Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
  • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
  • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
  • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring

Definitions

• the present invention relates to a process for the preparation of oligo / polythiophenes.
• OFETs Simple structuring and integration of OFETs into integrated organic semiconductor circuits makes possible low-cost solutions for smart cards or price tags, which hitherto can not be realized with the aid of silicon technology due to the price and lack of flexibility of the silicon components. Also, OFETs could be used as switching elements in large area flexible matrix displays.
• All compounds have continuous conjugated units and are subdivided into conjugated polymers and conjugated oligomers depending on their molecular weight and structure.
• a distinction is usually oligomers of polymers in that oligomers usually have a narrow molecular weight distribution and a molecular weight to about 10,000 g / mol (Da), whereas polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
• Da g / mol
• polymers usually have a correspondingly higher molecular weight and a broader molecular weight distribution.
• it makes more sense to differentiate on the basis of the number of repeating units since a monomer unit can certainly reach a molecular weight of 300 to 500 g / mol, as for example in (3,3 "-dihexyl) -quarterthiophene.
• the most important semiconducting poly- or oligomers include the poly / oligothiophenes whose monomer unit is e.g. 3-hexylthiophene.
• a distinction must in principle be made between two processes - the simple coupling reaction and the multiple coupling reaction in the sense of a polymerization mechanism.
• the polymerization in a catalytic cycle is started by the Kumada method (cross-coupling metathesis reaction) using a nickel catalyst (preferably Ni (dppp) Cl 2 ).
• the polymers are generally obtained via Soxhlet purifications of the necessary purity.
• the processes described in EP 1 026 138 and in the further literature are purely laboratory-technical.
• the reaction solution has a concentration of monomers of about 4-6% by weight and thus a maximum product concentration, e.g. for the poly-3-hexylthiophene of 2-3 wt .-%.
• An increase in the production amount takes place only by the enlargement of the approach such. in Example 2 in EP 1 028 136.
• the object of the present invention was therefore to provide a process which at least partially overcomes the disadvantages mentioned and enables the large-scale production of polythiophenes or oligothiophenes with defined average chain lengths and a narrow molecular weight distribution.
• the polymer concentration (at 100% conversion) defined by the concentration of the two solutions means, in the context of the invention, in particular the concentration of polymer which is present or would be present at (in the concrete applications mostly hypothetical) 100% conversion, when the first solution is added completely to the second solution.
• the polymer concentration defined by the concentration of the two solutions (at 100% conversion) is preferably> 6%, preferably> 9%, particularly preferably> 10%.
• thiophene derivative is understood to mean both mono-, di- or polysubstituted and unsubstituted thiophene.Preferred are thiophene derivatives which are alkyl-substituted, particularly preferably 3-alkyl-substituted thiophene derivatives.
• the term "leaving group” is understood in particular to mean any group which is capable of reacting by means of a metal or an organometallic compound to form a thiophene-organometallic compound.
• the at least one thiophene derivative contains at least two different leaving groups. This may be useful for achieving better regioselectivity of the polymer in many applications of the present invention.
• the leaving groups of the at least one thiophene derivative are identical.
• thiophene-organometallic compound is understood in particular to mean a compound in which at least one metal-carbon bond to one of the carbon atoms on the thiophene heterocycle is present.
• organometallic compound is understood in particular to mean an alkylmetalorganic compound.
• Preferred metals within the at least one thiophene-organometallic compound are tin, magnesium, zinc and boron. It should be understood that within the present invention, boron is also considered to be a metal. In the event that the process according to the invention proceeds with the participation of boron, the leaving group is preferably selected from the group comprising MgBr 1 MgI, MgCl, Li or mixtures thereof.
• organometallic compounds which are used in the process according to the invention are preferably organometallic Sn compounds, e.g.
• Tributylzinnchlorid such as activated zinc (Zn *) or borane compounds, such as B (OMe) 3 or B (OH) 3 , or Mg compounds, particularly preferably to organometallic Mg compounds, particularly preferably Grignard compounds of the formula R-Mg-X,
• R is alkyl, very particularly preferably C2-alkyl
• X is halogen, particularly preferably Cl, Br or I and particularly preferably Br.
• catalyst is understood in particular to mean a catalytically active metal compound.
• the at least one catalyst contains nickel and / or palladium. This has been found to be favorable in many application examples of the present invention.
