Reaction of perfluoroolefins with Bis (Silyl) ethers to produce fluorinated compounds

A process for producing a polymer consisting essentially of the repeat unit --[R.sub.f.sup.1 C.dbd.C(R.sub.f.sup.2)ORO]-- comprising, a condensation reaction of a bis(silyl)ether of the formula R.sup.2 R.sup.3 R.sup.4 SiOROSiR.sup.5 R.sup.6 R.sup.7 with a bis(vinyl) ether of the structure R.sub.f.sup.1 (F)C.dbd.C(R.sub.f.sup.2)OROC(R.sub.f.sup.2).dbd.C(F)R.sub.f.sup.1 in the presence of a suitable catalyst,

• wherein:
• R is a diradical of the formula:
• --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valences of the diradical not be attached to fluorine atoms, and when x is an integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --C.sub.6 H.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6 with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer of 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• or
• --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer of 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together wherein R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 taken together are --(CF.sub.2).sub.m --, R shall not be --CH.sub.2 (CF.sub.2).sub.s CH.sub.2 -- where s is an integer from 1 to 12 and wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.

The process of preparing a polymer consisting essentially of the repeat unit

• --[C(.dbd.CFR.sub.f.sup.1)OR.sup.8 O]-- (B)
• wherein R.sub.f.sup.1 is --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10 and wherein R.sup.8 is R, where R is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• by a polycondensation reaction whereby a bis(silyl) ether of the formula, R.sup.2 R.sup.3 R.sup.4 SiOROSiR.sup.5 R.sup.6 R.sup.7 and a perfluoroolefin of the formula R.sub.f.sup.1 (F)C.dbd.CF.sub.2 are reacted in the presence of a catalyst, and wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.

The process of preparing a macrocyclic compound of the structure:

• [C(R.sub.f.sup.1).dbd.C(R.sub.f.sup.2)ORO].sub.w (c)
• wherein R is a diradical of the formula
• --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f R.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• and R.sub.f.sup.1, R.sub.f.sup.2, are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 are as defined, then R shall not be --CH.sub.2 (CF).sub.s CH.sub.2 -- where s is an integer from 1 to 12, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 --, and w is 1, 2, 3 or 4;
• comprising a condensation reaction between a silyl ether of the formula R.sup.2 R.sup.3 R.sup.4 SiOROSiR.sup.5 R.sup.6 R.sup.7 and a perfluoroolefin of the formula R.sub.f.sup.1 (F)C.dbd.C(F)R.sub.f.sup.2 in dilute solution in a solvent in the presence of a catalyst, where R.sub.f.sup.1 and R.sub.f.sup.2 are as defined above and wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.

A process for preparing the macrocyclic compound of the structure:

• [C(R.sub.f.sup.1).dbd.C(R.sub.f.sup.2)ORO].sub.w (c)
• wherein R.sub.f.sup.1 and R.sub.f.sup.2 are R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 are as defined, then R shall not be --CH.sub.2 (CF).sub.s CH.sub.2 -- where s is an integer from 1 to 12, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 --, wherein w=2 or 4, comprising reacting a bis(vinyl)ether of the formula R.sub.f.sup.1 (F)C.dbd.C(R.sub.f.sup.2)ORO(R.sub.f.sup.2)C.dbd.C(F)R.sub.f.sup.1 with a bis(silyl) ether of the formula R.sup.2 R.sup.3 R.sup.4 SiOROSiR.sup.5 R.sup.6 R.sup.7 in dilute solution in a solvent and in the presence of a catalyst, at a temperature of -50.degree. C. to 120.degree. C., wherein R.sup.1 is --CH.sub.2-f R.sub.f, wherein f is 0 or an integer from 1 to 2x;
• and wherein R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 are as defined, then R shall not be --CH.sub.2 (CF).sub.s CH.sub.2 -- where s is an integer from 1 to 12, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 --;
• and wherein R is a diradical of the formula
• --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f R.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• and R.sub.f.sup.1, R.sub.f.sup.2, are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2) .sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 are as defined, then R shall not be --CH.sub.2 (CF).sub.s CH.sub.2 -- where s is an integer from 1 to 12, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 --, and w is 1, 2, 3 or 4.

A process for preparing A macrocyclic compound of the structure:

• ##STR62## wherein R.sub.f.sup.1 is --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10, R.sup.8 is R and R is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• and w is 1, 2, 3 or 4, comprising:
• reacting a bis(silyl)ether of the structure R.sup.2 R.sup.3 R.sup.4 SiOROSiR.sup.5 R.sup.6 R.sup.7 with a perfluoroolefin of the structure R.sub.f.sup.1 (F)C.dbd.CF.sub.2 in dilute solution in solvent and in the presence of a catalyst at a temperature of -50.degree. C. to 120.degree. C., wherein R.sub.f.sup.1 is --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10, and wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.

