Phosphorus compounds and their use as corrosion inhibitors for perfluoropolyethers

• US 6,184,187 B1
• Filed: 04/07/1998
• Issued: 02/06/2001
• Est. Priority Date: 04/07/1998
• Status: Expired due to Term

• Current Assignee: The Chemours Company FC, LLC (The Chemours Company)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Hofman, Michael A., Howell, Jon L.
• Primary Examiner(s): Medley, Margaret
• Assistant Examiner(s): Toomer, Cephia D.
• Application Number:
  US09/056,085
• Time in Patent Office: 1,036 Days
• Field of Search: 508/427, 508/588, 558/203, 558/204, 558/207, 558/194, 558/195
• US Class Current: 508/427
• CPC Class Codes: C07F 9/091 with hydroxyalkyl compounds with further substituents on alkyl
• CPC Class Codes: C07F 9/12 with hydroxyaryl compounds
• CPC Class Codes: C07F 9/3211 Esters of acyclic saturated acids which can have further substituents on alkyl
• CPC Class Codes: C07F 9/4006 Esters of acyclic acids which can have further substituents on alkyl
• CPC Class Codes: C07F 9/4075 Esters with hydroxyalkyl compounds
• CPC Class Codes: C07F 9/46 Phosphinous acids [R2POH], [R2P(= O)H]: Thiophosphinous acids including[R2PSH]; [R2P(=S)H]; Aminophosphines [R2PNH2]; Derivatives thereof
• CPC Class Codes: C07F 9/4816 Acyclic saturated acids or derivatices which can have further substituents on alkyl
• CPC Class Codes: C07F 9/5004 Acyclic saturated phosphines
• CPC Class Codes: C07F 9/5304 Acyclic saturated phosphine oxides or thioxides
• CPC Class Codes: C10M 107/38 containing halogen
• CPC Class Codes: C10M 137/02 having no phosphorus-to-carbon bond
• CPC Class Codes: C10M 137/12 having a phosphorus-to-carbon bond
• CPC Class Codes: C10M 169/04 Mixtures of base-materials and additives
• CPC Class Codes: C10M 2213/00 Organic macromolecular compounds containing halogen as ingredients in lubricant compositions
• CPC Class Codes: C10M 2213/023 used as base material
• CPC Class Codes: C10M 2213/043 used as base material
• CPC Class Codes: C10M 2213/0606 used as base material
• CPC Class Codes: C10M 2213/0623 used as base material
• CPC Class Codes: C10M 2223/02 having no phosphorus-to-carbon bonds
• CPC Class Codes: C10M 2223/04 Phosphate esters
• CPC Class Codes: C10M 2223/042 : Metal salts thereof
• CPC Class Codes: C10M 2223/043 : Ammonium or amine salts thereof
• CPC Class Codes: C10M 2223/049 : Phosphite
• CPC Class Codes: C10M 2223/06 : having phosphorus-to-carbon bonds
• CPC Class Codes: C10M 2223/061 : Metal salts
• CPC Class Codes: C10M 2223/063 : Ammonium or amine salts
• CPC Class Codes: C10M 2223/065 : containing sulfur
• CPC Class Codes: C10M 2223/10 : Phosphatides, e.g. lecithin, cephalin
• CPC Class Codes: C10M 2225/00 : Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
• CPC Class Codes: C10M 2225/02 : Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
• CPC Class Codes: C10N 2030/12 : Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
• CPC Class Codes: C10N 2040/08 : Hydraulic fluids, e.g. brake-fluids
• CPC Class Codes: C10N 2050/10 : Semi-solids; greasy
• CPC Class Codes: C23F 11/1673 : Esters of phosphoric or thiophosphoric acids
• CPC Class Codes: Y10T 428/31544 : Addition polymer is perhalogenated

Abstract

Novel phosphorus compounds are effective corrosion inhibitors for perfluoropolyether lubricating oils and greases, and hydraulic fluids.

Claims

1. A perfluoropolyether oil or grease containing 0.1 to 10% by weight of an aryl phosphorus compound selected from the group consisting of:

A. A perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound selected from the group consisting of partially esterified aryl phosphates, aryl phosphonates, and salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group;

B. Asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compounds being either (i) aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group, or (ii) aryl phosphines, phosphinites, phosphonites, phosphine oxides, phosphinates or phosphonates with no linking group between the phosphorus and a fluorocarbon group;

and combinations thereof wherein said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof.

