PROCESS FOR PREPARING A STORAGE-STABLE SILICONE RESIN

Abstract

A process is described for preparing a storage-stable mixture including an MDT silicone resin containing hydroxyl groups and an organic compound that contains at least one epoxy group.

Claims

1. A process for preparing a storage-stable mixture X, the process comprising the steps: a) preparing a mixture A from: 60 to 71% by weight of a chlorosilane of formula R1SiCl3, 15 to 25% by weight of a chlorosilane of formula (R2)2SiCl2, 7.5 to 20% by weight of a chlorosilane of formula (R3)3SiCl, and optionally an aromatic hydrocarbon AH, in which formulae the symbols R1, R2 and R3, which are identical or different, each represent: a linear or branched alkyl radical containing from 1 to 8 carbon atoms, a cycloalkyl radical containing from 5 to 8 ring carbon atoms, optionally substituted with at least one halogen, an aryl radical containing from 6 to 12 carbon atoms which is optionally substituted with at least one halogen, a radical with an alkyl part containing from 5 to 14 carbon atoms and an aryl part containing from 6 to 12 carbon atoms optionally substituted with at least one halogen, an alkyl containing from 1 to 6 carbon atoms and/or an alkoxyl containing from 1 to 3 carbon atoms, a hydrogen atom, and an alkenyl radical containing from 2 to 6 carbon atoms; b) adding the mixture A with stirring and while maintaining a temperature of from 5 C. to 60 C., to a two-phase mixture B comprised of an aqueous phase and a solvent phase prepared from water, an aromatic hydrocarbon AH and optionally an aqueous solution of hydrochloric acid CA, so as to perform hydrolysis of the chlorosilanes of the mixture AT; c) optionally maintaining the stirring for at least 1 hour at a temperature of from 30 C. to 60 C. allowing a post-hydrolysis condensation reaction; d) stopping the stirring so as to separate an aqueous phase and a solvent phase; e) isolating and washing the solvent phase with water; f) isolating the silicone resin R from the solvent phase; and g) adding at least one organic compound O containing at least one epoxy group E with stirring to the silicone resin R obtained in step f), and allowing the mixture X to be obtained, wherein the resulting mixture X comprises: i. a silicone resin R comprised of siloxyl units M, D and T with: M being a siloxyl unit of formula: (Z1)3SiO1/2, D being a siloxyl unit of formula: (Z2)2SIO2/2, and T being a siloxyl unit of formula: Z3SiO3/2 formulae in which the symbols Z1, Z2 and Z3, are identical or different, each represent: a linear or branched alkyl radical containing from 1 to 8 carbon atoms, a cycloalkyl radical containing from 5 to 8 carbon atoms, optionally substituted with at least one halogen, an aryl radical containing from 6 to 12 carbon atoms optionally substituted with at least one halogen, a radical with an alkyl part containing from 5 to 14 carbon atoms and an aryl part containing from 6 to 12 carbon atoms optionally substituted with at least one halogen, an alkyl radical containing from 1 to 6 carbon atoms and/or an alkoxyl radical containing from 1 to 3 carbon atoms, a hydroxyl radical, a hydrogen atom, or an alkenyl radical containing from 2 to 6 carbon atoms; and with the condition that, for at least one unit D or T, at least one symbol Z2 or Z3 is a hydroxyl radical, and ii. at least one organic compound O containing at least one epoxy group E.

2. The process as claimed in claim 1, in which, in step a), the mixture A is prepared using: 60 to 71% by weight of a chlorosilane of formula R1SiCl3, 19 to 25% by weight of a chlorosilane of formula (R2)2SiCl2, 7.5 to 16.5% by weight of a chlorosilane of formula (R3)3SiCl, and optionally an aromatic hydrocarbon AH, in which formulae the symbols R1, R2 and R3, are identical or different, each represent: a linear or branched alkyl radical containing from 1 to 8 carbon atoms, a cycloalkyl radical containing from 5 to 8 ring carbon atoms, optionally substituted with at least one halogen, an aryl radical containing from 6 to 12 carbon atoms which may be optionally substituted with at least one halogen, a radical with an alkyl part containing from 5 to 14 carbon atoms and an aryl part containing from 6 to 12 carbon atoms optionally substituted with at least one halogen, an alkyl containing from 1 to 6 carbon atoms and/or an alkoxyl containing from 1 to 3 carbon atoms, a hydrogen atom, and an alkenyl radical containing from 2 to 6 carbon atoms.

3. The process as claimed in claim 1, wherein in step g), the organic compound O containing at least one epoxy group E is added so that its weight content is from 0.1% to 1% relative to the weight of the silicone resin R.

4. The process as claimed in claim 1, wherein in step g), the organic compound O containing at least one epoxy group E is an epoxidized fatty acid ester.

