QUATERNISED POLYBENZIMIDAZOLE Russian patent published in 2016 - IPC C08G73/18 B01D53/22 B01D71/00 B01D71/58 C08J5/22 

FIELD: chemistry.

SUBSTANCE: invention discloses polymer forms of ionic liquids PFIL based on polybenzimidazole (PBI) and method for synthesis of such polymer forms of ionic liquids. The invention also relates to application of polymer forms of PBI-based ionic liquids and thereof-made membranes for sorption, filtration and separation of gases. Described are polymer forms of ionic liquids based on polybenzimidazole (PBI), having formulae III an IV, wherein A, B are repeating units and wherein molar part of A constitutes 0-99%, and molar part of B constitutes 1-100%; R₁ and R₂ are similar or different and each is selected from the group, consisting of C₁-C₂₀ alkyl, trialkylsilyl, cycloalkyl, aryl, arylene, alkylene or heterocyclic ring, such as the group of pyridine, pyrazine, furan, quinoline or thiophene, in form of linear, branched, cyclic or aromatic chain, and their derivatives, substituted by functional groups, such, for instance, as halogen, nitro, the group of ether, aldehyde, ketone, hydroxyl, carboxyl, the group of sulphonic acid or ester; X"' is selected from (C_nH_2n+1)COO, halogenacetate, (C_nF_2n+1)COO, ArCOO, wherein Ar can be substituted or non-substituted aromatic group, (C_nH_2n+1)SO₃, (C_nF_2n+1)SO₃, ArSO₃, wherein Ar can be substituted or non-substituted aromatic group, NO₃, NO₂, PO₃, BF₄, HPO₄-N(SO₂CF₃)₂, H₂PO₄, HSO₄, S₂O₃, ClO, BrO₃, CrO₄, HCO₃, C₂O₄, MnO₄, NH₂, FeCl₄ ^-,PF₆ ^-, (CN)₂N^-, C₁₆H₃₄PO₄ ^-, C₁₂H₂₅C₆H₄O₃ ^-, SCN^-, CH₂=CHCOOCH₂CH₂CH₂SO₃ ^-, CH₂=CHSO₃ ^-, C₆H₄CO₃SN^-, o-tosylate, pyrazolium anion, imidazolium anion, triazole anion, tetrazole anion, oxazole anion, indolium anion, benzotriazole anion, phanoxide anion, N(SO₂(C_nF_2n+1))₂ bis((perfluoroethyl)sulphonyl)imide (BETI^-), diethyleneglycolmonomethyl ether of sulphate (MDEGSO₄ ^-), alkylsulphate (C_nH_2n+1)SO₄ ^-, fluoroalkylsulphate (C_nF_2n+1)SO₄ ^- of tetracyanoborate (B(CN)₄ ^-), tetrafluorosucinate, hexafluoroglutarate, oxalate, malonate, glycolate, L-tartrate, maleate, mucobromate, nitrilotriacetate, 5-aminotetrazolate, DL-tartrate, lactate, gluconate, DL-malate or their mixtures, R represents tetraamine monomer, and R′ from formula III and IV is dicarboxylic acid of structure VI, wherein k = 1-30, containing alkyl, aryl, aromatic, arylene, alkylene, arylene-ether or heterocyclic ring groups, such as pyridine, pyrazine, furan, quinoline or thiophene, in form of linear, branched, cyclic or aromatic chain or their combination; X stands for H, O, N, S, halogen or their combination, n=0-10, and m=respective number of hydrogen atoms:

, ,

HOOC-(C_kH_mX_n)-COOH (VI). Also described is method for obtaining described above polymer forms of ionic liquids based on polybenzimidazole (PBI), which includes: a) interaction of PBI of formula

or ,

wherein R, R' and n correspond to definitions, given in the preceding items, with metal hydride to obtain respective metal salt and PBI; b) processing metal salt and PBI, obtained at stage (a), with reagent R₁X' or R₂X", wherein R₁ and R₂ are similar or different and each is selected from the group, consisting of C₁-C₂₀ alkyl, trialkylsilyl, cycloalkyl, aryl, arylene, alkylene or heterocyclic ring, such as the group of pyridine, pyrazine, furan, quinoline or thiophene, in form of linear, branched, cyclic or aromatic chain, and their derivatives, substituted by functional groups, such, for instance, as halogen, nitro, the group of ether, aldehyde, ketone, hydroxyl, carboxyl, the group of sulphonic acid or ester; X' and X" are selected from the group, consisting of I, Cl, Br, F, NO₂, to obtain N-quaternised form of PBI of formula III and IV, and c) anionic exchange of N-quaternised form of PBI from stage (b) by processing with metal salt to obtain polymer forms of ionic liquids of formula III and IV.

EFFECT: production of polymer forms of PBI-based ionic liquids with high stability and high sorption capacity by gases, such as CO₂, capable, in addition, of forming films, sheets, granules, flakes, powders, etc.

7 cl, 8 ex, 11 tbl, 5 dwg