Methods of making halogenated partially fluorinated compounds

This application is a national stage filing under 35 U.S.C. 371 of PCT/US2015/063947, filed Dec. 4, 2015, which claims the benefit of U.S. Application No. 62/095,300, filed Dec. 22, 2014, the disclosure of which is incorporated by reference in its/their entirety herein.

Methods of making halogenated partially fluorinated compounds from a perhalogenated terminal olefin are disclosed.

Bromine/iodine containing compounds are key materials for producing peroxide curable elastomers. They are used as chain transfer agents (CTA) and/or as cure site monomers (CSM) in polymer synthesis. For example, diiodoperfluorobutane [I(CF 2 ) 4 I] is a popular chain transfer agent.

Typically, α,ω-diiodo (per)fluoroalkanes are prepared by radical reaction of iodine with a fluoroolefin, reaction of ICF 2 I with a (fluoro)olefin, telomerization of a (fluoro)olefin with shorter-chained α,ω-diiodo fluoroalkanes, and coupling reactions of diiodofluoroalkanes.

Partially fluorinated α,ω-diiodo fluoroalkanes, such as I—CF 2 —CFH—CF 2 —I have been prepared by reaction of pentafluorocyclopropane (c-C 3 F 5 H) with iodine, as described in J. Am. Chem. Soc. 1995, 117, 5397-5398; or by the reaction of CF 2 I 2 with trifluoroethylene (CF 2 ═CHF), as described in J. Org. Chem. 2004, 69, 2394-2403.

There is a desire for alternative methods of making partially fluorinated compounds, which may be simpler, use more readily available starting materials, and/or are more cost effective than current manufacturing processes.

In one aspect, a method of making a partially fluorinated halogenated compound is described comprising:

(a) providing a compound having the following structure of formula (I):

wherein X and Y are independently selected from F and Cl; wherein R f is a fluorinated monovalent group comprising 1 to 10 carbon atoms; (b) contacting the compound with at least one of

(i) an iodine or bromine containing salt in the presence of an acid; and (ii) aqueous solution of HZ wherein Z is selected from I and Br to form the halogenated partially fluorinated compound of the formula (II):

wherein X and Y are independently selected from F and Cl; Z is selected from I and Br; and R′ f is a fluorinated monovalent group comprising 1 to 10 carbon atoms.

In another aspect, novel halogenated partially fluorinated compounds are described.

The above summary is not intended to describe each embodiment. The details of one or more embodiments of the invention are also set forth in the description below. Other features, objects, and advantages will be apparent from the description and from the claims.

As used herein, the term

“a”, “an”, and “the” are used interchangeably and mean one or more; and

“and/or” is used to indicate one or both stated cases may occur, for example A and/or B includes, (A and B) and (A or B).

Also herein, recitation of ranges by endpoints includes all numbers subsumed within that range (e.g., 1 to 10 includes 1.4, 1.9, 2.33, 5.75, 9.98, etc.).

Also herein, recitation of “at least one” includes all numbers of one and greater (e.g., at least 2, at least 4, at least 6, at least 8, at least 10, at least 25, at least 50, at least 100, etc.).

The present disclosure is directed toward the addition reaction of an iodine or bromine containing compound to a terminal double bond containing compound of the formula (I)

wherein X and Y are independently selected from F and Cl; wherein R f is a fluorinated monovalent group comprising 1 to 10 carbon atoms.

R f may be partially fluorinated (comprising at least one carbon-hydrogen bond and at least one carbon-fluorine bond) or perfluorinated (comprising at least one carbon-fluorine bond and no carbon-hydrogen bonds). R f may be linear, branched, or cyclic. R f may be saturated or unsaturated, optionally comprising at least one catenated O, S, and/or N (e.g, an ether linkage). In some embodiments, R f comprises at least one halogen selected from Cl, Br, and I.

In one embodiment, R f comprises a functional group selected from a sulfate, a carboxylate, a nitrile, and a sulfonate.

