Water-and oil-repellency imparting urethane oligomers comprising perfluoroalkyl moieties

• US 6,803,109 B2
• Filed: 03/09/2001
• Issued: 10/12/2004
• Est. Priority Date: 03/09/2001
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Qiu, Zai-Ming, Fan, Wayne W., Clark, John C.
• Primary Examiner(s): Trinh, Ba K.
• Assistant Examiner(s): OH, TAYLOR V
• Application Number:
  US09/803,702
• Publication Number:
  US 20030026997A1
• Time in Patent Office: 1,313 Days
• Field of Search: 525/123, 525/199, 525/276, 428/423.1, 428/411.1, 428/357, 428/289, 428/290, 428/365, 428/391, 428/395, 428/231.1, 560/158, 526/243, 526/248, 526/242, 526/245, 523/200, 524/539, 524/168, 524/462, 528/45, 528/70, 427/176, 427/389.4, 252/8.75, 252/8.8, 252/8.62, 556/421, 564/38, 546/292, 548/305, 548/306
• US Class Current: 428/423.1
• 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 41/4842 Fluorine-containing polymers
• CPC Class Codes: C04B 41/4884 Polyurethanes; Polyisocyanates
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C08G 18/3821 Carboxylic acids; Esters thereof with monohydroxyl compounds
• CPC Class Codes: C08G 18/3861 containing sulfonamide and/or sulfonylhydrazide groups
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/765 alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• CPC Class Codes: C08G 18/7831 containing biuret groups
• CPC Class Codes: C08G 18/8077 Oximes
• CPC Class Codes: C09D 175/04 Polyurethanes
• CPC Class Codes: D06M 13/428 containing fluorine atoms
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D06M 2200/11 Oleophobic properties
• CPC Class Codes: D06M 2200/12 Hydrophobic properties
• CPC Class Codes: Y10T 428/31551 Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]

Abstract

Fluorochemical urethane compositions comprising one or more compounds or oligomers having at least on fluorine-containing repeatable unit and at least one fluorine-containing terminal group are described. The compositions are useful as coatings or incorporated as melt additives. The fluorochemical compositions impart oil and water repellency to the substrate. In other aspects, this invention relates to processes for imparting oil and water repellency characteristics to substrates and articles.

Claims

1. Fluorochemical urethane composition comprising:

one or more oligomers comprising (i) at least one fluorine-containing repeatable unit and (ii) at least one fluorine-containing terminal group, and wherein said oligomers comprise the condition reaction product of;

(a) one or more fluorinated polyols;

(b) one or more polyisocyanates; and

(c) one or more monofunctional fluorine-containing compounds having one functional group that is reactive with the hydroxyl group of said polyol (a) or with the isocyanate group of the polyisocyanate (b).

2. The fluorochemical urethane composition of claim 1 further comprising the reaction product of one or more water-solubilizing compounds having one or more water solubilizing groups and at least one electrophilic or nucleophilic moiety, said solubilizing groups independently pendant from the repeatable unit, or the terminal group.

3. The fluorochemical urethane composition of claim 2 wherein said water-solubilizing group is selected from the group consisting of carboxylate, sulfate, sulfonate, phosphonate, ammonium, and quaternary ammonium groups.

4. The fluorochemical urethane composition of claim 1 further comprising the reaction product of one or more polymerizable compounds having one or more polymerizable groups and at least one electrophilic or nucleophilic moiety, said polymerizable groups independently pendant from the repeatable unit, or the terminal group.

5. The fluorochemical urethane composition of claim 4, wherein said polymerizable groups are selected from the group consisting of acrylate, methacrylate, vinyl, allyl, and glycidyl groups.

6. The fluorochemical urethane composition of claim 1 having the formula

7. The fluorochemical urethane composition of claim 6,

wherein Q is selected from the following structures, wherein each k is independently an integer from 0 to about 20, R₁′

is hydrogen, phenyl, or alkyl of 1 to about 4 carbon atoms, an R₂′

is alkyl of 1 to about 20 carbon atoms;

