WO2019178095A1 - Stable and ion-conductive hydrocarbon-fluorocarbon materials as electrolytes for fuel cells and batteries - Google Patents

Stable and ion-conductive hydrocarbon-fluorocarbon materials as electrolytes for fuel cells and batteries Download PDF

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WO2019178095A1
WO2019178095A1 PCT/US2019/021847 US2019021847W WO2019178095A1 WO 2019178095 A1 WO2019178095 A1 WO 2019178095A1 US 2019021847 W US2019021847 W US 2019021847W WO 2019178095 A1 WO2019178095 A1 WO 2019178095A1
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ring
bivalent
independently chosen
cycloalkyl
polymer
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PCT/US2019/021847
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French (fr)
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Yong Gao
Rong Jiang
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Energao, Inc.
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Publication of WO2019178095A1 publication Critical patent/WO2019178095A1/en

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Definitions

  • the present disclosure generally relates to a novel hydrocarbon- fluorocarbon copolymer material having (a) an acid or a conjugate acid group as a cation-conductive electrolyte, or (b) an anion-exchange group as an anion- conductive material, the use of the same in applications such as chlor-alkali cells, proton exchange membrane fuel cells (PEMFCs), alkaline membrane fuel cells, phosphoric acid fuel cells, methanol fuel cells, electrolytic cells, flow batteries, and other devices, and the methods to make the same.
  • PEMFCs proton exchange membrane fuel cells
  • alkaline membrane fuel cells phosphoric acid fuel cells
  • methanol fuel cells phosphoric acid fuel cells
  • electrolytic cells electrolytic cells
  • flow batteries and other devices
  • PFSAs Perfluorosulfonic acids
  • chlor-alkali cells for caustic soda production. It is estimated that over 108,000 tons of caustic soda is produced every day in the U.S.
  • a PFSA membrane is employed to separate anode and cathode and transports Na + cations in a chlor- alkali cell.
  • PFSA membranes have found applications in the emerging markets of fuel cells, flow batteries and electrolyzers.
  • PFSA membrane for example, in a hydrogen PEMFC, a thin PFSA membrane (-100 microns) separates anode and cathode and it is also responsible for transporting protons (H + ) from anode to cathode to counter electron discharges.
  • protons H +
  • the PFSA film delivers protons from anode to cathode, in which protons are oxidized with oxygen gas (air) to water.
  • the fuel cell generates electrons and only water is produced as a byproduct— no C0 2 is generated.
  • Flow batteries can be used for the large-scale storage of energy produced from power plants, wind farms and solar power stations.
  • PFSAs are commercially available from polymer manufacturers: Nafion ® from DuPont-Dow Chemicals, Aquivion ® produced by Solvay, Flemion ® from AGC Chemicals, and 3M PFSA supplied by 3M. All of these PFSAs are comprised of a fully-fluorinated polymer backbone and fluoro-side chains (Kusoglu and Weber, Chem. Rev. 2017, 1 17, 987-1 104). The high loadings of fluorine atoms in these PFSAs give rise to the high production costs of PFSAs, which has limited the development and adoption of fuel cell and flow battery technologies by our society. Equally important, fluoropolymers are difficult for biological degradation processes. Disposal of spent PFSAs can lead to significant
  • One strategy to address the cost and environmental protection challenges of PFSA is to fabricate hydrocarbon-fluorocarbon copolymers or hydrocarbon-fluorocarbon composite materials to replace all fluorinated PFSAs.
  • Hydrocarbon materials are usually significantly cheaper than fluoropolymers, due to the reduced loading of fluorine atoms. From the environmental protection point of view, a hydrocarbon polymer could be less difficult to be disposed. However, so far the progress in this area has been limited. Phase separation is a huge challenge for the use of a composite of physically blended hydrocarbon polymers and fluorocarbon polymers. It is well known that a fluorocarbon material usually forms a phase that is orthogonal to both hydrocarbon and aqueous phases (Kirsch in“Modern
  • fluorocarbon-hydrocarbon copolymers can also be developed into anion-exchange materials for alkaline fuel cells and alkaline membrane electrolyzers. Under an alkaline condition, the kinetics of the oxygen- reduction reaction can significantly enhanced— allowing the use of inexpensive metal catalysts such as silver and nickel to substitute expensive noble metal catalyst of Pt in alkaline membrane fuel cells.
  • inexpensive metal catalysts such as silver and nickel to substitute expensive noble metal catalyst of Pt in alkaline membrane fuel cells.
  • the structure and the fabrication method to produce anion-exchange hydrocarbon-fluorocarbon copolymers are also disclosed.
  • the present invention also covers a new group of totally fluorinated cation-conductive fluoropolymers. These polymers are synthesized by a ROMP polymerization of hydrocarbon-based monomers followed by a fluorination reaction to replace hydrogen atoms by fluorine atoms.
  • the present invention provides a polymer comprising a plurality of repeated unit of RU(alkane-F) containing a cycloalkane or an alkane with a fluoropolymer side chain, which has a formula selected from the group consisting of (I), (II), and (III):
  • the present disclosure provides a cation- exchange hydrocarbon-fluorocarbon co-polymer (CEHF) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed cation-exchange repeating unit of RU(CE) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
  • RU(CE) is a repeated unit containing a cation-exchange group, having a formula selected from the group consisting of (IV), (V) and (VI):
  • J is selected from the group consisting of SO3H, PO3H2, and CO2H;
  • RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VII), (VIII) and (IX):
  • AEHF-RING anion-exchange hydrocarbon-fluorocarbon co-polymer
  • RU(AE-RING) is a repeated unit containing an anion-exchange group, having a formula selected from the group consisting of (X) and (XI):
  • AE is an anion-exchange group
  • a further embodiment of the present invention provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-CHAIN) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion- exchange repeating unit of RU(AE-CHAIN) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure: (aikane-F
  • peated unit containing an anion-exchange group having a
  • AE is an anion-exchange group
  • Another embodiment of the present invention discloses a free- radical initiator polymer comprising a plurality of repeated unit of RU(alkane-azo) containing a cycloalkane or an alkane with an azo side chain, which has a formula selected from the group consisting of (l-azo), (ll-azo) and (lll-azo):
  • the present invention provides a cation-exchange fluorocarbon polymer (CEF) comprising a plurality of cation- exchange fluorocarbon repeating unit of RU(CE-F) and optionally random or sequentially placed fluorocarbon repeating unit of RU(F), having the following structure: wherein RU(CE-F) is a repeated fluorocarbon unit containing a cation-exchange group, having a formula selected from the group consisting of (IV-F-I), (IV-F-II), (V-F- I), (V-F-ll), (V-F-lll), and (Vl-F):
  • J f 1 and J f 2 is selected from the group consisting of SO 3 H, PO 3 H 2 , and CO 2 H;
  • RU(F) is a repeated unit of fluorocarbon residues, having a formula selected from the group consisting of (Vll-F), (Vlll-F) and (IX-F):
  • An embodiment of the present disclosure provides a polymer comprising a plurality of repeated unit of RU(alkane-F) containing a cycloalkane or an alkane with a fluoropolymer side chain, which has a formula selected from the group consisting of (I), (II) and (III):
  • Y 1 is selected from the group consisting of O, and a bivalent (Ci-C 6 )hydrocarbon residue;
  • R 1 , R 2 , R 3 , R 4 , and R 8 are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi 2 )alkyl, (C 5 -Ci 2 )cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci 2 )hydrocarbon residue;
  • R 5 , R 6 , and R 7 are independently selected from the group consisting of H, N0 2 , CN, Cl, Br, I, F, OR, NRR , SR, (CrCi 2 )alkyl and (C5-Ci 2 )cycloalkyl;
  • W 1 is a bivalent (C 2 -Ci 2 )hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR, COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (Cr
  • L 1 and L 2 are independently chosen from a direct bond or a bivalent (Cr
  • R f 1 and R 2 are independently selected from H, F, Cl, Br or CF 3 ;
  • R f 3 is selected from selected from the group consisting of H, F, Cl, Br, CF 3 , CF 2 CF 3 , CF 2 CF 2 CF 3 , CF 2 (CF 2 ) 2 CF 3 , OCF 3 , OCF 2 CF 3 , OCF 2 CF 2 CF 3 , OCF 2 CF(CF 3 )OCF 3 , and OCF 2 CF(CF 3 )OCF 2 CF 3 .
  • n is an integer number ranging from 2 to 1 ,000,000;
  • G 1 is a cycloalkane ring or a cycloalkene ring that has C 5 -Ci 2 on its ring.
  • the ring of G 1 is fused with the cycloalkyl ring containing Y 1 with two adjacent carbons in common;
  • a floating bond refers to a covalent bond that attaches R 5 , or R 6 , or R 7 or W 1 to a carbon on the cycloalkyl ring containing Y 1 provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 5 , or R 6 , or R 7 or W 1 can be attached to the cycloalkyl ring containing Y 1 .
  • a floating bond refers to a covalent bond that attached R 5 , or R 6 , or R 7 or W 1 to a carbon of G 1 or/and the cycloalkyl ring containing Y 1 provided that this carbon has a total of four covalent bonds including the floating bond.
  • R 5 , or R 6 , or R 7 or W 1 can be attached to the cycloalkyl ring containing Y 1 or/and the G 1 ring.
  • Y 1 is a bivalent (Cr Ce)hydrocarbon residue
  • R 1 , R 2 , R 3 , R 4 , and R 8 are independently selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C 6 )hydrocarbon residue
  • R 5 , R 6 , and R 7 and are independently chosen from H, F, (CrC 6 )alkyl or (C 5 - C 6 )cycloalkyl
  • W 1 is a bivalent (C 3 -C 8 )hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR, COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (
  • R f 3 is selected from the group consisting of H, F, CF 3 , CF 2 CF 3 , OCF 3 , OCF 2 CF 3 , 0CF 2 CF 2 CF 3 , 0CF 2 CF(CF 3 )0CF 3 , and OCF 2 CF(CF 3 )OCF 2 CF 3 ;
  • n is an integer number ranging from 2 to 500,000;
  • G 1 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
  • Y 1 is CH 2 ;
  • R 1 , R 2 , R 3 , R 4 , and R 8 are independently selected from H or F;
  • R 5 , R 6 , and R 7 are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl;
  • W 1 is a bivalent (C 3 -C 8 )hydrocarbon residue comprising CN;
  • L 1 and L 2 are independently chosen from a direct bond or a bivalent (Ci-C 8 )hydrocarbon residue;
  • R f 1 and R 2 are F;
  • R f 3 is F;
  • n is an integer number ranging from 2 to 100,000;
  • G 1 is a cycloalkane ring or a cycloalkene ring that has C 5 -C 6 on its ring.
  • Y 1 is CH 2 ; R 1 , R 2 , R 3 , R 4 , and R 8 are H; R 5 , R 6 , and R 7 are H; W 1 is OCH 2 CH 2 CH 2 CCNCH 3 ; L 1 is CH 2 CH 2 CH 2 ; L 2 is CH 2 CH 2 CH 2 CH 2 ; R f 1 and R 2 are F; R f 3 is F; n is an integer number ranging from 2 to 80,000; G 1 is cyclopentane.
  • Y 1 is CH 2 ; R 1 , R 2 , R 3 , R 4 , and R 8 are H; R 5 , R 6 , and R 7 are H; W 1 is OCH 2 CH 2 CH 2 CCNCH 3 ; L 1 is CH 2 CH 2 CH 2 ; L 2 is CH 2 CH 2 CH 2 CH 2 ; R f 1 and R 2 are F; R f 3 is F; n is an integer number ranging from 2 to 80,000; G 1 is cyclopentane.
  • the present invention also discloses a cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed cation-exchange repeating unit of RU(CE) and optionally random or sequentially placed hydrocarbon repeating unit of
  • n F , n CE and n H are the numbers of the repeating unit of RU(alkane-F), RU(CE) and RU(H), respectively; n F is an integer ranging from zero to 1 ,000,000; n CE is also an integer from 1 to 1 ,000,000; n H is another integer ranging from zero to 1 ,000,000;
  • RU(CE) is a repeated unit containing a cation-exchange group, having a formula selected from the group consisting of (IV), (V) and (VI):
  • Y 2 is chosen from O or a bivalent (Ci-C 6 )hydrocarbon residue
  • R 9 , R 10 , R 11 , R 12 , and R 16 are independently selected from the group consisting of H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer, or a bivalent (Ci-Ci2)hydrocarbon residue;
  • R 13 , R 14 , and R 15 are independently chosen from H, NO2, CN, F, Cl, Br, I, OR 1 ,
  • NR'R SR 1 , (Ci-Ci2)alkyl or (C5-Ci2)cycloalkyl, wherein R 1 and R 11 are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
  • W 2 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue or a direct bond;
  • G 2 is a cycloalkane ring or a cycloalkene ring that has C 5 -C 12 on its ring;
  • L 3 and L 4 are independently chosen from a group of a direct bond and a bivalent (Cr Ci2)hydrocarbon residue;
  • J is chosen from SO 3 H, PO 3 H 2 , or CO 2 H;
  • a floating bond refers to a covalent bond that attaches R 13 , or R 14 , or R 15 or W 2 to a carbon on the cycloalkyl ring containing Y 2 provided that this carbon has a total of four covalent bonds including the floating bond.
  • a floating bond refers to a covalent bond that attached R 13 , or R 14 , or R 15 or W 2 to a carbon of G 2 or/and the cycloalkyl ring containing Y 2 provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 13 , or R 14 , or R 15 or W 2 can be attached to the cycloalkyl ring containing Y 2 or/and the G 2 ring;
  • RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VI I), (VIII) and (IX):
  • Y 3 is chosen from O or a bivalent (Ci-C 6 )hydrocarbon residue
  • R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are independently selected from the group consisting of H, Cl, Br, I , F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue;
  • R 22 , R 23 , and R 24 are independently chosen from H, NO2, CN, F, Cl, Br, I, OR m , NR'NR'V, sp i n (C Ci2)alkyl or (C5-Ci2)cycloalkyl, wherein R and R IV are
  • G 3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring.
  • the ring of G 3 is fused with the cycloalkyl ring containing Y 3 with two adjacent carbons in common;
  • L 5 and L 6 are independently chosen from a direct bond or a bivalent (Cr
  • a floating bond refers to a covalent bond that attaches R 22 , or R 23 , or R 24 to a carbon on the cycloalkyl ring containing Y 3 provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 22 , or R 23 , or R 24 can be attached to the cycloalkyl ring containing Y 3 .
  • a floating bond refers to a covalent bond that attached R 22 , or R 23 , or R 24 to a carbon of G 3 or/and the cycloalkyl ring containing Y 3 provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 22 , or R 23 , or R 24 can be attached to the cycloalkyl ring containing Y 3 or/and the G 3 ring.
  • n F ranges from zero to 500,000; n CE is also an integer from 1 to 500,000; n H is another integer ranging from zero to 500,000; Y 2 is a bivalent (Ci-C 6 )hydrocarbon residue; R 9 , R 10 , R 11 , R 12 , and R 16 are H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C 6 )hydrocarbon residue; R 13 , R 14 , and R 15 are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; W 2 is a bivalent (Ci-C 6 )hydrocarbon residue or a direct bond; G 2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring
  • n F ranges from 1 to 100,000; n CE is also an integer from 1 to 100,000; n H is another integer ranging from zero to 100,000; Y 2 is CH 2 ; R 9 , R 10 , R 11 , R 12 , and R 16 are independently chosen from H or F; R 13 , R 14 , and R 15 are independently chosen from H, F, (Ci-Ce)alkyl or (C 5 - C 6 )cycloalkyl; W 2 is a bivalent (Ci-C 6 )hydrocarbon residue or a direct bond; G 2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
  • L 3 and L 4 are independently chosen from a direct bond or a bivalent (Cr
  • J is chosen from SO 3 H, PO 3 H 2 , or C0 2 H;
  • Y 3 is CH 2 ;
  • R 18 is chosen from SO 3 H, PO 3 H 2 , or C0 2 H;
  • R 19 , R 20 , R 21 , R 25 , and R 26 are H;
  • R 22 , R 23 , and R 24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl;
  • G 3 is a cycloalkane ring or a cycloalkene ring that has Cs-Ce on its ring;
  • L 5 and L 6 are independently chosen from a direct bond or a (Ci-Cslhydrocarbon residue.
  • n F ranges from 1 to 90,000; n CE is also an integer from 1 to 90,000; n H is another integer ranging from zero to 90,000; Y 2 is CH 2 ; R 9 , R 10 , R 11 , R 12 and R 16 are H; R 13 , R 14 , and R 15 are H;
  • W 2 is a bivalent (Ci-C 3 )hydrocarbon residue or a direct bond
  • G 2 is a cycloalkane ring that has C 5 on its ring
  • L 3 is CH 2 CH 2 CH 2
  • L 4 is CH 2 CH 2 CH 2 CH 2
  • J is selected from a group of S0 3 H and C0 2 H
  • Y 3 is CH 2
  • R 18 , R 19 , R 20 , R 21 , R 25 and R 26 are H;
  • R 22 , R 23 and R 24 are H; G 3 is a cycloalkane ring that has C 5 on its ring; L 5 is
  • L 6 is CH 2 CH 2 CH 2 CH 2 .
  • n F ranges from 1 to 80,000; n CE is also an integer from 1 to 80,000; n H is another integer ranging from zero to 80,000; Y 2 is CH 2 ; R 9 , R 10 ,
  • R 11 , R 12 , and R 16 are H; R 13 , R 14 , and R 15 are H; W 2 is a direct bond; G 2 is a cycloalkane ring that has C 5 on its ring; L 3 is CH 2 CH 2 CH 2 ; L 4 is CH 2 CH 2 CH 2 CH 2 ; J is C0 2 H; Y 3 is CH 2 ; R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are H; R 22 , R 23 , and R 24 are H; G 3 is cyclopentane; L 5 is CH 2 CH 2 CH 2 ; L 6 is CH 2 CH 2 CH 2 CH 2 .
  • n F ranges from 1 to 80,000; n CE is also an integer from 1 to 80,000; n H is another integer ranging from zero to 80,000; Y 2 is CH 2 ; R 9 , R 10 , R 11 , R 12 , and R 16 are H; R 13 , R 14 , and R 15 are H; W 2 is CH 2 CH 2 ; G 2 is a cycloalkane ring that has C 5 on its ring; L 3 is CH 2 CH 2 CH 2 ; L 4 is CH 2 CH 2 CH 2 CH 2 ; J is S0 3 H; Y 3 is CH 2 ; R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are H; R 22 , R 23 , and R 24 are H; G 3 is a cycloalkane ring that has C 5 on its ring; L 5 is CH 2 CH 2 CH 2 ; L 6 is CH 2 CH 2 CH 2 CH 2 .
  • AEHF-RING anion-exchange hydrocarbon-fluorocarbon co-polymer
  • m, q and r are the numbers of the repeating unit of RU(alkane-F), RU(AE-R!NG)-j— j-RU ⁇ H)-
  • m, q and r are the numbers of the repeating unit of RU(alkane-F), RU(AE- RING) and RU(H), respectively;
  • m is an integer ranging from zero to 1 ,000,000;
  • q is also an integer from 1 to 1 ,000,000;
  • r is another integer ranging from zero to
  • RU(AE-RING) is a repeated unit containing an anion-exchange group, having a formula selected from the group consisting of (X) and (XI):
  • Wavy lines indicate the points of attachment to adjacent repeating units of the polymer; Y 4 is selected from O or a bivalent (Cr
  • R 27 , R 28 , R 29 and R 30 are independently selected from the group consisting of H, Cl, Br, I, F, (Ci-Ci 2 )alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Cr
  • R 31 , R 32 , and R 33 are independently chosen from H, N0 2 , CN, F,
  • G 4 is a cycloalkane ring or a cycloalkene ring that has Cs-Ci 2 on its ring.
  • the ring of G 4 is fused with the cycloalkyl ring containing Y 4 with two adjacent carbons in common;
  • W 4 is chosen from a bivalent (Ci-Ci 2 )hydrocarbon residue and a direct bond;
  • AE is an anion-exchange group.
  • a floating bond refers to a covalent bond that attaches R 31 , or R 32 , or R 33 or W 4 to a carbon on the cycloalkyl ring containing Y 4 provided that this carbon has a total of four covalent bonds including the floating bond.
  • R 31 , or R 32 , or R 33 or W 4 can be attached to the cycloalkyl ring containing Y 4 .