2. The perfluoroether oil or grease of claim 1 containing 0.1 to 3% by weight of at least one partially esterified aryl phosphate, aryl phosphonate, or salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group.

3. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf—

Y—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur,

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_o—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

, (4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F, or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

j⁴ is —

CF₃, or —

C₂F₅; and

l is a number such that the molecular weight ranges from 400 to 15,000.

4. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf′

—

Y—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf′

is Z²—

(CF₂)_m;

Z² is F, Cl or H; and

m has a value from 2 to 20.

5. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [MO]_x[C₆R₅O_b]—

P(E)—

Y—

Rf″

—

Y—

P(E)—

[O_bC₆R₅]<sub>(2−

x)</sub>[OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000

X is F or CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H; and

s is a number such that the molecular weight ranges from 400 to 15,000.

6. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

, (4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF³, or —

C₂F₅; and

l is a number such that the molecular weight ranges from 400 to 15,000.

7. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [Rf′

—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf′

is Z²—

(CF₂)_m;

Z² is —

F, —

Cl or —

H; and

m has a value from 2 to 20.

8. The composition of claim 2 wherein said aryl phosphorus compound has the formula of [MO]_x[C₆R₅O_b]—

P(E)—

Rf″

—

P(E)—

[O_bC₆R₅]<sub>(2−

x)</sub>[OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H; and

s is a number such that the molecular weight ranges from 400 to 15,000.

9. The perfluoropolyether oil or grease composition of claim 1 containing 0.1 to 3% by weight of at least one asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound being either (i) aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group, or (ii) aryl phosphines, phosphinites, phosphonites, phosphine oxides, phosphinates or phosphonates with no linking group between the phosphorus and a fluorocarbon group.

10. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf—

Y—

]<sub>(3−

y)</sub>—

P(E)_a—

[O—

C₆R₅]_y wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

E is oxygen or sulfur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

;

(4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)_l—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5, and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and, the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅;

l is a number such that the molecular weight ranges from 400 to 15,000;

y is 0.05 to 2; and

a is 0 or 1.

11. The composition of claim 9 wherein said aryl phosphorus compound has the formula of (C₆R₅O)₂—

P(E)_a—

Y—

Rf″

—

Y—

P(E)_a—

(OC₆R₅)₂ wherein

Y is (CH₂)_z—

O(CH₂CH₂O)_z—

, in which z is 1 to 4 and z′

is 0, 1 or 2;

E is oxygen or sulfur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H;

s is a number such that the molecular weight ranges from 400 to 15,000; and

a is 0 or 1.

12. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf]₍₃₋

y)—

P(E)_a—

[O_bC₆R₅]_y wherein

E is oxygen or sulfur;

b is 0 or 1;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

;

(4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the elf ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅;

l is a number such that the molecular weight ranges from 400 to 15,000;

y is 0.05 to 2; and

a is 0 or 1.

13. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf′

]<sub>(3−

y)</sub>—

P(E)_a—

[O_bC₆R₅]_y wherein

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf′

is Z²—

(CF₂)_m;

Z² is F, Cl or H;

m has a value from 2 to 20;

y is 0.05 to 2; and

a is 0 or 1.

14. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [C₆R₅O]₂—

P(E)_a—

Rf″

—

P(E)_a—

[O—

C₆R₅]₂ wherein

E is oxygen or sulfur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

s is a number such that the molecular weight ranges from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H;

y is 0.05 to 2; and

a is 0 or 1.

15. The composition of claim 9 wherein said aryl phosphorus compound has the formula of [Rf′

″

—

C₆R₄—

O]_(3-u-w)—

P(E)—

[O_b—

C₆R′

₅]_w[OM′

]_u wherein

Rf′

″

is Rf′

or Rf″

;

M′

is an alkali metal, alkaline earth metal, or ammonium;

u and w are the same or different and are between 0 and 1;

R′

is an aryl group;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf′

is Z²—

(CF₂)_m;

m has a value from 2 to 20;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

s is a number such that the molecular weight ranges from 400 to 15,000;

X is —

F or —

CF₃; and

Q and Z², equal or different, are F, Cl or H.