5. The process as claimed in claim 1, wherein in step g), the organic compound O containing at least one epoxy group E is the 2-ethylhexyl ester of epoxidized soybean fatty acids.

6. The process as claimed in claim 1, wherein in step b), the two-phase mixture B is comprised of water, of an aqueous hydrochloric acid solution CA and of an aromatic hydrocarbon AH, and the hydrochloric acid concentration is less than 25% by weight relative to the aqueous phase of the two-phase mixture B.

7. The process as claimed in claim 1, wherein in step b), after the mixture A has been added to a two-phase mixture B, the concentration of aromatic hydrocarbon AH is from 40% to 70% by weight relative to the total weight of the chlorosilanes used and of the aromatic hydrocarbon AH.

8. The process as claimed in claim 1, wherein the aromatic hydrocarbon AH is toluene, xylene or a mixture thereof.

9. A storage-stable mixture X obtained by the process as described in claim 1, the mixture X comprising a silicone resin R and an organic compound O containing at least one epoxy group E.

10. An aqueous silicone dispersion Y comprising: at least one mixture X as described in claim 9, at least one surfactant S, and water W.

11. The aqueous silicone dispersion Y as claimed in claim 10, wherein the dispersion Y is in the form of an oil-in-water emulsion.

12. An aqueous formulation F, useful in the formulation of paints, the formulation comprising: an aqueous silicone dispersion Y as described in claim 10, the silicone dispersion optionally being present at up to 150% by weight relative to the total weight of one or more organic dispersions; a siliceous or nonsiliceous filler, optionally selected from the group consisting of: precipitated silica, fumed silica, colloidal silica or silica powder, carbonates, talc, TiO2, and mixtures thereof; one or more organic dispersions, optionally chosen from those comprising (co)polymers of styrene and/or (meth)acrylic acid; and at least one compound selected from the group consisting of: a thickener selected from the group consisting of acrylic cellulose-based thickeners, polyurethanes, natural gums, and mixtures thereof; a coalescer originally selected from organic solvents and optionally from glycols and/or aliphatic petroleum fractions; a wetting agent or dispersant optionally selected from phosphates and/or polyacrylics; a surfactant; a neutralizing agent; a biocide; a diluent; a plasticizer, optionally selected from nonreactive silicone oils; an antifoam; and a pigment or colorant (organic or mineral).

13. A paint P comprising the aqueous silicone dispersion Y as described in claim 10.

14. A method of making a paint, the method comprising making the paint with the aqueous silicone dispersion Y as described in claim 10.

15. A method of impregnating a porous construction material, the method comprising impregnating the material with a nonaqueous waterproofing composition which is a liquid silicone composition L comprising at least one mixture X as described in claim 9.

16. A process for waterproofing porous construction materials, the process comprising applying the nonaqueous liquid silicone composition L as described in claim 15 to the material.

17. The process as claimed in claim 16, wherein the porous construction material is a substrate selected from the group consisting of: stone, concrete, mortar, brick, tile and wood.

18. The process as claimed in claim 1, wherein the linear or branched alkyl radical is a methyl, an ethyl, a propyl or an octyl.

19. The process as claimed in claim 1, wherein the linear or branched alkyl radical is a methyl.

20. The process as claimed in claim 1, wherein when the aryl radical is substituted with at least one halogen, the at least one halogen is phenyl or dichlorophenyl.

21. The process according to claim 1, wherein when the stirring of step (c) is maintained, it is maintained from 1 to 8 hours.

22. The process according to claim 1, wherein the isolation and washing of the solvent phase in step (e) is performed until the pH of the water used in the washing is neutral.

23. The process of claim 1, wherein the silicone resin R is isolated from the solvent phase by devolatization

24. The process of claim 1, wherein when Z1, Z2 or Z3 represent a linear or branched alkyl radical, the radical is a methyl, an ethyl, a propyl or an octyl.

25. The process of claim 24, wherein the radical is a methyl.

26. The process of claim 1, wherein when Z1, Z2 or Z3 are an aryl radical and the aryl radical is substituted by at least one halogen, the at least one halogen is phenyl or a dichlorophenyl.

27. The process of claim 2, wherein when R1, R2 and R3 represent a linear or branched alkyl radical, the radical is a methyl, an ethyl, a propyl or an octyl.

28. The process of claim 27, wherein the radical is a methyl.

29. The process as claimed in claim 2, wherein when R1, R2 and R3 is an aryl radical substituted with at least one halogen, the at least one halogen is phenyl or a dichlorophenyl.

30. The process as claimed in claim 3, wherein the weight content is from 0.1% to 0.75% relative to the weight of the silicone resin R.

31. The process as claimed in claim 7, wherein the concentration of the aromatic hydrocarbon AH is from 49% to 61% by weight relative to the total weight of chlorosilanes used and of the aromatic hydrocarbon AH.