In one embodiment, R f is selected from —CF 2 —O—SO 2 F; —CF 2 —I; —CF 2 —Br; —O—(CF 2 ) a —F; —O—(CF 2 ) a —I; —O—(CF 2 ) a —Br; —O—(CF 2 ) b —O—CF═CXY wherein X and Y are independently selected from F and Cl; a is an integer from 1-10; and b is an integer from 2-4.

Exemplary, compounds of formula (I) have the structure:

X′—CF 2 —CF═CF 2 , CF 3 —O—CF═CF 2 , C 3 F 7 —O—CF═CF 2 , CF 3 CF 2 CF 2 —O—CF(CF 3 )—CF 2 —O—CF═CF 2 , X′—(CF 2 ) 1-4 —CF═CF 2 , CF 3 —O—(CF 2 ) 3 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 2-4 —O—CF═CF 2 , X′—CF 2 —CF 2 —O—(CF 2 ) 2-4 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) 2-4 —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) 2-4 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —O—(CF 2 ) 2-4 —O—CF 2 CF═CF 2 , X′—CF 2 —CF 2 —O—CF═CF 2 , X′—CF 2 —CF 2 —O—CF 2 —CF═CF 2 , X′—CF(CF 3 )—CF 2 —O—CF═CF 2 , X′—CF(CF 3 )—CF 2 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF═CF 2 , X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —O—CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF 2 —CF═CF 2 , or X′—CF 2 —CF 2 —O—(CF 2 ) 2 —(O—CF(CF 3 )CF 2 ) 1-2 —O—CF 2 ═CF 2 wherein X′ is selected from Br, I, C(O)X″, and SO 2 X″ wherein X″ is selected from F, Cl, OH, and salts thereof.

It has been discovered that by reacting the compound of formula (I) with either (i) an iodine or bromine containing salt in the presence of an acid or (ii) an aqueous solution of HZ wherein Z is selected from I and Br, the compound of formula (I) undergoes an addition reaction forming a halogenated partially fluorinated compound of formula II

wherein X and Y are the same as above, Z is selected from I and Br, and R′ f is a monovalent fluorinated group.

In one embodiment, R′ f is the same as R f in the starting material. In another embodiment R′ f is different from R f .

Exemplary, compounds of formula (II) have the structure:

X′—CF 2 —CFH—CF 2 —Z, CF 3 —O—CFH—CF 2 —Z, C 3 F 7 —O—CFH—CF 2 —Z, CF 3 CF 2 CF 2 —O—CF(CF 3 )—CF 2 —O—CFH—CF 2 —Z, X′—(CF 2 ) 1-4 —CFH—CF 2 —Z, CF 3 —O—(CF 2 ) 3 —O—CFH—CF 2 —Z, Z—CF 2 —CFH—O—(CF 2 ) 2-4 —O—CF═CF 2 , Z—CF 2 —CFH—O—(CF 2 ) 2-4 —O—CFH—CF 2 —Z, Z—CF 2 —CFH—O—(CF 2 ) 2-4 —O—CF 2 —CF═CF 2 , Z—CF 2 —CFH—O—(CF 2 ) 2-4 —O—CF 2 —CFH—CF 2 —Z, CF 2 ═CF—O—(CF 2 ) 2-4 —O—CF 2 —CFH—CF 2 —Z, Z—CF 2 —CFH—CF 2 —O—(CF 2 ) 2-4 —O—CF 2 —CF═CF 2 , Z—CF 2 —CFH—CF 2 —O—(CF 2 ) 2-4 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—(CF 2 ) 2-4 —O—CF 2 CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF(CF 3 )—CF 2 —O—CFH—CF 2 —Z, X′—CF(CF 3 )—CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) 1-2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—(CF 2 ) 2 —(O—CF(CF 3 )CF 2 ) 1-2 —O—CFH—CF 2 —Z wherein Z is Br and I; X′ is selected from Br, I, C(O)X″, and SO 2 X″

wherein X″ is selected from F, Cl, OH, and salts thereof. Exemplary salts of the C(O)OH include for example, ammonium salts, alkali and alkaline earth metal salts, such as C(O)ONa.

