HYDROPHOBIZING AGENT FOR MINERAL MATERIALS

Abstract

Described herein is a hydrophobizing agent for mineral materials, including: a polyion complex (i) including at least one polycation (i.1) and at least one polyanion (i.2), where the molar ratio of polycation:polyanion in the polyion complex is ≥1; and a silicone compound composition (ii). Also described herein are a process for producing the hydrophobizing agent, a method of using the hydrophobizing agent for the hydrophobizing of mineral binders and/or compositions which contain mineral binders and/or materials which include mineral binders, and a binder composition including one or more mineral binder(s) and a corresponding hydrophobizing agent.

Also described herein is a process for hydrophobizing materials which include mineral binders, and a hydrophobized material including mineral binders and obtained by this process.

Also described herein is a hydrophobized material which includes mineral binders, including the reaction product of one or more mineral binder(s), the hydrophobizing agent and water.

Claims

1. A hydrophobizing agent for mineral materials, comprising: i) a polyion complex comprising at least one polycation (i.1) and at least one polyanion (i.2), wherein the molar ratio of polycation:polyanion in the polyion complex is ≥1; ii) a silicone compound composition; and iii) a carrier composition which comprises at least one carrier selected from the group consisting of amorphous silicon dioxide, amorphous agglomerated silicon dioxide, quartz powder, limestone powder, aluminum oxide, illite, iron oxide and mixtures of two or more of these carriers.

2. The hydrophobizing agent as claimed in claim 1, wherein the polycations (i.1) of the polyion complex (i) are cationic polymers or copolymers, wherein the positive charge on the nitrogen atom of the quaternary ammonium cation is balanced by a singly charged anion.

3. The hydrophobizing agent as claimed in claim 1, wherein the polycations (i.1) of the polyion complex (i) are poly-N,N-disubstituted-3,4-dimethylenepyrrolidinium salts, of the general formula (I): ##STR00023## wherein R.sub.1 and R.sub.2 are selected independently from the group consisting of a hydrogen atom, a C.sub.1-C.sub.18-alkyl radical and a benzyl radical; and x is an integer.

4. The hydrophobizing agent as claimed in claim 1, wherein the polyanions (i.2) of the polyion complex (i) are copolymeric monobasic to polybasic polyanion esters (polycarboxylate ether, PCE) based on monounsaturated C.sub.3-C.sub.10-monocarboxylic, dicarboxylic and tricarboxylic acids.

5. The hydrophobizing agent as claimed in claim 1, wherein the polyion complex (i) has a molar ratio of polycations (i.1):polyanions (i.2) of >1.

6. The hydrophobizing agent as claimed in claim 18, wherein the polyion complex (i) has the general formula (Ib), ##STR00024## having the meanings indicated for R.sub.1, R.sub.2, R.sub.3, R.sub.4, Z, x and y for the general formulae (Ia), (Ia.1) and (Ia.3).

7. The hydrophobizing agent as claimed in claim 1, wherein the polyion complex (i) has a molar ratio of polycations (i.1):polyanions (i.2).

8. The hydrophobizing agent as claimed in claim 1, wherein the silicone compound composition (ii) comprises at least one silicone compound (ii.1) which is selected from the group consisting of monoorgano-C.sub.1-C.sub.20-trialkoxysilane, diorgano-C.sub.1-C.sub.20-dialkoxysilane, poly(organo-C.sub.1-C.sub.20-alkoxysiloxane) and mixtures of two or more of these silicone compounds.

9. The hydrophobizing agent as claimed in claim 1, wherein the carrier composition (iii) comprises at least amorphous agglomerated silicon dioxide.

10. A process for producing a hydrophobizing agent comprising i) a polyion complex comprising at least one polycation (i.1) and at least one polyanion (i.2), where the molar ratio of polycation:polyanion in the polyion complex is ≥1; ii) a silicone compound composition; and iii) a carrier composition; wherein the process comprises the steps: a) Providing a polyion complex (i) in an aqueous solution; b) Providing a carrier composition (iii); c) Mixing the aqueous solution of the polyion complex (i) as per (a) with carrier composition (iii) as per (b) to give a first mixture; and d) Adding a silicone compound composition (ii) which optionally contains a surfactant composition and/or a UV dye composition to the first mixture obtained in (c) to give a coated pulverulent carrier composition of the hydrophobizing agent.

11. A hydrophobizing agent obtained the process as claimed in claim 10.

12. A method of using the hydrophobizing agent as claimed in claim 1, the method comprising using the hydrophobizing agent for the hydrophobizing of mineral binders and/or of compositions which contain mineral binders and/or of materials which comprise mineral binders.

13. A binder composition comprising one or more mineral binder(s) and a hydrophobizing agent as claimed in claim 1.

14. A process for hydrophobizing materials which comprise mineral binders, comprising the steps A) Providing a binder composition comprising one or more mineral binder(s); B) Providing a hydrophobizing agent comprising a polyion complex (i) comprising at least one polycation (i.1) and at least one polyanion (i.2), wherein the molar ratio of polycation:polyanion in the polyion complex is ≥1; a silicone compound composition (ii); a carrier composition (iii); C) Mixing the binder composition as per (A) and the hydrophobizing agent as per (B) to give a mixture of binder composition and hydrophobizing agent; and D) Adding water (w) to the mixture of binder composition (b) and hydrophobizing agent, as obtained in (C) and mixing the components; to give a hydrophobized material comprising mineral binders.