—

SO₂NR₁′

(CH₂)_kO(O)C—

, —

CONH₁′

(CH₂)_kO(O)C—

, —

(CH₂)_kO(O)C—

,

—

CH₂CH(OR₂′

)CH₂O(O)C—

, —

(CH₂)_kC(O)O—

, —

(CH₂)_kSC(O)—

,

—

(CH₂)_kO(CH₂)_kO(O)C—

, —

(CH₂)_kS(CH₂)_kO(O)C—

, —

(CH₂)_kSO₂(CH₂)_kO(O)C—

,

—

(CH₂)_kS(CH₂)_kOC(O)—

, —

CH₂)_kSO₂NR₁′

(CH₂)_kO(O)C—

, —

(CH₂)_kSO₂—

,

—

SO₂NR₁′

)CH₂)_kO—

, —

SO₂NR₁′

(CH₂)_k—

, —

(CH₂)_kO(CH₂)_kC(O)O—

,

—

(CH₂)_kSO₂NR₁′

(CH₂)_kC(O)O—

, —

, (CH₂)_kSO₂(CH₂)_kC(O)O—

, —

CONR₁′

(CH₂)_kC(O)—

—

(CH₂)_kS(CH₂)_kC(O)O—

, —

CH₂CH(OR₂′

)CH₂C(O)O—

, —

SO₂NR₁′

(CH₂)_kC(O)O—

,

—

(CH₂)_kO—

, —

C_kH_2k—

OC(O)NH—

, —

C_kH_2k—

NR₁′

C(O)NH—

, —

OC(O)NR′

(CH₂)_k—

,

—

(CH₂)_kNR₁′

— and

—

(CH₂)_kNR₁′

C(O)O—

,

8. The fluorochemical urethane composition of claim 1 comprising oligomers of the Formula:

9. The fluorochemical urethane composition of claim 1 wherein the oligomer comprises the condensation reaction product of one or more fluorinated polyols, one or more non-fluorinated polyols, one or more polyisocyanates and one or more monofunctional fluorine-containing compounds.

10. The fluorochemical urethane composition of claim 1 wherein the oligomer comprises the condensation reaction product of one or more fluorinated polyols, an excess amount (relative to the polyol) of one or more linear alkylene diisocyanates, and sufficient fluorinated monoalcohols to react with the terminal isocyanate groups.

11. The fluorochemical urethane composition of claim 1 wherein the fluorine containing group of said fluorinated polyol is a perfluoroalkyl group of 1 to 12 carbon atoms.

12. The fluorochemical urethane composition of claim 1 wherein the fluorine containing group of said fluorinated polyol is a perfluoroalkyl group of 3 to 5 carbon atoms.

13. The fluorochemical urethane composition of claim 1 wherein the fluorine containing group of said fluorinated polyol is a perfluorobutyl group.

14. The fluorochemical urethane composition of claim 1 wherein the monofunctional fluorine-containing compound is a compound of the following formula:

15. The fluorochemical urethane composition of claim 14 wherein Q′

of said monofunctional fluorine-containing compound is select from hydroxyl, secondary amino, oxazolinyl, oxazolonyl, acetyl, acetonyl, carboxyl, isocyanato, epoxy, aziridinyl, thio, and acyl halide groups.

16. The fluorochemical urethane composition of claim 1 wherein said fluorochemical oligomer further comprises the reaction product of one or more non-fluorinated polyols.

17. A coating composition comprising a mixture comprising:

(a) a solvent; and

(b) the fluorochemical urethane composition of claim 1.

18. The coating composition of claim 17 wherein the fluorochemical urethane composition further comprises one or more water-solubilizing groups.

19. The coating composition of claim 18 wherein said mixture comprises an aqueous solution, dispersion or suspension.

20. An article comprising:

(a) a substrate having one or more surfaces; and

the fluorochemical urethane composition of claim 1 coated on one or more surfaces of said substrate.

21. The article of claim 20 wherein the fluorochemical urethane composition further comprises one or more water-solubilizing groups.

22. The article of claim 20 wherein the fluorochemical urethane composition further comprises one more polymerizable groups.

23. The article of claim 20 wherein the substrate is selected from the group consisting of hard substrates and fibrous substrates.

24. A method of imparting repellency to a substrate, having one or more surfaces, comprising the steps of:

applying the coating composition of claim 17 onto one or more surfaces of said substrate; and

curing the coating composition at ambient or elevated temperature.

25. A polymer composition comprising:

(a) the fluorochemical composition of claim 1; and

(b) at least one thermoplastic or thermoset polymer.

26. The composition of claim 25 wherein said thermoplastic polymer is selected from the group consisting of polypropylene, polyethylene, polyacrylates, polymethacrylates, copolymers of ethylene and one or more alpha-olefins, polyesters, polyurethanes, polycarbonates, polyetherimides, polyimides, polyetherketones, polysulfones, polystyrenes, ABS copolymers, polyamides, fluoroplastics, and blends thereof;

and said thermoset polymer is selected from the group consisting of polyurethanes, epoxy resins, fluoroelastomers, polyacrylates, polymethacrylates, and unsaturated polyesters, and blends thereof.

27. The composition of claim 25 wherein said composition is prepared by melt blending the fluorochemical composition and the thermoplastic polymer.

28. A shaped article comprising the polymer composition of claim 25, wherein said shaped article is selected from fibers, films, and molded articles.

29. A process for preparing shaped article comprising the steps of:

(a) combining the fluorochemical urethane composition of claim 1 and at least one thermoplastic polymer, and

(b) melt processing the resulting combination.