  • a floating bond refers to a covalent bond that is attached R 31 , or R 32 , or R 33 or W 4 to a carbon of G 4 or/and the cycloalkyl ring containing Y 4 provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 32 , or R 32 , or R 33 or W 4 can be attached to the cycloalkyl ring containing Y 4 or/and the G 4 ring
  • Y 3 is a bivalent (CrC 6 )hydrocarbon residue
  • R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are independently selected from the group consisting of H, (Ci-Ce)alkyl and (C5-C6)cycloalkyl
  • R 22 , R 23 , and R 24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl
  • G 3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring
  • L 5 and L 6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
  • m ranges from zero to 500,000; q is also an integer from 1 to 500,000; r is another integer ranging from zero to 500,000; Y 4 is a bivalent (C r C 6 )hydrocarbon residue; R 27 , R 28 , R 29 and R 30 are independently selected from the group consisting of H, F, (C r C 6 )alkyl, (C 5 - C 6 )cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-C 6 )hydrocarbon residue; R 31 , R 32 , and R 33 are independently chosen from H, F, (Ci-Ce)alkyl or (C 5 -C 6 )cycloalkyl; G 4 is a cycloalkane ring or a cycloalkene ring that has C 5 -C 6 on its ring; W 4 is chosen from a bivalent (Cr
  • AE is an anion-exchange group comprised of a combination of a cation chosen from benzimidazolium, imidazolium, ammonium, phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , CO 3 2 , HCO 3 ,
  • m ranges from 1 to 100,000; q is also an integer from 1 to 100,000; r is another integer ranging from zero to 100,000; Y 4 is CH 2 ; R 27 , R 28 , R 29 and R 30 are independently chosen from H or F; R 31 , R 32 , and R 33 are independently chosen from H, F, (Ci-Ce)alkyl or (C 5 - C 6 )cycloalkyl; G 4 is a cycloalkane ring or a cycloalkene ring that has C 5 -C 6 on its ring; W 4 is chosen from a bivalent (Ci-C 6 )hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation chosen from phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C0 3 2 , HCOs ,
  • m ranges from 1 to 90,000; q is also an integer from 1 to 90,000; r is another integer ranging from zero to 90,000; Y 4 is CH 2 ; R 27 ,
  • R 28 , R 29 and R 30 are H; R 31 , R 32 , and R 33 are H; G 4 is a cycloalkane ring that has C 5 on its ring; W 4 is chosen from a bivalent (Ci-C 3 )hydrocarbon residue and a direct bond; AE is an anion-exchange group comprised of a combination of a cation of amino-phosphonium and an anion of OH; Y 3 is CH 2 ; R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are H; R 22 , R 23 , and R 24 are H; G 3 is a cycloalkane ring that has C5 on its ring;
  • L 5 is CH 2 CH 2 CH 2 ;
  • L 6 is CH2CH2CH2CH2.
  • a final embodiment of this section provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-CHAIN) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion-exchange repeating unit of RU(AE-CHAIN) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
  • m’ is an integer ranging from 1 to 1 ,000,000
  • q’ is also an integer from 1 to 1 ,000,000
  • RU(AE-CHAIN) is a repeated unit containing an anion-exchange group, having a formula of (XII):
  • R 34 is independently selected from the group consisting of H, Cl,
  • Y 3 is a bivalent (Ci-C 6 )hydrocarbon residue
  • R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are independently chosen from H, (Cr C 6 )alkyl or (C 5 -C 6 )cycloalkyl
  • R 22 , R 23 , and R 24 are independently chosen from H, (C r C 6 )alkyl or (C 5 -C 6 )cycloalkyl
  • G 3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring
  • L 5 and L 6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
  • m’ ranges from 1 to 500,000; q’ is also an integer from 1 to 500,000; r is another integer ranging from zero to 500,000; R 34 is selected from a group of H, F, (C r C 6 )alkyl, (C 5 -C 6 )cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C 6 )hydrocarbon residue; L 7 and L 8 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue; W 5 is chosen from a bivalent (Cr
  • m’ ranges from 1 to 100,000; q’ is also an integer from 1 to 100,000; is another integer ranging from zero to 100,000; R 34 is chosen from H, F, (C r C 6 )alkyl and (C 5 -C 6 )cycloalkyl; L 7 and L 8 are independently chosen from a direct bond or a bivalent (Ci-C 8 )hydrocarbon residue; W 5 is chosen from a bivalent (Ci-C 6 )hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation selected from ammonium, phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C0 3 2 , HC0 3 , S0 3 2 , or HS0 3 ; Y 3 is CH 2 ;
  • R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are H;
  • R 22 , R 23 , and R 24 are independently chosen from H, (Ci-Ce)alkyl or (Cs-Celcycloalkyl;
  • G 3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
  • L 5 and L 6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
  • m’ ranges from 1 to 90,000; q’ is also an integer from 1 to 90,000; r is another integer ranging from zero to 90,000;
  • R 34 is H;
  • L 7 is CH 2 CH 2 CH 2 ;
  • L 8 is CH 2 CH 2 CH 2 CH 2 ;
  • W 5 is chosen from a bivalent (Cr C 3 )hydrocarbon residue or a direct bond;
  • AE is an anion-exchange group comprised of a combination of a cation chosen from ammonium, phosphonium, amino- phosphonium, or an anion of OH ;
  • Y 3 is CH 2 ;
  • R 18 , R 19 , R 20 , R 21 , R 25 , and R 26 are H;
  • R 22 , R 23 , R 24 are H;
  • G 3 is a cycloalkane ring that has C 5 on its ring;
  • L 5 is CH 2 CH 2 CH 2 ;
  • L 6 is CH 2 CH 2 CH 2 CH 2 CH 2 .
  • Those skilled in the art will appreciate that many of the polymers in this section like CEHF, AEHF-RING, and AEHF-CHAIN comprised of RU(alkane- F) can be synthesized via a ring-opening metathesis polymerization (ROMP) process for a hydrocarbon polymer backbone.
  • An azo free-radical initiator such as azo nitrile, azo ester, azo amide, azo imidazole and azo amidine can be introduced to the polymer side chain via a separate grafting step or using a monomer bearing an azo initiator for the ROMP reaction.
  • the azo radical- initiator Upon exposed to heat or lights, the azo radical- initiator will decompose and generate a free radical on the polymer side chain, which can lead to the polymerization of fluoro-monomers and thus graft a fluoropolymeric side chain to the ROMP polymer.
  • RU(alkane-azo) below can be employed for such syntheses.
  • An embodiment of this section provides a cation-exchange fluorocarbon polymer (CEF) comprising a plurality of cation-exchange fluorocarbon repeating unit of RU(CE-F) and optionally random or sequentially placed
  • CEF cation-exchange fluorocarbon polymer
  • x and y are the numbers of the repeating unit of RU(CE-F) and RU(F), respectively; x is an integer from 1 to 1 ,000,000; y is another integer ranging from zero to 1 ,000,000.
  • RU(CE-F) is a repeated fluorocarbon unit containing a cation- exchange group, having a formula selected from the group consisting of (IV-F-I), (IV- F-ll), (V-F-l), (V-F-ll), (V-F-lll), and (Vl-F):
  • Y f 1 is chosen from O or a bivalent (Ci-C 6 )fluorocarbon residue;
  • R f 4 , R f 5 , R f 6 , R f 7 , and R f 17 are independently chosen from F, (Ci-Ci2)fluoroalkyl, or (C 5 -Ci 2 )cyclofluoroalkyl;
  • R f 8 , R f 9 , R f 10 , R f 11 ⁇ R f 12 , R f 13 , R f 14 ' R f 15 and R f 16 are
  • W f 1 and W f 2 is chosen from a bivalent (Ci-Ci2)fluorocarbon residue or a direct bond
  • L f 1 and L 2 are independently chosen from a direct bond or a bivalent (Ci-Ci2)fluorocarbon residue
  • J f 1 and J 2 is chosen from SO3H, PO3H2, or C0 2 H.
  • RU(F) is a repeated unit of fluorocarbon residues, having a formula selected from the group consisting of (Vll-F), (Vlll-F) and (IX-F):
  • Y f 2 is chosen from O or a bivalent (Ci-C 6 )fluorocarbon residue; Rf 18 , Rf 19 , Rf 20 , R 21 , Rf 32 , and R f 33 are independently chosen from F, (Cr
  • R 22 , R 23 , R 24 , R 25 , R 26 , R 27 , R 28 , R 29 , Rf 30 , and R f 31 are independently chosen from N0 2 , CN, F, SO3H, (Ci-Ci 2 )fluoroalkyl or (C5-Ci 2 )cyclofluoroalkyl;
  • L f 3 and L 4 are independently chosen from a direct bond ora bivalent (Ci-Ci 2 )fluorocarbon residue.
  • x ranges from 1 to 500,000; y is also an integer from zero to 500,000; Y f 1 is a bivalent (Ci-C 6 )fluorocarbon residue;
  • R 4 , Rf 5 , R 8 , Rf 7 , and R f 17 are either F, (CrC 6 )fluoroalkyl, (C 5 -C 6 )cyclofluoroalkyl; R f 8 , Rf 9 , Rf 10 , Rf 11, Rf 12 , Rf 13 , Rf 14, Rf 15 and R f 16 are independently chosen from F, (C r Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl; W f 1 and W 2 are a bivalent (CrC 6 )fluoroalkyl, (C 5 -C 6 )cyclofluoroalkyl; W f 1 and W 2 are a bivalent (CrC 6 )fluoroalkyl, (C 5 -C 6 )cyclofluoroalkyl; R f 8 , Rf 9 , Rf 10 , Rf 11, Rf 12 , Rf 13 , Rf 14, R
  • L f 1 and L 2 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue; J f 1 and J 2 is chosen from SO3H, P03H 2 , orC0 2 H; Y 2 is a bivalent (Ci-C 6 )fluorocarbon residue; R f 18 , R f 19 , R 20 , R 21 , Rf 32 and R f 33 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5- C 6 )cyclofluoroalkyl;
  • R f 22 , R f 23 , R f 24 , R f 25 , R f 26 , R f 27 , R f 28 , R f 29 , R f 30 , and R f 31 are independently chosen from F, (Ci-C 6 )fluoroalkyl or (C5-C6) cyclofluoroalkyl; L f 3 and L 4 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue.
  • Y f 2 is CF 2 ;
  • R f 18 , R f 1 9 ,R f 20 , R f 21 , R f 32 and R f 33 are F;
  • R f 22 , R f 23 , R f 24 , R 25 , R 26 , R 27 , R 28 , R 29 , R f 30 , and R f 31 are independently chosen from F, (C r
  • Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl; L f 3 and L f 4 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue.
  • x ranges from 1 to 90,000; y is also an integer from zero to 90,000; Y f 1 is CF 2 ; R 4 , R f 5 , R f 6 , R f 7 , and R f 17 are F; R f 8 , R f 9 , R f 10 , R f 11 , R f 12 , R f 13 , R f 14, R f 15 and R f 16 are chosen from F, or (Cr Ce)fluoroalkyl; W f 1 and W 2 is a bivalent (Ci-C 4 )fluorocarbon residue or a direct bond; L f 1 is CF 2 CF 2 CF 2 ; L 2 is CF 2 CF 2 CF 2 CF 2 ; J f 1 and J 2 are independently chosen from SO 3 H, or C0 2 H; Y f 2 is CF 2 ; R f 18 , R f 19 , R
  • x ranges from 1 to 80,000; y is also an integer from zero to 80,000; Y f 1 is CF 2 ; R f 4 , R f 5 , R f 6 , R f 7 , and R f 17 are F; R f 8 , R f 9 , R f 10 , R f 11 ⁇ R f 12 , R f 13 , R f 14 ' R f 1 5 and R f 1 6 are F; W f 1 and W 2 are direct bonds; L f 1 is CF 2 CF 2 CF 2 ; L 2 is
  • L f 3 is CF 2 CF 2 CF 2 ;
  • L f 4 is CF 2 CF 2 CF 2 CF 2 .
  • x ranges from 1 to 80,000; y is also an integer from zero to 80,000; Y f 1 is CF 2 ; R 4 , R f 5 , R f 6 , R f 7 , and R f 17 are F; R f 8 , R f 9 , R f 10 , R f 12 , R f 13 , R f 14 ' R f 1 5 and R f 16 are F; R f 1 1 is CF 3 ; W f 1 is a direct bond; J f 1 is S0 3 H; W f 2 is CF 2 OCF 2 CF 2 ; J f 2 is C0 2 H; L f 1 is CF 2 CF 2 CF 2 ; L f 2 is
  • Y f 2 is CF 2 ;
  • R f 18 , R f 19 , R f 20 , R f 21 , R f 32 and R f 33 are F;
  • R f 22 , R f 23 , R f 24 , R f 25 , R f 26 , R f 27 , R f 28 , R f 29 , R f 30 , and R f 31 are F;
  • L f 3 is CF 2 CF 2 CF 2 ;
  • L f 4 is CF 2 CF 2 CF 2 CF 2 CF 2 .
  • An embodiment of this section provides a free-radical initiator polymer comprising a plurality of repeated unit of RU(alkane-azo) containing a cycloalkane or an alkane with an azo side chain, which has a formula selected from the group consisting of (l-azo), (I l-azo) and (I I l-azo):
  • Wavy lines indicate the points of attachment to adjacent repeating units of the polymer; Y 1 a is chosen from O, or a bivalent (Cr
  • R 1 a , R 2a , R 3a , R 4a , and R 8a are independently chosen from H, Cl, Br, I, F, (Ci-Ci 2 )alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue.
  • R 5a , R 6a , and R 7a are independently chosen from H, NO2, CN,
  • R 9a , R 1 1 a , and R 12a are independently chosen from (Ci-Ci2)hydrocarbon residues.
  • L 1 a and l_ 2a are independently chosen from a direct bond, or a bivalent (Ci-Ci2)hydrocarbon residue;
  • G 1 a is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring.
  • the ring of G 1 a is fused with the cycloalkyl ring containing Y 1 a with two adjacent carbons in common.
  • a floating bond refers to a covalent bond that attaches R 5a , or R 6a , or R 7a or W 1 a to a carbon on the cycloalkyl ring containing Y 1 a provided that this carbon has a total of four covalent bonds including the floating bond.
  • R 5a , or R 6a , or R 7a or W 1 a can be attached to the ring comprising Y 1 a .
  • a floating bond refers to a covalent bond that attached R 5a , or R 6a , or R 7a or W 1 a to a carbon of either G 1 a or the cycloalkyl ring containing Y 1 a provided that this carbon has a total of four covalent bonds including the floating bond.
  • Multiple R 5a , or R 6a , or R 7a or W 1 a can be attached to the ring comprising Y 1 a or/and G 1 a .
  • Y 1 a is a bivalent (Cr Ce)hydrocarbon residue
  • R 1 a , R 2a , R 3a , R 4a , and R 8a are independently chosen from H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, or a bivalent (Ci-C 6 )hydrocarbon residue
  • R 5a , R 6a , and R 7a are independently chosen from H, F, (C r C 6 )alkyl or (C 5 -C 6 )cycloalkyl
  • W 1 a is either a direct bond or a bivalent (Ci-C 6 )hydrocarbon residue
  • R 9a , R 11 a , and R 12a are independently chosen from (Ci-C 6 )hydrocarbon residues
  • R 10a and R 13a are independently chosen from CN, COOR
  • Y 1 a is CH 2 ;
  • R 1 a , R 2a , R 3a and R 4a , and R 8a are independently chosen from H, or F;
  • R 5a , R 6a , and R 7a are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl;
  • W 1 a is either a direct bond or a bivalent (C1-C5) hydrocarbon residue;
  • R 9a , R 11 a , and R 12a are independently chosen from (Ci-C 6 )hydrocarbon residues;
  • R 10a and R 13a are CN;
  • L 1 a and l_ 2a are independently chosen from a direct bond, or a bivalent (Cr
  • G 1 a is a cycloalkane ring or a cycloalkene ring that has C5- C 6 on its ring.
  • Y 1 a is CH 2 ;
  • R 1 a , R 2a , R 3a , R 4a , and R 8a are H;
  • R 5a , R 6a , and R 7a are H;
  • W 1 a is chosen from OCH 2 CH 2 CH 2 , OCH 2 CH 2 , OCH 2 , CH 2 OCH 2 CH 2 CH 2 , CH 2 OCH 2 CH 2 , CH 2 OCH 2 CH 2 , CH 2 OCH 2 , CH 2 SCH 2 CH 2 CH 2 , CH 2 SCH 2 CH 2 , or CH 2 SCH 2 ;
  • L 1 a is CH 2 CH 2 CH 2 ;
  • L 2a is
  • R 9a , R 1 1 a , and R 12a are CH 3 ; R 10a and R 13a are CN; G 1 a is a cycloalkane ring that has C5 on its ring.
  • Y 1 a is CH 2 ;
  • R 1 a , R 2a , R 3a , R 4a , and R 8a are H;
  • R 5a , R 6a , and R 7a are H;
  • W 1 a is OCH 2 CH 2 CH 2 ;
  • R 9a , R 11 a , and R 12a are CH 3 ;
  • R 10a and R 13a are CN;
  • L 1 a is CH 2 CH 2 CH 2 ;
  • l_ 2a is CH 2 CH 2 CH 2 CH 2 ;
  • G 1 a is a cycloalkane ring that has C5 on its ring.
  • Y 1 a is CH 2 ;
  • R 1 a , R 2a , R 3a , R 4 , and R 8a are H;
  • R 5a , R 6a , and R 7a are H;
  • W 1 a is
  • R 9a , R 1 1 a , and R 12a are CH 3 ; R 10a and R 13a are CN; L 1 a is
  • L 2a is CH 2 CH 2 CH 2 CH 2 ;
  • G 1 a is a cycloalkane ring that has C5 on its ring.
  • RU(alkane-azo) upon exposed to heat or lights, RU(alkane-azo) can undergo a decomposition process to release N 2 and generate a carbon radical on the carbon next to the azo functionality.
  • a radical can lead to the polymerization of fluoro-monomers, which will generate the polymer comprising a plurality of repeated unit of RU(alkane-F), CEHF, AEHF-RING, and AEHF-CHAI N.
  • An electrolyte is a substance having electrically-charged ions and ions can move to either a negative or positive electrode in an electric field.
  • the ion conductivity of purified type I water at 25°C is 5.6 x 10 '6 S/m and type I purified water is not deemed as an ion- conductive material.
  • Ion-conductive electrolytes herein are considered to have an ion conductivity larger than 5.6 x 10 '6 S/m at 25°C.
  • the ion conductivity of an ion- conductive electrolyte is typically at or larger than 1 .0 x 10 '5 S/m, at or above 1 .0 x 10 '4 S/m, at or preferably over 1 .0 x 10 '3 S/m, or most preferably at or larger than 1 .0 x 10 '2 S/m at 25°C.
  • Some measurement conditions used in an ion conductivity test may have effects on the ion conductivity of the test material, for example, the C0 2 concentration in the air and the water content in the test environment.
  • the present disclosure covers a C0 2 volume composition ranging from 0.010 v/v% to 100 v/v%, preferably at 0.035 v/v% of the earth atmosphere C0 2 concentration.
  • the water content in the test environment can range from a relative humidity of 1 % to 100% or with the test material completely submerged in water, preferably under 100% relative humidity.
  • the present invention provides a cation- conductive electrolyte comprising of an acid that is selected from the group consisting of (IV), (V) and (VI).
  • the present invention provides a cation- conductive electrolyte comprising of an acid that is selected from the group consisting of (X), (XI) and (XII).
  • a support can be added to the fluoropolymer electrolyte.
  • a support can be a solid, or a liquid, or a gel.
  • a solid support can be a poly(tetrafluoroethylene) film.
  • the solid membrane displays the desirable properties and the membrane thickness can be from 1 micron to 200 microns, including all values of 1 micron and ranges therebetween.
  • Examples of a liquid support material include water, sea water, ethanol, methanol, acetonitrile, thionyl chloride, dimethyl sulfoxide, dimethylformamide, and ionic liquids.
  • a liquid support material is a material at a liquid state at 25°C.
  • the liquid support material may or may not conduct ions.
  • a gel support is a material at a gel state at 25°C.
  • the gel support material may or may not conduct ions.
  • the support can be expanded
  • PTFE poly(tetrafluoroethylene) films.
  • the use of a PTFE support can enhance the mechanic strength of the ion-exchange fluorocarbon polymer and reduce the overall cost of the ion-conductive composite membranes.
  • the density as well as the thickness of the PTFE support are of importance to the mechanic properties and ion conductivity of the composite membranes.
  • the PTFE film supports in general need to have a polymer density ranging from 0.3 g/cm 3 to 1.8 g/cm 3 , preferably from 0.3 g/cm 3 to 1.2 g/cm 3 , and most preferably from 0.3 g/cm 3 to 1.0 g/cm 3 .
  • the thickness of the PTFE support can range from 20 microns to 180 microns, preferably from 20 microns to 150 microns, from 20 microns to 100 microns, and most preferably from 20 microns to 80 microns.
  • the support is a metal-organic framework (MOF).
  • MOF metal-organic framework
  • the electrolyte is comprised of MOF and a fluorocarbon polymer comprising a heteroaromatic group or a HPCA.
  • MOFs are compounds consisting of metal ions or clusters coordinated to often rigid organic molecules to form one-, two-, or three-dimensional structures that can be porous.
  • An example of MOFs is porous Zn-aminotriazolato-oxalate with a chemical formula of Zn 2 (C 2 0 4 )(C 2 N 4 H 3 ) 2 (H 2 0)o .5 (Chem. Commun. 2009, 5230).
  • the fluorocarbon polymer may be conjugated to the MOF by a variety of chemical bonds including, but not limited to, covalent bonding, non-covalent bonding, dative bonding, ionic bonding, hydrogen bonding, metallic bonding, or van der Waals bonding.
  • covalent bonding non-covalent bonding
  • dative bonding dative bonding
  • ionic bonding hydrogen bonding
  • metallic bonding metallic bonding
  • van der Waals bonding van der Waals bonding.
