Anionic/cationic masonry sealing systems

• US 20060047032A1
• Filed: 09/01/2004
• Published: 03/02/2006
• Est. Priority Date: 09/01/2004
• Status: Abandoned Application

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Miller, Chandra Tier, Corman, Faye Michelle
• Application Number:
  US10/931,848
• Publication Number:
  US 20060047032A1
• Time in Patent Office: Days
• US Class Current: 524/127
• CPC Class Codes: C08K 5/521 Esters of phosphoric acids, e.g. of H3PO4
• CPC Class Codes: C08K 5/527 Cyclic esters
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 27/22 modified by chemical after-treatment

Abstract

A composition comprising a mixture, having a maximum molar ratio of acid to base of 0.6 and providing water repellency when applied to a substrate surface without etching of said surface, of A) an anionic aqueous fluoroalkyl phosphate solution which provides at least about 75% of the total fluorine content of said composition, and B) a cationic copolymer of fluoroalkyl(meth)acrylate or perfluoroalkylether(meth)acrylate present at a minimum of 0.3 g per 100 g of said composition.

Claims

1. A composition comprising an aqueous first mixture, having a maximum molar ratio of acid to base of 0.6 and providing water repellency when applied to a substrate surface without etching of said surface, of

A. an anionic aqueous fluoroalkyl phosphate solution which provides at least about 75% of the total fluorine content of said first mixture comprising

a second mixture of mono(perfluoroalkyl) phosphate and bis(perfluoroalkyl) phosphate of Formula IA,

[R_f—

(O)_j]_x—

P(O)—

O⁻

X⁺)_(3-x) 

 

Formula 1A

wherein;

R_f is selected from the group consisting of

F(CF₂CF₂)_d(CH₂)_a—

,

F(CF₂CF₂)_dCH₂CH₂(OCH₂CH₂)_b—

,

F(CF₂CF₂)_d—

,

F(CF₂CF₂)_dCH═

CH(CH₂)C—

, and

C₈F₁₇SO₂N(R₅)CH₂CH₂—

;

a is from about 2 to about 10,

b is from about 3 to about 20,

c is from about 2 to about 20,

d is 1 to about 8, or a mixture thereof,

R₅ is H or an aliphatic group containing 1 to about 4 carbon atoms,

x is from about 1 to about 2,

j is 1 or 0, or a mixture thereof, and

X is hydrogen or M,

M is an ammonium ion, an alkali metal ion, or an alkanolammonium ion, or

2) a phosphate of the structure of Formula IB

wherein

R_f′

is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from about 2 to about 20 carbon atoms,

R⁶ is an alkylene group having from 1 to about 8 carbon atoms,

Z is —

O—

, —

S—

, or —

NH—

, and

M is as defined above in Formula IA, and

B. a cationic fluoroalkyl(meth)acrylate or perfluoroalkylether (meth)acrylate copolymer present at a minimum of 0.3 g per 100 g of said first mixture, and comprising monomers copolymerized in the following percentages by weight;

(a) from about 40% to about 92% of at least one monomer of formula 2A

R_f-Q-A-C(O)—

C(R₇)═

CH₂ 

 

2A

wherein;

R_f is a fluoroaliphatic group having a linear or branched perfluorocarbon chain having from about 2 to about 20 carbon atoms,

R₇ is H or an aliphatic group containing 1 to about 4 carbon atoms,

A is O, S or NR¹ wherein R¹ is H or an alkyl of 1 to about 4 carbon atoms, and

Q is alkylene of 1 to about 15 carbon atoms, hydroxyalkylene of 3 to about 15 carbon atoms, —

(C_nH_2n)(OC_qH_2q)_m—

, —

SO₂—

NR¹(C_nH_2n)—

, or —

CONR¹(C_nH_2n)—

, wherein R¹ is H or alkyl of 1 to about 4 carbon atoms, n is 1 to about 15, q is 2 to about 4, and m is 1 to about 15; and