In one embodiment, the compound of formula (I) is reacted with an iodine or bromine containing salt in the presence of an acid.

The iodine or bromine containing salt is of the formula Z i M +i , where Z is selected from I and Br, and M is a counter ion with a valency of i in the range of 1 to 4, preferably i is 1 to 2. In one embodiment, the counter ion is organic, such as an alkylammonium (e.g., tetramethylammonium, terabutylammonium, etc.). In another embodiment, the counter ion is inorganic, such as an ammonium, or a metal, such as alkali metal (e.g., Na, K, Li, etc.) or alkaline earth metal (e.g., Mg, Ca, etc.).

Typically the molar ratio of the salt to formula (I) is 0.5:1 to 10:1, preferably 1:1 to 5:1.

An acid is used to favor the addition reaction of the halogenide to the terminal olefin. Generally the lower the pKa (the stronger the acid) the better the yield for the addition reaction. In one embodiment the acid has a pKa of no more than 4.8 at 25° C., or even no more than 2. Exemplary acids include sulfonic acids (e.g. trifluoromethanesulfonic acid) and carboxylic acids (e.g. acetic acid and trifluoroacetic acid), or mixtures thereof. The acids may be diluted with water to any concentration, preferably the acids or mixtures thereof are used in the absence of water.

The reaction of the iodine or bromine containing salt with the compound of formula (I) may occur in an aqueous solution or a non-aqueous solution.

Exemplary solvents that are preferably used are non-reactive organic solvents, such as those which have a boiling point up to 275° C. (e.g. triglyme and tetraglyme), preferably those having a boiling point up to 170° C. (e.g. CH 3 CN, tetrahydrofuran, propionitrile, monoglyme, diglyme) or mixtures thereof. Exemplary solvents include: acetonitrile, diglyme, monoglyme, propionitrile, triglyme, tetraglyme, tetrahydrofuran, water, and mixtures thereof.

In one embodiment, the reaction of the iodine or bromine containing salt with the compound of formula (I) may occur at pressures from at least ambient (1 bar), 3 bar, or even 5 bar to pressures no higher than 10 bar, 15 bar, or even 20 bar. In one embodiment, the reaction of the iodine or bromine containing salt with the compound of formula (I) may occur at temperatures of at least −10° C., 0° C., 20° C., 25° C., 30° C., 40° C., or even 50° C.; and at most 275° C., 250° C., 220° C., 200° C., 180° C., 150° C., 120° C., 110° C., or even 100° C.

In another embodiment, the compound of formula (I) is reacted with an aqueous solution comprising HZ wherein Z is selected from I and Br.

In one embodiment, the molar ratio of HZ to formula (I) is 0.5:1 to 10:1, preferably 1:1 to 5:1.

In one embodiment, the reaction of HZ with the compound of formula (I) may occur at pressures from at least ambient (1 bar), 3 bar, or even 5 bar to pressures no higher than 10 bar, 15 bar, or even 20 bar. In one embodiment, the reaction of HZ with compound of formula (I) may occur at temperatures of at least −10° C., 0° C., 20° C., 25° C., 30° C., 40° C., or even 50° C.; and at most 275° C., 250° C., 220° C., 200° C., 180° C., 150° C., 120° C., 110° C., or even 100° C.

In one embodiment, the reaction of HZ with the compound of formula (I) can be conducted in the presence of cosolvents. Exemplary cosolvents that are preferably used are non-reactive organic solvents, as those which have a boiling point up to 275° C. (e.g. triglyme and tetraglyme), preferably those having a boiling point up to 170° C. (e.g. CH 3 CN, tetrahydrofuran, propionitrile, monoglyme, diglyme) or mixtures thereof. Exemplary solvents include: acetonitrile, diglyme, monoglyme, propionitrile, triglyme, tetraglyme, tetrahydrofuran, water, and mixtures thereof.