  • an imidazole ring or a triazole ring of the fluorocarbon polymer can be part of the MOF framework structure.
  • the support can be a metal salt such as phosphotungstic acid, heteropolyacid, silicotungstic acid, zirconium hydrogen phosphate, zirconia, and zirconium hydrogen sulfate.
  • a cation-conductive membrane transports proton from anode to cathode while being impermeable to gaseous and liquid fuels. It is highly desirable that an ion-exchange membrane can be: (a) low hydrogen, methanol, and other liquid fuel crossover; (b) mechanically strong and do not tear or fracture under fuel cell operations; (c) swelling less than 20% of original membrane thickness is ideal; and (d) proton conductivity of from 1.0 mS/cm to 500 mS/cm is desirable. The higher conductivity, the better.
  • the ion-conductive solid membrane has the maximum tensile in the machine direction for sheet processing (MD) or the maximum tensile strength in the transverse direction (TD) vertical to the MD direction both greater than 20 MPa under 50% relative humidity at 25 °C.
  • the cation-conductive solid membrane has the maximum tensile strengths in both MD and TD of 25 MPa or greater, under 50% relative humidity at 25 °C.
  • the cation-conductive solid membrane has the maximum tensile strengths in both MD and TD of 30 MPa or greater, under 50% relative humidity at 25 °C.
  • One embodiment of the present disclosure provides a fuel cell mainly comprising anode, cathode, catalyst and a fluorocarbon polymer-based electrolyte.
  • the fuel cell can have a solid membrane configuration or a liquid electrolyte configuration.
  • the fuel cell can use hydrogen, methanol, ethanol, hydrazine, glucose, aldehyde, carboxylic acid and boron-based chemicals as fuel.
  • the fluorocarbon polymer electrolyte can be used between anode and cathode to separate oxidative or reductive fuels.
  • a fluorocarbon polymer electrolyte can be added to an electrode as a catalyst ink to facilitate ion conduction.
  • the fuel cell can be a PEMFC or a PAFC or a methanol fuel cell.
  • the present disclosure provides an electrolytic cell mainly comprising anode, cathode, catalyst and a fluorocarbon polymer electrolyte.
  • Another embodiment of the present disclosure provides a metal- air battery mainly comprising anode, cathode, catalyst and a fluoropolymer electrolyte.
  • the present disclosure provides an electrolytic cell mainly comprising anode, cathode, catalyst and a fluorocarbon- hydrocarbon copolymer electrolyte.
  • aromatic refers to a compound that contains a set of covalently bond atoms with the characteristics: (a) a
  • Aromatic hydrocarbons can be monocyclic or polycyclic and include heteroaromatic hydrocarbons. Examples of aromatic hydrocarbons include benzene, phenol, aniline, triphenylphosphine, and triphenylphosphine oxide.
  • heteroaromatic refers to an aromatic hydrocarbon having at least one non-carbon atom in the ring.
  • Heteroaromatic hydrocarbons can be monocyclic or polycyclic. Examples of heteroaromatic hydrocarbons include quinoline, phenylalanine, phenanthroline, pyridine, pyrrole, imidazole, tetrazole, and furan.
  • reduct refers to two or more atoms bound together as a single unit and forming part of a molecule.
  • copolymer refers to a polymer made by reaction of two different monomers, with units of more than one kind. It can be either a block or a random or a sequentially placed copolymer.
  • Ci refers to a chemical group that has one carbon
  • C 6 refers to a residue that has six carbons.
  • fused refers to in a molecular or residual structure, two rings have at least two carbon atoms in common.
  • the term“monovalent” refers to a chemical group with a valence of one, which thus can form one covalent bond.
  • the term“bivalent” refers to a chemical group that can form two covalent bonds.
  • the term“radical”,“free radical” or“free-radical” refers to an uncharged molecule or group (typically highly reactive and short-lived) having an unpaired valence electron.
  • radical initiator refers to substances that can produce radical species under mild conditions and promote radical reactions (e.g., benzoyl peroxide and azobisisobutyronitrile).
  • living polymerization or“controlled polymerization” refers to is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed.
  • A“covalent bond” is a chemical bond that involves the sharing of electron pairs between atoms. Examples of“covalent bonds” includes C-C bonds, C-N bonds, and C-0 bonds.
  • Hydrocarbon refers to an organic compound that mainly consisting of hydrogen and carbon atoms. Examples include octane, benzene, diethyl ether, aniline, and pyridine.
  • Fluorocarbon refers to an organic compound derived by replacing all or most of the hydrogen atoms in a hydrocarbon by fluorine atoms (e.g., tetrafluoroethylene, tetradecafluorohexane). It could include fluoroalkanes and fluoroalkenes.
  • Fluoroalkyl refers to an organic compound derivative produced by replacing all or most of the hydrogen atoms in an alkyl group by fluorine atoms (e.g., trifluoromethyl).
  • Cyclofluoroalkyl refers to an organic compound derivative produced by replacing all or most of the hydrogen atoms in a cycloalkyl group by fluorine atoms (e.g., trifluoromethyl).
  • “functional group” or“functionality” refers to a group of atoms responsible for the characteristic reactions of a particular compound (e.g., ketone, alcohol, azo).
  • Polymer refers to a compound of high molecular weight derived either by the addition of many smaller molecules, as polyethylene, or by the condensation of many smaller molecules with the elimination of water, alcohol, or the like, as nylon.
  • A“fluoropolymer” or“fluorocarbon polymer” is a fluorocarbon based polymer with multiple strong carbon-fluorine bonds. Examples include poly(vinyl fluoride), polytetrafluoroethylene, perfluoroalkoxy and
  • fluoro-monomer or“fluoromonomer” refers to a fluorocarbon molecule that can be bonded to other identical molecules to form a polymer (e.g., tetrafluoroethylene, hexafluoropropylene).
  • fluoroalkene refers to an organic compound derived by replacing all or most of the hydrogen atoms in an alkene by fluorine atoms (e.g., tetrafluoroethylene).
  • An“ion-conductive material”,“ion conductive material”,“ion transportation material” or“electrolyte” is a material that can transport an ion from one site to another. Ionic conduction can lead to an electric current.
  • the SI unit of conductivity is Simens per meter (S/m) and, unless otherwise qualified, it generally refers to 25°C (standard temperature).
  • anion-conductive or“anion conductive” or“anion- exchange” or“anion exchange” refers to the migration of a negatively charged ion from one side to another in a medium.
  • solid refers to a solid state of matter under a temperature ranging from -70 to 200 °C.
  • residue or“unit” refers to a recognizable molecular part of a larger molecule (e.g., an amino acid is a residue or unit of a larger protein chain).
  • a floating bond refers to a covalent bond that is attached to a carbon on a ring provided that the carbon has a total of four covalent bonds including the floating bond.
  • numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, used to describe and claim certain embodiments of the present disclosure are to be understood as being modified in some instances by the term“about.”
  • the term“about” is used to indicate that a value includes the standard deviation of the mean for the device or method being employed to determine the value.
  • the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment.
  • the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
  • the terms“selected”,“chosen” and“or” refer to make one or more choices including a combination of choices from a number of possibilities.
  • Example 1 Random copolymerization of cis-cyclooctene and 2-[1-cyano-1- methyl-4- ⁇ [(5-norbomen-2-yl)methyl]amino ⁇ -4-oxobutylazo]-2-methyl-5- ⁇ [(5- norbomen-2-yl)methyl]amino ⁇ -5-oxovaleronitrile via ROMP (polymer 1).
  • Example 2 Block copolymerization of cis-cyclooctene and 2-[1 -cyano-1 - methyl-4- ⁇ [(5-norbornen-2-yl)methyl]amino ⁇ -4-oxobutylazo]-2-methyl-5- ⁇ [(5- norbornen-2-yl)methyl]amino ⁇ -5-oxovaleronitrile via ROMP (polymer 2).
  • Example 3 Free-radical polymerization of heptafluoropropyl trifluorovinyl ether using 2-[1 -Cyano-1 -methyl-4- ⁇ [(5-norbornen-2-yl)methyl]amino ⁇ -4- oxobutylazo]-2-methyl-5- ⁇ [(5-norbornen-2-yl)methyl]amino ⁇ -5-oxovaleronitrile as the initiator (polymer 3).
  • Example 4 Free-radical polymerization o ⁇ 2-(per ⁇ luoropropoxy)perfluoropropyl trifluorovinyl ether using 2-[1-Cyano-1-methyl-4-([(5-norbornen-2- yl)methyl]amino ⁇ -4-oxobutylazo]-2-methyl-5- ⁇ [(5-norbornen-2- yl)methyl]amino ⁇ -5-oxovaleronitrile as the initiator (polymer 4).
  • Example 5 ROMP copolymerization of cis-cyclooctene and polymer 4
  • Example 6 Catalytic hydrogenation of polymer 5.
  • Example 7 Synthesis of2-[1-cyano-1-methyl-4-([(5-norbornen-2- yl)methyl]amino ⁇ -4-oxobutylazo]-2-methyl-5- ⁇ [(5-norbornen-2- yl)methyl]amino ⁇ -5-oxovaleronitrile.
  • Example 8 Preparation of poly ⁇ 4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4- [4-poly(hexafluoropropylene)-4-cyano-pentan-1-oyl-amino]methyl-1,3- cyclopentylene ethylene ⁇ (polymer 8)
  • Example 9 Preparation of poly ⁇ 4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4- [4-poly(hexaf luoroporpylene)-4-cyano-1 -pentyloxy] methyl-1, 3-cyclopentylene ethylene ⁇ (polymer 9)
  • polymer 9c Preparation of poly ⁇ 4,5- dimethoxycarbonyl-1 ,3-cyclopentylene ethylene/4-[4-(1 -acetoxy-4-cyano-4-pentyl)azo-4-cyano-pentyl-1 -oxy]m ethyl- 1 ,3- cyclopentylene ethylene ⁇ (polymer 9c) from polymer 9b: the mixture of 1.50 g of polymer 9b, 0.6 g of 4-(1-acetoxy-4-cyano-4-pentyl)azo-4-cyano-1 -pentanol, 3.0 g of silver trifluoromethanesulfonate, and 2.18 g of 2,6-di-ferf-butylpyridine in 20 mL chloroform was stirred at ambient temperature for 12 h.
  • Example 10 Preparation of poly ⁇ 4-triphenylphosphoniumyl-1 ,3-cyclopentylene ethylene/4-[4-poly(hexafluoroporpylene)-4-cyano-1-pentyloxy]methyl-1,3- cyclopentylene ethylene ⁇ (polymer 10).
  • ROMP co-polymerization of (5-norbornen-2- yl)triphenylphosphonium bromide and (5-norbornen-2-yl)methyl iodide for the formation of poly(4-triphosphoniumyl-1 ,3-cyclopentylene vinylene/4-iodomethyl-1 ,3- cyclopentylene vinylene) (polymer 10a): to a mixture of 1.39 g of bicycle[2.2.1]hept- 5-enyl-2-triphenylphosphonium bromide (Bonjouklian and Ruden, J. Org.
  • Example 12 Preparation of poly(4,5-dicarboxyl-perfluoro-1,3-cyclopentylene ethylene/perfluoro-1,3-cyclopentylene ethylene) (polymer 12)
  • Example 13 Preparation of poly(4,5-dicarboxyl-perfluoro-1,3-cyclopentylene ethylene/perfluoro-1,8-octane-diyl) (polymer 13)

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Abstract

A ring-opening metathesis polymer that is grafted with a free-radical initiator is subject to the radical polymerization of a fluoroalkene for the production of an ion- exchange hydrocarbon-fluorocarbon copolymer. The ring-opening metathesis polymer can also undergo a direct fluorination reaction to yield an ion-exchange fluoropolymer. Such ion-conductive hydrocarbon-fluorocarbon copolymers and fluoropolymers are useful in making chlor-alkali cells, fuel cells, flow batteries, electrolyzers, and other electric devices.

Description

STABLE AND ION-CONDUCTIVE HYDROCARBON-FLUOROCARBON MATERIALS AS ELECTROLYTES FOR FUEL CELLS AND BATTERIES
FIELD
[0001] The present disclosure generally relates to a novel hydrocarbon- fluorocarbon copolymer material having (a) an acid or a conjugate acid group as a cation-conductive electrolyte, or (b) an anion-exchange group as an anion- conductive material, the use of the same in applications such as chlor-alkali cells, proton exchange membrane fuel cells (PEMFCs), alkaline membrane fuel cells, phosphoric acid fuel cells, methanol fuel cells, electrolytic cells, flow batteries, and other devices, and the methods to make the same.
BACKGROUND
[0002] Perfluorosulfonic acids (PFSAs) as cation-exchange materials are mainly used in chlor-alkali cells for caustic soda production. It is estimated that over 108,000 tons of caustic soda is produced every day in the U.S. A PFSA membrane is employed to separate anode and cathode and transports Na+ cations in a chlor- alkali cell. During recent years, PFSA membranes have found applications in the emerging markets of fuel cells, flow batteries and electrolyzers. For example, in a hydrogen PEMFC, a thin PFSA membrane (-100 microns) separates anode and cathode and it is also responsible for transporting protons (H+) from anode to cathode to counter electron discharges. In anode, hydrogen is reduced to protons and discharge electrons. Then, the PFSA film delivers protons from anode to cathode, in which protons are oxidized with oxygen gas (air) to water. During this process, the fuel cell generates electrons and only water is produced as a byproduct— no C02 is generated. Flow batteries can be used for the large-scale storage of energy produced from power plants, wind farms and solar power stations.
[0003] Several types of PFSAs are commercially available from polymer manufacturers: Nafion® from DuPont-Dow Chemicals, Aquivion® produced by Solvay, Flemion® from AGC Chemicals, and 3M PFSA supplied by 3M. All of these PFSAs are comprised of a fully-fluorinated polymer backbone and fluoro-side chains (Kusoglu and Weber, Chem. Rev. 2017, 1 17, 987-1 104). The high loadings of fluorine atoms in these PFSAs give rise to the high production costs of PFSAs, which has limited the development and adoption of fuel cell and flow battery technologies by our society. Equally important, fluoropolymers are difficult for biological degradation processes. Disposal of spent PFSAs can lead to significant
environment protection concerns.
[0004] One strategy to address the cost and environmental protection challenges of PFSA is to fabricate hydrocarbon-fluorocarbon copolymers or hydrocarbon-fluorocarbon composite materials to replace all fluorinated PFSAs. Hydrocarbon materials are usually significantly cheaper than fluoropolymers, due to the reduced loading of fluorine atoms. From the environmental protection point of view, a hydrocarbon polymer could be less difficult to be disposed. However, so far the progress in this area has been limited. Phase separation is a huge challenge for the use of a composite of physically blended hydrocarbon polymers and fluorocarbon polymers. It is well known that a fluorocarbon material usually forms a phase that is orthogonal to both hydrocarbon and aqueous phases (Kirsch in“Modern
Fluoroorganic Chemistry”, Wiley-VCH: Weinheim, Germany; 2004; pp 1-23.). Due to its“non-stick” nature, a fluorocarbon polymer does not bind well with a hydrocarbon material. Phase separation is frequently observed when a fluorocarbon polymer and a hydrocarbon polymer are physically blended to make a composite material (Lo Nostro, Adv. Colloid Interface Sci. , 1995, 56, 245-287). Phase separation in a cation conductor comprised of a physically blended fluorocarbon-hydrocarbon composite leads to the increase of the internal resistance in an electronic device, which can rapidly reduce the performance of fuel cells, electrolytic cells, and chlor-alkali cells.
[0005] In the present patent disclosure, we report the structure and the synthesis of a copolymer that is comprised of both a hydrocarbon segment and a fluorocarbon portion. The hydrocarbon and fluorocarbon fragments are covalently linked by C-C bonds, which can help reduce the phase separation of two phases. Such copolymers are produced by a combination of a ring-open metathesis polymerization (ROMP) reaction and a free-radical polymerization of fluoroalkenes.
[0006] In addition, such fluorocarbon-hydrocarbon copolymers can also be developed into anion-exchange materials for alkaline fuel cells and alkaline membrane electrolyzers. Under an alkaline condition, the kinetics of the oxygen- reduction reaction can significantly enhanced— allowing the use of inexpensive metal catalysts such as silver and nickel to substitute expensive noble metal catalyst of Pt in alkaline membrane fuel cells. The structure and the fabrication method to produce anion-exchange hydrocarbon-fluorocarbon copolymers are also disclosed.
[0007] Finally, the present invention also covers a new group of totally fluorinated cation-conductive fluoropolymers. These polymers are synthesized by a ROMP polymerization of hydrocarbon-based monomers followed by a fluorination reaction to replace hydrogen atoms by fluorine atoms.
SUMMARY
[0008] In one embodiment the present invention provides a polymer comprising a plurality of repeated unit of RU(alkane-F) containing a cycloalkane or an alkane with a fluoropolymer side chain, which has a formula selected from the group consisting of (I), (II), and (III):
Figure imgf000004_0001
[0009] In another embodiment the present disclosure provides a cation- exchange hydrocarbon-fluorocarbon co-polymer (CEHF) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed cation-exchange repeating unit of RU(CE) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
— j-Ru(alkane-F
Figure imgf000004_0002
RU(CE) is a repeated unit containing a cation-exchange group, having a formula selected from the group consisting of (IV), (V) and (VI):
Figure imgf000005_0001
wherein, J is selected from the group consisting of SO3H, PO3H2, and CO2H;
RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VII), (VIII) and (IX):
Figure imgf000005_0002
(Vii) (viii) _ and (|X)
[0010] Another embodiment of the present disclosure provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-RING) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion- exchange repeating unit of RU(AE-RING) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
Figure imgf000005_0003
RU(AE-RING) is a repeated unit containing an anion-exchange group, having a formula selected from the group consisting of (X) and (XI):
Figure imgf000005_0004
wherein, AE is an anion-exchange group.
[001 1 ] A further embodiment of the present invention provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-CHAIN) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion- exchange repeating unit of RU(AE-CHAIN) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure: (aikane-F
Figure imgf000006_0001
peated unit containing an anion-exchange group, having a
Figure imgf000006_0002
wherein, AE is an anion-exchange group.
[0012] Another embodiment of the present invention discloses a free- radical initiator polymer comprising a plurality of repeated unit of RU(alkane-azo) containing a cycloalkane or an alkane with an azo side chain, which has a formula selected from the group consisting of (l-azo), (ll-azo) and (lll-azo):
Figure imgf000006_0003
R13a' ' R1 ¾
(lli-azo)
[0013] In yet another embodiment, the present invention provides a cation-exchange fluorocarbon polymer (CEF) comprising a plurality of cation- exchange fluorocarbon repeating unit of RU(CE-F) and optionally random or sequentially placed fluorocarbon repeating unit of RU(F), having the following structure:
Figure imgf000007_0001
wherein RU(CE-F) is a repeated fluorocarbon unit containing a cation-exchange group, having a formula selected from the group consisting of (IV-F-I), (IV-F-II), (V-F- I), (V-F-ll), (V-F-lll), and (Vl-F):
Figure imgf000007_0002
wherein, Jf 1 and Jf 2 is selected from the group consisting of SO3H, PO3H2, and CO2H; RU(F) is a repeated unit of fluorocarbon residues, having a formula selected from the group consisting of (Vll-F), (Vlll-F) and (IX-F):
Figure imgf000008_0002
[0014] Other objects and features will be in part apparent and in part pointed out hereinafter.
DETAILED DESCRIPTION
(1) A hydrocarbon-fluorocarbon copolymer
[0015] An embodiment of the present disclosure provides a polymer comprising a plurality of repeated unit of RU(alkane-F) containing a cycloalkane or an alkane with a fluoropolymer side chain, which has a formula selected from the group consisting of (I), (II) and (III):
Figure imgf000008_0001
wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer; Y1 is selected from the group consisting of O, and a bivalent (Ci-C6)hydrocarbon residue;
R1 , R2, R3, R4, and R8 are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue;
R5, R6, and R7 are independently selected from the group consisting of H, N02, CN, Cl, Br, I, F, OR, NRR , SR, (CrCi2)alkyl and (C5-Ci2)cycloalkyl;
W1 is a bivalent (C2-Ci2)hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR, COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (Cr
Ci2)hydrocarbon residue;
L1 and L2 are independently chosen from a direct bond or a bivalent (Cr
Ci2)hydrocarbon residue;
Rf 1 and R 2 are independently selected from H, F, Cl, Br or CF3;
Rf 3 is selected from selected from the group consisting of H, F, Cl, Br, CF3, CF2CF3, CF2CF2CF3, CF2(CF2)2CF3, OCF3, OCF2CF3, OCF2CF2CF3, OCF2CF(CF3)OCF3, and OCF2CF(CF3)OCF2CF3.
n is an integer number ranging from 2 to 1 ,000,000;
G1 is a cycloalkane ring or a cycloalkene ring that has C5-Ci2 on its ring. The ring of G1 is fused with the cycloalkyl ring containing Y1 with two adjacent carbons in common;
[0016] In (I), a floating bond refers to a covalent bond that attaches R5, or R6, or R7 or W1 to a carbon on the cycloalkyl ring containing Y1 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5, or R6, or R7 or W1 can be attached to the cycloalkyl ring containing Y1.