32. The formulation F as claimed in claim 12, wherein the silicone dispersion is present at from 40% to 100% by weight relative to the total weight of one or more organic dispersions.

33. A paint P comprising the aqueous formulation F as described in claim 12.

34. A method of making a paint, the method comprising making the paint using the aqueous formulation F as described in claim 12.

Description

EXAMPLES

[0162] A) Starting Materials Used: [0163] Trimethylchlorosilane from the company Sigma-Aldrich. [0164] Dimethyldichlorosilane from the company Sigma-Aldrich. [0165] Methyltrichlorosilane from the company Sigma-Aldrich. [0166] Demineralized water. [0167] AH: Normapur-grade toluene from the company VWR International. [0168] CA: aqueous hydrochloric acid solution from the company VWR International (37 or 33% by weight). [0169] Organic compound O: Dehysol.sup.R B35 from the company BTC: 2-ethylhexyl ester of epoxidized fatty acids (CAS 68082-34-8).

[0170] For all the examples, the term neutral pH means a pH of 7 (pH paper precision).

[0171] B) Preparation of Mixtures X According to the Invention

[0172] 1. Mixture X1 According to the Invention

[0173] According to a direct hydrolysis process, a mixture of chlorosilanes, composed of 4.38 g of trimethylchloro-silane, 8.55 g of dimethyldichlorosilane and 26.95 g of methyltrichlorosilane is added under a stream of argon dropwise to a stirred reactor containing beforehand 43 g of toluene AH, 43.3 g of water and 18.9 g of a hydrochloric acid solution CA at 37% by weight (direct process). The temperature of the reaction medium is maintained between 5 and 60 C. At the end of the addition, 7 g of toluene AH are added and the temperature of the reaction medium is then maintained at 50 C. for 1 hour. On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 100 g of water are then added slowly so as to reduce the hydrochloric acid concentration of the aqueous phase. Once the stirring is stopped, the reaction medium separates into two phases. The aqueous phase is withdrawn and the organic phase is washed with water until the pH of the washing waters is neutral. The solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 2 hours. 17.6 g of silicone resin R1 are obtained, with a kinematic viscosity of 1209 mm.sup.2/s and a content of hydroxyl functions of 0.8% by weight, and to which is added 0.035 g of Dehysol.sup.RB35, organic compound O, so as to obtain the mixture X1.

[0174] .sup.29Si NMR analysis of the mixture X1 reveals the following distribution:

TABLE-US-00001 UNITS mol % relative to silicon M 10.88 D(OH) 0.70 D 22.72 T(OH) 7.86 T 57.84

[0175] The mixture X1 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability for the purposes of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X1 does not increase on storage by more than 10% relative.

[0176] 2. Mixture X2 According to the Invention

[0177] The preparation of the mixture X2 is similar to that of the mixture X1 with the exception of the duration of the steady stage at 50 C., which is 4 hours instead of one hour. On conclusion of the distillation of the solvent, 18.1 g of silicone resin R2 are obtained, to which is added 0.036 g of Dehysol.sup.R B35, organic compound O, so as to obtain the mixture X2 which has a kinematic viscosity of 1404 mm.sup.2/s and a content of hydroxyl functions of 0.6% by weight.

[0178] .sup.29Si NMR analysis of the mixture X2 reveals the following distribution:

TABLE-US-00002 UNITS mol % relative to silicon M 11.3 D(OH) 0.70 D 23.3 T(OH) 8.3 T 56.4

[0179] The mixture X2 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability within the meaning of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X2 does not increase on storage by more than 10% relative.

[0180] 3. Mixture X3 According to the Invention

[0181] The preparation of the mixture X3 is similar to the mixture X1 with the exception of the amounts of water and of hydrochloric acid at 37% by weight CA initially present in the reactor before adding the mixture of chlorosilanes, which are, respectively, 31.7 g and 37.3 g. On conclusion of the distillation of the solvent, 18 g of silicone resin X3 are obtained, to which is added 0.036 g of Dehysol.sup.R B35, organic compound O, so as to obtain the mixture X3 which has a kinematic viscosity of 979 mm.sup.2/s and a content of hydroxyl functions of 0.83% by weight.

[0182] .sup.29Si NMR analysis of the mixture X3 reveals the following distribution:

TABLE-US-00003 UNITS mol % relative to silicon M 10.5 D(OH) D 25.5 T(OH) 4.7 T 59.3

[0183] The mixture X3 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability within the meaning of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X3 does not increase on storage by more than 10% relative.

