Fluoropolymer nanocomposites

• US 5,726,247 A
• Filed: 06/14/1996
• Issued: 03/10/1998
• Est. Priority Date: 06/14/1996
• Status: Expired due to Fees

• Current Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Original Assignee: E. I. du Pont de Nemours and Company (Corteva, Inc.)
• Inventors: Sharp, Kenneth George, Michalczyk, Michael Joseph, Stewart, Charles Winfield
• Primary Examiner(s): DEAN JR, RALPH H
• Application Number:
  US08/663,821
• Time in Patent Office: 634 Days
• Field of Search: 525/104, 525/102, 525/326.2, 525/326.4, 428/421, 428/422
• US Class Current: 525/102
• CPC Class Codes: C03C 17/009 Mixtures of organic and inorganic materials, e.g. ormosils and ormocers
• CPC Class Codes: C04B 41/4842 Fluorine-containing polymers
• CPC Class Codes: C08K 5/5406 containing elements other than oxygen or nitrogen
• CPC Class Codes: C08L 2666/14 Macromolecular compounds according to C08L59/00 - C08L87/00; Derivatives thereof
• CPC Class Codes: C08L 27/12 containing fluorine atoms
• CPC Class Codes: C08L 83/00 Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
• CPC Class Codes: C09D 127/12 containing fluorine atoms
• CPC Class Codes: C23C 28/00 Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
• CPC Class Codes: C23C 30/00 Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: F16C 2240/64 in the nanometer range
• CPC Class Codes: Y10T 428/3154 Of fluorinated addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31544 Addition polymer is perhalogenated

Abstract

This invention relates to a fluoropolymer nanocomposite comprising a fluoropolymer phase and an inorganic oxide phase dispersed throughout, said inorganic oxide phase having either no particles or particles substantially all of which have a particle size of less than about 75 nm which can be determined by small angle x-ray scattering and transmission electron microscopy techniques. These nanocomposites are useful as protective coatings.

Claims

1. A fluoropolymer nanocomposite, comprising:

(a) a fluoropolymer phase comprising at least one fluoropolymer; and

(b) at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase and said inorganic oxide phase either exhibiting no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm; and

the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

2. The fluoropolymer nanocomposite of claim 1 wherein the inorganic oxide phase is continuous.

3. The fluoropolymer nanocomposite of claim 2 wherein the inorganic oxide phase and the fluoropolymer phase form a semi-interpenetrating network.

4. The fluoropolymer nanocomposite of claim 1 wherein the inorganic oxide phase is discontinuous.

5. The fluoropolymer nanocomposite of claim 4 wherein the particle size of substantially all particles of the inorganic oxide phase is from about 0.1 nm to about 50 nm.

6. The fluoropolymer nanocomposite of claim 1 wherein the at least one inorganic oxide precursor comprises a mixture of inorganic oxide precursors, each precursor being individually soluble or insoluble in the fluorinated solvent, provided said mixture is soluble in the fluorinated solvent.

7. The fluoropolymer nanocomposite of claim 1 wherein the inorganic oxide precursor is an alkoxide or fluoroalkoxide of Al, B, Ge, Si, Sn, Ti and Zr.

8. The fluoropolymer nanocomposite of claim 7 wherein the inorganic oxide precursor is a compound having the formula (R_f C_a H_2a O)_n MR^4-n, wherein:

M is Ge, Si or Sn;

a is 1 to 10;

n is 2, 3 or 4;

R_f has up to about of 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; and

R is selected from the group consisting of;

H, C₁ to about C₈ alkyl, C_a H_2a R_f, C₁ to about C₈ alkoxy, C₁ to about C₈ alkenyl, C₁ to about C₈ alkynyl, C₆ H₅, aryl, and aralkyl.

9. The fluoropolymer nanocomposite of claim 7 wherein the inorganic oxide precursor is a compound having the formula (R_f C_a H_2a O)_n M¹ R_4-n (HOR)_q¹, wherein

M¹ is Ti or Zr;

n is 2, 3, or 4;

R_f has up to about of 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

R is selected from the group consisting of;

H, C₁ to about C₈ alkyl, C_a H_2a R_f, C₁ to about C₈ alkoxy, C₁ to about C₈ alkenyl, C₁ to about C₈ alkynyl, C₆ H₅, aryl, and aralkyl;

a is an integer from 1 to about 10; and

q¹ is 0 or 1.

