Omega-hydrofluoroalkyl ethers, precursor carboxylic acids and derivatives thereof, and their preparation and application

• US 5,658,962 A
• Filed: 05/12/1995
• Issued: 08/19/1997
• Est. Priority Date: 05/20/1994
• Status: Expired due to Term

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Company
• Inventors: Moore, George G. I., Owens, John G., Flynn, Richard M., Guerra, Miguel A.
• Primary Examiner(s): Foelak, Morton
• Application Number:
  US08/440,450
• Time in Patent Office: 830 Days
• Field of Search: 510/415, 252/194, 521/114
• US Class Current: 521/114
• CPC Class Codes: A61K 49/0461 Dispersions, colloids, emulsions or suspensions
• CPC Class Codes: A61K 49/1806 Suspensions, emulsions, colloids, dispersions
• CPC Class Codes: A61K 49/226 Solutes, emulsions, suspensions, dispersions, semi-solid forms, e.g. hydrogels
• CPC Class Codes: A61K 9/0026 Blood substitute; Oxygen transporting formulations; Plasma extender
• CPC Class Codes: A62D 1/00 Fire-extinguishing compositions; Use of chemical substances in extinguishing fires fireproof paints C09D5/18; fireproofing materials C09K21/00
• CPC Class Codes: A62D 1/0028 Liquid extinguishing substances A62D1/0092 takes precedence
• CPC Class Codes: A62D 1/0035 Aqueous solutions
• CPC Class Codes: A62D 1/0085 containing perfluoroalkyl-terminated surfactant
• CPC Class Codes: B01D 12/00 Displacing liquid, e.g. from wet solids or from dispersions of liquids or from solids in liquids, by means of another liquid
• CPC Class Codes: B23K 35/386 for condensation soldering
• CPC Class Codes: C07C 2601/14 The ring being saturated
• CPC Class Codes: C07C 2602/28 Hydrogenated naphthalenes
• CPC Class Codes: C07C 41/16 by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
• CPC Class Codes: C07C 41/18 by reactions not forming ether-oxygen bonds
• CPC Class Codes: C07C 41/22 by introduction of halogens; by substitution of halogen atoms by other halogen atoms
• CPC Class Codes: C07C 41/24 by elimination of halogens, e.g. elimination of HCl
• CPC Class Codes: C07C 43/12 containing halogen
• CPC Class Codes: C07C 43/123 both carbon chains are substituted by halogen atoms
• CPC Class Codes: C07C 43/126 having more than one ether bond
• CPC Class Codes: C07C 43/13 containing hydroxy or O-metal groups C07C43/11 takes precedence
• CPC Class Codes: C07C 43/192 : containing halogen
• CPC Class Codes: C07C 43/313 : containing halogen
• CPC Class Codes: C07C 59/135 : containing halogen
• CPC Class Codes: C07C 69/708 : Ethers
• CPC Class Codes: C07D 319/06 : not condensed with other rings
• CPC Class Codes: C08J 2203/146 : Saturated hydrocarbons containing oxygen and halogen atoms, e.g. F3C-O-CH2-CH3
• CPC Class Codes: C08J 9/143 : Halogen containing compounds
• CPC Class Codes: C11D 1/004 : Surface-active compounds containing F
• CPC Class Codes: C11D 7/28 : containing halogen

Abstract

Normally liquid, omega-hydrofluoroalkyl ether compounds (and selected mixtures thereof) have a saturated perfluoroaliphatic chain of carbon atoms interrupted by one or more ether oxygen atoms. The compounds can be prepared, e.g., by decarboxylation of the corresponding fluoroalkyl ether carboxylic acids and are useful, e.g., in cleaning and drying applications.