[0184] 4. Mixture X4 According to the Invention

[0185] The preparation of the mixture X4 is similar to the mixture X1 with the exception of the mixture of chlorosilanes, which is composed of 3.01 g of trimethylchlorosilane, 8.9 g of dimethyldichlorosilane and 28 g of methyltrichlorosilane. On conclusion of the distillation of the solvent, 17.6 g of silicone resin R4 are obtained, to which is added 0.035 g of Dehysol.sup.R B35, organic compound O, so as to obtain the mixture X4 which has a kinematic viscosity of 12 319 mm.sup.2/s and a content of hydroxyl functions of 1.05% by weight.

[0186] Si NMR analysis reveals the following distribution:

TABLE-US-00004 UNITS mol % relative to silicon M 7.6 D(OH) D 23.6 T(OH) 12.0 T 56.0

[0187] The mixture X4 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability within the meaning of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X4 does not increase on storage by more than 10% relative.

[0188] 5. Mixture X5 According to the Invention

[0189] The preparation of the mixture X5 is similar to the mixture X1 with the exception of the mixture of chlorosilanes, which is composed of 5.99 g of trimethylchlorosilane, 8.16 g of dimethyldichlorosilane and 25.72 g of methyltrichlorosilane. On conclusion of the distillation of the solvent, 18.3 g of silicone resin R5 are obtained, to which is added 0.036 g of Dehysol.sup.R B35, organic compound O, so as to obtain the mixture X5 which has a kinematic viscosity of 300 mm.sup.2/s and a content of hydroxyl functions of 0.95% by weight.

[0190] .sup.29Si NMR analysis reveals the following distribution:

TABLE-US-00005 UNITS mol % relative to silicon M 14.7 D(OH) 0.52 D 21.2 T(OH) 9.2 T 54.4

[0191] The mixture X5 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability within the meaning of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X5 does not increase on storage by more than 10% relative.

[0192] 6. Mixture X6 According to the Invention

[0193] A mixture of chlorosilanes constituted of 174 g of trimethylchlorosilane, 339 g of dimethyldichlorosilane and 1069 g of methyltrichlorosilane is added slowly to a stirred 10-liter reactor containing 1800 g of water and 1800 g of toluene AH. The temperature of the reaction medium is maintained between 5 and 60 C.

[0194] At the end of addition of the chlorosilanes, the temperature of the reaction medium is maintained at 50 C. for 1 hour. On conclusion of the temperature maintenance, 200 g of toluene and 3000 g of water are added to the preceding mixture. After separation of the phases by settling, withdrawal of the aqueous phase and washing of the organic phase until a neutral pH is obtained, the solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 8 hours. After 8 hours of devolatization, 0.2% of Dehysol.sup.R B35, organic compound O, is added to the silicone resin R6 obtained. The mixture X6 thus obtained has a kinematic viscosity of 1270 mm.sup.2/s and a content of hydroxyl functions of 0.64% by weight.

[0195] The mixture X6 obtained according to a direct rather than an inverse hydrolysis process, in the absence of isopropyl ether during the direct hydrolysis step b) and containing organic compound O added during step g) of the process, has a stability within the meaning of the invention of greater than 6 months, i.e. the kinematic viscosity of the mixture X6 does not increase on storage by more than 10% relative.

[0196] C) Preparation of the Comparative Examples

[0197] 1. Comparative Test 1

[0198] The preparation of comparative test 1 is similar to the mixture X1 except for the fact that the toluene is replaced with isopropyl ether. On conclusion of the distillation of the solvent, 19 g of silicone resin are obtained, with a kinematic viscosity of 150 mm.sup.2/s and comprising 0.54% by weight of hydroxyl units, outside the target in terms of viscosity, i.e. the viscosity is not between outside the target in terms of viscosity, i.e. the viscosity is not between 300 and 25 000 mm.sup.2/s. All the factors being otherwise equal, the use of isopropyl ether as replacement for toluene does not make it possible to obtain a resin in accordance with the invention.

[0199] 2. Comparative Test 2

[0200] A mixture of chlorosilanes, composed of 8.57 g of dimethyldichlorosilane and 26.95 g of methyl-trichlorosilane, is added under a stream of argon dropwise to a stirred reactor containing 38.4 g of toluene, 38.7 g of water and 16.8 g of a hydrochloric acid solution at 37% by weight. The temperature of the reaction medium is maintained between 5 and 60 C. At the end of the addition, 6.2 g of toluene are added, and the temperature of the reaction medium is then maintained at 50 C. for 1 hour. On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 100 g of water are then added slowly so as to reduce the hydrochloric acid concentration of the aqueous phase. On stoppage of the stirring, no phase separation takes place and white solid is abundantly present on the walls. The absence of trimethylchlorosilane in the mixture A does not make it possible to obtain a resin as defined according to the invention. The inventor has, to his credit, identified the correct concentration range of the trimethylchlorosilane in the mixture A.