A process for preparing a bis(vinyl) ether of formula D of the structure:

• R.sub.f.sup.1 (F)C.dbd.C(R.sub.f.sup.2)OROC(R.sub.f.sup.2).dbd.C(F)R.sub.f.sup.1 (D),
• wherein:
• R is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and
• --CH.sub.4-d R.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, provided that when R.sub.f.sup.1 and R.sub.f.sup.2 are as defined, then R shall not be --CH.sub.2 (CF).sub.s CH.sub.2 -- where s is an integer from 1 to 12, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 --, comprising, reacting a bis(silyl) ether of the formula R.sup.2 R.sup.3 R.sup.3 SiOROSiR.sup.5 R.sup.6 R.sup.7 and perfluoroolefin of the formula R.sub.f.sup.1 (F)C.dbd.C(F)R.sub.f.sup.2 in the presence of a solvent and in the presence of a catalyst which is a source of fluoride ion, and wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.

A process for the preparation of

• composition R.sub.f.sup.1 (F)C.dbd.C(F)OR.sup.8 OC(F).dbd.C(F)R.sub.f.sup.1 (E),
• wherein:
• R.sub.f.sup.1 is --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• R.sup.8 is R and is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and
• --CH.sub.4-d F.sub.d R.sup.1 CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• comprising, a reaction of a bis(silyl)ether of the structure R.sup.2 R.sup.3 R.sup.4 SiOR.sup.8 OSiR.sup.5 R.sup.6 R.sup.7 with an excess of perfluoroolefin of the structure R.sub.f.sup.1 (F)C.dbd.CF.sub.2, in a solvent and in the presence of a catalyst, wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --;
• and wherein R.sub.f.sup.1 and R.sup.8 are as defined above.

A process for the preparation of

• R.sub.f.sup.1 R.sub.f.sup.2 C.dbd.C(R.sub.f.sup.6)OR.sup.8 OC(R.sub.f.sup.6).dbd.CR.sub.f.sup.2 R.sub.f.sup.1 (E')
• wherein:
• R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10;
• or R.sub.f.sup.1 and R.sub.f.sup.2 taken together where R.sub.f.sup.1 and R.sub.f.sup.2 are in the cis configuration are --(CF.sub.2).sub.m --, wherein m is 2, 3 or 4, C.sub.6 F.sub.5 --, C.sub.10 F.sub.7 -- or C.sub.12 F.sub.9 ;
• and each R.sub.f.sup.6 is independently the same as R.sub.f.sup.1, comprising a reaction of R.sup.2 R.sup.3 R.sup.4 SiOR.sup.8 OSiR.sup.5 R.sup.6 R.sup.7 with an excess of perfluoroolefin of the formula structure R.sub.f.sup.1 (F)C.dbd.CF.sub.2, in a solvent and in the presence of a catalyst, wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 -- and R.sup.8 is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x.

A process for preparing a polymer consisting essentially of the repeat unit:

• --[C(.dbd.CFR.sub.f.sup.1)OR.sup.8 O]-- (B)
• comprising, reacting a bis(silyl)ether of the structure R.sup.2 R.sup.3 R.sup.4 SiOR.sup.8 OSiR.sup.5 R.sup.6 R.sup.7 with a perfluoroolefin of the structure R.sub.f.sup.1 (F)CF.sub.2 or a bis(vinyl) ether of the formula R.sub.f.sup.1 (F)C.dbd.C(R.sub.f.sup.2)ORO(R.sub.f.sup.2)C.dbd.C(F)R.sub.f.sup.1 in the presence of a catalyst at a temperature of -50.degree. C. to 120.degree. C. wherein R.sub.f.sup.1 and R.sub.f.sup.2 are independently --C.sub.z F.sub.2z+1, wherein z is an integer from 1 to 10, wherein R.sup.8 is R, and R is a diradical of the formula --C.sub.x H.sub.2x-y F.sub.y -- where x is an integer from 2 to 20, y is 0 or an integer from 1 to 2x for a given value of x, but with the additional proviso that the carbon atoms containing the free valence of the diradical not be attached to fluorine atoms, and when x is a integer from 4 to 20 some of the carbon atoms may be internally interrupted with oxygen atoms forming ether structures and with the proviso that the oxygen atoms be separated by two or more carbon atoms;
• --CH.sub.4-a F.sub.a --, wherein a is 0, 1, 2, 3, or 4;
• --C.sub.10 H.sub.6-b F.sub.b --, wherein b is 0 or an integer from 1 to 6, with the proviso that the radical bonds are not on adjacent carbon atoms;
• --C.sub.12 H.sub.8-c F.sub.c --, wherein c is 0 or an integer from 1 to 8, with the proviso that the radical bonds are not on adjacent carbon atoms;
• and
• --CH.sub.4-d F.sub.d --R.sup.1 --CH.sub.4-e F.sub.e --, wherein d and e are independently 0 or an integer from 1 to 4, R.sup.1 is --CH.sub.2-f F.sub.f --, wherein f is 0 or an integer from 1 to 2x;
• wherein R.sup.8 is R and R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7 are wherein R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, R.sup.7 are independently CH.sub.3 -- or C.sub.2 H.sub.5 -- or one of R.sup.2, R.sup.3, R.sup.4, R.sup.5 R.sup.6, and R.sup.7 may be C.sub.6 H.sub.5 -- with the remainder of the groups being independently CH.sub.3 -- or C.sub.2 H.sub.5 --.