Fluoroalkyl-functional organopolysiloxane-containing compositions based on water, a process for their preparation and their use

A method of simultaneously hydrophobizing and oleophobizing surfaces, metals, plastics and mineral building materials, comprising:

• treating surfaces, metals, plastics, and mineral building material with an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-2 (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V
• R.sup.3 --Si(OR).sub.3 (V):
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water;
• which provides a dirt and color repellent effect.

A method of protecting buildings and facades, comprising:

• treating buildings or facades with an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.3 {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.c (I),
• wherein A is an aminoalkyl group of formula II;
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono- oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0, and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water.

A method of coating glass fibers, comprising:

• coating glass fibers with an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.3 {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.c (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or pentfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water.

A method of silanizing fillers and pigments, comprising:

• treating fillers or pigments with an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3 O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.c (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-i, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3 (OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --SI(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water.

A method of improving the rheological properties of polymer dispersions and emulsions, comprising:

• adding an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.3 {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I)
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono- oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group. R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3) (OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water;
• to polymer dispersions and emulsions.

A method of hydrophobizing and oleophobizing textiles, leather, cellulose and starch products, comprising:

• treating textiles, leather, cellulose and starch products with an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.3 {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.c (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water;
• and achieving a dirt- and color-repellent effect.

A method of releasing one surface from another, comprising:

• treating contacting surfaces with an aqueous organopolysiloxane-containing composition comprising organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g =0 if f=0 and g=1 if f>0, 0 .ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group. R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water;
• as a release agent.

A method of formulating a polymer composition, comprising:

• incorporating an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-2 (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water as a cross-linking agent in the composition.

A method of preparing a paint or coating formulation, comprising:

• incorporating an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y O}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1:
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group. R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3, in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R, in each case is identical or different, and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water in a paint or coating formulation.

A method of promoting adhesion of an adhesive substance, comprising:

• incorporating an aqueous organopolysiloxane-containing composition comprising:
• organopolysiloxanes of formula I:
• HO{Si(A)(CH.sub.3).sub.z (OH).sub.1-z O}.sub.a {Si(B)(R.sup.2).sub.y (OH).sub.1-y)}.sub.b {Si(C)(CH.sub.3)O}.sub.c {Si(D)(OH)O}.sub.d H.(HX).sub.e (I),
• wherein A is an aminoalkyl group of formula II:
• H.sub.2 N(CH.sub.2).sub.f (NH).sub.g (CH.sub.2).sub.h Si(OR).sub.3-z (CH.sub.3).sub.z (II),
• in which 0.ltoreq.f.ltoreq.6, g=0 if f=0 and g=1 if f>0, 0.ltoreq.h.ltoreq.6 and 0.ltoreq.z.ltoreq.1;
• B is a fluoroalkyl group of formula III:
• R.sup.1 --Y--(CH.sub.2).sub.2 Si(R.sup.2).sub.y (OR).sub.3-y(III),
• wherein R.sup.1 is a mono-, oligo- or perfluorinated alkyl group having 1-9 C atoms or a mono-, oligo- or perfluorinated aryl group, Y is a CH.sub.2, O or S group, R.sup.2 is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group and 0.ltoreq.y.ltoreq.1;
• C is an alkyl group of formula IV:
• R.sup.3 --Si(CH.sub.3)(OR).sub.2 (IV),
• and D is an alkyl group of formula V:
• R.sup.3 --Si(OR).sub.3 (V)
• wherein R.sup.3 in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms, and R in each case is identical or different and is a linear, branched or cyclic alkyl group having 1-8 C atoms or an aryl group;
• and wherein HX is an acid, wherein X is an inorganic or organic acid radical, and 0.ltoreq.y.ltoreq.1, 0.ltoreq.z.ltoreq.1, a>0, b>0, c.gtoreq.0, d.gtoreq.0, e.gtoreq.0 and (a+b+c+d).gtoreq.2, the composition being essentially free from organic solvents, having a flash point of more than 70.degree. C. and liberating essentially no alcohols by hydrolysis on dilution with water into an adhesive formulation.