• the at least one catalyst particularly preferably contains at least one compound selected from the group of nickel and palladium catalysts with ligands selected from the group consisting of tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis (2,4,6-trimethylphenyl) imidazolidinium chloride, l, 3-bis (2,6-diisopropylphenyl) imidazolidinium chloride or 1,3-diadamantyl imidazolidinium chloride or mixtures thereof; Bis (triphenylphosphine) - palladium ((Pd PPh 3) Cl 2), palladium II acetate (Pd (OAc) 2), tetrakis (triphenylphosphine) - palladium (Pd (PPh3) ,,), tetrakis (triphenylphosphine) nickel (Ni (PPh 3 ) 4 ), nickel H-acetylacetonate Ni (
• the amount of added catalyst is often dependent on the target molecular weight and is usually in the range of> 0.1 - ⁇ 20 mol%, preferably in the range of> 0.5- ⁇ 17.5 mol%, particularly preferably in the range of> 1- ⁇ 15 mol %, in each case based on the molar amount of the thiophene derivative used.
• the concentration of the thiophene-organometallic compound in the first solution is> 6% by weight. This has proven advantageous in many applications of the present invention.
• the concentration of the thiophene-organometallic compound in the first solution is> 8% by weight, more preferably> 10% by weight, and most preferably> 12% by weight.
• the volume ratio (in 1/1) of the first and second solutions is from> 3: 1 to ⁇ 20: 1.
• reaction behavior can be further improved in many applications of the present invention, at the same time the
• the volume ratio (in 1/1) of the first and the second solution is preferably from> 4: 1 to ⁇ 15: 1, more preferably> 5: 1 to ⁇ 10: 1.
• the dosing time (i.e., the time in which the first solution is completely added to the second solution) is
• V reactor means the volume
• a reactor the heat exchange surface of the vessel in which the reaction takes place.
• alkyl linear and branched C 1 -C 8 -alkyls
• long-chain alkyls linear and branched C5-C20 alkyls
• alkenyl C2-C8 alkenyl
• cycloalkyl C3-C8-cycloalkyl
• alkoxy Cl-C6-alkoxy
• long-chain alkoxy linear and branched C5-C20 alkoxy
• alkylene selected from the group comprising: methylene; 1, 1 -ethylene; 1,2-ethylene; 1, 1 -propylidenes; 1,2-propylene; 1, 3-propylene; 2,2-propylidenes; butan-2-ol-1,4-diyl; propan-2-ol-1,3-diyl; 1,4-butylene; cyclohexane-l, l-diyl; cyclohexane-1,2-diyl; cyclohexane-l, 3-diyl; cyclohexane-1,4-diyl; cyclopentane-l, l-diyl; cyclopentane-l, 2-diyl; and cyclopentane-1,3-diyl,
• aryl selected from aromatics having a molecular weight below 300Da.
• arylenes selected from the group comprising: 1,2-phenylenes; 1, 3-phenylene; 1, 4-phenylene; 1,2-naphthalenylenes; 1, 3-naphthalenylenes; 1,4-naphthalenylene; 2,3-naphtalenylene; 1-hydroxy-2,3-phenylene; 1-hydroxy-2,4-phenylene; 1-hydroxy-2, 5-phenylene; and 1-hydroxy-2,6-phenylene,
• heteroaryl selected from the group comprising: pyridinyl; pyrimidinyl; pyrazinyl; triazolyl; pyridazinyl; 1,3,5-triazinyl; quinolinyl; isoquinolinyl; quinoxalinyl; imidazolyl; pyrazolyl; benzimidazolyl; thiazolyl; oxazolidinyl; pyrrolyl; thiophenyl; carbazolyl; indolyl; and isoindolyl, wherein the heteroaryl may be linked to the compound via any atom in the ring of the selected heteroaryl.