The reactions described above involve the addition of the HBr an HI group across the double bond of formula (I), thus, the R f group should remain unchanged in the product (i.e., R′ f in formula (II)). However, as mentioned above, in one embodiment, R′ f is different from R f . Such differences may be due to the reaction of the iodine or bromine containing compounds (i.e., the iodine or bromine salts in the presence of an acid or HZ with Z═I, Br) with reactive groups located in the R f group (e.g. carboxylate, nitrile, or unsaturated groups).

When the compound of formula (I) comprises two terminal double bonds (such as divinyl ethers of the formula CF 2 ═CF—O—(CF 2 ) 2-4 —O—CF═CF 2 or CF 2 ═CF—O—CF═CF 2 ), the amount of compound according to formula (I) to the amount of the iodine or bromine containing compounds (i.e., the iodine or bromine salts in the presence of an acid or HZ with Z═I, Br) can be adjusted to favor the reaction of one or both terminal double bonds.

As will be shown in the examples, the preparation of I—CF 2 —CFH—CF 2 —I using the methods disclosed herein can occur in either a two-step or a one-step synthesis. For example, perfluoroallyl fluorosulfate (CF 2 ═CF—CF 2 —O—SO 2 F) can be reacted in a first step with an iodine containing salt via nucleophilic substitution reaction, followed by a second step, wherein the CF 2 ═CF—CF 2 —I is reacted with an iodine containing salt in the presence of an acid. Alternatively, the perfluoroallyl fluorosulfate can directly be reacted with an iodine containing salt in the presence of an acid.

Further, in another embodiment, the halogenated partially fluorinated compound of formula (II) can be reacted with a hydrocarbon olefin such as ethylene to elongate the halogenated partially fluorinated compound, adding, for example, a —CH 2 —CH 2 —group. This group on the elongated halogenated partially fluorinated compound can then be reduced to form a partially fluorinated compound according to formula (III):

R″—CFH—CF 2 —CH═CH 2

wherein R″ is selected from X′—CF 2 —, CH 2 ═CH—CF 2 —, CF 3 O—, CF 3 CF 2 CF 2 —O—, or CF 3 —O—(CF 2 ) 3 —O—, wherein X′ is selected from Br, I, C(O)X″, and SO 2 X″ wherein X″ is selected from F, Cl, OH, and salts thereof

Such insertions of the hydrocarbon olefin into the halogenated partially fluorinated compounds of formula (II) could be conducted by known methods in the absence or in the presence of a radical initiator (e.g. di-tert-butyl peroxide, azobisisobutyronitrile), in the absence or in the presence of a catalyst (e.g. Ni, Cu, Fe, CuCl/CH 3 CN, P(OEt) 3 , Ru/C, Pt/C, Ag/Al 2 O 3 , Ni(CO) 2 (PPh 3 ) 2 , W(CO) 5 P(OEt) 3 , Mo(CO) 5 (PPh 3 ), where Et is ethyl and Ph is phenyl). Exemplary reaction times are from at least 2, 3, 6, or even 10 hrs up to 12, 15, or even 24 hrs or more. Exemplary reaction temperatures are from at least 30, 50, 75, 100, or even 150° C. up to 175, 200, 225, or even 250° C. Typically the reaction is conducted in a steel or hastelloy autoclave.

Subsequently, the corresponding ethylene elongated compound can be reduced to a double bond by known methods (e.g. via KOH/phase transfer catalysts, KOH/EtOH, trialkylamines, Zn/DMF at temperatures ranging from at least 0, 25, 50, 75 or even 100° C. up to 175, 200, 225, or even 250° C.).

The compounds according to formulas (II) and (III) can be used, for example, as starting materials or building blocks in chemical synthesis, and/or as a chain transfer agents and/or cure site monomers in a fluoropolymer polymerization.