[0017] In (II), a floating bond refers to a covalent bond that attached R5, or R6, or R7 or W1 to a carbon of G1 or/and the cycloalkyl ring containing Y1 provided that this carbon has a total of four covalent bonds including the floating bond.
Multiple R5, or R6, or R7 or W1 can be attached to the cycloalkyl ring containing Y1 or/and the G1 ring.
[0018] In a preferred aspect of (I), (II) and (II I), Y1 is a bivalent (Cr Ce)hydrocarbon residue; R1 , R2, R3 , R4, and R8 are independently selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C6)hydrocarbon residue; R5, R6, and R7 and are independently chosen from H, F, (CrC6)alkyl or (C5- C6)cycloalkyl; W1 is a bivalent (C3-C8)hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR, COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (Ci-C6)hydrocarbon residue; L1 and L2 are independently chosen a direct bond or a bivalent (Ci-Csjhydrocarbon residue; Rf 1 and R 2 are independently chosen from H,
F, or CF3; Rf 3 is selected from the group consisting of H, F, CF3, CF2CF3, OCF3, OCF2CF3, 0CF2CF2CF3, 0CF2CF(CF3)0CF3, and OCF2CF(CF3)OCF2CF3; n is an integer number ranging from 2 to 500,000; G1 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
[0019] In a further preferred aspect of (I), (II) and (III), Y1 is CH2; R1 , R2, R3, R4, and R8 are independently selected from H or F; R5, R6, and R7 are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; W1 is a bivalent (C3-C8)hydrocarbon residue comprising CN; L1 and L2 are independently chosen from a direct bond or a bivalent (Ci-C8)hydrocarbon residue; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 100,000; G1 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
[0020] Without limiting the scope of the present invention, in an illustrative example of (I), (II) and (III), Y1 is CH2; R1, R2, R3, R4, and R8 are H; R5, R6, and R7 are H; W1 is OCH2CH2CH2CCNCH3; L1 is CH2CH2CH2; L2 is CH2CH2CH2CH2 ; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 80,000; G1 is cyclopentane.
[0021 ] In yet another illustrative example of (I), (II) and (II I), Y1 is CH2; R1 , R2, R3, R4, and R8 are H; R5, R6, and R7 are H; W1 is OCH2CH2CH2CCNCH3; L1 is CH2CH2CH2; L2 is CH2CH2CH2CH2 ; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 80,000; G1 is cyclopentane.
[0022] The present invention also discloses a cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed cation-exchange repeating unit of RU(CE) and optionally random or sequentially placed hydrocarbon repeating unit of
RU(H), having the following structure:
— J-Ru(alkane-F)j— RU(CE)-] - [-RU(H)— ]— j-j wherein,
nF, nCE and nH are the numbers of the repeating unit of RU(alkane-F), RU(CE) and RU(H), respectively; nF is an integer ranging from zero to 1 ,000,000; nCE is also an integer from 1 to 1 ,000,000; nH is another integer ranging from zero to 1 ,000,000;
[0023] RU(CE) is a repeated unit containing a cation-exchange group, having a formula selected from the group consisting of (IV), (V) and (VI):
Figure imgf000011_0001
wherein,
Y2 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R9, R10, R11 , R12, and R16 are independently selected from the group consisting of H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer, or a bivalent (Ci-Ci2)hydrocarbon residue;
R13, R14, and R15 are independently chosen from H, NO2, CN, F, Cl, Br, I, OR1,
NR'R", SR1, (Ci-Ci2)alkyl or (C5-Ci2)cycloalkyl, wherein R1 and R11 are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
W2 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue or a direct bond;
G2 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring;
L3 and L4 are independently chosen from a group of a direct bond and a bivalent (Cr Ci2)hydrocarbon residue;
J is chosen from SO3H, PO3H2, or CO2H;
[0024] In (IV), a floating bond refers to a covalent bond that attaches R13, or R14, or R15 or W2 to a carbon on the cycloalkyl ring containing Y2 provided that this carbon has a total of four covalent bonds including the floating bond.
Multiple R13, or R14, or R15 or W2 can be attached to the cycloalkyl ring containing Y2. [0025] In (V), a floating bond refers to a covalent bond that attached R13, or R14, or R15 or W2 to a carbon of G2 or/and the cycloalkyl ring containing Y2 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R13, or R14, or R15 or W2 can be attached to the cycloalkyl ring containing Y2 or/and the G2 ring;
[0026] RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VI I), (VIII) and (IX):
Figure imgf000012_0001
wherein,
Y3 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21 , R25, and R26 are independently selected from the group consisting of H, Cl, Br, I , F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue; R22, R23, and R24 are independently chosen from H, NO2, CN, F, Cl, Br, I, ORm, NR'NR'V, spin (C Ci2)alkyl or (C5-Ci2)cycloalkyl, wherein R and RIV are
independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G3 is fused with the cycloalkyl ring containing Y3 with two adjacent carbons in common;
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
Ci2)hydrocarbon residue;
[0027] In (VII), a floating bond refers to a covalent bond that attaches R22, or R23, or R24 to a carbon on the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3.
[0028] In (VIII), a floating bond refers to a covalent bond that attached R22, or R23, or R24 to a carbon of G3 or/and the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3 or/and the G3 ring.
[0029] In a preferred aspect of CEHF, nF ranges from zero to 500,000; nCE is also an integer from 1 to 500,000; nH is another integer ranging from zero to 500,000; Y2 is a bivalent (Ci-C6)hydrocarbon residue; R9, R10, R11 , R12, and R16 are H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C6)hydrocarbon residue; R13, R14, and R15 are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; W2 is a bivalent (Ci-C6)hydrocarbon residue or a direct bond; G2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; L3 and L4 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue; J is selected from the group consisting of SO3H, PO3H2, and CO2H; Y3 is a bivalent (Ci-C6)hydrocarbon residue; R18, R19, R20, R21 , R25, and R26 are independently selected from the group consisting of H, (Ci-Ce)alkyl and (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C6)hydrocarbon residue; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has Cs-Ce on its ring; L5 and L6 are independently chosen from a direct bond or a (CrC8)hydrocarbon residue.
[0030] In a further preferred aspect of CEHF, nF ranges from 1 to 100,000; nCE is also an integer from 1 to 100,000; nH is another integer ranging from zero to 100,000; Y2 is CH2; R9, R10, R11 , R12, and R16 are independently chosen from H or F; R13, R14, and R15 are independently chosen from H, F, (Ci-Ce)alkyl or (C5- C6)cycloalkyl; W2 is a bivalent (Ci-C6)hydrocarbon residue or a direct bond; G2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
L3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Cslhydrocarbon residue; J is chosen from SO3H, PO3H2, or C02H; Y3 is CH2; R18,
R19, R20, R21 , R25, and R26 are H; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has Cs-Ce on its ring; L5 and L6 are independently chosen from a direct bond or a (Ci-Cslhydrocarbon residue.
[0031 ] In yet another preferred aspect of CEHF, nF ranges from 1 to 90,000; nCE is also an integer from 1 to 90,000; nH is another integer ranging from zero to 90,000; Y2 is CH2; R9, R10, R11 , R12 and R16 are H; R13, R14, and R15 are H;
W2 is a bivalent (Ci-C3)hydrocarbon residue or a direct bond; G2 is a cycloalkane ring that has C5 on its ring; L3 is CH2CH2CH2; L4 is CH2CH2CH2CH2; J is selected from a group of S03H and C02H; Y3 is CH2; R18, R19, R20, R21, R25 and R26 are H;
R22, R23 and R24 are H; G3 is a cycloalkane ring that has C5 on its ring; L5 is
CH2CH2CH2; L6 is CH2CH2CH2CH2.
[0032] Without limiting the scope of the present invention, in an illustrative example of CEHF, nF ranges from 1 to 80,000; nCE is also an integer from 1 to 80,000; nH is another integer ranging from zero to 80,000; Y2 is CH2; R9, R10,
R11, R12, and R16 are H; R13, R14, and R15 are H; W 2 is a direct bond; G2 is a cycloalkane ring that has C5 on its ring; L3 is CH2CH2CH2; L4 is CH2CH2CH2CH2; J is C02H; Y3 is CH2; R18, R19, R20, R21, R25, and R26 are H; R22, R23, and R24 are H; G3 is cyclopentane; L5 is CH2CH2CH2; L6 is CH2CH2CH2CH2.
[0033] In yet another illustrative example of CEHF, nF ranges from 1 to 80,000; nCE is also an integer from 1 to 80,000; nH is another integer ranging from zero to 80,000; Y2 is CH2; R9, R10, R11 , R12, and R16 are H; R13, R14, and R15 are H; W2 is CH2CH2; G2 is a cycloalkane ring that has C5 on its ring; L3 is CH2CH2CH2; L4 is CH2CH2CH2CH2; J is S03H; Y3 is CH2; R18, R19, R20, R21 , R25, and R26 are H; R22, R23, and R24 are H; G3 is a cycloalkane ring that has C5 on its ring; L5 is CH2CH2CH2; L6 is CH2CH2CH2CH2.
[0034] Another embodiment in this section provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-RING) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion-exchange repeating unit of RU(AE-RING) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
- |-Ru(aikane-F)-j-— f-RU(AE-R!NG)-j— j-RU{H)-|— wherein, m, q and r are the numbers of the repeating unit of RU(alkane-F), RU(AE- RING) and RU(H), respectively; m is an integer ranging from zero to 1 ,000,000; q is also an integer from 1 to 1 ,000,000; r is another integer ranging from zero to
1 ,000,000.
[0035] RU(AE-RING) is a repeated unit containing an anion-exchange group, having a formula selected from the group consisting of (X) and (XI):
Figure imgf000015_0001
[0036] Wavy lines indicate the points of attachment to adjacent repeating units of the polymer; Y4 is selected from O or a bivalent (Cr
Ce)hydrocarbon residue; R27, R28, R29 and R30 are independently selected from the group consisting of H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Cr
Ci2)hydrocarbon residue.
[0037] R31 , R32, and R33 are independently chosen from H, N02, CN, F,
Cl, Br, I, ORv, NRVRVI, SRV, (CrCi2)alkyl or (C5-Ci2)cycloalkyl, wherein Rv and RVI are independently chosen from H or a (CrCi2)hydrocarbon residue;
G4 is a cycloalkane ring or a cycloalkene ring that has Cs-Ci2 on its ring. The ring of G4 is fused with the cycloalkyl ring containing Y4 with two adjacent carbons in common; W4 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue and a direct bond; AE is an anion-exchange group.
[0038] In (X), a floating bond refers to a covalent bond that attaches R31 , or R32, or R33 or W4 to a carbon on the cycloalkyl ring containing Y4 provided that this carbon has a total of four covalent bonds including the floating bond.
Multiple R31 , or R32, or R33 or W4 can be attached to the cycloalkyl ring containing Y4.
[0039] In (XI), a floating bond refers to a covalent bond that is attached R31 , or R32, or R33 or W4 to a carbon of G4 or/and the cycloalkyl ring containing Y4 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R32, or R32, or R33 or W4 can be attached to the cycloalkyl ring containing Y4 or/and the G4 ring
[0040] In RU(H), Y3 is a bivalent (CrC6)hydrocarbon residue; R18, R19, R20, R21 , R25, and R26 are independently selected from the group consisting of H, (Ci-Ce)alkyl and (C5-C6)cycloalkyl; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; L5 and L6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue. [0041] In a preferred aspect of AEHF-RING, m ranges from zero to 500,000; q is also an integer from 1 to 500,000; r is another integer ranging from zero to 500,000; Y4 is a bivalent (CrC6)hydrocarbon residue; R27, R28, R29 and R30 are independently selected from the group consisting of H, F, (CrC6)alkyl, (C5- C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-C6)hydrocarbon residue; R31, R32, and R33 are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G4 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; W4 is chosen from a bivalent (Cr
Ce)hydrocarbon residue and a direct bond.
[0042] AE is an anion-exchange group comprised of a combination of a cation chosen from benzimidazolium, imidazolium, ammonium, phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , CO3 2 , HCO3 ,
S03 2 , HSO3 , P04 3 , HPO2 , or H2P04 .
[0043] In a further preferred aspect of AEHF-RING, m ranges from 1 to 100,000; q is also an integer from 1 to 100,000; r is another integer ranging from zero to 100,000; Y4 is CH2; R27, R28, R29 and R30 are independently chosen from H or F; R31, R32, and R33 are independently chosen from H, F, (Ci-Ce)alkyl or (C5- C6)cycloalkyl; G4 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; W4 is chosen from a bivalent (Ci-C6)hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation chosen from phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C03 2 , HCOs , S03 2 , or HSOs ; Y3 is CH2; R18, R19, R20, R21 , R25, and R26 are H; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; L5 and L6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
[0044] Without limiting the scope of the present invention, in an illustrative example of AEHF-RING, m ranges from 1 to 90,000; q is also an integer from 1 to 90,000; r is another integer ranging from zero to 90,000; Y4 is CH2; R27,
R28, R29 and R30 are H; R31, R32, and R33 are H; G4 is a cycloalkane ring that has C5 on its ring; W4 is chosen from a bivalent (Ci-C3)hydrocarbon residue and a direct bond; AE is an anion-exchange group comprised of a combination of a cation of amino-phosphonium and an anion of OH; Y3 is CH2; R18, R19, R20, R21 , R25, and R26 are H; R22, R23, and R24 are H; G3 is a cycloalkane ring that has C5 on its ring;
L5 is CH2CH2CH2; L6 is CH2CH2CH2CH2.
[0045] A final embodiment of this section provides an anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF-CHAIN) comprising a plurality of repeated unit of RU(alkane-F), random or sequentially placed anion-exchange repeating unit of RU(AE-CHAIN) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
j-Ru(aikane-F)— jRU(AE-CHAIN)-|—-†RU(H}-†-^~
m
[0046] m’, q’, and are the numbers of the repeating unit of RU(alkane-
F), RU(AE-CHAIN) and RU(H), respectively; m’ is an integer ranging from 1 to 1 ,000,000; q’ is also an integer from 1 to 1 ,000,000; is another integer ranging from zero to 1 ,000,000.
[0047] RU(AE-CHAIN) is a repeated unit containing an anion-exchange group, having a formula of (XII):
Figure imgf000017_0001
[0048] R34 is independently selected from the group consisting of H, Cl,
Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue; L7 and L8 are independently chosen from a direct bond or (Ci-Ci2)hydrocarbon residue; W5 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue or a direct bond; AE is an anion- exchange group.
[0049] In RU(H) of AEHF-CHAIN, Y3 is a bivalent (Ci-C6)hydrocarbon residue; R18, R19, R20, R21 , R25, and R26 are independently chosen from H, (Cr C6)alkyl or (C5-C6)cycloalkyl; R22, R23, and R24 are independently chosen from H, (CrC6)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; L5 and L6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue. [0050] In a preferred aspect of AEHF-CHAIN, m’ ranges from 1 to 500,000; q’ is also an integer from 1 to 500,000; r is another integer ranging from zero to 500,000; R34 is selected from a group of H, F, (CrC6)alkyl, (C5-C6)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C6)hydrocarbon residue; L7 and L8 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue; W5 is chosen from a bivalent (Cr
Ce)hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation selected from benzimidazolium, imidazolium, ammonium, phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C03 2 , HCOs , S03 2 , HS03 , P04 3 , HPO2 , or H2P04 ; Y3 is a bivalent (C Ce)hydrocarbon residue; R18, R19, R20, R21 , R25, and R26 are independently chosen from H, (Ci-Ce)alkyl or (Cs-Celcycloalkyl; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (Cs-Celcycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring; L5 and L6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
[0051 ] In a further preferred aspect of AEHF-CHAI N, m’ ranges from 1 to 100,000; q’ is also an integer from 1 to 100,000; is another integer ranging from zero to 100,000; R34 is chosen from H, F, (CrC6)alkyl and (C5-C6)cycloalkyl; L7 and L8 are independently chosen from a direct bond or a bivalent (Ci-C8)hydrocarbon residue; W5 is chosen from a bivalent (Ci-C6)hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation selected from ammonium, phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C03 2 , HC03 , S03 2 , or HS03 ; Y3 is CH2;
R18, R19, R20, R21 , R25, and R26 are H; R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (Cs-Celcycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; L5 and L6 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue.
[0052] Without limiting the scope of the present invention, in an illustrative example of AEHF-CHAIN, m’ ranges from 1 to 90,000; q’ is also an integer from 1 to 90,000; r is another integer ranging from zero to 90,000;
R34 is H; L7 is CH2CH2CH2; L8 is CH2CH2CH2CH2; W5 is chosen from a bivalent (Cr C3)hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation chosen from ammonium, phosphonium, amino- phosphonium, or an anion of OH ; Y3 is CH2; R18, R19, R20, R21 , R25, and R26 are H; R22, R23, R24 are H; G3 is a cycloalkane ring that has C5 on its ring; L5 is CH2CH2CH2; L6 is CH2CH2CH2CH2.
[0053] Those skilled in the art will appreciate that many of the polymers in this section like CEHF, AEHF-RING, and AEHF-CHAIN comprised of RU(alkane- F) can be synthesized via a ring-opening metathesis polymerization (ROMP) process for a hydrocarbon polymer backbone. An azo free-radical initiator such as azo nitrile, azo ester, azo amide, azo imidazole and azo amidine can be introduced to the polymer side chain via a separate grafting step or using a monomer bearing an azo initiator for the ROMP reaction. Upon exposed to heat or lights, the azo radical- initiator will decompose and generate a free radical on the polymer side chain, which can lead to the polymerization of fluoro-monomers and thus graft a fluoropolymeric side chain to the ROMP polymer. RU(alkane-azo) below can be employed for such syntheses.
(2) A cation-exchange fluoropolymer
[0054] An embodiment of this section provides a cation-exchange fluorocarbon polymer (CEF) comprising a plurality of cation-exchange fluorocarbon repeating unit of RU(CE-F) and optionally random or sequentially placed
fluorocarbon repeating unit of RU(F), having the following structure:
Figure imgf000019_0001
[0055] x and y are the numbers of the repeating unit of RU(CE-F) and RU(F), respectively; x is an integer from 1 to 1 ,000,000; y is another integer ranging from zero to 1 ,000,000.
[0056] RU(CE-F) is a repeated fluorocarbon unit containing a cation- exchange group, having a formula selected from the group consisting of (IV-F-I), (IV- F-ll), (V-F-l), (V-F-ll), (V-F-lll), and (Vl-F):
Figure imgf000020_0001
[0057] Yf 1 is chosen from O or a bivalent (Ci-C6)fluorocarbon residue; Rf 4, Rf 5, Rf 6, Rf 7, and Rf 17 are independently chosen from F, (Ci-Ci2)fluoroalkyl, or (C5-Ci2)cyclofluoroalkyl; Rf 8, Rf 9, Rf 10, Rf 11· Rf 12, Rf 13, Rf 14' Rf 15 and Rf 16 are
independently chosen from NO2, CN, F, SO3H, (Ci-Ci2)fluoroalkyl or (C5- Ci2)cyclofluoroalkyl; Wf 1 and Wf 2 is chosen from a bivalent (Ci-Ci2)fluorocarbon residue or a direct bond; Lf 1 and L 2 are independently chosen from a direct bond or a bivalent (Ci-Ci2)fluorocarbon residue; Jf 1 and J 2 is chosen from SO3H, PO3H2, or C02H.
[0058] RU(F) is a repeated unit of fluorocarbon residues, having a formula selected from the group consisting of (Vll-F), (Vlll-F) and (IX-F):
Figure imgf000021_0001
[0059] Yf 2 is chosen from O or a bivalent (Ci-C6)fluorocarbon residue; Rf18, Rf19, Rf20, R 21, Rf32, and Rf 33 are independently chosen from F, (Cr
Ci2)fluoroalkyl, or (C5-Ci2)cyclofluoroalkyl; R22, R 23, R 24, R25, R26, R 27, R 28, R29, Rf30, and Rf 31 are independently chosen from N02, CN, F, SO3H, (Ci-Ci2)fluoroalkyl or (C5-Ci2)cyclofluoroalkyl; Lf 3 and L4 are independently chosen from a direct bond ora bivalent (Ci-Ci2)fluorocarbon residue.
[0060] In a preferred aspect of CEF, x ranges from 1 to 500,000; y is also an integer from zero to 500,000; Yf 1 is a bivalent (Ci-C6)fluorocarbon residue;
R4, Rf5, R8, Rf7, and Rf 17 are either F, (CrC6)fluoroalkyl, (C5-C6)cyclofluoroalkyl; Rf 8, Rf9, Rf10, Rf11, Rf12, Rf13, Rf14, Rf15 and Rf 16 are independently chosen from F, (Cr Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl; Wf 1 and W2 are a bivalent (Cr
Cs)fluorocarbon residue or a direct bond; Lf 1 and L2 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue; Jf 1 and J2 is chosen from SO3H, P03H2, orC02H; Y2 is a bivalent (Ci-C6)fluorocarbon residue; Rf 18, Rf 19, R20, R21, Rf32 and Rf 33 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5- C6)cyclofluoroalkyl;
Rf 22, Rf 23, Rf 24, Rf 25, Rf 26, Rf 27, Rf 28, Rf 29, Rf 30, and Rf 31 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5-C6) cyclofluoroalkyl; Lf 3 and L4 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue.
