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EP-4735509-A1 - ORGANOSILICON COMPOSITIONS

EP4735509A1EP 4735509 A1EP4735509 A1EP 4735509A1EP-4735509-A1

Abstract

Excellent improvements in water repellency of the hardened cement-based materials are obtained when the compositions of the present disclosure comprising the specific Polyether-modified Polysiloxane and Silicone Hydrophobic Agents are used as an admixture for mass hydrophobization of the cement-based materials with no significant loss of strength, especially compressive strength, which is not the case with these conventional Silicone Hydrophobic Agents.

Inventors

  • JIN, Dongbing
  • LIN, YUN
  • LEI, FANGHUA

Assignees

  • Wacker Chemie AG

Dates

Publication Date
20260506
Application Date
20230629

Claims (14)

  1. A composition comprising Component (1) Silicone Hydrophobic Agents and Component (2) Polyether-modified Polysiloxane of formula I; wherein each R independently represents a monovalent hydrocarbon radical having from 1 to 30 carbon atoms, preferably monovalent hydrocarbon radical having from 1 to 6 carbon atoms, more preferably monovalent alkyl radical having from 1 to 6 carbon atoms, such as methyl, ethyl radicals; R’ independently represents R or R*; R*=R 3 - [ (C 2 H 4 O) x (C 3 H 6 O) y ] R 4 ; R 3 =- (CH 2 ) p O-, p selected from 2-10; preferably 2, 3, 4, 5, 6, more preferably 3 or 4; R 4 selected from hydrogen, alkyl, aralkyl, aryl or R-C (O) -, preferably hydrogen, methyl, acetyl, more preferably hydrogen and methyl; x selected from 1-60, preferably 1-40, more preferably 1-20; y selected from 0-60, preferably 0-40, more preferably 0-20; The value of x plus y is selected from 2-60, preferably 3-40, more preferably 10-30; n selected from 0-20, preferably 0-15, more preferably 0-10; m selected from 1-20, preferably 5-20, more preferably 5-15; The value of n plus m is selected from 3-40, preferably 5-30 more preferably 10-20; with the proviso that when n = 0, at least one R' is selected from R*.
  2. The composition according to Claim 1, wherein the Component (2) is selected from Polyether-modified Polysiloxane of formula III or IV, wherein R, R*, n and m are as defined in formula I, and n is greater than 0.
  3. The composition according to Claims 1 or 2, wherein the value of y/x is selected from 0-3, preferably 0-1, more preferably 0; and/or y selected from 0-10, preferably 0-5, more preferably 0.
  4. The composition according to any of Claims 1-3, wherein the Component (1) Silicone Hydrophobic Agents, comprising silanes of the formula II; and/or the hydrolyzates of silanes of the formula II; and/or the oligomers of silanes of the formula II. R 1 R 2 i -Si- (OR 2 ) 3-i (II) Wherein R 1 is a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having from 1-16 carbon atoms, which may be interrupted by heteroatoms and/or carbonyl groups; Preferably hydrocarbon radical having from 3 to 16 carbon atoms, more preferably alkyl radical having from 3 to 8 carbon atoms, such as octyl radicals, butyl radicals; R 2 is independently at each occurrence a monovalent, optionally substituted, SiC-bonded hydrocarbon radical having from 1 to 8 carbon atoms, which may be interrupted by heteroatoms and/or carbonyl groups; Preferably alkyl radical having from 1 to 8 carbon atoms, more preferably R 2 is methyl, ethyl, n-propyl or isopropyl. i selected from 0-3, preferably 0 or 1, more preferably 0.
  5. The composition according to any of Claims 1-4, wherein the Component (1) Silicone Hydrophobic Agents comprising silane oligomers, Preferably, selected from a group consisting of butyltrimethoxysilane, butyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, isooctyltrimethoxysilane, isooctyltriethoxysilane oligomers thereof; And/or the aforesaid silane oligomers with a viscosity of 3-1000 mm2/s, 25℃, more preferably with viscosity of 3-500 mm2/s, 25℃, further preferably with viscosity of 3-300 mm2/s, 25℃.
  6. The composition according to any of Claims 1-5, wherein the composition comprising 20-80 wt%of Component (1) and 20-80 wt%of Component (2) , preferably 30-70wt%of Component (1) and 30-70wt%of Component (2) , more preferably 40-60wt%of Component (1) and 40-60wt%of Component (2) , based on 100wt%of the composition; and/or the weight ratio of Component (2) to Component (1) is selected from 0.01-80, preferably 0.02-20, more preferably 0.03-1.5; and/or Component (1) Silicone Hydrophobic Agents and Component (2) Polyether-modified Polysiloxane of formula I account for at least 20 wt%of the total weight of the composition, preferably at least 40 wt%, more preferably at least 50 wt%, such as 55%, 60%, 65%, 70%, 75%, 80%, based on 100wt%of the composition.
  7. The composition according to any of Claims 1-6, wherein the Component (2) with a viscosity of 50-700 mm 2 /s, 25℃, more preferably with viscosity of 100-500 mm 2 /s, 25℃, further preferably with viscosity of 150-400 mm 2 /s, 25℃.
  8. The waterproof composition comprising 20-60 wt%composition according to any of Claims 1-7, 35-75 wt%water, and 0.1-5 wt%emulsifier; preferably 30-55 wt%composition according to any of Claims 1-7, 40-65 wt%water, and 0.1-5 wt%emulsifier; more preferably 35-50 wt%composition according to any of Claims 1-7, 40-65 wt%water, and 0.1-5 wt%emulsifier.
  9. The waterproof composition comprising 10-50 wt%composition according to any of Claims 1-7 and 50-90 wt%solid carriers; preferably 15-40 wt%composition according to any of Claims 1-7 and 60-85 wt%solid carriers; more preferably 20-30 wt%composition according to any of Claims 1-7 and 70-80 wt%solid carriers.
  10. Use of the composition according to any of Claims 1-9 for mass hydrophobization of the cement-based materials.
  11. Use of the composition according to any of Claims 1-9 for mass hydrophobization of the cement-based materials to reduce the strength loss.
  12. Waterproof cement-based materials comprising the composition according to any of Claims 1-9 at an active ingredient dosage of 0.1-3wt%by mass of total cement, preferably 0.1-2wt%, preferably from 0.1%to 1%, the active ingredient comprises Component (1) Silicone Hydrophobic Agents and Component (2) Polyether-modified Polysiloxane of formula I.
  13. Waterproof cement-based materials according to Claim 12, wherein the Component (1) Silicone Hydrophobic Agents and Component (2) Polyether-modified Polysiloxane of formula I account for at least 95 wt%, preferably at least 98 wt%, more preferably at least 99 wt%of the total weight of active ingredients.
  14. Waterproof cement-based materials according to Claim 12 or 13 have the Rate of Decrease in 24h Water Absorption of higher than 72%and Retention of Compressive Strength-28d higher than 80%based on Blank without water-repellent admixtures, tested according to JGJ/T 70-2009.