[0201] 3. Comparative Test 3

[0202] A mixture of chlorosilanes, composed of 2.05 g of trimethylchlorosilane, 9.10 g of dimethyldichlorosilane and 28.80 g of methyltrichlorosilane, is added under a stream of argon dropwise to a stirred reactor containing 43 g of toluene, 43.3 g of water and 18.9 g of a hydrochloric acid solution at 37% by weight. The temperature of the reaction medium is maintained between 5 and 60 C. At the end of the addition, 7 g of toluene are added, and the temperature of the reaction medium is then maintained at 50 C. for 1 h. On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 100 g of water are then added slowly so as to reduce the hydrochloric acid concentration of the aqueous phase. On stoppage of the stirring, the reaction medium cannot be separated since it is heterogeneous: presence of solid gels. The presence of 5% of trimethylchlorosilane in the mixture A is not sufficient to prevent the formation of gels. The inventor has, to his credit, identified the correct concentration range of trimethylchlorosilane in the mixture A.

[0203] 4. Comparative Test 4

[0204] A mixture of chlorosilanes, composed of 2.02 g of trimethylchlorosilane, 9.10 g of dimethyldichlorosilane and 28.80 g of methyltrichlorosilane, is added under a stream of argon dropwise to a stirred reactor containing 43 g of toluene, 31.7 g of water and 37.3 g of a hydrochloric acid solution at 37% by weight. The temperature of the reaction medium is maintained between 5 and 60 C. At the end of the addition, 7 g of toluene are added, and the temperature of the reaction medium is then maintained at 50 C. for 1 hour. On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 100 g of water are then added slowly so as to reduce the hydrochloric acid concentration of the aqueous phase. On stoppage of the stirring, the reaction medium separates into two phases. The aqueous phase is withdrawn, but the medium is heterogeneous: presence of solid gels in the organic phase. The presence of 5% of trimethylchlorosilane in the mixture A is not sufficient to prevent the formation of gels, even in the presence of an amount of 37% hydrochloric acid solution that is larger than in comparative test 3. The inventor has, to his credit, identified the correct concentration range of trimethylchlorosilane in the mixture A.

[0205] 5. Comparative Test 5

[0206] A mixture of chlorosilanes, composed of 12.03 g of trimethylchlorosilane, 6.77 g of dimethyldichlorosilane and 21.18 g of methyltrichlorosilane, is added under a stream of argon dropwise to a stirred reactor containing 43 g of toluene, 43.3 g of water and 18.9 g of hydrochloric acid solution at 37% by weight. The temperature of the reaction medium is maintained between 5 and 60 C. At the end of the addition, 7 g of toluene are added, and the temperature of the reaction medium is then maintained at 50 C. for 1 hour. On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 100 g of water are then added slowly so as to reduce the hydrochloric acid concentration of the aqueous phase. On stoppage of the stirring, the reaction medium separates into two phases. The aqueous phase is withdrawn and the organic phase washed with water until the pH of the washing waters is neutral. The solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 2 hours. 18.8 g of silicone resin are obtained, with a viscosity of 23 mm.sup.2/s and comprising 0.8% by weight of hydroxyl functions, outside the target in terms of viscosity, i.e. the viscosity is not between 300 and 25 000 mm.sup.2/s.

[0207] The presence of 30% of trimethylchlorosilane in the mixture A does not make it possible to obtain a resin as defined according to the invention. The inventor has, to his credit, identified the correct concentration range of trimethylchlorosilane in the mixture A.

[0208] D) Influence of Dehysol.sup.R B35, Organic Compound O, on the Stability of the Mixture X

[0209] 1. Mixtures X7 and X7bis According to the Invention

[0210] Via a direct hydrolysis process, a mixture of chlorosilanes constituted of 174 g of trimethylchlorosilane, 339 g of dimethyldichlorosilane and 1069 g of methyltrichlorosilane is added slowly to a stirred 10-liter reactor containing 1718 g of water, 750 g of 33% hydrochloric acid CA and 1706 g of toluene AH. The temperature of the reaction medium is maintained between 5 and 60 C.

[0211] 278 g of toluene are added at the end of addition of the chlorosilanes.

[0212] The temperature of the reaction medium is then maintained at 50 C. for 1 hour.

[0213] On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 3967 g of water are added to the preceding mixture.

[0214] After separation of the phases by settling, withdrawal of the aqueous phase and washing of the organic phase until a neutral pH is obtained, the solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 2 to 5 hours.

[0215] a) After two hours of devolatilization, a sample is taken.

[0216] The silicone resin R7 obtained from this sample has a kinematic viscosity of 1938 mm.sup.2/s and a content of hydroxyl functions of 0.52%.

[0217] 0.2% by weight of Dehysol.sup.R B35, organic compound O, is added to part of the silicone resin. The mixture X7 is thus obtained.

[0218] The other part is kept without addition of Dehysol.sup.R B35, organic compound O.

[0219] Monitoring of the viscosity of the two parts over time shows the absence of increase in the presence of Dehysol.sup.R B35, organic compound O.

