Water-soluble fluorochemical polymers for use in water and oil repellent masonry treatments

• US 6,037,429 A
• Filed: 06/16/1995
• Issued: 03/14/2000
• Est. Priority Date: 06/16/1995
• Status: Expired due to Fees

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Savu, Patricia M., Linert, Jeffrey G.
• Primary Examiner(s): Reddick, Judy M.
• Application Number:
  US08/491,232
• Time in Patent Office: 1,733 Days
• Field of Search: 526/240, 526/241, 526/243, 526/242, 526/245, 526/248, 526/279, 526/246, 526/247
• US Class Current: 526/243
• CPC Class Codes: C04B 2111/203 Oil-proof or grease-repellant materials
• CPC Class Codes: C04B 2111/27 Water resistance, i.e. waterproof or water-repellent materials
• CPC Class Codes: C04B 28/02 containing hydraulic cements other than calcium sulfates
• CPC Class Codes: C04B 41/009 characterised by the material treated
• CPC Class Codes: C04B 41/4535 applied as a solution, emulsion, dispersion or suspension
• CPC Class Codes: C04B 41/4842 Fluorine-containing polymers
• CPC Class Codes: C04B 41/4922 applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
• CPC Class Codes: C04B 41/502 Water
• CPC Class Codes: C04B 41/63 Macromolecular compounds
• CPC Class Codes: Y10T 428/1376 Foam or porous material containing
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated
• CPC Class Codes: Y10T 428/31993 Of paper

Abstract

In one aspect, the present invention provides a water-soluble and shelf-stable aqueous fluorochemical polymeric treatment useful to treat porous substrates to render them repellent to water- and oil-based stains. The treatment comprises a water-soluble fluorochemical polymer containing only carbon atoms in the backbone, with a plurality of each of the following groups pendent from the backbone: (a) fluoroaliphatic groups, (b) carboxyl-containing groups, (c) oxyalkylene or polyoxyalkylene groups, and, optionally, (d) silyl groups.

Claims

1. A water-soluble fluorochemical polymer containing only carbon atoms in the backbone and consisting essentially of interpolymerized units of (a) 40 to 80 weight percent of monomers containing fluoroaliphatic groups, (b) 5 to 50 weight percent of monomers containing carboxyl-groups, (c) 5 to 50 weight percent of monomers containing oxyalkylene or polyoxyalkylene groups, and (d) 1 to 20 weight percent of monomers containing silyl groups.

2. The water-soluble fluorochemical polymer of claim 1 consisting essentially of monomer units having the formula:

##STR2## wherein;

R is hydrogen or an aliphatic group having from 1 to 4 carbon atoms;

R_f is a fluoroaliphatic group having a perfluorinated carbon chain from 3 to 20 carbon atoms in length;

R¹ is an organic divalent connecting group;

X is independently selected from the group consisting of oxygen, nitrogen, and sulfur;

R² is a short chain alkylene group;

m is 0 or 1;

M⁺ is a mono- or multivalent cation;

R_OA is an oxyalkylene- or polyoxyalkylene-containing group;

R³ is an organic divalent connecting group;

R⁴ is hydrogen, or a methyl, ethyl, or butyl group; and

a, b, c, and d are ≧

1.

3. The polymer of claim 2 wherein:

R¹ is selected from the group consisting of --C_y H_2y --, --CON(R⁵)C_y H_2y --, --SO₂ N(R⁵)C_y H_2y --, and --C_y H_2y SO₂ N(R⁵)C_y H_2y --, where R⁵ is hydrogen, or a methyl, ethyl, propyl, or butyl group and y is an integer equal to or between 1 and 6;

R_OA is an oxyalkylene or a polyoxyalkylene group of the formula --(C₂ H₄ O)_p (C₃ H₆ O)_q (C₄ H₈ O)_r R⁶ where R⁶ is hydrogen or an alkyl group having from 1 to 4 carbon atoms or an aryl group and where p, q, or r can be zero, but their sum, p+q+r, must be a number greater than or equal to 1; and

R³ is a methyl, ethyl, propyl, or butyl group.

4. The polymer of claim 2 wherein the polymer has a number average molecular weight between about 3500 and about 30,000 and a molecular weight distribution of greater than 1.5.

5. The water-soluble fluorochemical polymer of claim 1 wherein said monomers containing fluoroaliphatic groups comprise 50 to 70 percent by weight, the monomers containing carboxyl groups comprise 5 to 25 percent by weight, the monomers containing oxyalkylene or polyoxyalkylene groups comprise 5 to 35 percent by weight, and the monomers containing silyl groups comprise 2 to 15 percent by weight, of said polymer.