Poly-perfluoroalkyl-substituted alcohols and acids, and derivatives thereof

• US 5,491,261 A
• Filed: 07/01/1994
• Issued: 02/13/1996
• Est. Priority Date: 07/01/1994
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Deisenroth, Ted, Mueller, Karl F., Falk, Robert, Haniff, Marlon
• Primary Examiner(s): EVANS, JOSEPH
• Application Number:
  US08/270,083
• Time in Patent Office: 592 Days
• Field of Search: 562/564, 562/567, 562/568, 562/582, 562/586, 546/302, 546/548, 560/153, 560/179-184, 568/32, 568/45, 568/46, 568/589, 568/649, 568/674, 568/677, 564/203, 564/204, 564/209, 564/442, 564/462, 564/501, 564/504
• US Class Current: 562/582
• CPC Class Codes: C07C 217/28 having one amino group and at least two singly-bound oxygen atoms, with at least one being part of an etherified hydroxy group, bound to the carbon skeleton, e.g. ethers of polyhydroxy amines
• CPC Class Codes: C07C 229/12 to carbon atoms of acyclic carbon skeletons
• CPC Class Codes: C07C 229/16 to carbon atoms of hydrocarbon radicals substituted by amino or carboxyl groups, e.g. ethylenediamine-tetra-acetic acid, iminodiacetic acids
• CPC Class Codes: C07C 229/24 having more than one carboxyl group bound to the carbon skeleton, e.g. aspartic acid
• CPC Class Codes: C07C 271/20 to carbon atoms of hydrocarbon radicals substituted by nitrogen atoms not being part of nitro or nitroso groups
• CPC Class Codes: C07C 305/10 being further substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 323/12 the carbon skeleton being acyclic and saturated
• CPC Class Codes: C07C 43/178 containing hydroxy or O-metal groups
• CPC Class Codes: C07F 9/65742 non-condensed with carbocyclic rings or heterocyclic rings or ring systems
• CPC Class Codes: C08G 18/3275 containing two hydroxy groups
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C08G 18/6775 containing halogen
• CPC Class Codes: C08G 18/73 acyclic
• CPC Class Codes: C08G 18/751 containing only one cycloaliphatic ring
• CPC Class Codes: C14C 9/00 Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
• CPC Class Codes: D06M 15/507 Polyesters
• CPC Class Codes: D06M 15/576 containing fluorine
• CPC Class Codes: D21H 21/16 Sizing or water-repelling agents

Abstract

Di-, tri- and poly-perfluoroalkyl-substituted alcohols and acids and derivatives thereof are described which are prepared from perfluoroalkyl iodides and di-, tri- or polyallyl alcohols or acids. These compounds contain two or more perfluoroalkyl-iodoalkyl or perfluoroalkyl-alkenyl groups and one or two alcohol or acid groups or derivatized alcohol or acid functions. They can be reacted with isocyanates, epoxy compounds, anhydrides, acids or acid derivatives to prepare a great variety of oil- and water-repellent compositions which are useful for oil- and water-repellent treatment of textiles, glass, paper, leather and other substrates.

Claims

1. An oligo-perfluoroalkyl alcohol or acid of the formula I or II

View Dependent Claims (2, 3, 4, 5, 6, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18)

2. A compound of the formula I or II according to claim 1, wherein Q_F is Q_F2 and R_F is saturated, contains 6-18 carbon atoms, is fully fluorinated and contains at least one terminal perfluoromethyl group.

3. A compound of the formula I or II according to claim 2, wherein R_F is a fully fluorinated, linear carbon chain with 6 to 14 carbon atoms.

4. A compound of the formula I according to claim 1, wherein Y is a trivalent or tetravalent hydrocarbyl linking group with from 1 to 10 carbon atoms.

5. An alcohol of the formula I according to claim 2, which is selected from the group consisting of

(Q_F2 CH₂ OCH₂)₂ CHOH, (Q_F2 CH₂ OCH₂)₂ C(CH₂ OH)₂, (Q_F2 CH₂ OCH₂)₃ C--CH₂ OH and (Q_F2 CH₂ OCH₂)₂ C(C₂ H₅)CH₂ OH.

6. An acid of the formula I according to claim 1, which is selected from the group consisting of ##STR10##

8. A compound of the formula II according to claim 2, wherein r is equal to or greater than q and the sum of r plus q is 0 to 10.