15. A hydrophobized material comprising mineral binders and obtained by the process as claimed in claim 14.

16. A hydrophobized material which comprises mineral binders, comprising the reaction product of one or more mineral binder(s), a hydrophobizing agent as claimed in claim 1 and water.

17. The hydrophobizing agent as claimed in claim 1, wherein the polycations (i.1) of the polyion complex (i) are cationic polymers or copolymers which comprise at least one quaternary ammonium cation and which are selected from the group consisting of a) poly-N,N,N-tri-C.sub.1-C.sub.5-alkylammonioalkyl acrylate; b) poly-N,N,N-tri-C.sub.1-C.sub.5-alkylammonioalkyl methacrylate; c) poly-N,N,N-tri-C.sub.1-C.sub.5-alkylammonioalkylacrylamide; d) poly-N,N,N-tri-C.sub.1-C.sub.5-alkylammonioalkylmethacrylamide; e) poly-N-3-methyl-1-vinylimidazolium; f) quaternized poly[bis(2-chloroethyl) ether-alt-1,3-bis(3-dimethylaminopropyl)urea]; g) poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine); h) polydimethyldiallylammonium; i) poly(dimethyldiallylammonium-co-methyldiallylamine hydrochloride); and j) poly-N,N—R.sub.1,R.sub.2-disubstituted-3,4-dimethylenepyrrolidinium, wherein R.sub.1 and R.sub.2 are selected independently from the group consisting of a hydrogen atom, a C.sub.1-C.sub.18-alkyl radical and a benzyl radical; wherein the positive charge on the nitrogen atom of the quaternary ammonium cation is balanced by a singly charged anion.

18. The hydrophobizing agent as claimed in claim 1, wherein the polyion complex (i) has a molar ratio of polycations (i.1):polyanions (i.2) of >1, wherein the polycations (i.1) are poly-N,N-disubstituted-3,4-dimethylenepyrrolidinium salts and the polyanions (i.2) are polyanion esters based on monounsaturated C.sub.3-C.sub.10-monocarboxylic, dicarboxylic and tricarboxylic acids of the general formula (Ia), ##STR00025## wherein R.sub.3 is a hydrogen atom or a C.sub.1-C.sub.4-alkyl radical, R.sub.4 is selected from the group consisting of a hydrogen atom, a C.sub.1-C.sub.4-alkyl radical, and a —CH.sub.2—Z group, wherein Z is in each case a hydrogen atom or an N,N-disubstituted-3,4-dimethylenepyrrolidinium radical in which the positive charge on the nitrogen atom of the quaternary pyrrolidinium cation is balanced by a carboxylate anion radical, wherein the pyrrolidinium salt radical has the general formula (Ia.1), ##STR00026## wherein R.sub.1 and R.sub.2 are selected independently from the group consisting of a hydrogen atom, a C.sub.1-C.sub.18-alkyl radical, and a benzyl radical; x is the degree of polymerization; and W is Z or a double N,N-disubstituted-3,4-dimethylenepyrrolidinium radical in which the positive charges on the nitrogen atoms of the quaternary pyrrolidinium cations are balanced by a chloride anion and a carboxylate anion radical, wherein the bis-N,N-disubstituted-3,4-dimethylenepyrrolidinium salt radical has the general formula (Ia.2), ##STR00027##  having the meanings indicated above for R1, R2 and x for the general formula (Ia.1), or a polyethylene glycol monomethyl ether ester radical of the general formula (Ia.3), ##STR00028##  wherein  y is an integer from 1 to 100.

19. The hydrophobizing agent as claimed in claim 1, wherein the positive charge on the nitrogen atom of the quaternary ammonium cation is balanced by an anion selected from the group consisting of halide anion, chloride anion, methosulfate anion, ethosulfate anion and mixtures of two or more of these anions.

20. The hydrophobizing agent as claimed in claim 1, wherein the polyanions (i.2) of the polyion complex (i) are copolymeric monobasic to polybasic polyanion esters (polycarboxylate ether, PCE) based on monounsaturated C.sub.3-C.sub.10-monocarboxylic, dicarboxylic and tricarboxylic acids selected from the group consisting of methacrylic acid, maleic acid, methylenesuccinic acid, aconitic acid and mixtures of two or more of these acids which are present in the form of their alkali metal salts or ammonium salts.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0488] FIG. 1 Schematic depiction of the contact angle measurement points or in-principle sketch for the determination of the contact angle of water on set cement surfaces (at left) and at different heights in the test specimen;

[0489] FIG. 2 Graph of the individual measurements of the contact angles in the profile of the specimen with 2% by weight addition of powder 22 of test series 3/contact angle of water as a function of the height in the profile of the test specimen;

[0490] FIG. 3 Graph of the percentage capillary water absorption based on the dry weight of the set cement of the specimens with 1.5% by weight addition of the test series 4 over time, where “d” is used as abbreviation for “day” as unit of time;

[0491] FIG. 4 Averages of the contact angles of water on the surfaces of the set cement disks of test series 4 as a function of the powder used and the amount added.

LITERATURE CITED

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