# US 2013/0253221 A1 · Fluorinated oligomers having pendant bromine-containing moieties > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0253221 A1 - Document ID: US20130253221A1 - Status: Published application - Kind: A1 - Application number: 13/988,380 - Filed: 2011-12-06 - Published: 2013-09-26 - Earliest claimed: 2010-12-17 - Assignees: 3M Innovative Properties Company - Inventors: Zai-Ming Qiu - Web page: https://patentgrep.com/patent/US20130253221A1 ## CPC - C07C 313/04: Sulfinic acids; Esters thereof - C08F 8/04: Reduction, e.g. hydrogenation - C08F 8/20: Halogenation - C08F 214/18: Monomers containing fluorine - C08F 214/182: {Monomers containing fluorine not covered by the groups C08F214/20 - C08F214/28} - C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS - C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS ## Abstract Described herein is an oligomer having a pendant bromine-containing moiety according to formula II and/or formula III; and combinations thereof; wherein X1, X2, and X3 are each independently selected from F, Cl, H, and CF3; R is a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise a heteroatom; each Z1 and Z2 is independently selected from F and CF3; n is 0 or 1; q is 0 or 1; and m is at least 2. ## Claims ### Claim 1 A composition comprising an oligomer comprising a repeating unit selected from the group consisting of: (iii) and combinations thereof; wherein X1, X2, and X3 are each independently selected from F, Cl, H, and CF3; R is a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise a catenary heteroatom; each Z1 and Z2 is independently selected from F and CF3; n is 0 or 1; q is 0 or 1; and m is at least 2. ### Claim 2 (depends on 1) The composition of claim 1 further comprising a repeating unit of Formula (IV): wherein each X1, X2, and X3 are each independently selected from F, Cl, H, and CF3; R is a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise catenary heteroatoms; each Z1 and Z2 is independently selected from F and CF3; q is 0 or 1; n is 0 or 1; q+n is at least 1; p is at least 1; and G is F or a functionalized group, wherein the functionalized group is selected from the group consisting of —SO2M, —SO3M, —SO2NR1R2, —CO2M, —CO2R1, —CH2OR1, —SO2F, —SO2Cl, H, or I, wherein M is a cation and R1 and R2 are independently selected from a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise catenary heteroatoms. ### Claim 3 (depends on 1) The composition according to claim 1, further comprising a repeating unit: wherein Q is derived from a monomer and p is at least 1. ### Claim 4 (depends on 3) The composition according to claim 3, wherein the monomer is selected from: ethylene, tetrafluoroethylene, propylene, hexafluoropropylene, vinyl chloride, vinyl fluoride, a fluoroalkyl substituted ethylene, vinylidene fluoride, allyl iodide, fluorinated alkyl vinyl ethers, fluorinated alkoxy vinyl ethers, bromotrifluoroethylene, chlorotrifluoroethylene, CF3CH═CH2, C4F9CH═CH2, CF3OCF═CF2, C3F7OCF═CF2, CF2═CFOCF2CF(CF3)OCF2CF2CF3, CF2═CFOCF2CF2CF2CN, CF2═CFOCF2CF2CF2CO2CH3, CF2═CFOCF2CF(CF3)OCF2CF2CO2CH3, CF2═CFOCF2CF2CF2CH2OH, and CF2═CFOCF2CF2CF2OCF3. ### Claim 5 (depends on 1) The composition according to claim 1, wherein the X1, X2, and X3 are all F, n is 1, and R is a perfluorinated alkylene. ### Claim 6 (depends on 1) The composition according to claim 1, wherein R is selected from: —(CH2)a—, —(CF2)a—, —(CF2)a—O—(CF2)b—, —(CF2CF(CF3)O)a— and —(CF2)a—[O—(CF2)b]c—, —[(CF2)a—O]b—[(CF2)c—O]d—, —[(CF2)a—O—]b—[(CF2CF(CF3)O)c—]d—, and combinations thereof, wherein a, b, c, and d are each independently at least 1. ### Claim 7 A method