16. A perfluoropolyether oil or grease composition of containing 0.1 to 3% by weight of at least one salts of a partially esterified aryl phosphates having an aryl group between the phosphorus and a fluorocarbon;

said aryl phosphorus compound has the formula of [Rf′

″

—

C₆R₄—

O]_(3-u-w)—

P(E)—

[O_b—

C₆R′

₅]_w[OM′

]_u wherein

Rf′

″

is Rf′

or Rf″

;

M′

is an alkali metal, alkaline earth metal, or ammonium;

u and w are the same or different and are between 0 and 1;

R′

is an aryl group;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf′

is Z²—

(CF₂)_m;

m has a value from 2 to 20;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_rCF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

s is a number such that the molecular weight ranges from 400 to 15,000;

X is —

F or —

CF₃; and

Q and Z², equal or different, are F, Cl or H.

17. A perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compound selected from the group consisting of partially esterified aryl phosphates, aryl phosphonates, and salts thereof, containing either (i) a mono- or poly-alkylene oxide linking group between the phosphorus and a fluorocarbon group, or (ii) no linking group between the phosphorus and fluorocarbon group wherein said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof.

18. Compounds of claim 17 having the formula of [Rf—

Y—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

, (4) J₂—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio′

ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅; and

l is a number such that the molecular weight ranges from 400 to 15,000.

19. Compounds of claim 17 having the formula of [Rf′

—

Y—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf′

is Z²—

(CF₂)_m;

Z² is F, Cl or H; and

m has a value from 2 to 20.

20. Compounds of claim 17 having the formula of [MO]_x[C₆R₅O_b]—

P(E)—

Y—

Rf″

—

Y—

P(E)—

[O_bC₆R₅]<sub>(2−

x)</sub>[OM]_x wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

X is F or CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H; and

s is a number such that the molecular weight ranges from 400 to 15,000.

21. Compounds of claim 17 having the formula of [Rf—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_O—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_fCFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

, (4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of—

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅; and

l is a number such that the molecular weight ranges from 400 to 15,000.

22. Compounds of claim 17 having the formula of [Rf′

—

]<sub>(2−

x)</sub>—

P(E)—

[O_bC₆R₅][OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf′

is Z²—

(CF₂)_m;

Z² is —

F, —

Cl or —

H; and

m has a value from 2 to 20.

23. Compounds of claim 17 having the formula of [MO]_x[C₆R₅O_b]—

P(E)—

Rf″

—

P(E)—

[O_bC₆R₅]<sub>(2−

x)</sub>[OM]_x wherein

x is 0.05 to 1;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

each M is independently selected from the group consisting of hydrogen, alkali metal, alkaline earth metal, and ammonium;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H; and

s is a number such that the molecular weight ranges from 400 to 15,000.

24. Asymmetrical perfluoropolyether- or perfluoroalkyl-containing and phosphorus-containing compounds being aryl phosphites or phosphates containing a mono- or poly-alkylene oxide linking group between the phosphorus and a perfluoroether group.

25. Compounds of claim 24 having the formula of [Rf—

Y—

]<sub>(3−

y)</sub>—

P(E)_a—

[O—

C₆R₅]_y wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

E is oxygen or sulfur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)CF₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

;

(4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the cld ratio ranges from 0.01 to 0.5, and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and, the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅;

l is a number such that the molecular weight ranges from 400 to 15,000;

y is 0.05 to 2; and

a is 0 or 1.

26. Compounds of claim 24 having the formula of (C₆R₅O)₂—

P(E)_a—

Y—

Rf″

—

Y—

P(E)_a—

(OC₆R₅)₂ wherein

Y is (CH₂)_zO(CH₂CH₂O)_z, in which z is 1 to 4 and z′

is 0, 1 or 2;

E is oxygen or sulfiur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H;

s is a number such that the molecular weight ranges from 400 to 15,000; and

a is 0 or 1.

