Method for producing reactive intermediates for transport polymerization

1 . A method of producing a reactive intermediate having at least two free radicals from a precursor having a general formula of X m —Ar—(CZ′Z″Y) n via a reactor made at least partially of a material M that is reactive with the precursor to produce at least one of M a Y b and M c X d , wherein Ar is an aromatic moiety, the method comprising:

heating the reactor;

introducing a flow of precursor into the reactor;

contacting the precursor with the material M to form the reactive intermediate and at least one of M a Y b and M c X d ; and

reducing M a Y b to M and a compound comprising Y and/or reducing M c X d to M and a compound comprising X after forming the reactive intermediate and the at least one of M a Y b and M c X d .

2 . The method of claim 1 , wherein X and Y are leaving groups each comprising one or more of ketene and carboxyl groups, bromine, iodine, —NR 2 , —N + R 3 , —SR, —SO 2 R, —OR, ═N + ═N—, —C(O)N 2 , and —OCF—CF 3 , wherein R is an alkyl or aromatic group.

3 . The method of claim 1 , wherein Y is Br, and wherein m=0 and n=2.

4 . The method of claim 1 , wherein M comprises one or more comprises one or more of chromium, nickel, titanium, gold, iron, platinum, chromium, silver, cobalt and tungsten.

5 . The method of claim 4 , wherein Z′ is F, Z″ is F, M is nickel and Y is Br.

6 . The method of claim 1 , wherein heating the reactor comprises heating the reactor to a temperature lower than a temperature at which Y is dissociated from the precursor in the absence of M.

7 . The method of claim 1 , wherein introducing a flow of precursor into the reactor comprises introducing a flow of 1-6 sccm of precursor into the reactor.

8 . The method of claim 1 , wherein heating the reactor comprises heating a heater body within the reactor substantially exclusively via radiative heating.

9 . The method of claim 1 , wherein heating the reactor comprises heating an interior surface of the reactor to an average temperature equal to or less than 700 degrees Celsius.

10 . The method of claim 9 , wherein the average temperature equal to or less than 700 degrees Celsius has a variation of equal to or less than +/−20 degrees Celsius across the interior surface of the reactor.

11 . The method of claim 1 , wherein Ar is a phenyl or a partially or fully substitute phenyl.

12 . The method of claim 1 , wherein reducing M a Y b to M and a compound comprising Y comprises reacting M a Y b with hydrogen.

13 . The method of claim 12 , wherein M is nickel and Y is bromine, and wherein reducing M a Y b comprises reacting NiBr 2 with hydrogen to form Ni and HBr.

14 . The method of claim 1 , wherein reducing M a Y b comprises first converting M a Y b to an oxide, and then reducing the oxide.

15 . The method of claim 14 , wherein M is nickel and Y is bromine, and wherein reducing M a Y b comprises converting NiBr 2 to NiO, and then converting NiO to nickel and H 2 O.

16 . The method of claim 1 , wherein reducing M a Y b to M comprises heating M a Y b to a temperature at which M a Y b decomposes into. M and Y.

17 . A method of producing a reactive intermediate of the general formula Ar—(CF 2 *) 2 from a precursor having a general formula of Ar—(CF 2 Br) 2 via a reactor made at least partially of a material M that is reactive with the precursor to produce MBr b , wherein Ar is an aromatic moiety and wherein * is a free radical, the method comprising:

heating the reactor;

introducing a flow of precursor into the reactor;

contacting the precursor with the material M to form the reactive intermediate and MBr b ; and

reducing MBr b to M and a compound comprising Br after forming MBr b and the reactive intermediate.

18 . The method of claim 17 , wherein M comprises one or more of chromium, nickel, titanium, gold, iron, platinum, chromium, silver, cobalt and tungsten.

19 . The method of claim 17 , wherein heating the precursor comprises heating the precursor to a temperature lower than a temperature at which Br is dissociated from the precursor in the absence of M.

20 . The method of claim 17 , wherein introducing a flow of precursor into the reactor comprises introducing a flow of 1-6 sccm of precursor into the reactor.

21 . The method of claim 17 , wherein heating the reactor comprises heating a heater body within the reactor substantially exclusively via radiative heating.

22 . The method of claim 17 , wherein heating the reactor comprises heating an interior surface of the reactor to an average temperature equal to or less than 700 degrees Celsius.

23 . The method of claim 22 , wherein the average temperature equal to or less than 700 degrees Celsius has a variation equal to or less than +/−20 degrees Celsius across the interior surface of the reactor.

24 . The method of claim 17 , wherein Ar is a phenyl or partially or fully substituted phenyl.

25 . The method of claim 17 , wherein reducing MBr b to M and a compound comprising Br comprises reacting MBr b with hydrogen.

26 . The method of claim 25 , wherein M is nickel, and wherein reducing MBr b comprises reacting NiBr 2 with hydrogen to form Ni and HBr.

27 . The method of claim 17 , wherein reducing MBr b comprises first converting MBr b to an oxide, and then reducing the oxide.

28 . The method of claim 27 , wherein M is nickel, and wherein reducing converting MBr b to an oxide and then reducing the oxide comprises converting NiBr 2 to NiO, and then converting NiO to nickel and H 2 O.

29 . The method of claim 17 , wherein reducing MBr b comprises heating MBr b to a temperature at which MBr b thermally decomposes into M and Br 2 .