9. A compound according to claim 8, wherein r is is equal to or greater than q and is0 to 5 and q is 0 to 3.

10. A compound of the formula II according to claim 2, wherein L is O and

a) c and d are 1 and Z is phenyl, carboxyphenyl, p--n--C₁ -C₁₀ alkylphenyl, a monovalent alkyl or alkenyl radical with 1-20 carbon atoms which may be interrupted by --O--, --S-- or --NR₁ -- groups, and may be substituted by one or two carboxyl groups, or is hydroxy-C₂ -C₅ alkylene, or

b) c is 2, d is 1 and Z is 1,4-phenylene or a divalent alkylene radical which may be interrupted by --O--, --S-- or --NR₁ -- groups and substituted by one or two carboxyl groups, or

c) c is 3, d is 1 and Z is a trivalent alkylene radical which may be interrupted by --O--, --S-- or --NR₁ -- groups, or

d) c is 4, d is 1 and Z is a tetravalent residue of a polyol.

11. A compound of the formula II according to claim 2, wherein L is S and

a) d is 2 and Z is either a direct bond if e is 1 or e is 0, or

b) d and c are 1 and Z is a monovalent linear or branched alkyl radical with 1-20 carbon atoms, hydroxy-C₂ -C₅ alkylene, carboxy--C₂ -C₄ alkylene or --CH(COOH)CH₂ COOH, or

c) d is 1, c is 2 and Z is a divalent C₂ -C₂₀ alkylene radical which may be interrupted by --O-- or --NR₁ --.

12. A compound of the formula II according to claim 2, wherein L is NR'"'"', wherein R'"'"' is U--OH, C₁ -C₅ alkyl or carboxymethylene, c, d and e are each 1 and Z is monovalent.

13. A compound of the formula II according to claim 12, wherein R'"'"' is U--OH and Z is a monovalent alkyl radical with 1-20 carbon atoms which may be interrupted by --O--, --S-- or --NR₁ -- groups or a phenyl radical, which radicals may be substituted by hydroxy, carboxy or sulfonate groups.

14. A compound of the formula II according to claim 13, wherein Z is the residue minus 1 NH₂ radical of butylamine, aminoethanol, 1,1-dihydroxymethylaminopropane, tris(hydroxymethyl)aminomethane, glucamine, p-aminobenzoic acid, beta-alanine or HOOC--CH(NH₂)--A, wherein A is the radical residue of an a-amino acid selected from glycine, alanine, aspartic acid, glutamic acid and taurine.

15. A compound of the formula II according to claim 13, wherein Z is HOOC--CH₂ CH₂ --, HOOC--CH₂ --, HOOC--CH(CH₃)--, --CH₂ CH₂ SO₃ H, --CH(COOH)--(CH₂)_1-2 COOH, --C(C₂ H₅)(CH₂ OH)₂ or (CH₃)₂ N(CH₂)₃ --.

16. A compound of the formula II according to claim 12, wherein c is 2 to 4, d is 2 and R'"'"' is U--OH, or d is 1, R'"'"' is alkyl with 1-5 carbon atoms or a carboxymethylene group and Z is a divalent alkylene radical with 2 to 12 carbon atoms which be interrupted by --O--, --S-- or --NR₁ -- groups and substituted by hydroxy, carboxy or sulfonate groups.

17. A compound of the formula II according to claim 16, wherein Z is the diradical residue (minus 2 NH₂ or NHR₁ groups) of 1,3-diaminopropane, 1,3-diamino-2-hydroxypropane, 2-(2-aminoethylamino)-ethanol, N,N'"'"'-bis(2-hydroxyethyl)-ethylenediamine, ethylenediamine diacetic acid or lysine.

18. An alcohol of the formula II according to claim 2, which is selected from the group consisting of

(Q_F2 CH₂ OCH₂ CH(OH)CH₂)₂ N--C(CH₂ OH)₂ C₂ H₅, (Q_F2 CH₂ OCH₂ CH(OH)CH₂)₂ S, (Q_F2 CH₂ OCH₂ CH(OCH₂ CH₂ OH)CH₂)₂ S and Q_F2 CH₂ OCH₂ CH(OH)CH(OH)CH₂ OCH₂ Q_F2.

7. An acid of the formula ##STR11## where Q_F is Q_F1 or Q_F2, in which Q_F1 is R_F CH₂ CHI-- and Q_F2 is R_F CH═

CH--, and R_F is a monovalent, perfluorinated, alkyl or alkenyl, straight, branched or cyclic organic radical having three to twenty fully fluorinated carbon atoms, which radical can be interrupted by divalent oxygen or sulfur atoms, with each R_F radical being identical or different from the other R_F radicals.