Heteroatom containing perfluoroalkyl terminated neopentyl glycols and compositions therefrom

• US 4,946,992 A
• Filed: 04/14/1989
• Issued: 08/07/1990
• Est. Priority Date: 06/20/1988
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Falk, Robert A., Clark, Kirtland P., Jacobson, Michael, Karydas, Athanasios
• Primary Examiner(s): WELSH JR, MAURICE
• Application Number:
  US07/339,326
• Time in Patent Office: 480 Days
• Field of Search: 560/227, 564/102, 564/203, 564/506, 568/28, 568/29, 568/30, 568/31, 568/32, 568/46, 568/674
• US Class Current: 560/227
• CPC Class Codes: C07C 215/18 with hydroxy groups and at least two amino groups bound to the carbon skeleton
• CPC Class Codes: C07C 311/04 to acyclic carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
• CPC Class Codes: C07C 313/12 having sulfur atoms of sulfenic groups bound to acyclic carbon atoms
• CPC Class Codes: C07C 317/18 with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• CPC Class Codes: C07C 323/25 the carbon skeleton being acyclic and saturated
• CPC Class Codes: C07C 323/41 Y being a hydrogen or an acyclic carbon atom
• CPC Class Codes: C07C 43/137 containing halogen
• CPC Class Codes: C07D 305/06 with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
• CPC Class Codes: C08G 18/38 having heteroatoms other than oxygen C08G18/32 takes precedence
• CPC Class Codes: C08G 18/3812 having fluorine atoms
• CPC Class Codes: C08G 18/3861 containing sulfonamide and/or sulfonylhydrazide groups
• CPC Class Codes: C08G 18/387 in addition to a perfluoroalkyl group
• CPC Class Codes: C08G 18/4607 having halogens
• CPC Class Codes: C08G 18/5015 having fluorine atoms
• CPC Class Codes: C08G 63/6824 derived from polycarboxylic acids and polyhydroxy compounds
• CPC Class Codes: C08G 65/18 Oxetanes
• CPC Class Codes: C08G 65/226 containing fluorine
• CPC Class Codes: C08G 71/04 Polyurethanes
• 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: D06N 3/146 : characterised by the macromolecular diols used

Abstract

Heteroatom containing perfluoroalkyl terminated neopentyl glycols of the formulas HO[--CH₂ C(CH₂ X--E--R_f)₂ CH₂ O]_1-3 --H or HO[--CH₂ C(CH₂ X--R_f)₂ CH₂ O]_1-3 --H are prepared from halogenated neopentyl glycols or oxetanes and thiols of the formula R_f --E--SH, amines of the formuls R_f --E--NH--R, alcohols of the formula R_f --E--OH or perfluoro-amides, wherein R_f is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms.

The polymeric reaction products of said fluorinated diols, and optionally other diols with isocyanates to prepare polyurethanes; with amines and isocyanated to prepare polyureas/polyurethanes; with acids or derivatives to prepare polyesters or polycarbonates are disclosed. These include polymeric, random or block urethane, and/or urea, and/or ester compositions containing the residue of at least one R_f -neopentyl glycol containing two perfluoroalkyl hetero groups.

These polymeric compositions provide improved thermal stability and useful low surface energy oil and water repellent coatings, and soil-release properties for textiles, glass, paper, leather and other materials.

Claims

1. A compound of formula I or II ##STR27## wherein R_f is a straight or branched chain perfluoroalkyl of 1 to 18 carbon atoms or said perfluoroalkyl substituted by perfluoroalkoxy of 2 to 6 carbon atoms,

E is branched or straight chain alkylene of 1 to 10 carbon atoms or said alkylene interrupted by one to three groups selected from the group consisting of --NR--, --O--, --COO--, --OOC--, --CONR--, --NRCO--, --SO₂ NR--, and --NRSO₂ --, or terminated at the R_f end with --CONR--or --SO₂ NR--, where R_f is attached to the carbon or sulfur atom, and for formula I, X is --S--, --O--, --SO₂ --, or --NR--, and for formula II, X is --CONR--or --SO₂ NR--, where R_f is attached to the carbon or sulfur atom, and where R is independently hydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbon atoms, and m is 1, 2 or 3.

2. A compound of formula I or II according to claim 1 wherein R_f is a straight or branched chain perfluoroalkyl of 2 to 12 carbon atoms or perfluoroalkyl of 2 to 6 carbon atoms substituted by perfluoroalkoxy of 2 to 6 carbon atoms, and m is 1 to 2.

3. A compound of formula I according to claim 1 wherein R_f is perfluoroalkyl of 2 to 12 carbon atoms or perfluoroalkyl of 2 to 6 carbon atoms substituted by perfluoroalkoxy of 2 to 6 carbon atoms, E is alkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂ CH₂ --,--CH₂ CH₂ SO₂ NHCH₂ CH₂ --. --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂ NHCH₂ CH₂ --, X is --O--, and m is 1 or 2.

4. A compound of formula I according to claim 1 wherein R_f is perfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, --O--, and m is 1.

5. A compound of formula I according to claim 1 wherein R_f is perfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, X is --O--, and m is 2.

6. A compound according to claim 1 which is (R_f SO₂ N(C₂ H₅)CH₂)₂ C(CH₂ OH)₂

7. A compound according to claim 1 which is (R_f CH₂ OCH₂)₂ C(CH₂ OH)₂ where R_f is a mixture of C₄ F₉, C₆ F₁₃, C₈ F₁₇, and C₁₀ F₂₁.