[0220] The organic compound O thus makes it possible to stabilize the resin according to the invention, i.e. the kinematic viscosity of the mixture X7 does not increase on storage by more than 10% relative.

[0221] On the other hand, the part without Dehysol.sup.R B35, i.e. without the organic compound O, has a kinematic viscosity that is multiplied by 1.85 over 6 months of storage.

[0222] The resin in the absence of the organic compound O is not stable on storage.

[0223] The addition of the organic compound O is necessary for the stability of the resin which may optionally be emulsified.

[0224] b) In parallel to the sampling, devolatilization is continued. After five hours of devolatilization, 0.2% of Dehysol.sup.R B35, organic compound O, is added to the silicone resin R7bis obtained. The mixture X7bis thus obtained has a kinematic viscosity of 1860 mm.sup.2/s and a content of hydroxyl functions of 0.59% by weight.

[0225] 2. Mixtures X8 and X9 According to the Invention

[0226] Via a direct hydrolysis process, a mixture of chlorosilanes constituted of 174 g of trimethylchlorosilane, 339 g of dimethyldichlorosilane and 1069 g of methyltrichlorosilane is added slowly to a stirred 10-liter reactor containing 3345 g of water, 1647 g of 33% hydrochloric acid CA and 1706 g of toluene AH. The temperature of the reaction medium is maintained between 5 and 60 C.

[0227] 278 g of toluene are added at the end of addition of the chlorosilanes.

[0228] The temperature of the reaction medium is then maintained at 50 C. for 1 hour.

[0229] On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C., 2000 g of water are added to the preceding mixture.

[0230] After separation of the phases by settling, withdrawal of the aqueous phase and washing of the organic phase until a neutral pH is obtained, the solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 2 to 5 hours 30 minutes.

[0231] a) After two hours of devolatilization, a sample is taken. 0.2% of Dehysol.sup.R B35, organic compound O, is added to the silicone resin R8 obtained. The mixture X8 thus obtained has a content of hydroxyl functions of 0.19% by weight and a viscosity of 5485 mm.sup.2/s which does not increase on storage.

[0232] The organic compound O thus makes it possible to stabilize the resin according to the invention, i.e. the kinematic viscosity of the mixture X8 does not increase on storage by more than 10% relative.

[0233] b) In parallel to the sampling, devolatilization is continued. After five hours 30 minutes of devolatilization, 0.2% of Dehysol.sup.R B35, organic compound O, is added to the silicone resin R9 obtained. The mixture X9 thus obtained has a viscosity of 3487 mm.sup.2/s and a content of hydroxyl functions of 0.21% by weight.

[0234] E) Preparation of Emulsions

[0235] 1. Starting Materials Used [0236] Mixture X of silicone resin R and of an organic compound O containing at least one epoxy group E according to the invention. [0237] Water-soluble hydroxylated alkylamino silane: aqueous hydrolyzate of gamma-aminopropyltriethoxysilane containing 20% active material, from which the alcohol has been removed by stripping (commercial product Silquest.sup.R VS142 from Momentive) [0238] Silane bearing alkoxy group: OTES=octyltriethoxysilane from Sigma-Aldrich [0239] Surfactants S: an ethoxylated (8 ethoxy units) fatty alcohol (chain of 13 carbons), sold under the name ROX by the company Solvay

[0240] 2. Mixture X10 According to the Invention

[0241] Via a direct hydrolysis process, a mixture of chlorosilanes constituted of 174 g of trimethylchlorosilane, 339 g of dimethyldichlorosilane and 1069 g of methyltrichlorosilane is added slowly to a stirred 10-liter reactor containing 1800 g of water, 670 g of hydrochloric acid at 37% by weight CA and 1706 g of toluene AH. The temperature of the reaction medium is maintained between 5 and 60 C.

[0242] 278 g of toluene are added at the end of addition of the chlorosilanes.

[0243] The temperature of the reaction medium is then maintained at 50 C. for 1 hour.

[0244] On conclusion of the temperature maintenance, the reaction medium is cooled to 30 C. and 3967 g of water are added to the preceding mixture.

[0245] After separation of the phases by settling, withdrawal of the aqueous phase and washing of the organic phase until a neutral pH is obtained, the solvent of the organic phase is evaporated off at 60 C. under a pressure of less than 5 mbar for 8 hours. After 8 hours of devolatilization, 0.2% of Dehysol.sup.R B35, organic compound O, is added to the silicone resin obtained. The mixture X10 thus obtained has a viscosity of 1019 mm.sup.2/s and a content of hydroxyl functions of 0.49% by weight.

