Fluoride-modified additive for cementitious products, process for its preparation and use thereof

A fluoromodified admixture for cementitious products comprising

• (i) a1) 1 to 100 parts by weight of at least one fluoromodified (polymeric) hydrophobization and oleophobization component (A) having a polymer bound fluorine content of 0.5 to 90% by weight a (blocked) isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic isocyante group or an aromatic isocyanate group, and a molecular mass of 275 to 100,000 Dalton of at least one of formula (I)
• [CF3—(CF2)x—(CH2)y]m—R1—(NCO)n (I),
• formula (II)
• [CF3—(CF2)x—(CH2)y—O-Az]m-R1—(NCO)n (II),
• or formula (III)
• [CF3—CF2—CF2—(O—CF(CF3)—CF2)x—O—CF(CF3)]m—R1—(NCO)n (III);
• wherein
• x is from 3 to 20;
• y is from 1 to 6;
• z is from 1 to 100;
• m is from 1 to 3;
• n is from 1 to 6;
• R1 is at least one of an inorganic or organic, (cyclo)aliphatic or aromatic radical and has from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms and 0 to 100 Si atoms;
• A is CRiRii—(CRiiiRiv)p—O,
• Ri, Rii, Riii, Riv are independently selected from H, a (cyclo)aliphatic or aromatic organic radical having 1 to 20 C atoms, and p is 1 to 20, wherein the polyalkylene oxide structural unit Az is a homopolymer, copolymer or block copolymer of an alkylene oxide;
• and
• b1) 1 to 100 parts by weight of at least one water-emulsifiable or water-soluble (polymeric) hydrophilization component (B) having a polymer bound ethylene oxide content of 0.5 to 90% by weight, an isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic isocyante group or an aromatic isocyanate group, and a molecular mass of from 101 to 100,000 Dalton of formula (IV)
• (R3—O-Az′)m′-R2—(NCO)n′ (IV)
• wherein
• z′ is from 1 to 50;
• m′ is from 1 to 3;
• n′ is from 1 to 6;
• R2 is at least one of an inorganic or organic, (cyclo)aliphatic or aromatic radical having from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms and from 0 to 100 Si atoms;
• R3 is from H, a (cyclo)aliphatic or aromatic organic radical having 1 to 20 C atoms;
• and optionally
• c1) 1 to 100 parts by weight of at least one fluoromodified and amphiphilic (polymeric) hydrophobization and oleophobization component (C) having a polymer bound fluorine content of 0.5 to 90% by weight, a polymer bound ethylene oxide content of 0.5 to 90% by weight, a (blocked) isocyanate content of 0.5 to 50% by weight, at least one of a (cyclo)aliphatic or aromatic isocyanate group and a molecular mass of from 275 to 100,000 Dalton of formula (V);
• [(CF3—(CF2)x—(CH2)y)]m(R3—O-Az′)m′-R4—(NCO)n″ (V),
• or formula (VI)
• [(CF3—(CF2)x—(CH2)y)—O-Az]m(R3—O-Az′)m′-R4—(NCO)n″ (VI),
• or formula (VII)
• [CF3—CF2—CF2—(O—CF(CF3)—CF2)x—O—CF(CF3)]m(R3—O-Az′)m′-R4—(NCO)n″ (VII);
• wherein
• n″ is from 1 to 6,
• R4 is an inorganic or organic, (cyclo)aliphatic or aromatic radical having from 1 to 100 C atoms, from 0 to 100 N atoms, from 0 to 100 O atoms or and from 0 to 100 Si atoms;
• and
• R3, m, m′, x, y and Az′ are as defined above,
• and optionally
• d1) from 1 to 50 parts by weight of at least one polyisocyanate component (D), comprising at least one diisocyanate, polyisocyanate, polyisocyanate derivative or polyisocyanate homolog having two or more of (cyclo)aliphatic or aromatic isocyanate groups, or both (cyclo)aliphatic and aromatic isocyanate groups, and a molecular mass of 100 to 2,500 Dalton,
• or
• (ii) a2) from 1 to 100 parts by weight of at least one component (A), and
• c2) from 1 to 100 parts by weight of at least one component (C), and
• d2) optionally from 1 to 50 parts by weight of at least one component (D),
• or
• (iii) b3) from 1 to 100 parts by weight of at least one component (B), and
• C3) from 1 to 100 parts by weight of at least one component (C), and
• d3) optionally from 1 to 50 parts by weight of at least one component (D),
• or
• (iv) c4) from 1 to 100 parts by weight of at least one component (C), and
• d4) 1 to 50 parts by weight of at least one component (D),
• and
• e) from 0 to 100 parts by weight of at least one water-emulsifiable, hydrophobic or amphiphilic antiefflorescence component (E), comprising 10 to 90% by weight of a (polymer) bound fatty acid ester having two or three hydroxyl groups based on (un)saturated fatty acids and (cyclo)aliphatic or aromatic epoxy resins or polyepoxides having two or three epoxy groups reactive to fatty acids and a molecular mass of from 500 to 50,000 Dalton or a 1,2-dihydroxyalkanediol having from 5 to 50 carbon atoms having two hydroxyl groups reactive to polyisocyanates and 90 to 10% by weight of further polymer bound constituents,
• f) from 0 to 50 parts by weight of a catalyst component (K),
• g) from 0 to 50 parts by weight of a solvent component (L), and
• h) from 0 to 50 parts by weight of a formulation component (F):
• wherein the fluoromodified admixture has a mean isocyanate functionality <3, a content of aliphatic or (cyclo)aliphatic isocyanate groups of 0.1 to 10% by weight, a content of at least one of urethane groups or urea groups of 2.5 to 25% by weight, a polymer bound fluorine content of 0.5 to 60% by weight and a content of ethylene oxide monomers bound within polyether chains of 30 to 90% by weight.