Polymers containing sulfonamide sodium or lithium salts, methods for production thereof and uses of same as electrolytes for batteries

Patent metadata

Field	Value
Publication number	US-10109883-B2
Application number	US-201515327606-A
Country	US
Kind code	B2
Filing date	Jul 20, 2015
Priority date	Jul 23, 2014
Publication date	Oct 23, 2018
Grant date	Oct 23, 2018

Abstract

The invention relates to novel polymers containing grafted sodium or lithium sulphonamides, production methods thereof and uses of same as electrolytes in batteries.

First claim

The invention claimed is:

1. A polymer selected from the group consisting of polymers of formulas I, II, III, IV, V, VI, VII, VIII, IX, X, XI, XII, XIII, XIV and XV

wherein:
M represents a lithium or sodium atom
R represents
an alkyl group having 1 to 30 linear or branched carbon atoms optionally substituted by a cycloalkyl, aryl motif; a cycloalkyl group, optionally substituted by aromatic groups;
an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl chains, nitrile functions, alkylsulfonyl functions, fluorine atoms;

m represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif functionalized by a sulfonamide motif(s), this percentage varying between 50 and 100%,
n represents the percentage of polymer units having an oxoaryl or a dioxoaryl motif non-functionalized by one or more sulfonamide motif(s), this percentage varying between 0 and 50%,
p represents the number of polymer units of the polymer, p varying from 40 to 300.

2. The polymer according to claim 1 , wherein:
M represents a lithium or sodium atom,
R represents:
an alkyl with 1 to 10 carbon atoms;
a 2,2-difluoroethyl, 2,2-difluro-2-(trifluoromethyl)ethyl group;
an aryl group of the phenyl, tolyl, naphthyl, trifluoromethylphenyl, bis (trifluoromethyl) phenyl, cyanophenyl, alkylsulfonylphenyl, aryl sulfonylphenyl, methoxyphenyl, butoxyphenyl, pentafluorophenyl, alkylsulfonylphenyl or fluorophenyl type;

m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a sulfonamide motif, this percentage varying between 90 and 100%;
n represents the percentage of polymer units having no oxoaryl or dioxoaryl motif non-functionalized by a sulfonamide motif, this percentage varying between 0 and 10%;
p represents the number of polymer units of the polymer, p varying from 40 to 300.

3. The polymer according to claim 2 , wherein R is selected from the group consisting of methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, and ethylhexyl groups.

4. The polymer according to claim 1 , wherein:
M represents a lithium or sodium atom,
R is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl) methyl, ((1R)-7, 7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl) methyl, (1S)-(7,7-dimethyl-2-oxobicyclo[2.2 1]heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, 4-cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl, 2-(trifluoromethyl)phenyl, 4-methylphenyl, 1-naphthyl, 2-naphthyl, 3,5-difluorobenzyl, 4-fluorobenzyl, 3-trifluoromethylbenzyl, 4-trifluoromethylbenzyl, 2,5-dimethylbenzyl, 2-phenylethyl, 4-methoxyphenyl, 4-n-butylphenyl, 4-t-butylphenyl, 4-butoxyphenyl, 2-fluoro-5-(trifluoromethyl)phenyl, 4-ethylphenyl, phenoxyethyl, methoxyethyl, ethoxyethyl, 4-methoxyphenoxyethyl group;
m represents the percentage of polymer units having a dioxoaryl motif functionalized by a sulfonamide, this percentage varying between 90 and 100%;
n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a sulfonamide, this percentage varying between 0 and 10%;
p represents the number of polymer units of the polymer, p varying from 60 to 200.