[0061] In a further preferred aspect of CEF, x ranges from 1 to 100,000; y is also an integer from zero to 100,000; Yf 1 is CF2; R 4, Rf 5, R 6, Rf 7, and Rf 17 are F; Rf8, Rf9, Rf10, Rf11, Rf12, Rf13, Rf14, Rf15 and Rf 16 are chosen from F, (Ci-C6)fluoroalkyl or (C5-C6)cyclofluoroalkyl; Wf 1 and W2 is a bivalent (Ci-C6)fluorocarbon residue or a direct bond; Lf 1 and Lf 2 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue; Jf 1 and Jf 2 are independently chosen from SO3H,
PO3H2, or C02H; Yf 2 is CF2; Rf 18, Rf 1 9,Rf 20, Rf 21 , Rf 32 and Rf 33are F; Rf 22, Rf 23, Rf 24, R 25, R 26, R 27, R 28, R 29, Rf 30, and Rf 31 are independently chosen from F, (Cr
Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl; Lf 3 and Lf 4 are independently chosen from a direct bond or a bivalent (Ci-Cslfluorocarbon residue.
[00010] In yet another further preferred aspect of CEF, x ranges from 1 to 90,000; y is also an integer from zero to 90,000; Yf 1 is CF2; R 4, Rf 5, Rf 6, Rf 7, and Rf 17are F; Rf 8, Rf 9, Rf 10, Rf 11 , Rf 12, Rf 13, Rf 14, Rf 15 and Rf 16 are chosen from F, or (Cr Ce)fluoroalkyl; Wf 1 and W2 is a bivalent (Ci-C4)fluorocarbon residue or a direct bond; Lf 1 is CF2CF2CF2; L 2 is CF2CF2CF2CF2; Jf 1 and J 2 are independently chosen from SO3H, or C02H; Yf 2 is CF2; Rf 18, Rf 19, Rf 20, Rf 21, Rf 32, and Rf 33 are F; Rf 22, Rf 23, Rf 24, R 25, R 26, R 27, R 28, R 29, Rf 30, and Rf 31 are F; Lf 3 is CF2CF2CF2; Lf 4 is CF2CF2CF2CF2.
[0062] Without limiting the scope of the present invention, in an illustrative example of CEF, x ranges from 1 to 80,000; y is also an integer from zero to 80,000; Yf 1 is CF2; Rf 4, Rf 5, Rf 6, Rf 7, and Rf 17are F; Rf 8, Rf 9, Rf 10, Rf 11· Rf 12, Rf 13, Rf 14' Rf 1 5 and Rf 1 6 are F; Wf 1 and W2 are direct bonds; Lf 1 is CF2CF2CF2; L 2 is
CF2CF2CF2CF2; Jf 1 and Jf 2 are C02H; Yf 2 is CF2; Rf 18, Rf 19, Rf 20, Rf 21, Rf 32 and Rf 33 are F; Rf 22, Rf 23, Rf 24, Rf 25, Rf 26, Rf 27, Rf 28, Rf 29, Rf 30, and Rf 31 are F;
Lf 3 is CF2CF2CF2; Lf 4 is CF2CF2CF2CF2.
[0063] In another illustrative example of CEF, x ranges from 1 to 80,000; y is also an integer from zero to 80,000; Yf 1 is CF2; R 4, Rf 5, Rf 6, Rf 7, and Rf 17 are F; Rf 8, Rf 9, Rf 10, Rf 12, Rf 13, Rf 14' Rf 1 5 and Rf 16 are F; Rf 1 1 is CF3; Wf 1 is a direct bond; Jf 1 is S03H; Wf 2 is CF2OCF2CF2; Jf 2 is C02H; Lf 1 is CF2CF2CF2; Lf 2 is
CF2CF2CF2CF2; Yf 2 is CF2; Rf 18, Rf 19, Rf 20, Rf 21 , Rf 32 and Rf 33 are F; Rf 22, Rf 23, Rf 24, Rf 25, Rf 26, Rf 27, Rf 28, Rf 29, Rf 30, and Rf 31 are F; Lf 3 is CF2CF2CF2; Lf 4 is CF2CF2CF2CF2.
[0064] Those skilled in the art will appreciate that one strategy to synthesize CEF first involves a ROMP polymerization of hydrocarbon monomers. Then, a direct fluorination reaction that replaces hydrogen atoms attached to carbons will convert such a hydrocarbon polymer to a fluorinated polymer of CEF. (3) A hydrocarbon polymer bearing an azo free-radical initiator.
[0065] An embodiment of this section provides a free-radical initiator polymer comprising a plurality of repeated unit of RU(alkane-azo) containing a cycloalkane or an alkane with an azo side chain, which has a formula selected from the group consisting of (l-azo), (I l-azo) and (I I l-azo):
Figure imgf000023_0001
R 13a' ' 1 ¾
(lll-azo)
[0066] Wavy lines indicate the points of attachment to adjacent repeating units of the polymer; Y1 a is chosen from O, or a bivalent (Cr
Ce)hydrocarbon residue; R1 a, R2a, R3a, R4a, and R8a are independently chosen from H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue.
[0067] R5a, R6a, and R7a are independently chosen from H, NO2, CN,
Cl, Br, I, F, ORv", NRVIIRVI", SRV", (Ci-Ci2)alkyl or (C5-Ci2)cycloalkyl; wherein Rv" and Rv are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
R9a, R1 1 a, and R12a are independently chosen from (Ci-Ci2)hydrocarbon residues.
[0068] R10a and R13a are independently chosen from CN, COORlx, CONRlxRx, or CNRIXNRXRXI, wherein RIX, Rx and RXI are independently chosen from H or a (Ci-Ci2)hydrocarbon residue; W1 a is either a direct bond or a bivalent (Cr Cio)hydrocarbon residue; -N=N- can be either cis or trans. [0069] L1 a and l_2a are independently chosen from a direct bond, or a bivalent (Ci-Ci2)hydrocarbon residue; G1 a is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G1 a is fused with the cycloalkyl ring containing Y1 a with two adjacent carbons in common.
[0070] In (l-azo), a floating bond refers to a covalent bond that attaches R5a, or R6a, or R7a or W1 a to a carbon on the cycloalkyl ring containing Y1 a provided that this carbon has a total of four covalent bonds including the floating bond.
Multiple R5a, or R6a, or R7a or W1 a can be attached to the ring comprising Y1 a.
[0071 ] In (I l-azo), a floating bond refers to a covalent bond that attached R5a, or R6a, or R7a or W1 a to a carbon of either G1 a or the cycloalkyl ring containing Y1 a provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5a, or R6a, or R7a or W1 a can be attached to the ring comprising Y1 a or/and G1 a.
[0072] In a preferred aspect of RU(alkane-azo), Y1 a is a bivalent (Cr Ce)hydrocarbon residue; R1 a, R2a, R3a, R4a, and R8a are independently chosen from H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, or a bivalent (Ci-C6)hydrocarbon residue; R5a, R6a, and R7a are independently chosen from H, F, (CrC6)alkyl or (C5-C6)cycloalkyl; W1 a is either a direct bond or a bivalent (Ci-C6)hydrocarbon residue; R9a, R11 a, and R12a are independently chosen from (Ci-C6)hydrocarbon residues; R10a and R13a are independently chosen from CN, COORlx, or CNRlxNRxRxl, wherein RIX, Rx and RXI are independently chosen from H or a (Ci-Ci2)hydrocarbon residue; L1 a and l_2a are independently chosen from a direct bond, or a bivalent (Ci-Cslhydrocarbon residue; G1 a is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
[0073] In a further preferred aspect of RU(alkane-azo), Y1 a is CH2; R1 a, R2a, R3a and R4a, and R8a are independently chosen from H, or F; R5a, R6a, and R7a are independently chosen from H, F, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; W1 a is either a direct bond or a bivalent (C1-C5) hydrocarbon residue; R9a, R11 a, and R12a are independently chosen from (Ci-C6)hydrocarbon residues; R10a and R13a are CN; L1 a and l_2a are independently chosen from a direct bond, or a bivalent (Cr
Cs)hydrocarbon residue; G1 a is a cycloalkane ring or a cycloalkene ring that has C5- C6 on its ring. [0074] In another further preferred aspect of RU(alkane-azo), Y1 a is CH2; R1 a, R2a, R3a, R4a, and R8a are H; R5a, R6a, and R7a are H; W1 a is chosen from OCH2CH2CH2, OCH2CH2, OCH2, CH2OCH2CH2CH2, CH2OCH2CH2, CH2OCH2, CH2SCH2CH2CH2, CH2SCH2CH2, or CH2SCH2; L1 a is CH2CH2CH2; L2a is
CH2CH2CH2CH2; R9a, R1 1 a, and R12a are CH3; R10a and R13a are CN; G1 a is a cycloalkane ring that has C5 on its ring.
[0075] Without limiting the scope of the present invention, in an illustrative example of RU(alkane-azo), Y1 a is CH2; R1 a, R2a, R3a, R4a, and R8a are H; R5a, R6a, and R7a are H; W1 a is OCH2CH2CH2; R9a, R11 a, and R12a are CH3; R10a and R13a are CN; L1 a is CH2CH2CH2; l_2a is CH2CH2CH2CH2; G1 a is a cycloalkane ring that has C5 on its ring.
[0076] In yet another illustrative example of RU(alkane-azo), Y1 a is CH2; R1 a, R2a, R3a, R4, and R8a are H; R5a, R6a, and R7a are H; W1 a is
CH2OCH2CH2CH2; R9a, R1 1 a, and R12a are CH3; R10a and R13a are CN; L1 a is
CH2CH2CH2; L2a is CH2CH2CH2CH2; G1 a is a cycloalkane ring that has C5 on its ring.
[0077] Those skilled in the art will appreciate that upon exposed to heat or lights, RU(alkane-azo) can undergo a decomposition process to release N2 and generate a carbon radical on the carbon next to the azo functionality. Such a radical can lead to the polymerization of fluoro-monomers, which will generate the polymer comprising a plurality of repeated unit of RU(alkane-F), CEHF, AEHF-RING, and AEHF-CHAI N.
(4) Fluorocarbon and/or hydrocarbon polymer-based electrolytes and devices.
[0078] An electrolyte is a substance having electrically-charged ions and ions can move to either a negative or positive electrode in an electric field.
According to ASTM D1 193-91 specifications, the ion conductivity of purified type I water at 25°C is 5.6 x 10'6 S/m and type I purified water is not deemed as an ion- conductive material. Ion-conductive electrolytes herein are considered to have an ion conductivity larger than 5.6 x 10'6 S/m at 25°C. For practical applications in an electric device like a fuel cell or a metal-air battery, the ion conductivity of an ion- conductive electrolyte is typically at or larger than 1 .0 x 10'5 S/m, at or above 1 .0 x 10'4 S/m, at or preferably over 1 .0 x 10'3 S/m, or most preferably at or larger than 1 .0 x 10'2 S/m at 25°C. Some measurement conditions used in an ion conductivity test may have effects on the ion conductivity of the test material, for example, the C02 concentration in the air and the water content in the test environment. The present disclosure covers a C02 volume composition ranging from 0.010 v/v% to 100 v/v%, preferably at 0.035 v/v% of the earth atmosphere C02 concentration. The water content in the test environment can range from a relative humidity of 1 % to 100% or with the test material completely submerged in water, preferably under 100% relative humidity. Those skilled in the art will appreciate the variation of the ion conductivity measurement conditions.
[0079] In one embodiment, the present invention provides a cation- conductive electrolyte comprising of an acid that is selected from the group consisting of (IV), (V) and (VI).
[0080] In another embodiment, the present invention provides a cation- conductive electrolyte comprising of an acid that is selected from the group consisting of (X), (XI) and (XII).
[0081] In one aspect, a support can be added to the fluoropolymer electrolyte. Such a support can be a solid, or a liquid, or a gel. A solid support can be a poly(tetrafluoroethylene) film. The solid membrane displays the desirable properties and the membrane thickness can be from 1 micron to 200 microns, including all values of 1 micron and ranges therebetween. Examples of a liquid support material include water, sea water, ethanol, methanol, acetonitrile, thionyl chloride, dimethyl sulfoxide, dimethylformamide, and ionic liquids. A liquid support material is a material at a liquid state at 25°C. The liquid support material may or may not conduct ions. A gel support is a material at a gel state at 25°C. The gel support material may or may not conduct ions.
[0082] In a preferred aspect, the support can be expanded
poly(tetrafluoroethylene) (PTFE) films. The use of a PTFE support can enhance the mechanic strength of the ion-exchange fluorocarbon polymer and reduce the overall cost of the ion-conductive composite membranes.
[0083] The density as well as the thickness of the PTFE support are of importance to the mechanic properties and ion conductivity of the composite membranes. The PTFE film supports in general need to have a polymer density ranging from 0.3 g/cm3 to 1.8 g/cm3, preferably from 0.3 g/cm3 to 1.2 g/cm3, and most preferably from 0.3 g/cm3 to 1.0 g/cm3. The thickness of the PTFE support can range from 20 microns to 180 microns, preferably from 20 microns to 150 microns, from 20 microns to 100 microns, and most preferably from 20 microns to 80 microns.
[0084] In another preferred aspect, the support is a metal-organic framework (MOF). The electrolyte is comprised of MOF and a fluorocarbon polymer comprising a heteroaromatic group or a HPCA. MOFs are compounds consisting of metal ions or clusters coordinated to often rigid organic molecules to form one-, two-, or three-dimensional structures that can be porous. An example of MOFs is porous Zn-aminotriazolato-oxalate with a chemical formula of Zn2(C204)(C2N4H3)2(H20)o.5 (Chem. Commun. 2009, 5230). Depending upon the particular embodiment, the fluorocarbon polymer may be conjugated to the MOF by a variety of chemical bonds including, but not limited to, covalent bonding, non-covalent bonding, dative bonding, ionic bonding, hydrogen bonding, metallic bonding, or van der Waals bonding. An example is that an imidazole ring or a triazole ring of the fluorocarbon polymer can be part of the MOF framework structure.
[0085] In yet another preferred embodiment, the support can be a metal salt such as phosphotungstic acid, heteropolyacid, silicotungstic acid, zirconium hydrogen phosphate, zirconia, and zirconium hydrogen sulfate.
[0086] In a PEMFC or PAFC or methanol fuel cell, a cation-conductive membrane transports proton from anode to cathode while being impermeable to gaseous and liquid fuels. It is highly desirable that an ion-exchange membrane can be: (a) low hydrogen, methanol, and other liquid fuel crossover; (b) mechanically strong and do not tear or fracture under fuel cell operations; (c) swelling less than 20% of original membrane thickness is ideal; and (d) proton conductivity of from 1.0 mS/cm to 500 mS/cm is desirable. The higher conductivity, the better.
[0087] In particular, the mechanical properties of a solid membrane used in a fuel cell is of importance for its applications, especially at an elevated temperature, Membrane creep and microcrack fracture can lead to pinholes in a membrane and thus give rise to reactant gas crossover.
[0088] In one embodiment, the ion-conductive solid membrane has the maximum tensile in the machine direction for sheet processing (MD) or the maximum tensile strength in the transverse direction (TD) vertical to the MD direction both greater than 20 MPa under 50% relative humidity at 25 °C.
[0089] In another aspect, the cation-conductive solid membrane has the maximum tensile strengths in both MD and TD of 25 MPa or greater, under 50% relative humidity at 25 °C.
[0090] In yet another embodiment, the cation-conductive solid membrane has the maximum tensile strengths in both MD and TD of 30 MPa or greater, under 50% relative humidity at 25 °C.
[0091] The maximum tensile strengths of a membrane can be tested by following ASTM D882.
[0092] One embodiment of the present disclosure provides a fuel cell mainly comprising anode, cathode, catalyst and a fluorocarbon polymer-based electrolyte. The fuel cell can have a solid membrane configuration or a liquid electrolyte configuration. The fuel cell can use hydrogen, methanol, ethanol, hydrazine, glucose, aldehyde, carboxylic acid and boron-based chemicals as fuel. In one aspect, the fluorocarbon polymer electrolyte can be used between anode and cathode to separate oxidative or reductive fuels. In another aspect, a fluorocarbon polymer electrolyte can be added to an electrode as a catalyst ink to facilitate ion conduction. The fuel cell can be a PEMFC or a PAFC or a methanol fuel cell.
[0093] In yet another embodiment, the present disclosure provides an electrolytic cell mainly comprising anode, cathode, catalyst and a fluorocarbon polymer electrolyte.
[0094] Another embodiment of the present disclosure provides a metal- air battery mainly comprising anode, cathode, catalyst and a fluoropolymer electrolyte.
[0095] In yet another embodiment, the present disclosure provides an electrolytic cell mainly comprising anode, cathode, catalyst and a fluorocarbon- hydrocarbon copolymer electrolyte.
DEFINITIONS
[0096] Definitions and methods described herein are provided to better define the present disclosure and to guide those of ordinary skill in the art in the practice of the present disclosure. Unless otherwise noted, terms are to be understood according to conventional usage by those of ordinary skill in the relevant art.
[0097] The term“aromatic”, abbreviated as“Ar”, refers to a compound that contains a set of covalently bond atoms with the characteristics: (a) a
delocalized conjugated p system, most commonly an arrangement of alternating single and double bonds; (b) coplanar structure, with all the contributing atoms in the same plane; (c) contributing atoms arranged in one or more rings; and (d) a total of 4n + 2 number of p electrons, where n=0, 1 , 2, 3, etc. Aromatic hydrocarbons can be monocyclic or polycyclic and include heteroaromatic hydrocarbons. Examples of aromatic hydrocarbons include benzene, phenol, aniline, triphenylphosphine, and triphenylphosphine oxide.
[0098] The term“heteroaromatic” refers to an aromatic hydrocarbon having at least one non-carbon atom in the ring. Heteroaromatic hydrocarbons can be monocyclic or polycyclic. Examples of heteroaromatic hydrocarbons include quinoline, phenylalanine, phenanthroline, pyridine, pyrrole, imidazole, tetrazole, and furan.
[0099] The term“residue” refers to two or more atoms bound together as a single unit and forming part of a molecule.
[0100] The term“copolymer” refers to a polymer made by reaction of two different monomers, with units of more than one kind. It can be either a block or a random or a sequentially placed copolymer.
[0101] In the present disclosure,“Cx” has been used to represent a structure that is comprised of the number (x) of carbon atoms. For example, Ci refers to a chemical group that has one carbon; C6 refers to a residue that has six carbons.
[0102] The term“fused” refers to in a molecular or residual structure, two rings have at least two carbon atoms in common.
[0103] The term“monovalent” refers to a chemical group with a valence of one, which thus can form one covalent bond.
[0104] The term“bivalent” refers to a chemical group that can form two covalent bonds. [0105] The term“radical”,“free radical” or“free-radical” refers to an uncharged molecule or group (typically highly reactive and short-lived) having an unpaired valence electron.
[0106] The term“radical initiator”,“free radical initiator” or“free-radical initiator” refers to substances that can produce radical species under mild conditions and promote radical reactions (e.g., benzoyl peroxide and azobisisobutyronitrile).
[0107] The term“living polymerization” or“controlled polymerization” refers to is a form of chain growth polymerization where the ability of a growing polymer chain to terminate has been removed.
[0108] A“covalent bond” is a chemical bond that involves the sharing of electron pairs between atoms. Examples of“covalent bonds” includes C-C bonds, C-N bonds, and C-0 bonds.
[0109] “Hydrocarbon” refers to an organic compound that mainly consisting of hydrogen and carbon atoms. Examples include octane, benzene, diethyl ether, aniline, and pyridine.
[0110] “Fluorocarbon” refers to an organic compound derived by replacing all or most of the hydrogen atoms in a hydrocarbon by fluorine atoms (e.g., tetrafluoroethylene, tetradecafluorohexane). It could include fluoroalkanes and fluoroalkenes.
[011 1] “Fluoroalkyl” refers to an organic compound derivative produced by replacing all or most of the hydrogen atoms in an alkyl group by fluorine atoms (e.g., trifluoromethyl).
[0112] “Cyclofluoroalkyl” refers to an organic compound derivative produced by replacing all or most of the hydrogen atoms in a cycloalkyl group by fluorine atoms (e.g., trifluoromethyl).
[0113] The term“functional group” or“functionality” refers to a group of atoms responsible for the characteristic reactions of a particular compound (e.g., ketone, alcohol, azo).
[0114] “Polymer” refers to a compound of high molecular weight derived either by the addition of many smaller molecules, as polyethylene, or by the condensation of many smaller molecules with the elimination of water, alcohol, or the like, as nylon. [0115] A“fluoropolymer” or“fluorocarbon polymer” is a fluorocarbon based polymer with multiple strong carbon-fluorine bonds. Examples include poly(vinyl fluoride), polytetrafluoroethylene, perfluoroalkoxy and
poly(chlorotrifluoroethylene).
[0116] The term“fluoro-monomer” or“fluoromonomer” refers to a fluorocarbon molecule that can be bonded to other identical molecules to form a polymer (e.g., tetrafluoroethylene, hexafluoropropylene).
