Patent EA-001312-B1 (EA)
Title: Poly(9.9<'>-spiro-bisfuoroenes), the productionand use of same
Inventor: RIETZ RALF-ROMAN
IPC: C08G61/00
Filed: 1996-11-19
Abstract: 1. A soluble poly(bis-9,9'-fluorene) comprising identical or different structural repeating units of the formula I,    where the two R1 are, independently of one another, H, C1-C18-alkyl, C6-C14-aryl, C7-C15-aralkyl, C1-C18-alkoxy, R2-(O-CnH2n)m-O-, C1-C18-alkylthio, C1-C18-dialkylamino, -C(O)OH, -C  (O)O- C1-C18-8alkyl, -C(O)-N(C1-C18-alkyl)2, -SO3, -SO3 C1-C18-alkyl, -SO2-N(C1-C18-alkyl)2, C1-C17-alkyl-C(O)-O- or C1-C17-alkyl-C(O)-, R2 is H or C1-C12-alkyl, n is from 2 to 6 and m is from 1 to 12. 2. A polymer according to claim 1, wherein the alkyl groups in alkyl, alkoxy, alkylthio, diaminoalkyl, carboxylic ester or sulfonic ester, carboxamide or sulfonamide, alkyl-CO2- and alkyl-C(O)- radicals R1 are linear or branched and contain from 1 to 12 C atoms. 3. A polymer according to claim 1, wherein aryl radicals R1 preferably contain f rom 6 to 10 C atoms. 4. A polymer according to claim 1, wherein aralkyl radicals R1 contain from 7 to 12 C atoms and the alkylene group in the aralkyl radical contains 1 or 2 C atoms. 5. A polymer according to claim 1, wherein the two R1 in the polymer of the formula I are identical radicals. 6. A polymer according to claim 1, wherein each R1 in the polymer of the formula I is H, C1-C12-alkyl-C(O)- or C1-C12-alkoxy. 7. A polymer according to claim 1, which is soluble and at least partially cross linked and comprises structural units of the formula Ia, Ib or both structural units,   where R1 is as defined above. 8. A polymer according to claim 1, wherein the degree of polymerization is from 2 to 100. 9. A polymer according to claim 1, wherein the degree of polymerization is from 3 to 50. 10. A polymer according to claim 1, wherein the degree of polymerization is from  3 to 40. 11. A polymer according to claim 1, wherein the degree of polymerization is from 5 to 30. 12. A process for preparing poly(bis-9,9'-fluorenes) comprising identical or different structural repeating units of the formula I,   and, if desired, identical or different structural units of the formulae      where R1 is as defined in claim 1, wherein which comprises cationically-oxidatively polymerizing  a) at least one halogen-free 9,9'-bisfluorene of the formula II,   where R1 is as defined in claim 1, which comprises cationically-oxidatively polymerizing in the presence of an inert solvent. 13. A process for preparing poly(bis-9,9'-fluorenes) comprising identical or different structural repeating units of the formula I,   where R1 is as defined in claim 1, wherein which comprises reacting a 2,2'-dihalo-9,9'-spirobisfluorene of the formula III,   where R1 is as defined in claim 1 and X is halogen, in the presence of an inert solvent, an alkali metal or alkaline earth metal and transition metal complex or metal salt of a transition metal. 14. A process according to claim 13, wherein X is Cl or Br. 15. A compound of the formula IV,   where X is halogen and R3 is C1-C18-alkyl, C6-C14-aryl, C7-C15-aralkyl, C1-C18-alkoxy, R2-(O-CnH2n)m-O-, C1-C16-alkylthio, C1-C18-dialkylamino, -C(O)OH, -C(O)O- C1-C18-alkyl, -C(O)-N(C1-C18-alkyl)2, -SO3H, SO3- C1-C18-alkyl, -SO2-N(C1-C18-alkyl)2, C1-C17-alkyl-C(O)-O- or C1-C17-alkyl-C(O)-, R2 is H or C1-C12-alkyl, n is from 2 to 6 and m is from 1 to 12. 16. A compound according to claim 15, wherein X is Cl or Br. 17. A process for preparing compounds of the formula IV according to claim 15, w hich comprises reacting a compound of the formula V,   where R3 is as defined in claim 15, in an inert solvent with elemental halogen in the presence of an excess of a Lewis acid. 18. A process according to claim 17, wherein the reaction temperature is from room temperature to 200 degree C. 19. A process according to claim 17, wherein the halogen is used in equimolar amounts. 20. A process according to claim 17, wherein the Lewis acid is BF3, BCl3, AlBr3, AlCl3, ZnCl2, ZnBR2, FeCl2, FeCl3, FeBR2, FeBR3, TiCl4, TiBR4, SnCl2, SnBR2, SnCl4 or SnBR4. 21. A process according to claim 17, wherein the Lewis acid is used in an amount of at least 1 mol per 1 mol of the compound of the formula V. 22. A process according to claim 21, wherein the Lewis acid is used in an amount of at least 4 mol. 23. A composition comprising (a) a solvent and (b) a poly(bis-9,9'-fluorene) having identical or different structural repeating units of the formula I according to claim 1. 24. A composition according to claim 23, wherein the amount of dissolved poly(bi s-9,9'-fluorene) is from 0.01 to 80% by weight, based on the total amount of the composition. 25. A composition according to claim 23 which further comprises at least one fluorescent dye (fluorophore) whose absorption band overlaps the emission band (fluorescent emission) of the polymer of the formula I. 26. A composition according to claim 25, wherein the amount of additional fluorescent dye is from 0.000001 to 10% by weight, based on the amount of polymer. 27. A composition according to claim 25, wherein the fluorescent dye is a rhodamine, fluorescein, cumarin, distyrylbiphenyl, stilbene, phthalocyanine, naphthalocyanine, or a metal complex of a transition metal or lanthanide metal. 28. A support material which is coated on at least one side with a polymer according to claim 1 29. A support material according to claim 28, wherein the polymer further comprises at least one fluorescent dye (fluorophore) which is homogeneously dispersed and has an ab sorption band which overlaps the emission band (fluorescent emission) of the polymer of t he formula 1. 30. A support material according to claim 28 which is an inorganic or organic support material. 31. A support material according to claim 28 which is opaque, translucent or transparent. 32. A support material according to claim 28 which is selected from the group consisting of plastics, glass, ceramics, minerals, rocks, metal oxides and metal mixed oxides, metal nitrides, metal carbides, semiconductors, transparent electric conductors, metal s and metal alloys. 33. An electroluminescent composition according to claim 32 which comprises an electric conductor as support material which is coated on at least one side with a polymer according to the invention either alone or in admixture with at least one additional fluorophore whose absorption band overlaps the emission band (fluorescent emission) of the polymer of the formula I. 34. A support material according to claim 28 or 33, wherein the thickness of the polymer layer is from 0.1 to 1000 μm. 35. The use of a polymer according to the invention, which may, if desired, be additionally doped with at least one further fluorophore, as active radiative layer for light-emitting diodes, VDUs and display elements.