Claims

1. A method of displacing water from a surface which comprises contacting the surface with a liquid composition comprising a normally liquid omega-hydrofluoroalkyl ether compound having a saturated perfluoroaliphatic chain of carbon atoms interrupted by one or more ether oxygen atoms, the chain carbon atom at one end (the proximal end) of the chain being that of a difluoromethyl group which is bonded to another chain carbon atom or to a said ether-oxygen atom, the carbon atom at the other end (the distal end) of the chain being part of a distal group selected from the group consisting of difluoromethyl, difluorochloromethyl, a straight-chain perfluoroalkyl, a branched-chain perfluoroalkyl, and a perfluoroalkyl substituted with a saturated perfluoroalicyclic moiety, with the proviso that where said difluoromethyl group at the proximal end is bonded to a said ether-oxygen atom, then said straight-chain perfluoroalkyl has at least 6 chain carbon atoms and said branched-chain perfluoroalkyl has at least 4 carbon atoms.

4. The method of claim 1 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the general formula:

space="preserve" listing-type="equation">X--R.sub.f --O--(R.sub.f '"'"'--O).sub.n --R.sub.f "--H

wherein;

H is a primary hydrogen atom;

X is a fluorine atom, a primary hydrogen atom, or a primary chlorine atom;

n is an integer of 0 to 7; and

R_f, R_f '"'"', and R_f " are independently selected from the group consisting of linear or branched, unsubstituted perfluoroalkylene groups;

linear or branched, perfluoroalkyl- or perfluorocycloalkyl-substituted perfluoroalkylene groups; and

linear or branched perfluoroalkylene groups substituted with an ether oxygen-containing moiety;

with the proviso that when X is H or Cl, R_f has 1 to 18 chain carbon atoms, R_f '"'"' has 1 to 12 chain carbon atoms, and R_f " has 2 to 12 chain carbon atoms;

and with the further proviso that when X is F, then R_f has at least 4 chain carbon atoms, R_f '"'"' has 1 or more chain carbon atoms, and R_f " has 2 or more chain carbon atoms.

5. The method of claim 4 wherein said X is a fluorine atom.

2. A method of removing a contaminant from an article comprising contacting said article with a composition comprising at least one normally liquid omega-hydrofluoroalkylether compound having a saturated perfluoroaliphatic chain of carbon atoms interrupted by one or more ether oxygen atoms, the chain carbon atom at one end (the proximal end) of the chain being that of a difluoromethyl group which is bonded to another chain carbon atom or to a said ether-oxygen atom, the carbon atom at the other end (the distal end) of the chain being part of a distal group selected from the group consisting of difluoromethyl, difluorochloromethyl, a straight-chain perfluoroalkyl, a branched-chain perfluoroalkyl, and a perfluoroalkyl substituted with a saturated perfluoroalicyclic moiety, with the proviso that where said difluoromethyl group at the proximal end is bonded to a said ether-oxygen atom, then said straight-chain perfluoroalkyl has at least 6 chain carbon atoms and said branched-chain perfluoroalkyl has at least 4 carbon atoms.

3. The method of claim 2 further comprising the step of contacting said article simultaneously or sequentially with a composition comprising at least one organic solvent.

6. The method of claim 2 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the general formula:

space="preserve" listing-type="equation">X--R.sub.f --O--(R.sub.f '"'"'--O).sub.n --R.sub.f "--H

wherein;

H is a primary hydrogen atom;

X is a fluorine atom, a primary hydrogen atom, or a primary chlorine atom;

n is an integer of 0 to 7; and

R_f, R_f '"'"', and R_f " are independently selected from the group consisting of linear or branched, unsubstituted perfluoroalkylene groups;

linear or branched, perfluoroalkyl- or perfluorocycloalkyl-substituted perfluoroalkylene groups; and

linear or branched perfluoroalkylene groups substituted with an ether oxygen-containing moiety;

with the proviso that when X is H or Cl, R_f has 1 to 18 chain carbon atoms, R_f '"'"' has 1 to 12 chain carbon atoms, and R_f " has 2 to 12 chain carbon atoms;

and with the further proviso that when X is F, then R_f has at least 4 chain carbon atoms, R_f '"'"' has 1 or more chain carbon atoms, and R_f " has 2 or more chain carbon atoms.

7. The method of claim 6 wherein said X is a fluorine atom.