R is hydrogen or a C1 to about C2 alkyl group,

(b) from about 1% to about 50% of a monomer of formula 2B

(CH₂═

C(R₇)COW(CH₂)_r+NR²R³R⁴)Y⁻

 

 

2B

wherein

R₇ is H or an aliphatic group containing 1 to about 4 carbon atoms,

R² and R³ are each independently alkyl of 1 to about 4 carbon atoms, hydroxyethyl, or benzyl or R² and R³ together with the nitrogen atom form a morpholine, pyrrolidine, or piperidine ring,

R⁴ is H or alkyl of 1 to about 4 carbon atoms or R², R³, and R⁴ together with the nitrogen form a piperidine ring,

W is —

O—

or —

NR⁴—

r is 2 to 4, and

Y⁻

is an anion,

provided that the nitrogen is from about 40% to 100% quaternized; and

(c) from 0% to about 20% of an anionic monomer or a monomer which is potentially anionic by varying the pH;

(d) from about 0% to about 10% of a vinyl derivative of formula 2C

R₈—

CH═

CH₂ 

 

2C

wherein

R₈ is an alkyl carboxylate or alkyl ether group containing from 1 to about 18 carbon atoms; and

(e) from 0 to about 25% of at least one monomer of formula 2D

CH₂═

C(R₉)—

C(O)—

O—

V—

OH 

 

2D

wherein

R₉ is H or an alkyl of 1 to about 4 carbon atoms, and

V is an alkylene of from about 2 to about 4 carbon atoms; and

(f) from 0 to about 30% of any monomer other than the monomers of components (a) to (e) described above;

provided that the weight percents for components (a) to (f) described above total 100%.

2. The composition of claim 1 wherein the fluoroalkyl phosphate solution of component A is a mixture of mono(perfluoroalkyl) phosphate and bis(perfluoroalkyl) phosphate of Formula IA.

3. The composition of claim 2 wherein the fluoroalkyl phosphate solution of component A is a mixture of perfluoroalkylethyl phosphate diethanolamine salts.

6. The composition of claim 1 which provides stain resistance when applied to a substrate surface.

7. The composition of claim 1 further comprising a microbicide.

8. The composition of claim 1 wherein the fluoroalkyl phosphate solution provides about 80% of the total fluorine content.

9. The composition of claim 1 wherein the total fluorine content is from about 0.25 to about 7.5 percent by weight.

10. A process for the preparation of a composition of claim 1 comprising 1) addition of water to a dispersion of the cationic copolymer of component B and mixing to yield a diluted copolymer, 2) addition of the anionic fluoroalkyl phosphate solution of component A to the diluted copolymer of component B, and 3) mixing or homogenizing.

11. The process of claim 10 wherein the amount of water added to component B per 100 g of composition is equal to 100 minus the total weight of component A and component B.

12. A method of treating a substrate comprising application to the surface of the substrate of a composition of claim 1.

13. The method of claim 12 wherein the composition is applied as a first coating followed by at least one additional coating.

14. The method of claim 13 wherein the additional coating is applied prior to the first coating becoming dry.

15. The method of claim 12 wherein the substrate is a composition containing calcium carbonate.

16. The method of claim 12 wherein the substrate is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials such as terrazzo, gypsum board, marble, statuary, monuments, or wood.

17. A substrate treated with the composition of claim 1.

18. The substrate of claim 17 which is a composition containing calcium carbonate.

19. The substrate of claim 17 which is unglazed concrete, brick, tile, stone, granite, limestone, grout, mortar, composite materials such as terrazzo, gypsum board, marble, statuary, monuments, or wood.

20. The substrate of claim 17 which after treatment has water repellency, oil repellency and stain resistance.

4. The composition of claim 4 wherein the copolymer of component B is a copolymer prepared by copolymerization of formula 2A and formula 2B.

5. The composition of claim 4 wherein component B is a copolymer of perfluoroalkylethyl(meth)acrylate, and dimethylaminoethyl(meth)acrylate.