[0246] 3. Process for Preparing Aqueous Dispersions Y

[0247] Several protocols for preparing aqueous dispersions Y may be envisaged. Without this being limiting, the protocol retained in the present example is that consisting in:

[0248] 1) Mixing 15.8 g of water and 25.3 g of surfactant S in a 1 L tank equipped with a rotary anchor

[0249] 2) Incorporating, into this mixture of water and surfactant S, 342.8 g of the mixture X and then 14.5 g of silane OTES, this incorporation being performed gradually and under stirring of about 100 rpm so as to obtain an oil-in-water emulsion.

[0250] 3) Performing a post-addition of 14.5 g of water-soluble silane Silquest VS142 and continuing the stirring for about 1 hour.

[0251] 4) Adding 184.6 g of water to dilute the emulsion to the desired active material content.

[0252] A liquid of white appearance is thus obtained, the volume-mean diameter of which, determined by laser particle size analysis using a Mastersizer 2000 machine (Malvern), is given below for 3 different silicone resins.

TABLE-US-00006 Emulsion Y1 Y2 Y3 Mixture X emulsified X9 X10 X7bis Content of OH (% by 0.21% 0.49% 0.59% weight) of the mixture X according to the invention Viscosity of the 3487 mm.sup.2/s 1019 mm.sup.2/s 1860 mm.sup.2/s mixture X according to the invention D[4,3]of the 0.197 m 0.179 m 0.201 m emulsion

[0253] The particle size of the emulsion is measured by laser scattering using a MasterSizer 2000-Hydro 2000G particle size analyzer according to standard ISO 13320 (2009).

[0254] F) Formulation of Paints

[0255] In order to evaluate the provision of the emulsions Y of mixtures X on the final properties of the paint, two types of paint are prepared. One P1 has VPC/CVCP ratio of 1.13 and the other P2 has a VPC/CVPC ratio of 0.80. Their compositions are given in the table below.

[0256] The critical volume-based pigment concentration CVPC is the value of the volume-based pigment concentration for which the binder very exactly fills the volume left available between the particles of pulverulent material assumed to be in contact and above which certain properties of the film are appreciably modified.

[0257] The volume-based pigment concentration VPC is the ratio, expressed as a percentage, of the total volume of pigments and/or filler materials and/or other solid particles not forming a film, contained in a product, to the total volume of nonvolatile materials.

[0258] The constituents and composition of the paints are as follows:

TABLE-US-00007 Mass (g) per Mass (g) per 100 g of 100 g of paint of paint of Function/ VPC/ VPC/ chemical CVPC = 1.13 CVPC = 0.8 Constituent Supplier nature P1 P2 Water 26.2 24.3 Ecodis Coatex Dispersant 0.5 0.5 P90 BYK.sup.R 037 BYK Antifoam 0.2 0.2 Tiona.sup.R 595 Cristal TiO.sub.2 pigment 14 12.2 Durcal.sup.R 5 Omya Calcium 25 19.2 carbonate Calibrite.sup.R Omya Calcium 11 8.3 SL carbonate Talc Imerys Talc 6 4.4 Luzenac.sup.R 10MO Craymul.sup.R Cray Acrylic 9.2 17.6 2423 Valley styrene Emulsion Y1 According Silicone 5.6 10.7 or Y2 or Y3 to the emulsion invention Dowanol Dow Coalescence 0.3 0.7 DPnB Chemicals agent BYK.sup.R E420 BYK Thickener 0.4 0.4 Coapur Coatex Polyurethane 1.3 1.3 830W thickener Acticide.sup.R Thor Biocide 0.3 0.3 MBS

[0259] 1. Wet Abrasion Resistance (WAR) Test

[0260] A paint for interior or exterior application must be able to be cleaned easily without being degraded. For this type of product, the binding power of the polymer, i.e. its ability to ensure cohesion of the assembly, is a deciding factor.

[0261] One means for quantifying this property consists in evaluating the wet abrasion resistance of a paint.

[0262] Definitions of the Wet Abrasion Resistance

[0263] According to standard ISO 11998, the wet abrasion resistance is equal to the loss of thickness of a film of paint after a defined abrasion cycle performed using a standardized machine.

[0264] Principle

[0265] It is a matter of evaluating the ability of a film of paint of defined thickness to withstand the abrasive action exerted by the to-and-fro movement of a brush or an abrasive pad, in aqueous medium.

[0266] Expressing the Results

[0267] For Standard ISO 19988

[0268] For each test specimen, apply the following formula: .sub.m*10.sup.6/(39*387*d.sub.s) in which:

[0269] .sub.m is the weight difference of the test specimens before and after the test,

[0270] d.sub.s is the dry density of the paint.

[0271] For each paint, calculate the mean and the standard deviation.

[0272] Express the result in m, which corresponds to a loss of thickness of the film of paint. A classification of paints as a function of the loss of thickness and of the number of abrasion cycles exists:

[0273] Class 1: <5 m at 200 abrasion cycles, for paints with a high binder content.

