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

• US 20030166487A1
• Filed: 09/12/2002
• Published: 09/04/2003
• Est. Priority Date: 05/20/1994
• Status: Active Grant

• Current Assignee: 3M Innovative Properties Company (3M Company)
• Original Assignee: 3M Innovative Properties Company (3M Company)
• Inventors: Moore, George G. I., Owens, John G., Flynn, Richard M., Guerra, Miguel A.
• Granted Patent: US 6,863,211 B2
• Time in Patent Office: Days
• US Class Current: 510/412
• 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 normally liquid, omega-hydrofluoroalkyl ether compound represented by the general formula:

X—

R_f—

O—

(R_f′

—

O)_n—

R_f″

—

H

wherein;

H is a primary hydrogen atom;

X is a fluorine 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 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.

2. A compound according to claim 1 represented by the formula:

X—

R_f—

O

CF₂CF₂—

O

_mR_f″

—

H

where m is an integer of 0 to 7, and H, X, R_f, and R_f″

are as defined in claim 1.

3. A compound according to claim 1 represented by the formula:

F—

R_f—

O

R_f′

—

O

_pR_f″

—

H

where p is an integer of 0 to 2 and H, R_f, R_f′

, and R_f″

are as defined in claim 1, except that R_f has 4 to 12 chain carbon atoms, R_f′

has 1 to 12 chain carbon atoms, and R_f″

has 2 to 12 chain carbon atoms.

4. A compound according to claim 1 represented by a formula selected from the group consisting of

C₈F₁₇—

O—

C₂F₄H, C₇F₁₅—

O—

C₂F₄H, C₆F₁₃—

O—

C₂F₄—

O—

CF₂H,

C₄F₉—

O—

C₂F₄H, C₄F₉—

O—

(CF₂)₅H, C₅F₁₁—

O—

(CF₂)₅H, C₈F₁₇—

O—

(CF₂)₅H, C₄F₉—

O—

CF₂C(CF₃)₂CF₂H, C₆F₁₃—

O—

C₂F₄H, C₄F₉—

O—

(CF₂)₄—

O—

(CF₂)₃H,

(C₂F₅)₂CFCF₂—

O—

C₂F₄H, c-C₆F₁₁CF₂—

O—

C₂F₄H, C₄F₉—

O—

C₂F₄—

O—

C₃F₆H,

C₆F₁₃—

O—

C₄F₈H, C₆F₁₃—

O—

C₃F₆H, C₅F₁₁—

O—

(CF₂)₄H, C₄F₉—

O—

C₃F₆H,

C₈F₁₇OCF₂OC₃F₆H,

C₅F₁₁OCF₂C(CF₃)₂CF₂H, (C₄F₉O)₂CFCF₂H, CF₃O(CF₂)₉H,

and (iso-C₃F₇)₂CFOC₂F₄H.

6. A process for preparing an omega-hydrofluoroalkyl ether compound of claim 1, which comprises decarboxylating the corresponding precursor fluoroalkyl ether carboxylic acid, hydrolyzable derivative of said carboxylic acid, or hydrolyzable precursor to said carboxylic acid or said derivative, said decarboxylating being carried out by contacting said precursor carboxylic acid or ester with a solution of inorganic base in protic solvent and heating the resulting reaction mixture.

7. The process according to claim 6 wherein said precursor carboxylic acid or ester is represented by the formula

R_fp—

O—

(R_f′

—

O)_n—

R_f″

-Z′

where

R_fp is F—

R_f where R_f is as defined in claim 1;

R_f′

is as defined in claim 1;

R_f″

is —

(CF₂)_m—

where m is an integer of at least 2;

n is an integer of 0 to 7; and

Z′

is CO₂H, CO₂R, COF, COCl, CONR¹R², or —

CF₂OC(O)R_f,

where R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, fluoroalkyl, and aryl, and where R¹ and R² are independently selected from the group consisting of hydrogen, alkyl, cycloalkyl, and heteroatom-containing cycloalkyl.