• heteroarylenes selected from the group comprising: pyridinediyl; quinolindiyl; pyrazodiyl; pyrazoldiyl; triazolediyl; pyrazinediyl, thiophenediyl; and imidazolediyl, wherein the heteroarylene acts as a bridge in the compound via any atom in the ring of the selected heteroaryl, especially preferred are: pyridine-2,3-diyl; pyridin-2,4-diyl; pyridin-2,5-diyl; pyridine-2,6-diyl; pyridine-3,4-diyl; pyridine-3,5-diyl; quinolin-2,3-diyl; quinolin-2,4-diyl; quinoline-2, 8-diyl; isoquinoline-1, 3-diyl; isoquinoline-1,4-diyl; pyrazole-1, 3-di
• heterocycloalkylenes selected from the group comprising: piperidin-l, 2-ylene; piperidin-2,6-ylene; piperidin-4,4-ylidene; l, 4-piperazine-1,4-ylene; 1,4-piperazine-2,3-ylene; 1,4-piperazine-2,5-ylene; l, 4-piperazin-2,6-ylene; l, 4-piperazine-1,2-ylene; l, 4-piperazine-l, 3-ylene; 1, 4-piperazine-1, 4-ylene; tetrahydrothiophen-2,5-ylene; tetrahydrothiophen-3,4-ylene; tetrahydrothiophen-2,3-ylene; tetrahydrofuran-2,5-ylene; tetrahydrofuran-3,4-ylene; tetrahydrofuran-2,3-ylene; pyrrolidine-2,5-ylene; pyrrolidin-3,4-ylene;
• heterocycloalkyl selected from the group comprising: pyrrolinyl; pyrrolidinyl; morpholinyl; piperidinyl; piperazinyl; hexamethylene imine; 1,4-piperazinyl; tetrahydrothiophenyl; tetrahydrofuranyl; 1, 4,7-triazacyclononanyl; 1, 4,8,1-tetraazacyclotetradecanyl; 1,4,7,10,13-pentaazacyclopentadecanyl; 1,4-diaza-7-thiacyclononanyl; 1,4-diaza-7-oxa-cyclononanyl; 1, 4,7,10-tetraazacyclododecanyl; 1, 4-dioxanyl; 1, 4,7-trithiacyclononanyl; tetrahydropyranyl; and oxazolidinyl, wherein the heterocycloalkyl may be linked to the compound via any atom in the ring
• halogen selected from the group comprising: F; Cl; Br and I
• haloalkyl selected from the group consisting of mono-, di-, tri-, poly- and perhalogenated linear and branched C 1 -C 8 -alkyl
• pseudohalogen selected from the group consisting of -CN, -SCN, -OCN, N3, -CNO, -SeCN.
• alkyl linear and branched C 1 -C 6 -alkyl
• long-chain alkyls linear and branched C5-C10 alkyl, preferably C6-C8 alkyl,
• alkenyl C3-C6 alkenyl
• cycloalkyl C6-C8-cycloalkyl
• alkoxy Cl-C4-alkoxy
• long-chain alkoxy linear and branched C5-C10 alkoxy, preferably linear C6-C8 alkoxy,
• Alkylene selected from the group comprising: methylenes; 1,2-ethylene; 1, 3-propylene; butan-2-ol-1,4-diyl; 1,4-butylene; cyclohexane-1, 1-diyl; cyclohexane-l, 2-diyl; cyclohexane-l, 4-diyl; cyclopentane-1, 1-diyl; and cyclopentane-1,2-diyl,
• Aryl selected from the group comprising: phenyl; biphenyl; naphthalenyl; anthracenyl; and phenanthrenyl,
• Arylene selected from the group comprising: 1, 2-phenylene; 1, 3-phenylene; 1, 4-phenylene; 1, 2-naphthalenylenes; 1,4-naphthalenylene; 2,3-naphthalenylenes and 1-hydroxy-2,6-phenylenes,
• Heteroarylene thiophene, pyrrole, pyridine, pyridazine, pyrimidine, indole, thienothiophene,
• Halogen selected from the group comprising: Br and Cl, more preferably Br.
• the at least one thiophene derivative contains at least one compound of the general formula:
• R is selected from the group consisting of hydrogen, hydroxyl, halogen, pseudohalogen, formyl, carboxy and / or carbonyl derivatives, alkyl, long-chain alkyl, alkoxy, long-chain alkoxy, cycloalkyl, haloalkyl, aryl, arylenes, haloaryl, heteroaryl, heteroarylenes, Heterocycloalkylenes, heterocycloalkyl, halo-heteroaryl, alkenyl, haloalkenyl, alkynyl, haloalkynyl, keto, ketoaryl, halo-ketoaryl, ketoheteroaryl, ketoalkyl, halo-ketoalkyl, ketoalkenyl, halo-ketoalkenyl, phosphoalkyl, phosphonates, phosphates, phosphine, phosphine oxide, phosphoryl, phosphoaryl, sulphonyl,
• X and X 'independently of one another are a leaving group, preferably halogen, particularly preferably Cl, Br or I and particularly preferably Br.