10. The fluoropolymer nanocomposite of claim 7 wherein the inorganic oxide precursor is a compound having the formula (R_f C_a H_2a O)_n'"'"' M'"'"'R_3-n'"'"', wherein:

M'"'"' is Al or B;

n'"'"' is 1, 2 or 3;

R_f has up to about of 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

R is selected from the group consisting of;

H, C₁ to about C₈ alkyl, C_a H_2a R_f, C₁ to about C₈ alkoxy, C₁ to about C₈ alkenyl, C₁ to about C₈ alkynyl, C₆ H₅, aryl, and aralkyl;

a is an integer from 1 to about 10.

11. The fluoropolymer nanocomposite of claim 7 wherein the inorganic oxide precursor is a chelating compound having the formula (R_f C_a H_2a O)_n" M"^cn D^d p, wherein:

D is a chelating ligand, optionally fluorinated;

M" is Si, Al, Ti or Zr;

cn is a silicon, aluminum, titanium or zirconium coordination number, being in each case an integer having a value of 4-6;

d is a number, either 2 or 3, corresponding to the chelating ability of the ligand D, d being 2 for a bidentate ligand and 3 for a tridentate ligand;

p is either 1, 2 or 3, except that for d=3, p always is 1;

n" is cn-(d×

p);

R_f has up to about of 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2;

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ; and

a is an integer from 1 to about 10.

12. The fluoropolymer nanocomposite of claim 1 wherein the inorganic oxide precursor is a fluorine-bearing silane.

13. The fluoropolymer nanocomposite of claim 12 wherein the inorganic oxide precursor is a compound selected from the group consisting of:

a compound having the formula;

space="preserve" listing-type="equation">(R.sub.f C.sub.a H.sub.2a O).sub.t SiR.sub.4-t (I)

wherein;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

R is selected from the group consisting of;

hydrogen, C₁ to about C₈ alkyl, C_a H_2a R_f, C₁ to about C₈ alkoxy, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy, C₂ to about C₈ alkenyl, C₂ to about C₈ alkynyl, C₆ H₅, aryl, and aralkyl;

t is 1, 2, 3 or 4; and

a is an integer from 1 to about 10;

a compound having the formula;

space="preserve" listing-type="equation">X(Si(OC.sub.a H.sub.2a R.sub.f).sub.3).sub.n (II)

wherein;

X is at least one organic link selected from the group consisting of;

(a) R¹_m SiY_4-m ;

(b) ring structures ##STR14## (c) R¹_m Si(OSi(CH₃)₂ Y)_4-m ;

(d) CH₃ SiY₂ OSiY₂ CH₃ ;

(e) Y₃ SiOSiY₃ ;

(f) Y₂ (CH₃)Si(CH₂)_b Si(CH₃)Y₂ ;

(g) Y₃ Si(CH₂)_b SiY₃ ;

(h) Y₃ SiC₆ H₄ SiY₃ ;

(i) substituted benzene, including all isomers, selected from the group consisting of;

(i) C₆ H₃ (SiZ_3-c Y_c)₃ ;

(ii) C₆ H₂ (SiZ_3-c Y_c)₄ ;

(iii) C₆ H(SiZ_3-c Y_c)₅ ; and

(iv) C₆ (SiZ_3-c Y_c)₆ ; and

(j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of;

(i) 1,2-C₆ H₁₀ (Y)₂ ;

1,3-C₆ H₁₀ (Y)₂ ;

1,4-C₆ H₁₀ (Y)₂ ;

(ii) 1,2,4-C₆ H₉ (Y)₃ ;

1,2,3-C₆ H₉ (Y)₃ ;

1,3,5-C₆ H₉ (Y)₃ ;

(iii) 1,2,3,4-C₆ H₈ (Y)₄ ;

1,2,4,5-C₆ H₈ (Y)₄ ;

1,2,3,5-C₆ H₉ (Y)₄ ;

(iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and

(v) C₆ H₆ (Y)₆ ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl;