[0117] The term“fluoroalkene” refers to an organic compound derived by replacing all or most of the hydrogen atoms in an alkene by fluorine atoms (e.g., tetrafluoroethylene).
[0118] An“ion-conductive material”,“ion conductive material”,“ion transportation material” or“electrolyte” is a material that can transport an ion from one site to another. Ionic conduction can lead to an electric current. The SI unit of conductivity is Simens per meter (S/m) and, unless otherwise qualified, it generally refers to 25°C (standard temperature).
[0119] The term“anion-conductive” or“anion conductive” or“anion- exchange” or“anion exchange” refers to the migration of a negatively charged ion from one side to another in a medium.
[0120] The term“cation-conductive” or“cation conductive” or“cation- exchange” or“cation exchange” refers to the migration of a positively charged ion from one side to another in a medium.
[0121] The term“solid” refers to a solid state of matter under a temperature ranging from -70 to 200 °C.
[0122] The term“residue” or“unit” refers to a recognizable molecular part of a larger molecule (e.g., an amino acid is a residue or unit of a larger protein chain).
[0123] The rule of“a carbon atom has four covalent bonds; a hydrogen atom has one covalent bond; and an oxygen atom is attached with two covalent bonds” are applied through this invention disclosure. Those skilled in the art can appreciate it that a hydrogen atom may not always be shown in a chemical formula when it is covalently bonded to a carbon atom. A floating bond refers to a covalent bond that is attached to a carbon on a ring provided that the carbon has a total of four covalent bonds including the floating bond.
[0124] In some embodiments, numbers expressing quantities of ingredients, properties such as molecular weight, reaction conditions, and so forth, used to describe and claim certain embodiments of the present disclosure are to be understood as being modified in some instances by the term“about.” In some embodiments, the term“about” is used to indicate that a value includes the standard deviation of the mean for the device or method being employed to determine the value. In some embodiments, the numerical parameters set forth in the written description and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the present disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable. The numerical values presented in some embodiments of the present disclosure may contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements. The recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein.
[0125] In some embodiments, the terms“a” and“an” and“the” and similar references used in the context of describing a particular embodiment
(especially in the context of certain of the following claims) can be construed to cover both the singular and the plural, unless specifically noted otherwise. In some embodiments, the term“or” as used herein, including the claims, is used to mean “and/or” unless explicitly indicated to refer to alternatives only or the alternatives are mutually exclusive.
[0126] The terms“comprise,”“have” and“include” are open-ended linking verbs. Any forms or tenses of one or more of these verbs, such as “comprises,”“comprising,”“comprised of”,“has,”“having,”“includes” and“including,” are also open-ended. For example, any method that“comprises,”“has” or“includes” one or more steps is not limited to possessing only those one or more steps and can also cover other unlisted steps. Similarly, any composition or device that
“comprises,”“has” or“includes” one or more features is not limited to possessing only those one or more features and can cover other unlisted features.
[0127] The terms“selected”,“chosen” and“or” refer to make one or more choices including a combination of choices from a number of possibilities.
[0128] All methods described herein can be performed in any suitable order unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language ( e.g .“such as”) provided with respect to certain embodiments herein is intended merely to better illuminate the present disclosure and does not pose a limitation on the scope of the present disclosure otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the present disclosure.
[0129] Groupings of alternative elements or embodiments of the present disclosure disclosed herein are not to be construed as limitations. Each group member can be referred to and claimed individually or in any combination with other members of the group or other elements found herein. One or more members of a group can be included in, or deleted from, a group for reasons of convenience or patentability. When any such inclusion or deletion occurs, the specification is herein deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.
[0130] Citation of a reference herein shall not be construed as an admission that such is prior art to the present disclosure.
[0131] Having described the present disclosure in detail, it will be apparent that modifications, variations, and equivalent embodiments are possible without departing the scope of the present disclosure defined in the appended claims. Furthermore, it should be appreciated that all examples in the present disclosure are provided as non-limiting examples. EXAMPLES
[0132] The following non-limiting examples are provided to further illustrate the present disclosure. It should be appreciated by those of skill in the art that the techniques disclosed in the examples that follow represent approaches the inventors have found function well in the practice of the present disclosure, and thus can be considered to constitute examples of modes for its practice. However, those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments that are disclosed and still obtain a like or similar result without departing from the spirit and scope of the present disclosure.
[0133] The following examples illustrate various embodiments of the disclosure. Chemicals and organic solvents mentioned below were purchased from Sigma-Aldrich (Milwaukee, Wl) or Fisher Scientific (Pittsburgh, PA) and used as received. Water was obtained from a Milli-Q water system purchased from Millipore Corporation (Milford, MA). The heavy metal and bacterial contaminant levels in Milli- Q water were below 10 parts per billion. Some fluorination of ROMP polymer experiments were conducted with the assistance from the researchers at Institut de Chemie de Clermont-Ferrand in France. The nomenclature of graft polymers in our examples could follow the IUPAC nomenclature methods, which is illustrated in a paper (Wilks, J. Chem. Inf. Comput. Sci., 1997, 137, 209-223).
Example 1: Random copolymerization of cis-cyclooctene and 2-[1-cyano-1- methyl-4-{[(5-norbomen-2-yl)methyl]amino}-4-oxobutylazo]-2-methyl-5-{[(5- norbomen-2-yl)methyl]amino}-5-oxovaleronitrile via ROMP (polymer 1).
[0134] In a 50 mL round-bottom flask, the mixture of 600 mg of cis- cyclooctene and 20 mg of 2-[1-Cyano-1-methyl-4-{[(5-norbornen-2-yl)methyl]amino}- 4-oxobutylazo]-2-methyl-5-{[(5-norbornen-2-yl)methyl]amino}-5-oxovaleronitrile in 10 mL chloroform was treated with 3.8 mg of (1 ,3-Bis(2,4,6-trimethylphenyl)-2- imidazolidinylidene)-dichloro(phenylmethylene)-(tricyclohexylphosphine)ruthenium (Grubbs’ 2nd generation catalyst) in 1 mL chloroform. The mixture was stirred at 25 °C for 12 h. Then, 20 mL of dichloromethane was added to get the precipitate of the copolymer. The polymer was washed with dichloromethane 20 mL x 3. IR (KBr) 3428, 2378, 1686, 1400 cm 1. Example 2: Block copolymerization of cis-cyclooctene and 2-[1 -cyano-1 - methyl-4-{[(5-norbornen-2-yl)methyl]amino}-4-oxobutylazo]-2-methyl-5-{[(5- norbornen-2-yl)methyl]amino}-5-oxovaleronitrile via ROMP (polymer 2).
[0135] In a 50 mL round-bottom flask, the mixture of 600 mg of cis- cyclooctene in 10 mL chloroform was treated with 3.8 mg of Grubbs’ 2nd generation catalyst in 1 mL chloroform. The mixture was stirred at 25 °C for 10 min and then 20 mg of 2-[1 -Cyano-1 -methyl-4-{[(5-norbornen-2-yl)methyl]amino}-4-oxobutylazo]-2- methyl-5-{[(5-norbornen-2-yl)methyl]amino}-5-oxovaleronitrile in 1 mL chloroform was introduced. The mixture was further stirred at 25 °C for 12 h. Then, 20 mL of dichloromethane was added to get the precipitate of the copolymer. The polymer was washed with dichloromethane 20 mL x 3. IR (KBr) 3428, 2378, 1686, 1400 cm
1
Example 3: Free-radical polymerization of heptafluoropropyl trifluorovinyl ether using 2-[1 -Cyano-1 -methyl-4-{[(5-norbornen-2-yl)methyl]amino}-4- oxobutylazo]-2-methyl-5-{[(5-norbornen-2-yl)methyl]amino}-5-oxovaleronitrile as the initiator (polymer 3).
[0136] In a pressure reactor, 1 g of 2-[1 -Cyano-1 -methyl-4-{[(5- norbornen-2-yl)methyl]amino}-4-oxobutylazo]-2-methyl-5-{[(5-norbornen-2- yl)methyl]amino}-5-oxovaleronitrile was introduced to a mixture of 10 mL acetone and 0.2 mL trifluoroacetic acid. Acetone was de-oxygenized via freeze-thaw three times. Then, 2.1 g of heptafluoropropyl trifluorovinyl ether was introduced and the mixture was sealed in the pressure reactor. After 12 h at 60 °C, the mixture was cooled down to ambient temperature and the solvent was removed in vacuo. The polymer was re-dissolved in 10 mL chloroform and a precipitate was obtained by the addition of 20 mL dichloromethane to the mixture. The polymer was further washed with dichloromethane 20 mL x 3 and dried. 1 H NMR (DMSO-d6, 400 MHz) d 6.17- 5.90 (m, 2 H), 2.75-1.08 (m, 16 H); 19F NMR (DMSO-d6, 400 MHz) d -75.8, -82.1 , - 120.7, -128.6, -148.7. Example 4: Free-radical polymerization o†2-(per†luoropropoxy)perfluoropropyl trifluorovinyl ether using 2-[1-Cyano-1-methyl-4-([(5-norbornen-2- yl)methyl]amino}-4-oxobutylazo]-2-methyl-5-{[(5-norbornen-2- yl)methyl]amino}-5-oxovaleronitrile as the initiator (polymer 4).
[0137] The similar procedure used in example 3 was adopted except that 2-(perfluoropropoxy)perfluoropropyl trifluorovinyl ether was used to replace heptafluoropropyl trifluorovinyl ether. 1H NMR (400 MHz, DMSO-d6) d 6.17-5.90 (m, 2 H), 2.75-1.08 (m, 16 H); 19F NMR (DMSO-d6, 400 MHz) d -71.9, -74.1 , -78.0, - 80.5, -80.7.
Example 5: ROMP copolymerization of cis-cyclooctene and polymer 4
(polymer 5).
[0138] In a 50 mL round-bottom flask, the mixture of 600 mg of cis- cyclooctene and 50 mg of polymer 4 in 10 mL chloroform was treated with 3.8 mg of Grubbs’ 2nd generation catalyst in 1 mL chloroform. The mixture was stirred at 25 °C for 12 h. Then, 20 mL of dichloromethane was added to get the precipitate of the copolymer. The polymer was washed with dichloromethane 20 mL x 3. . 1 H NMR (400 MHz, DMSO-d6) d 6.02-5.83, 3.20-0.85; 19F NMR (DMSO-d6, 400 MHz) d - 71.9, -74.1 , -78.0, -80.5, -80.7.
Example 6: Catalytic hydrogenation of polymer 5.
[0139] In a pressure reactor, to the mixture of 200 mg of polymer 5 in 8 mL methanol and 20 mL chloroform was added 20 mg of Wilkinson’s catalyst and 0.2 mL trifluoroacetic acid. The system was under 600 psi hydrogen pressure at 60 °C for one week. Then, the mixture was cooled down to ambient temperature and the solvent was removed in vacuo. (DMSO-d6, 400 MHz) shows -40% C=C was reduced.
Example 7: Synthesis of2-[1-cyano-1-methyl-4-([(5-norbornen-2- yl)methyl]amino}-4-oxobutylazo]-2-methyl-5-{[(5-norbornen-2- yl)methyl]amino}-5-oxovaleronitrile.
[0140] To a mixture of 879 mg of 1-(bicyclo[2.2.1]hept-5-en-2- yl)methanamine and 500 mg of 4,4'-azobis(4-cyanovaleric acid) in 20 mL chloroform was added 3.7 g of (benzotriazol-l-yloxy)tripyrrolidinophosphonium
hexafluorophosphate and 140 mg of trimethylamine in 10 mL chloroform at 0 °C. After 0 °C for 12 h in dark, the mixture was washed with 1 M HCI (20 mL x 2) and water (20 mL x 2). The organic layer was dried over anhydrous Na2S04 and concentrated in vacuo (keep temperature under 25 °C). Flash chromatography (20% EtOAc in hexane) led to—1.1 g of the product. 1H NMR (CDCI3, 400 MHz) 6 6.40- 5.81 (br, 4 H), 2.92-1.05 (br, 16 H).
Example 8: Preparation of poly{4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4- [4-poly(hexafluoropropylene)-4-cyano-pentan-1-oyl-amino]methyl-1,3- cyclopentylene ethylene} (polymer 8)
[0141] ROMP co-polymerization of c/s-5-norbornene-2,3-dicarboxylic anhydride and 2-[(fe/?-butoxycarbonylamino)methyl]-5-norbornene for the formation of poly{4,5-dicarboxylic anhydride-1 ,3-cyclopentylene vinylene/4-[(ferf- butoxycarbonylamino)methyl-1 ,3-cyclopentylene vinylene} (polymer 8a): 2.21 g of c/s-5-norbornene-2,3-dicarboxylic anhydride and 0.3 g of 2 -[(tert- butoxycarbonylamino)methyl]-5-norbornene in 10 mL chloroform was mixed with 1 1 mg of the Grubbs’ 2nd generation catalyst at ambient temperature. After 12 h, the solvent was removed in vacuo. The residue was washed with methanol 10 mL x 3 to yield 1.3 g of pale yellow solid.
[0142] Hydrogenation reduction of the C=C bonds in the backbone of polymer 8a to yield poly{4,5-dicarboxylic anhydride-1 ,3-cyclopentylene ethylene/4- [(fe/?-butoxycarbonylamino)methyl-1 ,3-cyclopentylene ethylene} (polymer 8b): the mixture of 1.2 g of polymer 8a, 0.1 mL of acetic acid, and 14 mg of Crabtree’s catalyst in 10 mL chloroform was subject to 600 psi H2 pressure at 60 °C for seven days. After cooling down to ambient temperature, the solvent was removed in vacuo and the polymer was washed with 10 mL x 3 ethyl acetate and 10 mL x 3
dichloromethane to yield polymer 8b (950 mg). 1 H NMR (400 MHz, CDCI3) d 3.4-3.3 (m), 3.05-2.95 (m), 2.82-2.80 (m), 2.6-2.5 (m), 1.88-1.80 (m), 1.78-1.60 (m), 1.58- 1.50 (s). The near complete disappearance of the olefinic signals in the 1H NMR suggests that over 99% C=C bonds were reduced by hydrogenation.
[0143] Preparation of poly{4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4-[4-(1-cyano-1-methyl)ethylazo-4-cyano-pentanoyl-amino]methyl-1 ,3- cyclopentylene ethylene} (polymer 8c) from polymer 8b: the mixture 900 mg of polymer 8b in 2 M NaOH was heated to 100 °C for 12 h. After cooling down to ambient temperature, the solution was acidified to pH 3-4 by using 1 M H2S04. The aqueous solution was extracted with dichloromethane 20 ml_ x 3. The combined organic layers were dried over anhydrous Na2S04 and the solvent was removed in vacuo to give rise to 250 mg powder. The solid was dissolved in 10 mL
dichloromethane and 3 mL trifluoroacetic acid (TFA) was added. After 12 h at ambient temperature, the solvent and TFA were removed in vacuo to yield a solid residue.
[0144] The aforementioned solid residue in 10 mL dichloromethane was treated with 230 mg of 4-(1-cyano-1-methyl-ethylazo)-4-cyano-pentanoyl chloride (Prucker and Rilhe, Macromolecules, 1998, 31 , 592-601 ). Then, 630 mg of triethylamine was introduced. After 12 h at 0 °C, the solvent was removed in vacuo and the residue was washed with diethyl ether 10 mL x 5 to yield polymer 8c.
[0145] Preparation of polymer 8 from polymer 8b: 240 mg polymer 8b and 3.26 g of hexafluoropropylene in 10 mL acetone was heated to 60 °C in a pressure bottle. After 48 h, the solvent was removed in vacuo and the residue was washed with ethyl ether to yield polymer 8 as a solid. Elemental analysis: F, 42.38 wt%.
Example 9: Preparation of poly{4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4- [4-poly(hexaf luoroporpylene)-4-cyano-1 -pentyloxy] methyl-1, 3-cyclopentylene ethylene} (polymer 9)
[0146] ROMP co-polymerization of dimethyl 5-norbornene-2,3- dicarboxylate and (5-norbornen-2-yl)methyl iodide for the formation of poly(4,5- dimethoxycarbonyl-1 ,3-cyclopentylene vinylene/4-iodomethyl-1 ,3-cyclopentylene vinylene) (polymer 9a): to a mixture of 3 g dimethyl 5-norbornene-2,3-dicarboxylate and 491 mg (5-norbornen-2-yl)methyl iodide (Leung, Lai and Williams, J.
Organomet. Chem., 2000, 604, 197-201 ) in 24 mL CH2CI2 was added 30 mg of the Grubbs’ 2nd generation catalyst. After 12 h at ambient temperature, the solvent was removed in vacuo and the residue was washed with methanol 15 mL x 2 and sorbents to yield 2.65 g of polymer 9a as a solid. FT-IR experiments confirmed the formation of polymer 9a.
[0147] Hydrogenation reduction of the C=C bonds in the backbone of polymer 9a to yield poly(4,5-dimethoxycarbonyl-1 , 3-cyclopentylene ethylene/4- iodomethyl-1 ,3-cyclopentylene ethylene) (polymer 9b): the mixture of 2.64 g of polymer 9a, 0.1 mL acetic acid, and 26 mg of Crabtree’s catalyst in 14 mL chloroform was subjected to 600 psi H2 pressure at 60 °C. After 1 1 days, the mixture was cooled down to ambient temperature and the solvent was removed in vacuo.
The residue was washed with hexane 20 mL x 5 and dichloromethane 20 mL x 5 to yield 1.5 g of polymer 9b. 1 H NMR suggest that over 80% of C=C bonds were reduced to C-C single bonds.
[0148] Preparation of poly{4,5- dimethoxycarbonyl-1 ,3-cyclopentylene ethylene/4-[4-(1 -acetoxy-4-cyano-4-pentyl)azo-4-cyano-pentyl-1 -oxy]m ethyl- 1 ,3- cyclopentylene ethylene} (polymer 9c) from polymer 9b: the mixture of 1.50 g of polymer 9b, 0.6 g of 4-(1-acetoxy-4-cyano-4-pentyl)azo-4-cyano-1 -pentanol, 3.0 g of silver trifluoromethanesulfonate, and 2.18 g of 2,6-di-ferf-butylpyridine in 20 mL chloroform was stirred at ambient temperature for 12 h. Then, the solution was washed with 2 M HCI and the solid was filtered out. The organic layer was further washed with 1 M ethylenediaminetetraacetic acid 10 mL x 1 , 1 M HCM O mL x l and water 10 mL x 1. The solvent was then removed in vacuo to yield polymer 9c.
[0149] Preparation of poly{4,5-dicarboxyl-1 ,3-cyclopentylene ethylene/4-[4-poly(hexafluoroporpylene)-4-cyano-1-pentyloxy]methyl-1 ,3- cyclopentylene ethylene} (polymer 9) from polymer 9c: 1.5 g polymer 9c and 5.2 g of hexafluoropropylene in 10 mL acetone was heated to 60 °C in a pressure bottle.
After 48 h, the solvent was removed in vacuo and the residue was washed with ethyl ether to yield a solid polymer, which was suspended in 2 M NaOH at 60 °C for 48 h. Then, the polymer was acidified in 1 M H2S04. Filtration followed by drying gave rise to polymer 9. Elemental analysis: F, 44.17 wt%.
Example 10: Preparation of poly{4-triphenylphosphoniumyl-1 ,3-cyclopentylene ethylene/4-[4-poly(hexafluoroporpylene)-4-cyano-1-pentyloxy]methyl-1,3- cyclopentylene ethylene} (polymer 10).
[0150] ROMP co-polymerization of (5-norbornen-2- yl)triphenylphosphonium bromide and (5-norbornen-2-yl)methyl iodide for the formation of poly(4-triphosphoniumyl-1 ,3-cyclopentylene vinylene/4-iodomethyl-1 ,3- cyclopentylene vinylene) (polymer 10a): to a mixture of 1.39 g of bicycle[2.2.1]hept- 5-enyl-2-triphenylphosphonium bromide (Bonjouklian and Ruden, J. Org. Chem., 1977, 42, 4095-4103) and 75 mg (5-norbornen-2-yl)methyl iodide in 10 mL chloroform was added 12 mg of the Grubbs’ 2nd generation catalyst. After 12 h at ambient temperature, the solvent was removed in vacuo and the residue was washed with methanol 15 ml_ x 2 to yield 1.4 g of polymer 10a. 1 H NMR confirmed polymer 10a.
[0151] Hydrogenation reduction of the C=C bonds in the backbone of polymer 10a to yield poly(4-triphosphoniumyl-1 ,3-cyclopentylene ethylene/4- iodomethyl-1 ,3-cyclopentylene ethylene) (polymer 10b): the mixture of 1.39 g polymer 10a and 1 1 mg of Crabtree’s catalyst in 10 mL chloroform/methanol (1 :1 ) was under 600 psi H2 pressure at 60 °C for 48 h. After cooling down to ambient temperature, the solvent was removed in vacuo to yield 1.17 g of polymer 10b. 1 H NMR shows that over 90% of C=C is reduced.