5. A normally liquid, omega-hydrofluoroalkyl ether compound represented by the general formula:

X—

R_f—

O—

(R_f′

—

O)_n—

R_f′

″

—

H

wherein;

H is a primary hydrogen atom;

X is a fluorine 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 F, then R_f has at least 4 chain carbon atoms, and each of R_f′ and

R_f′

″

independently has 1 or more chain carbon atoms;

and with the further proviso that when n is zero, then R_f is a perfluorocycloalkyl-substituted perfluoroalkylene group.

8. A method for converting —

CF₂Cl groups to —

CF₂H groups comprising the step of contacting at least one compound containing at least one —

CF₂Cl group with hydrogen gas, said contacting being carried out at a temperature below about 200°

C. in the presence of both a solution of base and a catalytic amount of at least one metal or supported metal, said metal being selected from the group consisting of nickel, palladium, and platinum.

9. In a method of vapor phase soldering wherein a component to be soldered is immersed in or enveloped by a body of fluorinated liquid vapor to melt the solder, and the component is then withdrawn from the body of vapor, the improvement comprising using as the fluorinated liquid a composition comprising at least one 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.

10. The process of claim 9 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the general formula:

X—

R_f—

O—

(R_f′

—

O)_n—

R_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.

11. The process of claim 10 wherein said X is a fluorine atom.

12. The process of claim 10 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the formula:

X—

R_f—

O—

(CF₂CF₂—

O)_m—

R_f″

—

H

where m is an integer of 0 to 7, and H, X, R_f, and R_f″

are as defined in claim 10.

13. The process of claim 10 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the formula:

F—

R_f—

O—

(R_f′

—

O)_p—

R_f″

—

H

where p is an integer of 0 to 2, and H, R_f, R_f′

, and R_f″

are as defined in claim 10, except that R_f has 4 to 12 chain carbon atoms, R_f′

has 1 to 12 chain carbon atoms, and R_f″

has 2 to 12 chain carbon atoms.

14. The process of claim 10 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by a formula selected from the group consisting of

C₈F₁₇—

O—

C₂F₄H, C₇F₁₅—

O—

C₂F₄H, C₆F₁₃—

O—

C₂F₄—

O—

CF₂H,

C₄F₉—

O—

C₂F₄H, HCF₂CF₂—

O—

CF₂CF₂—

O—

CF₂CF₂H, C₄F₉—

O—

(CF₂)₅H,

C₅F₁₁—

O—

(CF₂)₅H, C₈F₁₇—

O—

(CF₂)₅H, C₄F₉—

O—

CF₂C(CF₃)₂CF₂H,

H(CF₂)₄—

O—

(CF₂)₄H, Cl(CF₂)₄—

O—

(CF₂)₄H, C₆F₁₃—

O—

C₂F₄H,

C₄F₉—

O—

(CF₂)₄—

O—

(CF₂)₃H,

(C₂F₅)₂CFCF₂—

O—

C₂F₄H, c-C₆F₁₁CF₂—

O—

C₂F₄H, C₄F₉—

O—

C₂F₄—

O—

C₃F₆H,

C₆F₁₃—

O—

C₄F₈H, C₆F₁₃—

O—

C₃F₆H, C₅F₁₁—

O—

(CF₂)₄H, C₄F₉—

O—

C₃F₆H,

C₈F₁₇OCF₂OC₃F₆H, HC₃F₆OC₃F₆H,

C₅F₁₁OCF₂C(CF₃)₂CF₂H, (C₄F₉O)₂CFCF₂H, CF₃O(CF₂)₉H,

and (iso-C₃F₇)₂CFOC₂F₄H.

15. The process of claim 9 wherein said normally liquid omega-hydrofluoroalkyl ether compound is represented by the general formula:

X—

R_f—

O—

(R_f′

—

O)_n—

R_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 and each of R_f′ and

R_f″

independently has 1 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, and each of R_f′ and

R_f″

independently has 1 or more chain carbon atoms;

and with the still further proviso that when n is zero, then R_f is a perfluorocycloalkyl-substituted perfluoroalkylene group.