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R¹ is C₁ to about C₈ alkyl or aryl;

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl or aryl, provided that at least one of R⁴ to R⁷ is hydrogen;

m is 0, 1 or 2;

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

a is an integer from 1 to about 10;

b is an integer from 1 to about 10;

c is 1, 2 or 3; and

n is an integer greater than or equal to 2;

IIA;

a compound having the formula;

space="preserve" listing-type="equation">X(R.sup.10 Si(OC.sub.a H.sub.2a R.sub.f).sub.2).sub.n (IIA)

wherein;

X is at least one organic link selected from the group consisting of;

(a) R¹_m SiY_4-m ;

(b) ring structures ##STR15## (c) R¹_m Si(OSi(CH₃)₂ Y)_4-m ;

(d) CH₃ SiY₂ OSiY₂ CH₃ ;

(e) Y₃ SiOSiY₃ ;

(f) Y₂ (CH₃)Si(CH₂)_b Si(CH₃)Y₂ ;

(g) Y₃ Si(CH₂)_b SiY₃ ;

(h) Y₃ SiC₆ H₄ SiY₃ ;

(i) substituted benzene, including all isomers, selected from the group consisting of;

(i) C₆ H₃ (SiZ_3-c Y_c)₃ ;

(ii) C₆ H₂ (SiZ_3-c Y_c)₄ ;

(iii) C₆ H(SiZ_3-c Y_c)₅ ; and

(iv) C₆ (SiZ_3-c Y_c)₆ ; and

(j) substituted cyclohexane, including all stereoisomers, selected from the group consisting of;

(i) 1,2-C₆ H₁₀ (Y)₂ ;

1,3-C₆ H₁₀ (Y)₂ ;

1,4-C₆ H₁₀ (Y)₂ ;

(ii) 1,2,4-C₆ H₉ (Y)₃ ;

1,2,3-C₆ H₉ (Y)₃ ;

1,3,5-C₆ H₉ (Y)₃ ;

(iii) 1,2,3,4-C₆ H₈ (Y)₄ ;

1,2,4,5-C₆ H₈ (Y)₄ ;

1,2,3,5-C₆ H₉ (Y)₄ ;

(iv) 1,2,3,4,5-C₆ H₇ (Y)₅ ; and

(v) C₆ H₆ (Y)₆ ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

Z is C₁ to about C₄ alkyl, 3,3,3-trifluoropropyl, aralkyl or aryl;

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R¹ is C₁ to about C₈ alkyl or aryl;

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen;

R¹⁰ is C₁ to about C₈ alkyl or C_a H_2a R_f ;

m is 0, 1 or 2;

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

a is an integer from 1 to about 10;

b is an integer from 1 to about 10;

c is 1, 2 or 3; and

n is an integer greater than or equal to 2;

a compound having the formula;

space="preserve" listing-type="equation">(CF.sub.2).sub.v YSi(OR.sup.13).sub.3 !.sub.2 (III)

wherein;

R¹³ is C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy, halogen or C_a H_2a R_f ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

a is an integer from 1 to about 10;

v is an even integer from 2 to about 14;

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; and

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

IIIA;

a compound having the formula;

space="preserve" listing-type="equation">(CF.sub.2).sub.v (YSiR.sup.10 (OR.sup.10).sub.2).sub.2 (IIIA)

wherein;

R¹⁰ is C₁ to about C₈ alkyl or C_a H_2a R_f ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

a is an integer from 1 to about 10;

v is an even integer from 2 to about 14; and

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R¹³ is C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy, halogen or C_a H_2a R_f ;

R¹ is C₁ to about C₈ alkyl or aryl;

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; and

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

a fluoroalkylphenylsilane having the formula;

##STR16## wherein;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

Ar is a divalent aromatic radical;

W is selected from the group consisting of

(e) C₁ to about C₈ alkyl;

(f) R_f --Ar, wherein each of R_f and Ar is as defined above;

(g) halogen selected from the group consisting of chlorine, bromine and iodine;

(h) C₁ to about C₈ alkoxy;