[0152] Preparation of poly{4-triphenylphosphoniumyl-1 ,3- cyclopentylene ethylene/4-[4-poly(hexafluoroporpylene)-4-cyano-1-pentyloxy]methyl-
1.3-cyclopentylene ethylene} (polymer 10): to the mixture of 66 mg of polymer 10b, 46 mg of 4-(1-acetoxy-4-cyano-4-pentyl)azo-4-cyano-1-pentanol, and 180 mg of 2,6- di-ferf-butylpyridine in 10 mL CH2CI2 at 0 °C was added 242 mg of silver
trifluoromethanesulfonate. After 12 h, the solution was washed with 1 M HCI and the solid was filtered out. The organic layer was further washed with 1 M
ethylenediaminetetraacetic acid 10 mL x 1 , 1 M HCI 10 mL x 1 and water 10 mL x 1. The solvent was then removed in vacuo to yield a solid.
[0153] Then, to the aforementioned solid in 15 mL acetone was added
1.5 mL hexafluoropropylene in a pressure bottle. After 48 h at 60 °C, the solvent was removed in vacuo to yield polymer 10. Elemental analysis: F, 38.10 wt%.
Example 11: Preparation of poly(4,5-dicarboxyl-perfluoro-1,3-cyclopentylene ethylene) (polymer 11)
[0154] 3.0 g of c/s-5-norbornene-2,3-dicarboxylic anhydride in 10 mL chloroform was mixed with 16 mg of the Grubbs’ 2nd generation catalyst. After 12 h at ambient temperature, the solvent was removed in vacuo. The residue was washed with methanol 20 mL x 3 to yield 2.8 g of poly(4,5-dicarboxylic anhydride-
1.3-cylcopebtylene vinylene) as a solid. 1H NMR (400 MHz, CDCI3) d 6.36 (m), 3.62 (m), 3.50 (s), 3.50 (m), 1.80-1.58 (m). Direct fluorination of this solid polymer using gaseous molecular fluorine F2 was followed by using the similar methods as those reported in the paper (Peyroux, Dubois, Tomasella, Petit, and Flahaut, Appl. Surf.
Sci, 2014, 315, 426-431 ) to yield a solid, which was hydrolyzed in NaOH followed by acidification by dilute H2S04 to give rise to polymer 1 1.
Example 12: Preparation of poly(4,5-dicarboxyl-perfluoro-1,3-cyclopentylene ethylene/perfluoro-1,3-cyclopentylene ethylene) (polymer 12)
[0155] To the mixture of 1.5 g of c/s-5-norbornene-2,3-dicarboxylic anhydride and 4.56 g of 2-norborene in 26 mL chloroform was added 47 mg of the Grubbs’ 2nd generation catalyst. After 12 h at ambient temperature, the solvent was removed in vacuo. The residue was washed with methanol 20 mL x 3 to yield 3.9 g of poly(4,5-dicarboxylic anhydride-1 ,3-cylcopebtylene vinylene/1 ,3-cyclopentylene vinylene) as a solid. 1H NMR (400 MHz, CDCI3) d 5.6-5.15 (m), 3.6-3.4 (m), 3.50 (s), 2.85-2.65 (m), 2.58-2.30 (m), 2.0-2.62 (m), 1.43-1.05 (m), 1.15-0.92 (m). Direct fluorination of this solid polymer using gaseous molecular fluorine F2 was followed by using the similar methods as those reported in the paper (Peyroux, Dubois,
Tomasella, Petit, and Flahaut, Appl. Surf. Sci, 2014, 315, 426-431 ) to yield a solid, which was hydrolyzed in NaOH followed by acidification by dilute H2S04 to give rise to polymer 12.
Example 13: Preparation of poly(4,5-dicarboxyl-perfluoro-1,3-cyclopentylene ethylene/perfluoro-1,8-octane-diyl) (polymer 13)
[0156] To the mixture of 1.5 g of c/s-5-norbornene-2,3-dicarboxylic anhydride and 4.25 g of cis- cyclooctene in 24 mL chloroform was added 40 mg of the Grubbs’ 2nd generation catalyst. After 12 h at ambient temperature, the solvent was removed in vacuo. The residue was washed with methanol 20 mL x 3 to yield 4.4 g of poly(4,5-dicarboxylic anhydride-1 , 3-cylcopebtylene vinylene/1 ,3- cyclopentylene vinylene) as a solid. 1 H NMR (400 MHz, CDCI3) d 5.65-5.21 (m), 3.45-2.90 (m), 2.18-1.80 (m), 1.42-1.07 (m). Direct fluorination of this solid polymer using gaseous molecular fluorine F2 was followed by using the similar methods as those reported in the paper (Peyroux, Dubois, Tomasella, Petit, and Flahaut, Appl. Surf. Sci, 2014, 315, 426-431 ) to yield a solid, which was hydrolyzed in NaOH followed by acidification by dilute H2S04 to give rise to polymer 13.

Claims

CLAIMS What is claimed is:
1. A polymer comprising a plurality of repeated unit of RU(alkane-F) containing a cycloalkane or an alkane with a fluoropolymer side chain, which has a formula selected from the group consisting of (I), (II) and (III):
Figure imgf000042_0001
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y1 is selected from the group consisting of O, and a bivalent (Ci-Ce)hydrocarbon residue;
R1 , R2, R3, R4, and R8 are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ci2)hydrocarbon residue;
R5, R6, and R7 are independently selected from the group consisting of H, NO2, CN, Cl, Br, I, F, OR, NRR , SR, (CrCi2)alkyl and (C5-Ci2)cycloalkyl;
W1 is a bivalent (C2-Ci2)hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR, COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (Cr
Ci2)hydrocarbon residue;
L1 and L2 are independently selected form the group consisting of a direct bond, and a bivalent (Ci-Ci2)hydrocarbon residue; Rf 1 and Rf 2 are independently selected from the group consisting of H, F, Cl, Br and CF3;
Rf 3 is selected from the group consisting of H, F, Cl, Br, CF3, CF2CF3, CF2CF2CF3, CF2(CF2)2CF3, OCF3, OCF2CF3, OCF2CF2CF3, OCF2CF(CF3)OCF3, and
OCF2CF(CF3)OCF2CF3.
n is an integer number ranging from 2 to 1 ,000,000; and
G1 is a cycloalkane ring or a cycloalkene ring that has Cs-Ci2 on its ring. The ring of G1 is fused with the cycloalkyl ring containing Y1 with two adjacent carbons in common;
A floating bond refers to a covalent bond that attaches R5, or R6, or R7 or W1 in (I) to a carbon on the cycloalkyl ring containing Y1 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5, or R6, or R7 or W1 can be attached to the cycloalkyl ring containing Y1; In (II), a floating bond refers to a covalent bond that attached R5, or R6, or R7 or W1 to a carbon of G1 or/and the cycloalkyl ring containing Y1 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5, or R6, or R7 or W1 can be attached to the cycloalkyl ring containing Y1 or/and the G1 ring.
2. A polymer according to claim 1 , wherein Y1 is a bivalent (Cr
Ce)hydrocarbon residue; R1, R2, R3 , R4, and R8 are independently selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-C6)hydrocarbon residue;
R5, R6, and R7 and are independently selected from the group consisting of H, F, (Cr C6)alkyl and (C5-C6)cycloalkyl; W1 is a bivalent (C3-C8)hydrocarbon residue comprising a functional group selected from the group consisting of CN, COOR,
COO, CONRR’, CONR, CNRNR’R”, and CNRNR’, wherein R, R’ and R” are independently chosen from H or a (Ci-C6)hydrocarbon residue; L1 and L2 are independently chosen from a direct bond or a bivalent (Ci-Csjhydrocarbon residue; Rf 1 and R 2 are independently chosen from H, F, or CF3; Rf 3 is selected from the group consisting of H, F, CF3, CF2CF3, OCF3, OCF2CF3, OCF2CF2CF3,
OCF2CF(CF3)OCF3, and OCF2CF(CF3)OCF2CF3; n is an integer number ranging from 2 to 500,000; and 1 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
3. A polymer according to claim 2, wherein Y1 is CH2; R1 , R2, R3, R4, and R8 are independently chosen from H or F; R5, R6, and R7 are independently chosen from H, F, (CrC6)alkyl or (C5-C6)cycloalkyl; W1 is a bivalent (C3-C8)hydrocarbon residue comprising CN; L1 and L2 are independently chosen from a direct bond or a bivalent (Ci-Cslhydrocarbon residue; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 100,000; and G1 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
4. A polymer according to claim 3, wherein Y1 is CH2; R1 , R2, R3, R4, and R8 are H; R5, R6, and R7are H; W1 is selected from the group consisting of
OCH2CH2CH2CCNCH3, OCH2CH2CCNCH3, OCH2CCNCH3,
CH2OCH2CH2CH2CCNCH3, CH2OCH2CH2CCNCH3, CH2OCH2CCNCH3,
CH2SCH2CH2CH2CCNCH3, CH2SCH2CH2CCNCH3, and CH2SCH2CCNCH3; L1 is CH2CH2CH2; L2 is CH2CH2CH2CH2; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 90,000; and G1 is a cycloalkane ring that has C5 on its ring.
5. A polymer according to claim 4, wherein Y1 is CH2; R1 , R2, R3, R4, and R8 are H; R5, R6, and R7 are H; W 1 is OCH2CH2CH2CCNCH3; L1 is CH2CH2CH2; L2 is CH2CH2CH2CH2 ; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 80,000; and G1 is a cycloalkane ring that has C5 on its ring.
6. A polymer according to claim 4, wherein Y1 is CH2; R1 , R2, R3, R4, and R8 are H; R5, R6, and R7 are H; W 1 is CH2OCH2CH2CH2CCNCH3; L1 is CH2CH2CH2; L2 is CH2CH2CH2CH2 ; Rf 1 and R 2 are F; Rf 3 is F; n is an integer number ranging from 2 to 80,000; and G1 is a cycloalkane ring that has C5 on its ring.
7. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) comprising a plurality of repeated unit of RU(alkane-F) according to any of claims 1 - 6, random or sequentially placed cation-exchange repeating unit of RU(CE) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
— f-Ru(alkane-
Figure imgf000044_0001
Wherein, nF, nCE and nH are the numbers of the repeating unit of RU(alkane-F), RU(CE) and RU(H), respectively; nF is an integer ranging from zero to 1 ,000,000; nCE is also an integer from 1 to 1 ,000,000; nH is another integer ranging from zero to 1 ,000,000; RU(CE) is a repeated unit containing a cation-exchange group, having a formula selected from the group consisting of (IV), (V) and (VI):
Figure imgf000045_0001
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y2 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R9, R10, R11 , R12, and R16 are independently selected from the group consisting of H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ci2)hydrocarbon residue;
R13, R14, and R15 are independently selected from the group consisting of H, NO2, CN, F, Cl, Br, I, OR1, NR'R", SR1, (Ci-Ci2)alkyl and (C5-Ci2)cycloalkyl, wherein R1 and R11 are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
W2 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue or a direct bond;
G2 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring;
L3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Ci2)hydrocarbon residue; and
J is chosen from SO3H, PO3H2, or CO2H;
A floating bond refers to a covalent bond that attaches R13, or R14, or R15 or W2 in (IV) to a carbon on the cycloalkyl ring containing Y2 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R13, or R14, or R15 or W2 can be attached to the cycloalkyl ring containing Y2; In (V), a floating bond refers to a covalent bond that attached R13, or R14, or R15 or W2 to a carbon of G2 or/and the cycloalkyl ring containing Y2 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R13, or R14, or R15 or W2 can be attached to the cycloalkyl ring containing Y2 or/and the G2 ring;
RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VII), (VIII) and (IX):
Figure imgf000046_0001
(VII) (Vlll) , and (IX)
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y3 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21, R25, and R26 are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and to a bivalent (Ci-Ci2)hydrocarbon residue;
R22, R23, and R24 are independently selected from the group consisting of H, NO2, CN, F, Cl, Br, I, OR1", NRmRlv, SR1", (Ci-Ci2)alkyl and (C5-Ci2)cycloalkyl, wherein R1" and RIV are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G3 is fused with the cycloalkyl ring containing Y3 with two adjacent carbons in common; and
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
Ci2)hydrocarbon residue;
A floating bond refers to a covalent bond that attaches R22, or R23, or R24 in (VII) to a carbon on the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3; In (VIII), a floating bond refers to a covalent bond that attached R22, or R23, or R24 to a carbon of G3 or/and the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3 or/and the G3 ring.
8. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) according to claim 7,
Wherein,
nF ranges from zero to 500,000; nCE is also an integer from 1 to 500,000; nH is another integer ranging from zero to 500,000;
Y2 is a bivalent (Ci-C6)hydrocarbon residue;
R9, R10, R11 , R12, and R16 are independently selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-C6)hydrocarbon residue;
R13, R14, and R15 are independently chosen from H, F, (Ci-Ce)alkyl or (Cs- C6)cycloalkyl;
W2 is a bivalent (Ci-C6)hydrocarbon residue or a direct bond;
G2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
L3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Csjhydrocarbon residue;
J is chosen from SO3H, PO3H2, or CO2H;
Y3 is a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21 , R25, and R26 are independently selected from the group consisting of H, (CrC6)alkyl and (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-C6)hydrocarbon residue;
R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (Cs-Cejcycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has Cs-Ce on its ring; and
L5 and L6 are independently chosen from a direct bond or a (Ci-Csjhydrocarbon residue.
9. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) according to claim 8,
Wherein,
nF ranges from 1 to 100,000; nCE is also an integer from 1 to 100,000; nH is another integer ranging from zero to 100,000;
Y2 is CH2;
R9, R10, R11 , R12, and R16 are independently selected from the group consisting of H and F; R13, R14, and R15 are independently selected from the group consisting of H, F, (Cr Ce)alkyl and (C5-C6)cycloalkyl;
W2 is a bivalent (Ci-C6)hydrocarbon residue or a direct bond;
G2 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
L3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Cs)hydrocarbon residue;
J is chosen from SO3H, PO3H2, or CO2H;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has Cs-Ce on its ring; and
L5 and L6 are independently chosen from a direct bond or a (Ci-Cslhydrocarbon residue.
10. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) according to claim 9,
Wherein,
nF ranges from 1 to 90,000; nCE is also an integer from 1 to 90,000; nH is another integer ranging from zero to 90,000;
Y2 is CH2;
R9, R10, R11 , R12 and R16 are H;
R13, R14, and R15 are H;
W2 is a bivalent (Ci-C3)hydrocarbon residue or a direct bond;
G2 is a cycloalkane ring that has C5 on its ring;
L3 is CH2CH2CH2; L4 is CH2CH2CH2CH2;
J is chosen from S03H or C02H;
Y3 is CH2;
R18, R19, R20, R21, R25 and R26 are H;
R22, R23 and R24 are H;
G3 is a cycloalkane ring that has C5 on its ring;
L5 is CH2CH2CH2; and
L6 is CH2CH2CH2CH2.
11. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) according to claim 1 0,
Wherein,
nF ranges from 1 to 80,000; nCE is also an integer from 1 to 80,000; nH is another integer ranging from zero to 80,000;
Y2 is CH2;
R9, R10, R11 , R12, and R16 are H;
R13, R14, and R1 5 are H;
W2 is a direct bond;
G2 is a cycloalkane ring that has C5 on its ring;
L3 is CH2CH2CH2;
L4 is CH2CH2CH2CH2;
J is C02H;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, and R24 are H;
G3 is a cycloalkane ring that has Cs on its ring;
L5 is CH2CH2CH2; and
L6 is CH2CH2CH2CH2.
12. A cation-exchange hydrocarbon-fluorocarbon copolymer (CEHF) according to claim 1 0,
Wherein,
nF ranges from 1 to 80,000; nCE is also an integer from 1 to 80,000; nH is another integer ranging from zero to 80,000;
Y2 is CH2;
R9, R10, R11 , R12, and R16 are H;
R13, R14, and R1 5 are H;
W 2 is CH2CH2;
G2 is a cycloalkane ring that has C5 on its ring;
L3 is CH2CH2CH2;
L4 is CH2CH2CH2CH2; J is SO3H;
Y3 is CH2;
R18, R19, R20, R21 , R25, and R26 are H;
R22, R23, and R24 are H;
G3 is a cycloalkane ring that has Cs on its ring;
L5 is CH2CH2CH2; and
L6 is CH2CH2CH2CH2.
13. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- RING) comprising a plurality of repeated unit of RU(alkane-F) according to any of claims 1 -6, random or sequentially placed anion-exchange repeating unit of RU(AE- RING) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
— |~Ru(afkane-F
Figure imgf000050_0001
Wherein,
m, q and r are the numbers of the repeating unit of RU(alkane-F), RU(AE-RING) and RU(H), respectively; m is an integer ranging from zero to 1 ,000,000; q is also an integer from 1 to 1 ,000,000; r is another integer ranging from zero to 1 ,000,000; RU(AE-RING) is a repeated unit containing an anion-exchange group, having a formula selected from the group consisting of (X) and (XI):
Figure imgf000050_0002
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y4 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R27, R28, R29 and R30 are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and to a bivalent (Ci-Ci2)hydrocarbon residue; R31, R32, and R33 are independently selected from the group consisting of H, NO2, CN, F, Cl, Br, I, ORv, NRVRVI, SRV, (Ci-Ci2)alkyl and (C5-Ci2)cycloalkyl, wherein Rv and RVI are independently chosen from H and a (Ci-Ci2)hydrocarbon residue;
G4 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G4 is fused with the cycloalkyl ring containing Y4 with two adjacent carbons in common;
W4 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue and a direct bond;
AE is an anion-exchange group;
A floating bond refers to a covalent bond that attaches R31 , or R32, or R33 or W4 in (X) to a carbon on the cycloalkyl ring containing Y4 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R31 , or R32, or R33 or W4 can be attached to the cycloalkyl ring containing Y4; In (XI), a floating bond refers to a covalent bond that attached R31, or R32, or R33 or W4 to a carbon of G4 or/and the cycloalkyl ring containing Y4 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R32, or R32, or R33 or W4 can be attached to the cycloalkyl ring containing Y4 or/and the G4 ring;
RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from a group of (VII), (VIII) and (IX):
Figure imgf000051_0001
(VII) (Vlll) , and (IX)
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y3 is selected from a group of O and a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21, R25, and R26 are independently selected from a group of H, Cl, Br, I, F, (Ci-Ci2)alkyl, (C5-Ci2)cycloalkyl, and a point of attachment to an adjacent repeating unit of the polymer or to a bivalent (Ci-Ci2)hydrocarbon residue; R22, R23, and R24 are independently chosen from H, N02, CN, F, Cl, Br, I, ORm, N R'N R'V S RIM (C Ci2)alkyl and (C5-Ci2)cycloalkyl, wherein Rm and RIV are independently chosen from H or a (CrCi2)hydrocarbon residue;
G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G3 is fused with the cycloalkyl ring containing Y3 with two adjacent carbons in common;
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
Ci2)hydrocarbon residue;
A floating bond refers to a covalent bond that attaches R22, or R23, or R24 in (VII) to a carbon on the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3; In (VIII), a floating bond refers to a covalent bond that attached R22, or R23, or R24 to a carbon of G3 or/and the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3 or/and the G3 ring.
14. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- RING) according to claim 13,
Wherein,
m ranges from zero to 500,000; q is also an integer from 1 to 500,000; r is another integer ranging from zero to 500,000;
Y4 is a bivalent (Ci-C6)hydrocarbon residue;
R27, R28, R29 and R30 are independently selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ce)hydrocarbon residue;
R31, R32, and R33 are independently chosen from H, F, (Ci-Ce)alkyl or (Cs- C6)cycloalkyl;
G4 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
W4 is chosen from a bivalent (Ci-Ce)hydrocarbon residue or a direct bond;
AE is an anion-exchange group comprised of a combination of a cation selected from selected from the group consisting of benzimidazolium, imidazolium, ammonium, phosphonium, amino-phosphonium, and an anion chosen from OH , Cl , Br , G, F, C03 2 , HC03 , S03 2 , HSO3-, P04 3 , HPO2 , or H2P04 ;
Y3 is a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21, R25, and R26 are independently selected from the group consisting of H, (Ci-Ce)alkyl and (Cs-Celcycloalkyl;
R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; and
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
Cslhydrocarbon residue.
15. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- RING) according to claim 14,
Wherein,
m ranges from 1 to 100,000; q is also an integer from 1 to 100,000; r is another integer ranging from zero to 100,000;
Y4 is CH2;
R27, R28, R29 and R30 are independently chosen from H or F;
R31, R32, and R33 are independently chosen from H, F, (Ci-Ce)alkyl or (Cs- C6)cycloalkyl;
G4 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring;
W4 is chosen from a bivalent (Ci-C6)hydrocarbon residue or a direct bond;
AE is an anion-exchange group comprised of a combination of a cation chosen from phosphonium, amino-phosphonium, or an anion chosen from OH , Cl , Br , I , F , C03 2 , HCO3-, S03 2 , or HSO3-;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, and R24 are independently chosen from H, (Ci-Ce)alkyl or (C5-C6)cycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; and
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
Cslhydrocarbon residue.
16. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- RING) according to claim 15, Wherein,
m ranges from 1 to 90,000; q is also an integer from 1 to 90,000; r is another integer ranging from zero to 90,000;
Y4 is CH2;
R27, R28, R29 and R30 are H;
R31, R32, and R33 are H;
G4 is a cycloalkane ring that has C5 on its ring;
W4 is chosen from a bivalent (Ci-C3)hydrocarbon residue or a direct bond;
AE is an anion-exchange group comprised of a combination of a cation of amino- phosphonium and an anion of OH;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, and R24 are H;
G3 is a cycloalkane ring that has C5 on its ring;
L5 is CH2CH2CH2; and
L6 is CH2CH2CH2CH2.
17. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- CHAIN), comprising a plurality of repeated unit of RU(alkane-F) according to any of claims 1-6, random or sequentially placed anion-exchange repeating unit of RU(AE- CHAIN) and optionally random or sequentially placed hydrocarbon repeating unit of RU(H), having the following structure:
— |-Ru(aikane-F)|--~|RU(AE-CHAIN)† [RU{H} -r
Wherein,
m’, q’, and are the numbers of the repeating unit of RU(alkane-F), RU(AE-CHAIN) and RU(H), respectively; m’ is an integer ranging from 1 to 1 ,000,000; q’ is also an integer from 1 to 1 ,000,000; is another integer ranging from zero to 1 ,000,000; RU(AE-CHAIN) is a repeated unit containing an anion-exchange group, having a formula of (XII):
Figure imgf000055_0001
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
R34 is independently selected from the group consisting of H, Cl, Br, I, F, (Cr Ci2)alkyl, (Cs-C^jcycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ci2)hydrocarbon residue;
L7 and L8 are independently chosen from a direct bond or (Ci-Ci2)hydrocarbon residue;
W5 is chosen from a bivalent (Ci-Ci2)hydrocarbon residue or a direct bond;
AE is an anion-exchange group;
RU(H) is a repeated unit of hydrocarbon residues, having a formula selected from the group consisting of (VII), (VIII) and (IX):
Figure imgf000055_0002
(VII) (VIII) , and (IX)
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y3 is chosen from O or a bivalent (Ci-C6)hydrocarbon residue;
R18, R19, R20, R21 , R25, and R26 are independently selected from the group consisting of H, Cl, Br, I , F, (CrCi2)alkyl, (Cs-C^jcycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ci2)hydrocarbon residue; R22, R23, and R24 are independently selected from the group consisting of H, NO2, CN, F, Cl, Br, I, OR1", NRmRlv, SR1", (Ci-Ci2)alkyl and (C5-Ci2)cycloalkyl, wherein R1" and RIV are independently chosen from H or a (Ci-Ci2)hydrocarbon residue; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G3 is fused with the cycloalkyl ring containing Y3 with two adjacent carbons in common;
L5 and L6 are independently chosen from a direct bond or a (CrCi2)hydrocarbon residue;
A floating bond refers to a covalent bond that attaches R22, or R23, or R24 in (VII) to a carbon on the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3; In (VIII), a floating bond refers to a covalent bond that attached R22, or R23, or R24 to a carbon of G3 or/and the cycloalkyl ring containing Y3 provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R22, or R23, or R24 can be attached to the cycloalkyl ring containing Y3 or/and the G3 ring.
18. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- CHAIN) according to claim 17,
Wherein,
m’ ranges from 1 to 500,000; q’ is also an integer from 1 to 500,000; is another integer ranging from zero to 500,000;
R34 is selected from the group consisting of H, F, (Ci-Ce)alkyl, (C5-C6)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Cr Ce)hydrocarbon residue;
L7 and L8 are independently chosen from a direct bond or a bivalent (Cr
C8)hydrocarbon residue;
W5 is chosen from a bivalent (Ci-Ce)hydrocarbon residue or a direct bond;
AE is an anion-exchange group comprised of a combination of a cation selected from the group consisting of benzimidazolium, imidazolium, ammonium,
phosphonium, amino-phosphonium, and an anion chosen from OH , Cl , Br , I , F , C03 2 , HCO3-, S03 2 , HSO3-, P04 3 , HPO2 , or H2P04 ;
Y3 is a bivalent (Ci-Ce)hydrocarbon residue;
R18, R19, R20, R21, R25, and R26 are independently chosen from H, (Ci-C6)alkyl or (C5- C6)cycloalkyl;
R22, R23, and R24 are independently chosen from H, (Ci-C6)alkyl or (Cs-Cejcycloalkyl; G3 is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring; and L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
C8)hydrocarbon residue.
19. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- CHAIN) according to claim 18,
Wherein,
m’ ranges from 1 to 100,000; q’ is also an integer from 1 to 100,000; is another integer ranging from zero to 100,000;
R34 is chosen from H, F, (Ci-Ce)alkyl or (Cs-Celcycloalkyl;
L7 and L8 are independently chosen from a direct bond or a bivalent (Cr
C8)hydrocarbon residue;
W5 is chosen from a bivalent (Ci-C6)hydrocarbon residue or a direct bond;
AE is an anion-exchange group comprised of a combination of a cation selected from the group consisting of ammonium, phosphonium, amino-phosphonium, and an anion chosen from OH , Cl , Br , G, F , CO32 , HC03 , SO32 , or HS03 ;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, and R24 are independently chosen from H, (Ci-C8)alkyl and (C5- C6)cycloalkyl;
G3 is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring; and
L5 and L6 are independently chosen from a direct bond or a bivalent (Cr
C8)hydrocarbon residue.
20. An anion-exchange hydrocarbon-fluorocarbon co-polymer (AEHF- CHAIN) according to claim 19,
Wherein,
m’ ranges from 1 to 90,000; q’ is also an integer from 1 to 90,000; is another integer ranging from zero to 90,000;
R34 is H;
L7 is CH2CH2CH2;
L8 is CH2CH2CH2CH2;
W5 is chosen from a bivalent (Ci-C3)hydrocarbon residue or a direct bond; AE is an anion-exchange group comprised of a combination of a cation selected from the group consisting of ammonium, phosphonium, amino-phosphonium and an anion of OH ;
Y3 is CH2;
R18, R19, R20, R21, R25, and R26 are H;
R22, R23, R24 are H;
G3 is a cycloalkane ring that has C5 on its ring;
L5 is CH2CH2CH2; and
L6 is CH2CH2CH2CH2.
21. A free-radical initiator polymer comprising a plurality of repeated unit of RU(alkane-azo) containing a cycloalkane or an alkane with an azo side chain, which has a formula selected from the group consisting of (l-azo), (ll-azo) and (lll-azo):
Figure imgf000058_0001
P' Rl2a
R13a R
(I I i-azo)
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Y1 a is chosen from O, or a bivalent (Ci-C6)hydrocarbon residue; R1 a, R2a, R3a, R4a, and R8a are independently selected from the group consisting of H, Cl, Br, I, F, (CrCi2)alkyl, (C5-Ci2)cycloalkyl, a point of attachment to an adjacent repeating unit of the polymer, and a bivalent (Ci-Ci2)hydrocarbon residue;
R5a, R6a, and R7a are independently selected from the group consisting H, N02, CN, Cl, Br, I, F, ORv", NRVIIRVI", SRV", (Ci-Ci2)alkyl and (C5-Ci2)cycloalkyl; wherein Rv" and Rv are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
R9a, R1 1 a, and R12a are independently chosen from (Ci-Ci2)hydrocarbon residues; R10a and R13a are independently selected from the group consisting of CN, COORlx, CONRlxRx, and CNRIXNRXRXI, wherein RIX, Rx and RXI are independently chosen from H or a (Ci-Ci2)hydrocarbon residue;
W1 a is either a direct bond or a bivalent (Ci-Cio)hydrocarbon residue;
-N=N- can be either cis or trans;
L1 a and l_2a are independently chosen from a direct bond, or a bivalent (Cr
Ci2)hydrocarbon residue;
G1 a is a cycloalkane ring or a cycloalkene ring that has C5-C12 on its ring. The ring of G1 a is fused with the cycloalkyl ring containing Y1 a with two adjacent carbons in common;
A floating bond refers to a covalent bond that attaches R5a, or R6a, or R7a or W1 a in (I- azo) to a carbon on the cycloalkyl ring containing Y1 a provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5a, or R6a, or R7a or W1 a can be attached to the ring comprising Y1 a; In (ll-azo), a floating bond refers to a covalent bond that attached R5a, or R6a, or R7a or W1 a to a carbon of either G1 a or the cycloalkyl ring containing Y1 a provided that this carbon has a total of four covalent bonds including the floating bond. Multiple R5a, or R6a, or R7a or W1 a can be attached to the ring comprising Y1 a or/and G1 a.
22. A free-radical initiator polymer according to claim 21 , wherein Y1 a is a bivalent (Ci-C6)hydrocarbon residue; R1 a, R2a, R3a, R4a, and R8a are independently chosen from H, F, (Ci-Ce)alkyl, (Cs-Cejcycloalkyl, or a point of attachment to an adjacent repeating unit of the polymer or a bivalent (Ci-C6)hydrocarbon residue; R5a, R6a, and R7a are independently chosen from H, F, (Ci-Ce)alkyl or (Cs-Cejcycloalkyl; W1 a is either a direct bond or a bivalent (Ci-C6)hydrocarbon residue; R9a, R1 1a, and R12a are independently chosen from (Ci-C6)hydrocarbon residues; R10a and R13a are independently chosen from CN, COORlx, or CNRlxNRxRxl, wherein RIX, Rx and RXI are independently chosen from H or a (Ci-Ci2)hydrocarbon residue; L1 a and l_2a are independently chosen from a direct bond, or a bivalent (Ci-C8)hydrocarbon residue; and G1 a is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
23. A free-radical initiator polymer according to claim 22, wherein Y1 a is CH2; R1 a, R2a, R3a and R4a, and R8a are independently chosen from H, or F; R5a, R6a, and R7a are independently chosen from H, F, (CrC6)alkyl or (C5-C6)cycloalkyl; W1 a is either a direct bond or a bivalent (CrC5) hydrocarbon residue; R9a, R11 a, and R12a are independently chosen from (Ci-C6)hydrocarbon residues; R10a and R13a are CN; L1 a and L2a are independently chosen from a direct bond, or a bivalent (Cr
Cs)hydrocarbon residue; and G1 a is a cycloalkane ring or a cycloalkene ring that has C5-C6 on its ring.
24. A free-radical initiator polymer according to claim 23, wherein Y1 a is CH2; R1 a, R2a, R3a, R4a, and R8a are H; R5a, R6a, and R7a are H; W1 a is chosen from OCH2CH2CH2, OCH2CH2, OCH2, CH2OCH2CH2CH2, CH2OCH2CH2, CH2OCH2, CH2SCH2CH2CH2, CH2SCH2CH2, or CH2SCH2; L1 a is CH2CH2CH2; L2a is
CH2CH2CH2CH2; R9a, R1 1 a, and R12a are CH3; R10a and R13a are CN; and G1 a is a cycloalkane ring that has C5 on its ring.
25. A free-radical initiator polymer according to claim 24, wherein Y1 a is CH2; R1 a, R2a, R3a, R4a, and R8a are H; R5a, R6a, and R7a are H; W1 a is OCH2CH2CH2; R9a, R1 1 a, and R12a are CH3; R10a and R13a are CN; L1 a is CH2CH2CH2; L2a is
CH2CH2CH2CH2; and G1 a is a cycloalkane ring that has C5 on its ring.
26. A free-radical initiator polymer according to claim 24, wherein Y1 a is CH2; R1 a, R2a, R3a, R4, and R8a are H; R5a, R6a, and R7a are H; W1 a is
CH2OCH2CH2CH2; R9a, R1 1 a, and R12a are CH3; R10a and R13a are CN; L1 a is
CH2CH2CH2; L2a is CH2CH2CH2CH2; and G1 a is a cycloalkane ring that has C5 on its ring.
27. A cation-exchange fluorocarbon polymer (CEF) comprising a plurality of cation-exchange fluorocarbon repeating unit of RU(CE-F) and optionally random or sequentially placed fluorocarbon repeating unit of RU(F), having the following structure:
Figure imgf000061_0001
Wherein,
x and y are the numbers of the repeating unit of RU(CE-F) and RU(F), respectively; x is an integer from 1 to 1 ,000,000; y is another integer ranging from zero to
1 ,000,000;
RU(CE-F) is a repeated fluorocarbon unit containing a cation-exchange group, having a formula selected from the group consisting of (IV-F-I), (IV-F-II), (V-F-l), (V- F-ll), (V-F-l II), and (Vl-F):
Figure imgf000061_0002
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Yf 1 is chosen from O or a bivalent (Ci-C6)fluorocarbon residue;
Rf 4, Rf 5, R ®, Rf 7, and Rf 17 are independently chosen from F, (Ci-Ci2)fluoroalkyl, or (C5-Ci2)cyclofluoroalkyl; Rf8, Rf9, Rf1 0, Rf1 1 , Rf12, Rf1 3, Rf14, Rf1 5 and Rf 16 are independently chosen from NO2, CN, F, SO3H , (Ci-Ci2)fluoroalkyl or (Cs-C^jcyclofluoroalkyl;
Wf 1 and W2 are independently chosen from a bivalent (Ci-Ci2)fluorocarbon residue or a direct bond;
Lf1 and L 2 are independently chosen from a direct bond or a bivalent (Cr
Ci2)fluorocarbon residue;
Jf1 and J 2 are independently chosen from SO3H, PO3H2, or C02H;
RU(F) is a repeated unit of fluorocarbon residues, having a formula selected from the group consisting of (Vll-F), (Vlll-F) and (IX-F):
Figure imgf000062_0001
Wherein,
wavy lines indicate the points of attachment to adjacent repeating units of the polymer;
Yf 2 is chosen from O or a bivalent (Ci-C6)fluorocarbon residue;
Rf1 8, Rf1 9, R 20, R 21 , Rf32, and Rf 33 are independently chosen from F, (Cr
Ci2)fluoroalkyl, or (Cs-C^jcyclofluoroalkyl;
R 22, R 23, R 24, R 25, R 26, R 27, R 28, R 29, Rf 30, and Rf 31 are independently chosen from NO2, CN, F, SO3H, (Ci-Ci2)fluoroalkyl or (Cs-C^jcyclofluoroalkyl; and
Lf3 and L 4 are independently chosen from a direct bond or a bivalent (Cr
Ci2)fluorocarbon residue.
28. A cation-exchange fluorocarbon polymer (CEF) according to claim 27, Wherein,
x ranges from 1 to 500,000; y is also an integer from zero to 500,000; Yf1 is a bivalent (Ci-C6)fluorocarbon residue;
Rf4, Rf5, Rf6, Rf7, and Rf 17 are independently chosen from F, (Ci-C6)fluoroalkyl, or (C5- C6)cyclofluoroalkyl;
Rf8, Rf9, Rf10, Rf11, Rf12, Rf13, Rf14, Rf 15 and Rf 16 are independently chosen from F, (Cr Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl;
Wf1 and W2 are independently chosen from a bivalent (Ci-Cslfluorocarbon residue or a direct bond;
Lf1 and L2 are independently chosen from a direct bond or a bivalent (Cr
Cs)fluorocarbon residue;
Jf1 and J 2 is chosen from SO3H, PO3H2, orC02H;
Y2 is a bivalent (Ci-C6)fluorocarbon residue;
Rf18, Rf19, R20, R 21, Rf32 and Rf 33 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5-C6)cyclofluoroalkyl;
R22, R23, R24, R25, R26, R27, R28, R29, Rf 30, and Rf 31 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5-C6) cyclofluoroalkyl; and
Lf3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Cs)fluorocarbon residue.
29. A cation-exchange fluorocarbon polymer (CEF) according to claim 28, Wherein,
x ranges from 1 to 100,000; y is also an integer from zero to 100,000;
Yf1 is CF2;
Rf 4, Rf 5, Rf 6, Rf 7, and Rf 17 are F;
Rf8, Rf9, Rf10, Rf11, Rf12, Rf13, Rf14, Rf 15 and Rf 16 are independently chosen from F, (Cr Ce)fluoroalkyl or (C5-C6)cyclofluoroalkyl;
Wf1 and W2 are independently chosen from a bivalent (Ci-C6)fluorocarbon residue or a direct bond;
Lf1 and L2 are independently chosen from a direct bond or a bivalent (Cr
Cs)fluorocarbon residue;
Jf1 and J 2 are independently chosen from SO3H, PC>3H2, orC02H;
Yf2 is CF2;
Rf18, Rf19, Rf20, Rf 21, Rf 32 and Rf 33are F; and R22, R23, R24, R25, R26, R27, R28, R29, Rf 30, and Rf 31 are independently chosen from F, (Ci-C6)fluoroalkyl or (C5-C6)cyclofluoroalkyl;
Lf3 and L4 are independently chosen from a direct bond or a bivalent (Cr
Cs)fluorocarbon residue.
30. A cation-exchange fluorocarbon polymer (CEF) according to claim 29,
Wherein,
x ranges from 1 to 90,000; y is also an integer from zero to 90,000;
Yf 1 is CF2;
R4, Rf 5, R6, Rf 7, and Rf 17are F;
Rf 8, Rf 9, Rf10, Rf11' Rf12, Rf13, Rf14' Rf 15 and Rf 16 are chosen from F, or (C
C6)fluoroalkyl;
Wf 1 and Wf 2 are chosen from a bivalent (Ci-C4)fluorocarbon residue ora direct bond; Lf 1 is CF2CF2CF2;
Lf 2 is CF2CF2CF2CF2;
Jf 1 and J2 are independently chosen from SO3H, or CO2H;
Yf2 is CF2;
Rf 18, Rf 19, Rf 20, Rf 21, Rf 32, and Rf 33 are F;
Rf 22, Rf 23, Rf 24, Rf 25, Rf 26, Rf 27, Rf 28, Rf 29, Rf 30, and Rf 31 are F;
Lf 3 is CF2CF2CF2; and
Lf 4 is CF2CF2CF2CF2.
31. A cation-exchange fluorocarbon polymer (CEF) according to claim 30, Wherein,
x ranges from 1 to 80,000; y is also an integer from zero to 80,000;
Yf1 is CF2;
R4, Rf 5, Rf 6, Rf 7, and Rf 17are F;
Rf 8, Rf 9, Rf10, Rf11' Rf12, Rf13, Rf14' Rf 15 and Rf 16 are F;
Wf1 and W2 are direct bonds;
Lf1 is CF2CF2CF2;
Lf 2 is CF2CF2CF2CF2;
Jf1 and J 2 are CO2H;
Y2 is CF2; p 18 p 19 p 20 p 21
Kf , Kf , Kf , Kf , Rf 32 and Rf 33 are F;
p 22 p 23 p 24 p 25
Kf , Kf , Kf , Kf , Rf26 Rf 27, Rf 28, Rf 29, Rf30, and Rf 31 are F;
Lf 3 is CF2CF2CF2; and
Lf 4 is CF2CF2CF2CF2.
32. A cation-exchange fluorocarbon polymer (CEF) according to claim 30,
Wherein,
x ranges from 1 to 80,000; y is also an integer from zero to 80,000;
Yf1 is CF2;
R 4, Rf 5, Rf 6, Rf 7, and Rf 17 are F;
Rf 8, Rf 9, Rf1 0, Rf12, Rf1 3, Rf1 4' Rf1 5 and Rf 16 are F;
Rf1 1 is CF3;
Wf 1 is a direct bond;
Jf1 is SOsH ;
Wf 2 is CF2OCF2CF2;
J 2 is C02H;
Lf1 is CF2CF2CF2;
Lf 2 is CF2CF2CF2CF2;
Yf2 is CF2;
Rf1 8, Rf1 9, R 20, R 21 , Rf 32 and Rf 33 are F;
P 22 p 23 p 24 p 25 p 26 p 27 p 28 p 29 p 30
Kf , Kf , Kf , Kf , Kf , Kf , Kf , Kf , Kf , and Rf31 are F;
Lf3 is CF2CF2CF2; and
Lf 4 is CF2CF2CF2CF2.
33. A solid composite comprising optionally a solid support, and a polymer according to any of claims 1 -32.
34. A device selected from an electrolytic cell, an electric storage device, an electric generation device, a water purification device and a chlor-alkali cell comprising a polymer according to any of claims 1 -32, or a composite according to claim 33.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5180750A (en) * 1988-07-29 1993-01-19 Asahi Glass Company Ltd. Anion exchanger
US6011074A (en) * 1996-12-31 2000-01-04 The Dow Chemical Company Ion-exchange polymers having an expanded microstructure
US20170044290A1 (en) * 2014-04-29 2017-02-16 Midwest Energy Group Inc. Stable and ion-conductive fluoropolymer-based electrolytes
US9580592B2 (en) * 2011-01-21 2017-02-28 Solvay Specialty Polymers Italy S.P.A. Liquid compositions of fluorinated anion exchange polymers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5180750A (en) * 1988-07-29 1993-01-19 Asahi Glass Company Ltd. Anion exchanger
US6011074A (en) * 1996-12-31 2000-01-04 The Dow Chemical Company Ion-exchange polymers having an expanded microstructure
US9580592B2 (en) * 2011-01-21 2017-02-28 Solvay Specialty Polymers Italy S.P.A. Liquid compositions of fluorinated anion exchange polymers
US20170044290A1 (en) * 2014-04-29 2017-02-16 Midwest Energy Group Inc. Stable and ion-conductive fluoropolymer-based electrolytes

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