Description

Organosilicon Compositions Field of the Invention The present disclosure relates to water-repellent material, especially relates to use of Organosilicon Compositions for mass hydrophobization of cement-based materials. Background of the Invention Inorganic building materials such as concrete and mortar have many micropores and capillaries which are easily penetrated by moisture and water, causing damage to the structure of the building such as steel corrosion, freeze-thaw damage, alkali-aggregate reaction, etc., seriously affecting its service life. It is therefore necessary to provide waterproof protection to the building surface. Silicon-organic compounds have long been used in building protection because of their excellent impregnating effect to repel water and dirt, their environmental friendliness, and their physiological acceptability. Silicon-organic compounds have long been used in building protection because of their excellent impregnating effect to repel water and dirt, their environmental friendliness, and their physiological acceptability. Customary impregnants contain alkoxysilanes having a hydrophobic alkyl group, with alkyl groups having 8 carbon atoms, in particular n-octyl groups or 1, 4, 4-trimethylpentyl groups, being particularly widely used. Typical representatives of such hydrophobicizing silanes are n-octyltriethoxysilane and 1, 4, 4-trimethylpentyltriethoxysilane. Most commercially available compositions for hydrophobicizing building materials contain not only the abovementioned silanes but also further silicon-organic compounds, in particular methyl silicone resins, linear polydimethylsiloxanes or else linear polydimethylsiloxanes modified with, for example, amino groups. The corresponding mixtures can be applied neat, as a solution in an organic solvent or as aqueous emulsion. In principle, a distinction can be made between two application forms. In the first, an existing construction, e.g. a concrete bridge, a house or a roof tile is subsequently hydrophobicized by means of a coating formulation. Here, the coating material applied can also penetrate into the substrate, at least in the case of porous building materials, and thus produce at least a certain effect at depth. In contrast to paints or varnishes applied exclusively to the surface, minor surface damage does not inevitably lead to a loss of the  hydrophobic protective effect. However, greater damage or drilled holes, cut edges, sawn or broken edges lead to a loss of the protective effect at the places concerned in the case of exclusively surface-impregnated materials. While subsequent surface hydrophobization is usually the only practical impregnation method for existing constructions, in the production of components based on hydraulic binders, e.g. concrete or fibrocement, the hydrophobicizing agent can be added before the setting process. This bulk hydrophobization, also known as mass hydrophobization, has the advantage that in this way the entire volume of the component and not only the surface thereof is provided with water-repellent protection. The protective action is thus not lost when the component is damaged or intentionally sawn or provided with drilled holes. In addition, bulk hydrophobization saves the additional working step of subsequent coating of the cured component. CN112939512A discloses a dry powder waterproofing agent for bulk hydrophobization of cement-based materials by addition prior to cement curing, which adds polyether trisiloxane to improve the dispersion of the stearate. However, its hydrophobic effect is not as satisfactory as that of silane waterproofers. CN1106363C discloses a process to produce integrally waterproofed concrete in which an aqueous hydrolysable emulsion comprising organosilicon compounds is added before curing to the fresh concrete mix prepared from water, inorganic and optionally organic constituents, which emulsion contains at least one alkoxysilane and optionally an organosilicon compound acting as a surfactant. Although these organosilicon agents show excellent ability in mass hydrophobization, it will reduce the strength of concrete with higher content for lower strength, because organosilicon delays the hydration process of concrete. To balance the strength of the concrete, it is necessary to reduce the dosage of organosilicon agents in cement-based materials. meanwhile, their waterproofing properties do not perform at optimum levels. There is a lack of a silicone-based hydrophobic agent on the market that can guarantee the strength of building substrates such as cement mortar and achieve a further breakthrough in waterproofing performance. Due to its amphiphilicity, Polyether-modified Polysiloxane is used as a surfactant in a wide range of applications, but there is no research or application of Polyether-modified Polysiloxane as a hydrophobic agent. Polyether-modified silanes are listed in  CN1106363C as a surfactant for silicone waterproofing emulsio