(i) C₁ to about C₈ fluoroalkoxy; and

(j) C₁ to about C₁₀ carboxy or fluorocarboxy; and

each of Q and T independently is selected from the group consisting of

(k) halogen selected from the group consisting of chlorine, bromine and iodine;

(l) C₁ to about C₈ alkoxy;

(m) C₁ to about C₈ fluoroalkoxy; and

(n) C₁ to about C₁₀ carboxy or fluorcarboxy;

a dioxolane having the formula;

##STR17## wherein;

R¹³ is C₁ to about C₈ alkyl, C₁ to about C₈ carboxy, C₁ to about C₈ fluorocarboxy, halogen or C_a H_2a R_f ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O) q--CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

R¹¹ and R¹² are each independently selected from C₁ to C₃ fluoroalkyl or fluorine;

a is an integer from 1 to about 10; and

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; and

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero;

VA;

a dioxolane having the formula;

##STR18## wherein;

R¹⁰ is C₁ to about C₈ alkyl or C_a H_2a R_f ;

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more H;

R¹¹ and R¹² are each independently selected from C₁ to C₃ fluoroalkyl or fluorine;

a is an integer from 1 to about 10; and

Y is --(CR² R³)_k CR⁴ R⁵ CR⁶ R⁷ (CR⁸ R⁹)_h --

R¹³ is C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy, halogen or C_a H_2a R_f ;

R² to R⁹ are each independently hydrogen, C₁ to about C₈ alkyl, or aryl, provided that at least one of R⁴ to R⁷ is hydrogen; and

k and h are each independently an integer from 0 to 10, provided that at least one of k or h is zero; and

a compound having the formula;

##STR19## wherein;

y is an integer from 2 to about 10;

R_f has up to about 18 carbon atoms and is selected from the group consisting of

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

Ar is a divalent aromatic radical;

W is selected from the group consisting of

(e) C₁ to about C₈ alkyl;

(f) R_f --Ar, wherein each of R_f and Ar is as defined above;

(g) halogen selected from the group consisting of chlorine, bromine and iodine;

(h) C₁ to about C₈ alkoxy;

(i) C₁ to about C₈ fluoroalkoxy; and

(j) C₁ to about C₈ carboxy or fluorocarboxy; and

each of Q and T independently is selected from the group consisting of

(k) halogen selected from the group consisting of chlorine, bromine and iodine;

(l) C₁ to about C₈ alkoxy;

(m) C₁ to about C₈ fluoroalkoxy; and

(n) C₁ to about C₁₀ carboxy or fluorocarboxy.

14. The fluoropolymer nanocomposite of claim 13 wherein the inorganic oxide precursor is selected from the group consisting of:

Si(OCH₂ CF₃)₄ ;

Si(OCH₂ C₃ F₇)₄ ;

HSi(OCH₂ C₃ F₇)₃ ;

F(CF₂)₆ CH₂ CH₂ Si(OCH₂ CH₃)₃ ;

F(CF₂)₆ CH₂ CH₂ Si(OCH₂ CF₃)₃ ;

F(CF₂)₆ CH₂ CH₂ Si(OCH₃)₃ ;

(CH₃ O)₃ Si(OCH₂ CH₂ C₆ F₁₃);

(CH₃ O)₂ Si(OCH₂ CH₂ C₆ F₁₃)₂ ;

Si(OCH₂ CH₂ C₆ F₁₃)₄ ;

HSi(OCH₂ CF₃)₃ ;

(CH₃ O)₃ Si(OCH₂ CF₃ CF₃);

(CH₃ O)₃ Si(OCH₂ C₃ F₇);

(CH₃ O)₂ Si(OCH₂ CF₃)₂ ;

(CH₃ O) Si(OCH₂ CF₃)₃ ;

(CH₃ O)Si(OCH₂ C₃ F₇)₃ ;

(CH₃ O)₂ Si(OCH₂ C₃ F₇)₂ ;

CH₂ ═

CHSi(OCH₂ CF₃)₃ ;

CH₂ ═

CHSi(OCH₂ C₃ F₇)₃ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ CF₃)₃)₄ ;

Si(OSi(CH₃)₂ CH₂ CH₂ Si(OCH₂ C₃ F₇)₃)₄ ;