for making a fluorinated polysulfonyl bromide oligomer comprising: (i) providing a polysulfinate oligomer comprising a repeating unit according to Formula I: wherein X1, X2, and X3 are each independently selected from F, Cl, H, and CF3; R is a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise a catenary heteroatom; each Z1 and Z2 is independently selected from F and CF3; n is 0 or 1; q is 0 or 1; and m is at least 2; and M is a cation; and (ii) brominating the polysulfinate oligomer according to Formula I. ### Claim 8 A method for making a fluorinated polybromide oligomer comprising: (i) providing a polysulfinate oligomer comprising a repeating unit according to Formula I: wherein X1, X2, and X3 are each independently selected from F, Cl, H, and CF3; R is a linear or branched linking group, which may be saturated or unsaturated, substituted or unsubstituted, and may comprise a catenary heteroatom; each Z1 and Z2 is independently selected from F and CF3; n is 0 or 1; q is 0 or 1; and m is at least 2 and M is a cation; (ii) brominating the sulfinate oligomer according to Formula I; and (iii) introducing an energy source. ### Claim 9 (depends on 8) The method according to claim 8, wherein the energy source is added during the step of brominating the polysulfinate oligomer. ### Claim 10 (depends on 7) The method according to claim 7, wherein the brominating step is conducted in the presence of water. ### Claim 11 (depends on 8) The method according to claim 8, wherein the brominating step is conducted in the presence of water. ### Claim 12 (depends on 8) The method according to claim 8, wherein the energy source is added after brominating the sulfinate oligomer. ### Claim 13 (depends on 8) The method according to claim 8, wherein the energy source is selected from the group consisting of: heat, electromagnetic-radiation, and combinations thereof. ### Claim 14 (depends on 8) The method according to claim 8, wherein a brominating agent used in the brominating step is selected from the group consisting essentially of: diatomic bromine, hypobromite, and combinations thereof. ### Claim 15 (depends on 7) The method according to any claim 7, wherein the X1, X2, and X3 are all F, and R is a perfluorinated alkylene. ### Claim 16 (depends on 8) The method according to any claim 8, wherein the X1, X2, and X3 are all F, and R is a perfluorinated alkylene. ### Claim 17 (depends on 7) The method according to claim 7, wherein R is selected from: —(CH2)a—, —(CF2)a—, —(CF2)a—O—(CF2)b—, —(CF2CF(CF3)O)a— and —(CF2)a[O—(CF2)b]c—, —[(CF2)a—O—]b—[(CF2)c—O—]d, —[(CF2)a—O—]b—[(CF2CF(CF3)O)c—]d—, and combinations thereof, wherein a, b, c, and d are independently at least 1. ### Claim 18 (depends on 8) The method according to claim 8, wherein R is selected from: —(CH2)a—, —(CF2)a—, —(CF2)a—O—(CF2)b—, —(CF2CF(CF3)O)a— and —(CF2)a—[O—(CF2)b]c—, —[(CF2)a—O—]b—[(CF2)c—O—]d, —[(CF2)a—O—]b—[(CF2CF(CF3)O)c—]d—, and combinations thereof, wherein a, b, c, and d are independently at least 1. ### Claim 19 (depends on 3) The composition according to claim 3, wherein the monomer is selected from a non-fluorinated olefin, a partially fluorinated olefin, a perfluorinated olefin, and combinations thereof. ### Claim 20 (depends on 3) The composition according to claim 3, wherein the monomer is selected from the following Formula: CY2═CY(R3), wherein each Y is independently selected from H, Cl or F; and R3 is selected from I, Br, O—Rf-U and Rf-U wherein U=I, F, H, Br, CH2OH, CO2R1, CN, C(O)NR1R2, P(O)(OR1)2, OR1, OCF3 or OC3F7, and Rf is a perfluorinated or partially fluorinated alkylene group optionally containing O atoms.