• the first and / or the second solution contain a solvent selected from the group of aliphatic hydrocarbons, e.g. Alkanes, in particular pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons, such as. Benzene, toluene and xylenes, as well as ether group-containing compounds, e.g. Diethyl ether, tert-butyl methyl ether, dibutyl ether, amyl ether, dioxane and tetrahydrofuran (THF) and solvent mixtures of the abovementioned groups.
• aliphatic hydrocarbons e.g. Alkanes, in particular pentane, hexane, cyclohexane or heptane
• unsubstituted or substituted aromatic hydrocarbons such as. Benzene, toluene and xylenes
• Solvents containing ether groups are preferably used in the process according to the invention. Very particular preference is tetrahydrofuran. However, it is also possible and preferred for many embodiments of the present invention to use as solvent mixtures of two or more of these solvents. For example, you can Mixtures of the solvent preferably used tetrahydrofuran and alkanes, for example hexane (eg, contained in commercially available solutions of starting materials such as organometallic compounds) can be used. It is important in the context of the invention that the solvent, the solvents or mixtures thereof be chosen so that the thiophene derivatives used or the polymerization-active monomers are present in dissolved form in the first solution. Also suitable for the workup are halogenated aliphatic hydrocarbons such as methylene chloride and chloroform.
• a hydrolyzing solvent is added to the polymerization solution to terminate the reaction ("quenching"), preferably an alkyl alcohol, more preferably ethanol or methanol, most preferably methanol.
• the workup is preferably carried out so that the precipitated product is filtered off, washed with the precipitant and then taken up in a solvent.
• purification in the soxhlet can be carried out, preferably using nonpolar solvents, such as e.g. Hexane can be used as extractant.
• nonpolar solvents such as e.g. Hexane
• the process is used for the preparation of copolymers and / or block polymers.
• first the first and second solution according to the method according to the invention is implemented, followed by a metered addition of at least one further solution consisting of polymerization thiophene monomer and / or two solutions consisting of a) at least one thiophene monomer having two leaving groups and b) a metal or an organometallic compound for the purpose of chain extension based on the same thiophene derivative and / or at least one other thiophene derivative for the preparation of Block copolymers or copolymers.
• the erfmdungssiee process is used to produce poly- and oligothiophenes. Preference is given to the preparation of degrees of polymerization or number of repeating units n in the chain of> 2 to ⁇ 5000, in particular from> 5 to ⁇ 2500, more preferably from> 100 to ⁇ 1000.
• the molecular weight is dependent on the molecular weight of the monomeric thiophene derivative from> 1000 to ⁇ 300,000, preferably from> 2000 to ⁇ 100,000, particularly preferably from> 5,000 to ⁇ 80,000, particularly preferably from> 10,000 to ⁇ 60,000.
• n> 2 to ⁇ 20 monomer units preferably from> 3 to ⁇ 10, particularly preferably from> 4 to ⁇ 8.
• a narrow molecular weight distribution with a polydispersity index PDI of> 1 to ⁇ 3, preferably PDI ⁇ 2, more preferably PDI> 1.1 to ⁇ 1.7.
• the poly- and oligomers prepared according to the method are also distinguished by the presence of one or two leaving groups at the chain end, which in the further course can serve as substitution sites for functionalizations or end-capping reactions.
• the thiophene derivative having only one leaving group has a further functionalizable radical, preferably in the 5-position, which is preferably selected from the group phosphoalkyl, phosphonates, phosphates, phosphine, Phosphine oxide, phosphoryl, phosphoaryl, sulphonyl, sulphoalkyl, sulphoarenyl, sulphonates, sulphates, sulphones or mixtures thereof has proven to be advantageous for many applications of the present invention.
• suitable temperatures are in a preferred embodiment of the invention in the range of> 20 ° to ⁇ +200 0 C, preferably in the range of> +60 to ⁇ +160 0 C and especially> +80 to ⁇ + 140 0 C.
• the reaction is carried out at elevated pressures, preferably at> 1-30 bar, in particular at> 2-15 bar and more preferably in the range of> 4-10 bar.
• the inventive method is characterized in particular in many applications by the possibility of targeted adjustment of a desired average chain length as well as the production of products with a narrow molecular weight distribution.
• oligothiophenes obtainable by the process according to the invention.
• Example 1 is to be understood as illustrative only and not as a limitation of the present invention, which is defined purely by the claims.

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