Si(CH₂ CH₂ Si(OCH₂ CF₃)₄ ;

Si(CH₂ CH₂ Si(OCH₂ C₃ F₇)₃)₄ ;

(CH₃ ((CCF₃ CH₂ O)₃ SiCH₂ CH₂ SiO)₄ ;

(CH₃ ((C₃ F₇ CH₂ O)₃ SiCH₂ CH₂)SiO)₄ ;

(C₃ F₇ CH₂ O)₃ Si(CH₂)₂ (CF₂)₆ (CH₂)₂ Si(OCH₂ C₃ F₇)₃ ;

(CF₂)₆ (CH₂)₂ Si(OCH₂ CF₃)₃ !₂ ;

C₈ F₁₇ C₆ H₄ (OCH₃)₃ ;

C₈ F₁₇ C₆ H₄ (OCH₂ CF₃)₃ ;

C₈ F₁₇ CH₂ CH₂ Si(OCH₃)₃ ;

C₈ F₁₇ CH₂ CH₂ Si(OCH₂ C₃ F₇)₃ ;

##STR20##

15. The fluoropolymer nanocomposite of claim 1 wherein the inorganic oxide precursor is an oligomeric compound selected from the group consisting of:

an oligomeric compound having the formula

space="preserve" listing-type="equation">Si(OC.sub.a H.sub.2a R.sub.f).sub.4-z O.sub.z /2 (VII)

wherein;

z is a number from about 0.5 to about 3.0;

a is an integer from 1 to about 10; and

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

an oligomeric compound having the formula;

space="preserve" listing-type="equation">R.sub.f --(CH.sub.2).sub.y --Si(OR.sup.14).sub.3-z O.sub.z /2(VIII)

wherein;

z is a number from about 0.5 to about 3.0;

y is an integer from 2 to about 10;

each R¹⁴ is independently C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy or C_a H_2a R_f ;

a is an integer from 1 to about 10; and

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen;

an oligomeric compound having the formula;

space="preserve" listing-type="equation">R.sub.f --Ar--Si(OR.sup.14).sub.3-z O.sub.z /2 (IX)

wherein;

z is a number from about 0.5 to about 3.0;

each R¹⁴ is independently C₁ to about C₈ alkyl, C₁ to about C₁₀ carboxy, C₁ to about C₁₀ fluorocarboxy or C_a H_2a R_f ;

a is an integer from 1 to about 10;

Ar is a divalent aromatic radical; and

R_f has up to about 18 carbon atoms and is selected from the group consisting of;

(a) C₁ to about C₁₈ perfluoroalkyl;

(b) -- CF₂ CF(CF₃)O!_r --CF₂ --CF₂ --CF₃, wherein r is an integer of at least 1;

(c) --CF₂ --(CF₂ --O)_q --CF₃, wherein q is an integer of at least 2; and

(d) --CH₂ --C(CF₃)₂ --CF₂ --CF₂ --CF₃ ;

each R_f optionally substituted with one or more hydrogen.

16. The fluoropolymer nanocomposite of claim 1 wherein the fluoropolymer is selected from the group consisting of:

polytetrafluoroethylene;

a copolymer derived from tetrafluoroethylene and hexafluoropropylene;

a copolymer derived from tetrafluoroethylene and perfluoromethylvinylether;

a copolymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether;

a copolymer derived from tetrafluoroethylene and 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole; and

a copolymer derived from tetrafluoroethylene and hexafluoropropylene oxide.

17. The fluoropolymer nanocomposite of claim 16 wherein the fluoropolymer is the copolymer derived from tetrafluoroethylene and hexafluoropropylene or a copolymer derived from tetrafluoroethylene and 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

18. A process for the preparation of a fluoropolymer nanocomposite comprising (a) a fluoropolymer phase comprising at least one fluoropolymer;

and (b) a partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase and exhibiting no particles or substantially all particles having a particle size of less than about 75 nm;

comprising;

(a) contacting at least one fluoropolymer soluble in a fluorinated solvent with at least one inorganic oxide precursor soluble in the fluorinated solvent and an optional gelling agent in the presence of the fluorinated solvent to form a solution;

(b) allowing the inorganic oxide precursor to partially or fully cross-link to form an inorganic oxide phase dispersed within a fluoropolymer phase; and

(c) optionally, isolating the fluoropolymer nanocomposite.