5. A method for synthesis of a polymer according to claim 1 , comprising:
in a first step, performing chlorosulfonation of a polymer selected from the group consisting of polymers of formulas XVI, XVII, XVIII, XIX, XX, XXI, XXII, and XXIII by a mixture of chlorosulfonic acid, thionyl chloride and a formamide

wherein:
p represents the number of polymer units of the polymer, p varying from 40 to 300, in order to obtain a polymer selected from the group consisting of the polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII

wherein:
m represents the percentage of polymer units having an oxoaryl or dioxoaryl motif functionalized by a chlorosulfonated group, this percentage varying between 50 and 100%,
n represents the percentage of polymer units having a dioxoaryl motif non-functionalized by a chlorosulfonated group, this percentage varying between 0 and 50%,
p represents the number of polymer units of the polymer, p varying from 40 to 300, in a second step, producing a reaction on the polymer selected from the group consisting of polymers of formulas XXIV, XXV, XXVI, XVII, XXVIII, XIX, XXX, XXXI, XXXII, XXXIII, XXXIV, XXXV, XXXVI, XXXVII and XXXVIII with an amine of formula XXXIX in a solvent medium
R—NH 2   (XXXIX)

wherein
R represents a group or different groups chosen from:
an alkyl or cycloalkyl group having 1 to 30 linear or branched carbon atoms, optionally substituted by a cycloalkyl, aryl, perfluoroalkyl, polyfluoroalkyl, mono or polyethoxyl motif;
an aryl or polyaryl group optionally substituted by alkyl, cycloalkyl, polyfluoro- or perfluoroalkyl, motifs, by nitrile functions, by alkyl- or alkylsulfonyl functions, by fluorine atoms;

for obtaining a polymer selected from the group consisting of polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV

wherein
m represents the percentage of polymer units having a functionalized oxoaryl or dioxoaryl motif having a sulfonamide function, this percentage varying between 50 and 100%,
n represents the percentage of polymer units having an oxoaryl or dioxoaryl motif non-functionalized by a sulfonamide function, this percentage varying between 0 and 50%,
p represents the number of polymer units of the polymer, p varying from 40 to 300, in a third step, producing a reaction on the polymer selected from the group consisting of polymers of formula XL, XLI, XLII, XLIII, XLIV, XLV, XLVI, XLVII, XLVIII, XLIX, L, LI, LII, LIII and LIV with a lithium or sodium base at a temperature of between 0 and 80° C. in a solvent medium.

6. The method according to claim 5 , wherein the R group of the XXXIX amine is a methyl, ethyl, propyl, cyclopropyl, butyl, 1-decyl, 1-dodecyl, 1-hexanedecyl, 1-octyldecyl, (7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl) methyl, ((1R)-7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl) methyl, (1S)-(7,7-dimethyl-2-oxobicyclo[2.2.1]heptan-1-yl) methyl, cyclohexylmethyl, phenyl, tolyl, naphthyl, 4-trifluoromethylphenyl, 3,5-bis(trifluoromethyl)phenyl, 4-cyanophenyl, nonafluorobutyl, pentafluorophenyl, 2,3,5,6-tetrafluorophenyl, 4-fluorophenyl, 2,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4,5,6-pentafluorophenyl, 4-cyanophenyl, 4-(trifluoromethyl)phenyl, 3-(trifluoromethyl)phenyl, 2-(trifluor

Assignees

• Cdp Innovation
• Centre Nat Rech Scient
• Univ Aix Marseille
• Cpd Innovation

Inventors

• Desmurs Jean-Roger
• DUNACH CLINET Elisabet
• Knauth Philippe
• MORIZUR Vincent
• Olivero Sandra

Classifications

• B01J39/19

  obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds · CPC title

• C08L71/00

  Compositions of polyethers obtained by reactions forming an ether link in the main chain (of polyacetals C08L59/00; of epoxy resins C08L63/00; of polythioether-ethers C08L81/02; of polyether-sulfones C08L81/06); Compositions of derivatives of such polymers · CPC title

• C08G65/4056

  (I) or (II) containing sulfur (as the sulfone group C08G75/23) · CPC title

• C08G75/23

  Polyethersulfones · CPC title

• H01M2300/0082

  Organic polymers · CPC title