27. Compowuds of claim 24 having the formula of [Rf]₍₃₋

y)—

P(E)_a—

[O_bC₆R₅]_y wherein

E is oxygen or sulfur;

b is 0 or 1;

Rf is a polyether chain having a molecular weight ranging from 400 to 15,000 comprising repeating units selected from the group consisting of (1) J—

O—

(CF(CF₃)CF₂O)_c—

(CFXO)_d—

CFZ—

, (2) J¹—

O—

(CF₂CF₂O)_e—

(CF₂O)_f—

CFZ¹, (3) J—

(CF(CF₃)C₂O)_g—

(CF₂CF₂O)_h—

(CFX—

O)_i—

CFZ—

;

(4) J²—

O—

(CF(CF₃)CF₂O)_j—

CF(CF₃)—

, (5) J³—

O—

(CQZ²—

CF₂CF₂—

O)_k—

CQZ²—

CF₂—

, and (6) J⁴—

O—

(CF₂CF₂O)₁—

CF₂—

;

J is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

C₃F₇, —

CF₂Cl, —

C₂F₄Cl, and —

C₃F₆Cl;

X is —

F or —

CF₃;

Z is —

F, —

Cl, or —

CF₃;

Z¹ is —

F or —

Cl;

c and d are numbers such that the c/d ratio ranges from 0.01 to 0.5 and the molecular weight ranges from 400 to 15,000;

J¹ is a fluoroalkyl group selected from the group consisting of —

CF₃, —

C₂F₅, —

CF₂Cl, and —

C₂F₄Cl;

e and f are numbers such that the e/f ratio ranges from 0.5 to 2 and the molecular weight ranges from 400 to 15,000;

g, h and i are numbers such that (g+h) ranges from 1 to 50, the i/(g+h) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

J² is —

C₂F₅ or —

C₃F₇;

j is a number such that the molecular weight ranges from 400 to 15,000;

J³ is selected from the group consisting of —

CF₃, —

C₂F₅, and —

C₃F₇;

Q and Z², equal or different, are —

F, —

Cl or —

H;

k is a number such that the molecular weight ranges from 400 to 15,000;

J⁴ is —

CF₃, or —

C₂F₅;

l is a number such that the molecular weight ranges from 400 to 15,000.

y is 0.05 to 2; and

a is 0 or 1.

28. Compounds of claim 24 having the formula of [C₆R₅O]₂—

P(E)_a—

Rf″

—

P(E)_a—

[O—

C₆R₅]₂ wherein

E is oxygen or sulfur;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000 selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

s is a number such that the molecular weight ranges from 400 to 15,000;

X is —

F or —

CF₃;

Q and Z², equal or different, are —

F, —

Cl or —

H; and

a is 0 or 1.

29. Salts of partially esterified aryl phosphates having an aryl group between the phosphorus and a fluorocarbon;

said salt is selected from the group consisting of alkali metal salts, alkaline earth metal salts, ammonium salts, and combinations thereof and has the formula of[Rf′

″

—

C₆R₄—

O]<sub>(3-u-w)—

P(E)—

[Ob</sub>—

C₆R′

₅]_w[OM′

]_u wherein

Rf′

″

is Rf′

or Rf″

;

M′

is an alkali metal, alkaline earth metal, or ammonium;

u and w are the same or different and are between 0 and 1;

R′

is an aryl group;

E is oxygen or sulfur;

b is 0 or 1;

each R is independently selected from the group consisting of hydrogen, halogen, alkyl, aryl, nitro, cyano, alkoxy, primary and secondary amino, sulfonyl, carboxyl, and phenoxy;

Rf′

is Z²—

(CF₂)_m;

m has a value from 2 to 20;

Rf″

is a perfluoropolyether chain having a number average molecular weight of 500 to 15,000, selected from the group consisting of (i) —

(CF₂CF₂O)_n—

(CF₂O)_o—

CF₂—

, (ii) —

(C₃F₆O)_p—

(CF₂CF₂O)_q—

(CFXO)_r—

CF₂—

, and (iii) —

((CQZ²)CF₂CF₂O)_s—

CF₂—

CF₂—

;

the units with formulae C₂F₄O and CF₂O are randomly distributed along the chain;

n and o are integers, whose ratio, n/o, is in the range of from 0.3 to 5;

p, q and r are numbers such that (p+q) ranges from 1 to 50, and the r/(p+q) ratio ranges from 0.1 to 0.05, and the molecular weight is from 400 to 15,000;

s is a number such that the molecular weight ranges from 400 to 15,000;

X is —

F or —

CF₃; and

Q and Z², equal or different, are F, Cl or H.