reaction is continued,

-the formed hydrolysis alcohol is then removed by distillation, water is optionally added, the reaction product is filtered after cooling to room temperature, and to the filtrate thus obtained at least one particulate filler according to component (vi) is added with stirring, and optionally adjusted to a pH value of 3.0 to 6.5 by addition of an acid according to component (iii).

8. the method according to claim 7, wherein said step of treating,

it is characterized in that the preparation method is characterized in that,

After the metering in of components (ii) and (i), stirring is carried out for a period of 30 to 90 minutes and heating is carried out to a temperature of 50 to 70 ℃.

9. the method according to claim 7 or 8,

It is characterized in that the preparation method is characterized in that,

After metering in component (iv) and optionally (v), stirring is carried out for a period of 30 to 300 minutes and the reaction is continued at a temperature of 50 to 70 ℃.

10. The method according to any one of claims 7 to 9,

It is characterized in that the preparation method is characterized in that,

The hydrolysis alcohol, methanol and/or ethanol formed in the reaction is removed from the system under reduced pressure, and the amount of alcohol removed in the process is optionally replaced by a corresponding amount of water.

11. The method according to any one of claims 7 to 10,

It is characterized in that the preparation method is characterized in that,

After cooling to room temperature, the reaction product was filtered through a paint filter.

12. The method according to any one of claims 7 to 11,

It is characterized in that the preparation method is characterized in that,

At least one particulate filler selected from the group consisting of precipitated silica, pyrogenic silica, crystalline silica, kaolin, feldspar, talc, zinc oxide, iron (III) oxide, alumina, titanium dioxide is dispersed into the reaction product or the filtrate and is adjusted in the process to a filler content of 5 to 70% by weight, based on the composition.

13. An aqueous sol-gel composition obtainable according to any one of claims 7 to 12.

14. Use of an aqueous sol-gel composition according to any one of the preceding claims, wherein zinc particles [ also shortly called zinc powder ] are dispersed into an aqueous, storage-stable sol-gel composition, wherein the zinc particles have an average particle size of 3 μm to 90 μm and are used as catalyst for the curing of the dispersion, and the dispersion thus obtained is used as anticorrosive agent or as additive in anticorrosive agents or in paints or lacquers.

15. Use of an aqueous sol-gel composition according to any one of the preceding claims as a storage stable precursor for zinc paint.

16. Use of an aqueous sol-gel composition according to any one of the preceding claims as a storage stable precursor for zinc paint, wherein in the formulation of zinc paint zinc chloride and/or magnesium chloride is added to the aqueous sol-gel composition in addition to zinc powder.

Example (b):

Raw materials and abbreviations used:

trade name	Description of the invention	Manufacturer(s)
			Dynasylan® GLYMO	3-Glycidoxypropyltrimethoxysilane (GLYMO)	Evonik Degussa
Dynasylan® 1122	Bis (triethoxysilylpropyl) amine (bis-AMEO)	Evonik Degussa
			Dynasylan® AMEO	3-Aminopropyltriethoxysilane (AMEO)	Evonik Degussa
Dynasylan® PTMO	Propyl trimethoxy silane (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
			Köstrosol® 3550	Silica sol, 35nm	Chemische Werke Bad Köstritz
HP 1535	Silica sol, 15nm	Silco International, USA
			SI 5540	Silica sol, 130nm	Silco International, USA

analyzing and detecting:

And (3) pH value measurement:

The pH of the reaction mixture was determined by means of pH paper (special indicator pH 2.5 to 4.5, Merck; pH-Fix 0.0 to 6.0, Machery-Nagel).

Determination of the dry residue (solids content):

The solids content (also referred to as dry residue) of the aqueous silane system was determined as follows:

1 g of the sample was weighed into a small porcelain bowl and dried in a drying cabinet to constant weight at 105 ℃.

Determination of SiO2 content:

To 1.0 to 5.0 g of sample in a 400 ml beaker, kjeldahl tablets and 20 ml of sulfuric acid were added and first slowly heated. During this process, the beaker was covered with a watch glass. The temperature was raised until the sulfuric acid was strongly fuming and all organic components were destroyed and the solution remained clear and light colored. The cold decomposition solution was diluted to about 200 ml with distilled water and briefly boiled (water was allowed to flow under the acid at the edge of the beaker). The residue was filtered through a white belt filter and washed with hot water until the pH of the wash water was shown to be > 4 (pH paper). The filter was dried in a platinum crucible, ashed, and fired in a muffle furnace at 800 ℃ for 1 hour. After weighing, the residue is fuming with hydrofluoric acid (aberraucht), the crucible is fired by means of a blast burner and optionally again at 800 ℃ and weighed after cooling. The difference between the two weighings corresponds to the content of SiO 2.

evaluation: d x 100/E = weight% of SiO2

d = difference in weight in mg before and after fuming with hydrofluoric acid (afluororen)

100= converted as%

e = initial weight in mg.

Determination of free methanol and ethanol content:

determination of the alcohol by means of GC:

Column: RTX 200 (60 m)

Temperature program: 90-10-25-240-0

A detector: FID

Injection amount: 1.0. mu.l

internal standard: 2-butanol.