The reactions disclosed herein involve contacting the compound of formula (I) with an iodide or bromide ion in the presence of an acid. Advantageously, the reactions can be conducted at mild pressures and temperatures (for example, ambient pressure at 100° C.). Advantageously, in one embodiment, the resulting products can be isolated from the reaction by phase separation. For example, the reaction product is washed with an aqueous solution which separates the compound of formula (II) from the starting materials and by-products. In one embodiment the desired product is isolated via distillation.

Exemplary embodiments of the present disclosure are listed below:

(a) providing a compound having the following structure of formula (I):

wherein X and Y are independently selected from F and Cl; wherein R f is a fluorinated monovalent group comprising 1 to 10 carbon atoms; (b) contacting the compound with at least one of

(i) an iodine or bromine containing salt in the presence of an acid; and (ii) aqueous solution of HZ wherein Z is selected from I and Br to form the halogenated partially fluorinated compound of the formula (II):

wherein X and Y are independently selected from F and Cl; Z is selected from I and Br; and R′ f is a fluorinated monovalent group comprising 1 to 10 carbon atoms.

Embodiment 2: The method of embodiment 1, wherein R f comprises at least one catenated oxygen or sulfur atom.

Embodiment 3: The method of any one of the previous embodiments, wherein R f comprises at least one halogen selected from at least one Cl, Br, and I.

Embodiment 4: The method of any one of the previous embodiments, wherein R f is a linear, branched or cyclic group.

Embodiment 5: The method of any one of the previous embodiments, wherein R f is selected from —CF 2 —O—SO 2 F; —CF 2 I; —CF 2 Br; —O—(CF 2 ) a —F; —O—(CF 2 ) a —I; —O—(CF 2 ) a —Br; —O—(CF 2 ) b —O—CF═XY wherein X and Y are independently selected from F and Cl and a is an integer from 1-10 and b is an integer from 2-4.

Embodiment 6: The method of any one of the previous embodiments, wherein the compound of formula (I) is selected from:

X′—CF 2 —CF═CF 2 , CF 3 —O—CF═CF 2 , C 3 F 7 —O—CF═CF 2 , CF 3 CF 2 CF 2 —O—CF(CF 3 )—CF 2 —O—CF═CF 2 , X′—(CF 2 ) m —CF═CF 2 , CF 3 —O—(CF 2 ) 3 —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) n —O—CF═CF 2 , X′—CF 2 —CF 2 —O—(CF 2 ) m —O—CF═CF 2 , CF 2 ═CF—O—(CF 2 ) n —O—CF 2 —CF═CF 2 , CF 2 ═CF—CF 2 —O—(CF 2 ) n —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —O—(CF 2 ) n —O—CF 2 CF═CF 2 , X′—CF 2 —CF 2 —O—CF═CF 2 , X′—CF 2 —CF 2 —O—CF 2 —CF═CF 2 , X′—CF(CF 3 )—CF 2 —O—CF═CF 2 , X′—CF(CF 3 )—CF 2 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF═CF 2 , X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —O—CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —O—CF 2 —CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF═CF 2 , X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF 2 —CF═CF 2 , and X′—CF 2 —CF 2 —O—(CF 2 ) 2 —(O—CF(CF 3 )CF 2 ) p —O—CF 2 ═CF 2 wherein X′ is selected from Br, I, C(O)X″, and SO 2 X″ wherein X″ is selected from F, Cl, OH, and salts thereof; m is an integer from 1-4; n is an integer from 2-4; and p is an integer from 1-2.

Embodiment 7: The method of any one of the previous embodiments, wherein R′ f is the same as R f .

Embodiment 8: The method of any one of the previous embodiments, wherein the iodine or bromine containing salt is selected from alkaline halogenides, alkaline earth halogenides, and tetraalkylammonium halogenides.

Embodiment 9: The method of any one of the previous embodiments, wherein the pKa of the acid is at most 4.8.

Embodiment 10: The method of any one of the previous embodiments, wherein the contacting of the compound of formula (I) with the iodine or bromine containing salt occurs in the presence of a solvent.