[0274] Class 2: 5 m and <20 m at 200 abrasion cycles, the paint is scrubbable.

[0275] Class 3: 20 m and <70 m at 200 abrasion cycles, the paint is washable.

[0276] Class 4: <70 m at 40 abrasion cycles

[0277] Class 5: 70 m at 40 abrasion cycles.

[0278] 2. Water Permeability (W24)

[0279] The procedure (standard NF EN 1062-3, February 1999) specifies a method for determining the permeability to liquid water of paint products and of similar products, applied to exterior masonry and concrete. This method is applicable to paint products and coating systems for porous supports, for instance: bricks, concrete and renderings.

[0280] Principle

[0281] Coatings for exterior masonry and concrete play an important role for preventing the penetration of runoff water into porous mineral supports. This criterion is evaluated by means of mineral blocks of high porosity, one of the faces of which is coated with the coating or the coating system. The test specimen is immersed in water, under given conditions, and the test specimens are weighed at regular time intervals. The permeability to liquid water is determined by the change in mass when the change in mass is directly proportional to the square root of the time interval.

[0282] Expressing the Results

[0283] Determine the increase in the mass of water as being the function of the square root of time. The slope of the linear part of the curve is the coefficient of the transmission of liquid water W in kg/m.sup.2.Math.Vt of hours. To obtain the coefficient W, it is necessary to divide the increase in mass by the surface area, in m.sup.2, or to divide the slope by the surface area. The surface area will be the surface area not covered with paraffin. Normally, W is calculated for a period of 24 hours. If the part of the curve is obtained before 24 hours, the number of hours must be indicated as the W index (e.g. W6).

[0284] 3. Steam Permeability Sd

[0285] The procedure makes it possible, according to standard NF EN ISO 7783-2, to determine the capacity of a film of paint to allow steam to pass through.

[0286] The paint is applied to a porous polyethylene plaque 250 m thick. After several washing/drying cycles, the coated plaques are cut up and placed on crucibles containing 150 mL of a saturated ammonium dihydrogen phosphate solution. From the measured loss of mass, the Sd factor is determined, corresponding to the thickness (in meters) of the layer of air at rest allowing a stream of steam equivalent to the stream observed through the paint film.

[0287] 4. Results of the Evaluation of the Paints:

TABLE-US-00008 Aqueous dispersion used in the Paint type P1 Paint type P2 paint type P1 VPC/CVPC = 1.13 VPC/CVPC = 0.8 or P2 WAR (m) W24 (kg/m.sup.2 .Math. h.sup.0.5) Sd (m) Emulsion Y1 12.5 0.10 0.12 Emulsion Y2 11.5 0.10 0.06 Emulsion Y3 14.5 0.10 0.02

[0288] These paints have satisfactory performance qualities, corresponding to the following classification according to the standards mentioned above: class 2 for the WAR (between 5 and 20 m), class 3 for W24 (0.10 kg/m.sup.2.Math.h.sup.0.5) and class 1 for Sd (<0.14 m).

[0289] G) Use of a Nonaqueous Liquid Silicone Composition L as Waterproofing for Porous Construction Materials 1. Starting Materials Used [0290] Mixture X of silicone resin R and of an organic compound O containing at least one epoxy group E according to the invention. [0291] Butyl titanate MA Ti(OBu).sub.4 from the company Dorf Ketal Specialty Catalysts LLC (USA) [0292] Ethyl silicate C Si(OEt).sub.4 from the company Bluestar Silicones [0293] White spirit from the company Quimidroga S.A. (Spain)

[0294] 2. Formulation of the Nonaqueous Silicone Composition L1

[0295] Several protocols for preparing the nonaqueous liquid silicone composition L may be envisaged. Without this being limiting, the protocol selected in the present example is that consisting in introducing and homogenizing in a 150 mL beaker 4.2 g of mixture X8 according to the invention, 0.32 g of butyl titanate, 0.22 g of ethyl silicate and 71.4 g of white spirit. The nonaqueous silicone composition L1 is obtained.

[0296] 3. Treatment of Stones

[0297] After homogenization, the nonaqueous silicone composition L1 is used for the following treatments: [0298] 3 stones (in this instance Savonnieres stones) are treated by dipping in the solution for a time of 2 times 10 seconds with an interval of one minute. [0299] The stones are left to dry for 15 days at 23 C. under an atmosphere at 50% relative humidity.

[0300] 4. Evaluation of the Waterproofing

[0301] The waterproofing is then evaluated by capillarity water uptake: the treated stones are placed in contact with the water and are then weighed regularly. A mean is taken on the 3 stones, and the decrease in water absorption is determined by normalizing the water uptake of the samples with that of an untreated control. After 28 days of contact with water, a 90% decrease in water absorption is then obtained, reflecting good waterproofing efficiency of the treated stones.