19. The process of claim 18 wherein the fluorinated solvent is selected from the group consisting of:

perfluoro(butyl THF), a mixture of perfluorotrialkylamines, C₃ F₇ OCHFCF₃, hexafluorobenzene, perfluorophenanthrene, perfluoromethylcyclohexane, and perfluoro(n-ethylmorpholine).

20. The process of claim 18 wherein the gelling agent is selected from the group consisting of:

trifluoroacetic acid, perfluoropropionic acid, and trifluoromethanesulfonic acid.

21. The process of claim 18 wherein the gelling agent is formic acid in tetrahydrofuran or in methylene chloride and the gelling agent is contacted within the inorganic oxide precursor prior to contact with the fluoropolymer and fluorinated solvent.

22. A coating composition, comprising a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

23. A coated substrate wherein the coating comprises a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

24. The coated substrate of claim 23 wherein the substrate is selected from the group consisting of:

glass, ceramic, plastic, rubber, elastomer, wood and metal.

25. A coated substrate wherein the coating is a multilayer coating comprising:

a primer, a top coat, and optionally one or more intermediate coats between the primer and the topcoat, wherein the topcoat is a fluoropolymer and the primer is a coating comprising, a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

26. The coated substrate of claim 25 wherein the substrate is selected from the group consisting of:

glass, ceramic, plastic, rubber, elastomer, wood and metal.

27. The coated substrate of claim 25 wherein the topcoat is a co-polymer derived from tetrafluoroethylene and bis 2,2-(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

28. The coated substrate of claim 25 wherein the topcoat is a co-polymer derived from tetrafluoroethylene and hexafluoropropylene.

29. The coated substrate of claim 25 wherein the topcoat is a co-polymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether.

30. An anti-reflective coating for an optoelectronic display device, comprising:

a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

31. The anti-reflective coating of claim 30 wherein the fluoropolymer is a co-polymer derived from tetrafluoroethylene and bis-2,2-(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

32. The anti-reflective coating of claim 30 wherein the fluoropolymer is a copolymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether.

33. An interlayer dielectric coating having improved dimensional stability and improved bonding to metal top coats after thermal cycling, comprising:

a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent.

34. The interlayer dielectric coating of claim 33 wherein the fluoropolymer is a co-polymer derived from tetrafluoroethylene and bis-2,2-(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

35. The interlayer dielectric coating of claim 33 wherein the fluoropolymer is a co-polymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether.

36. An article of cookware comprising a metal substrate coated with a scratch-resistant, non-stick coating system wherein said coating system comprises a primer applied to a metal substrate and a topcoat adhered to said primer,

said primer comprising:

a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent; and

said topcoat comprising a copolymer derived from tetrafluoroethylene and 2,2-bis(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

37. The article of claim 36 wherein the fluoropolymer is a co-polymer derived from tetrafluoroethylene and bis-2,2-(trifluoromethyl)-4,5-difluoro-1,3-dioxole.

38. The article of claim 36 wherein the fluoropolymer is a co-polymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether.

39. An article of cookware comprising a metal substrate coated with a scratch-resistant, non-stick coating system wherein said coating system comprises a primer applied to a metal substrate and a topcoat adhered to said primer,

said primer comprising:

a fluoropolymer nanocomposite, said fluoropolymer nanocomposite comprising, a fluoropolymer phase comprising at least one fluoropolymer, and at least one partially or fully cross-linked inorganic oxide phase prepared from at least one inorganic oxide precursor, said inorganic oxide phase being dispersed within said fluoropolymer phase, said inorganic oxide phase exhibiting either no particles or substantially all particles present in the inorganic oxide phase having a particle size of less than about 75 nm, the fluoropolymer and the inorganic oxide precursor being soluble in a fluorinated solvent; and

said topcoat comprising a copolymer derived from tetrafluoroethylene and hexafluoropropylene.

40. The cookware of claim 39 wherein the fluoropolymer is a copolymer derived from tetrafluoroethylene and at least one perfluoroalkylvinylether.