Embodiment 11: The method of embodiment 10, wherein the solvent is selected from acetonitrile, diglyme, monoglyme, propionitrile, tetraglyme, triglyme, tetrahydrofuran, and water.

Embodiment 12: The method of any one of the previous embodiments, wherein the contacting of the compound with the iodine or bromine containing salt or the aqueous solution of HZ is conducted at a pressure of 1 to 20 bar and a temperature of 20 to 200° C.

Embodiment 13: The method of any one of the previous embodiments, further comprising, (c) reacting the halogenated partially fluorinated compound of formula (II) with a (terminal) hydrocarbon olefin to elongate the halogenated partially fluorinated compound.

reducing the elongated halogenated partially fluorinated compound of embodiment 13 to form a compound of formula (III):

R″—CFH—CF 2 —CH═CH 2

wherein R″ is selected from X′—CF 2 —, CH 2 ═CH—CF 2 —, CF 3 O—, CF 3 CF 2 CF 2 —O—, and CF 3 —O—(CF 2 ) 3 —O—, wherein X′ is selected from Br, I, C(O)X″, and SO 2 X″ wherein X″ is selected from F, Cl, OH, and salts thereof.

Br—CF 2 —CFH—CF 2 —I, CF 3 —O—CFH—CF 2 —I, C 3 F 7 —O—CFH—CF 2 —Z, CF 3 —CF 2 —CF 2 —O—CF(CF 3 )—CF 2 —O—CFH—CF 2 —Z, I—(CF 2 ) n —CFH—CF 2 —I, I—(CF 2 ) m —CFH—CF 2 —Br, Br—(CF 2 ) m —CFH—CF 2 —I, Br—(CF 2 ) q —CFH—CF 2 —Br, CF 3 —O—(CF 2 ) 3 —O—CFH—CF 2 —Z, Z—CF 2 —CFH—O—(CF 2 ) n —O—CF═CF 2 , Z—CF 2 —CFH—O—(CF 2 ) n —O—CFH—CF 2 —Z, Z—CF 2 —CFH—O—(CF 2 ) n —O—CF 2 —CF═CF 2 , Z—CF 2 —CFH—O—(CF 2 ) n —O—CF 2 —CFH—CF 2 —Z, CF 2 ═CF—O—(CF 2 ) n —O—CF 2 —CFH—CF 2 —Z, Z—CF 2 —CFH—CF 2 —O—(CF 2 ) n —O—CF 2 —CF═CF 2 , Z—CF 2 —CFH—CF 2 —O—(CF 2 ) n —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—(CF 2 ) n —O—CF 2 CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF(CF 3 )—CF 2 —O—CFH—CF 2 —Z, X′—CF(CF 3 )—CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CFH—CF 2 —Z, X′—CF 2 —CF 2 —CF 2 —(O—CF(CF 3 )—CF 2 ) p —O—CF 2 —CFH—CF 2 —Z, X′—CF 2 —CF 2 —O—(CF 2 ) 2 —(O—CF(CF 3 )CF 2 ) p —O—CFH—CF 2 —Z, wherein Z is Br, I; X′ is selected from Br, I, C(O)X″, and SO 2 X″ wherein X″ is selected from F, Cl, OH, and salts thereof; m is an integer from 1-4; n is an integer from 2-4; and p is 1 or 2; and q is 3 or 4.

Advantages and embodiments of this disclosure are further illustrated by the following examples, but the particular materials and amounts thereof recited in these examples, as well as other conditions and details, should not be construed to unduly limit this invention. In these examples, all percentages, proportions and ratios are by weight unless otherwise indicated.

All materials are commercially available, for example from Sigma-Aldrich Chemical Company; Milwaukee, Wis., or known to those skilled in the art unless otherwise stated or apparent.

These abbreviations are used in the following examples: b.p.=boiling point, g=gram, h and hr=hour, min=minutes, mol=mole, mbar=millibar, and L=liter.