Aqueous dispersions of fluorinated polyurethanes and their use for textile coatings

• US 4,983,666 A
• Filed: 01/22/1990
• Issued: 01/08/1991
• Est. Priority Date: 12/30/1986
• Status: Expired due to Term

• Current Assignee: Solvay Solexis SPA (Solvac SA)
• Original Assignee: Ausimont, S.p.A., Larac S.p.A.
• Inventors: Gambini, Tiziana, Zavatteri, Ignazio
• Primary Examiner(s): Foelak, Morton
• Assistant Examiner(s): Daley, Dennis R.
• Application Number:
  US07/467,324
• Time in Patent Office: 351 Days
• Field of Search: 524/591, 524/439, 524/846, 524/805, 524/832, 524/500, 524/539
• US Class Current: 524/539
• CPC Class Codes: C08G 18/0804 Manufacture of polymers containing ionic or ionogenic groups
• CPC Class Codes: C08G 18/12 using two or more compounds having active hydrogen in the first polymerisation step
• CPC Class Codes: C08G 18/302 Water
• CPC Class Codes: C08G 18/50 having heteroatoms other than oxygen
• CPC Class Codes: C08G 18/5015 having fluorine atoms
• CPC Class Codes: C08G 18/672 Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• CPC Class Codes: D06M 15/576 containing fluorine

Abstract

Aqueous dispersions of fluorinated polyurethanes obtained by the reaction of an organic diisocyanate with a mixture of diols containing ionizable groups and macroglycols comprising polyols and at least 1% by weight of one or more hydroxy- and/or carboxy-capped fluoropolyethers. Said fluorinated polyurethanes are salified, to transform the ionizable groups into hydrophilic cations and/or anions, and are then dispersed in water to be used in textile coatings.

Claims

1. Stable aqueous dispersions of fluorinated polyurethanes containing in their macromolecules hydrophilic ionic groups, both of anionic and cationic character, obtained by the process comprising the steps:

(a) preparing a fluorinated polyisocyanate, by reaction between an organic diisocyanate and a mixture comprising diols containing ionizable groups and macroglycols comprising polyols and at least 1% by weight of one or more hydroxy- and/or carboxy-capped fluoropolyoxyalkylene ethers;

(b) salifying the so-obtained fluorinated polyisocyanate, to convert the ionizable groups into hydrophilic cations or anions; and

(c) dispersing and chain extending the salified fluorinated polyisocyanate in water.

2. Aqueous dispersions according to claim 1, wherein the molar ratio between the isocyanate groups to the sum of the hydroxyl groups is within the range of from 1.2 to 2.

3. Aqueous dispersions according to claim 2, wherein the molar ratio between the isocyanate groups to the sum of the hydroxyl groups is 1.5.

4. Aqueous dispersions according to claim 1, 2 or 3, wherein the macroglycols comprise from 3 to 15% by weight of one or more hydroxy- and/or carboxy-capped fluoropolyoxyalkylene ethers.

5. Aqueous dispersions according to claim 1, 2 or 3, wherein the hydroxy- and/or carboxy-capped fluoropolyoxyalkylene ethers have a molecular weight within the range of from 500 to 7000, preferably of from 1000 to 2500.

6. Aqueous dispersions according to claim 1, 2 or 3, wherein the hydroxy- and/or carboxy-capped fluoropolyoxyalkene ethers are selected from the class consisting of those having the formulae:

##STR3## wherein;

R₁ is selected from --(CH₂)_x --, --(CH₂ O)_y CH₂ --, --(CH₂)_x OCH₂ --, wherein x and y are integers within the range of from 1 to 4;

m and n are integers, wherein the m/n ratio is within the range of from 0.2 to 2, preferably within the range of from 0.5 to 1.2;

R_f is a perfluoroalkylene radical;

X is --F or --CF₃ ;

Y represents an --OH and/or a --COOH group; and

k, j, w, u, d, b, r, c, v, z, a, g are integers which make it possible for the above-mentioned molecular weights to be obtained.

7. Aqueous dispersions according to claim 6, wherein the hydroxy- and/or carboxy-capped fluoropolyoxyalkylene ethers are α

, ω

-bis-(hydroxymethyl)-polyoxyperfluoroalkylene and α

, ω

-(polyoxyperfluoroalkane)-dioic acid, with an average molecular weight of 2,000.

12. Aqueous dispersions according to claim 1, 2 or 3, wherein the salified fluorinated polyisocyanate dispersed in water having a content of solids higher than 20% by weight, preferably within the range of from 30 to 50% by weight.

13. Aqueous dispersions according to claim 1, 2 or 3, wherein the fluorinated polyurethanes contain in their macromolecule ionic groups in an amount within the range of from 10 to 60 milliequivalents per 100 g of polymer, preferably of from 20 to 40 meq/100 g of polymer.

8. Stable aqueous dispersions of fluorinated polyurethanes containing in their macromolecule hydrophilic ionic groups, of either anionic or cationic nature, obtained by the process comprising the following steps:

(i) preparing a fluorinated polyisocyanate prepolymer by reacting an organic diisocyanate with a mixture comprising diols containing ionizable groups and macroglycols comprising polyols and at least 1% by weight one or more hydroxy- and/or carboxy-capped fluoropolyoxyalkylene ethers;

(ii) converting of the fluorinated polyisocyanic prepolymer into an oligo-urethane having unsaturated vinyl end groups, by reacting a compound containing hydroxyl reactive with the isocyanate groups selected from the class consisting of hydroxy-alkyl-acrylates or -methacrylates having the formula;

##STR4## wherein R₂ is hydrogen or a (C₁ -C₄)-alkyl radical and W is a hydroxyalkyl radical;

(iii) salifying of the so-obtained oligo-urethane to convert the ionizable groups into hydrophilic cations or anions;

(iv) dispersing the salified oligo-urethane in water; and

(v) polymerizing the unsaturated end groups of said oligo-urethane dispersed in water.

9. Aqueous dispersions according to claim 8, wherein the hydroxyalkyl-acrylates or -methacrylates are those wherein R is hydrogen or a methyl radical, and W is a 2-hydroxyethyl-, 2-hydroxypropyl-, 3-hydroxypropyl- or 4-hydroxybutyl-radical.

10. Aqueous dispersions according to claim 8, wherein the hydroxyalkyl-acrylates or -methacrylates are used in such a an amount as to have NCO-eq/OH-eq ratios, to the free isocyanate groups present in the polyisocyanic prepolymer, within the range of from 0.5 to 1.1, preferably equal to 1.

11. Aqueous dispersions according to claim 9, wherein the hydroxyalkyl-acrylates or -methacrylates are used in such an amount as to have NCO-eq/OH-eq ratios, to the free isocyanate groups present in the polyisocyanic prepolymer, within the range of from 0.5 to 1.1, preferably equal to 1.