EP2121798A1 - Verfahren zur darstellung von thiophenen - Google Patents

Verfahren zur darstellung von thiophenen

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Publication number
EP2121798A1
EP2121798A1 EP07856486A EP07856486A EP2121798A1 EP 2121798 A1 EP2121798 A1 EP 2121798A1 EP 07856486 A EP07856486 A EP 07856486A EP 07856486 A EP07856486 A EP 07856486A EP 2121798 A1 EP2121798 A1 EP 2121798A1
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EP
European Patent Office
Prior art keywords
solution
polymerization
leaving groups
thiophene derivative
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP07856486A
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German (de)
English (en)
French (fr)
Inventor
Frank Rauscher
Björn HENNINGER
Leslaw Mleczko
Kilian Tellmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer Intellectual Property GmbH
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Bayer Technology Services GmbH
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Filing date
Publication date
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Publication of EP2121798A1 publication Critical patent/EP2121798A1/de
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • 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 invention relates to a process for the preparation of thiophenes.
  • the aim of the process is to produce semiconducting polymers or semiconducting oligomers having a defined average molecular weight and a narrow molecular weight distribution.
  • 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.
  • EP402269 describes the preparation of oligothiophenes by oxidative coupling, for example using iron chloride (page 7, lines 20-30, page 9, lines 45-55).
  • the synthetic method leads to oligothiophenes which are present in the cationic form and thus in a conductive form and no longer in the neutral, semiconducting form (EP402269, p. 8, lines 28-29).
  • These oligothiophenes are therefore unusable for use in semiconductor electronics, since the oligothiophenes, although good in the cationic form conduct electricity, but have no semiconductor effect.
  • the product after purification by recrystallization, also contains chlorine and copper, of which at least the chlorine is at least partially chemically bound to the oligothiophene and can not be further removed by further elaborate purification (Katz et al., Chem. Mater., 1995, 7, 2235).
  • An improvement of this method is described in DE10248876 and is based on the fact that the organolithium intermediate to be coupled is present in dissolved form prior to the addition of the catalyst.
  • a part is converted into the organometallic intermediate with the aid of magnesium or an alkylmagnesium halide and then linked to the unreacted part by the addition of a nickel catalyst.
  • the monomer used such as e.g. a terthiophene for the synthesis of a hexathiophene
  • the hexathiophene is obtained by a multi-step linkage of a thiophene.
  • Stille and Suzuki methods are more commonly used in the stepwise synthesis of oligomers, particularly from different building blocks (HCStarck, DE10353094, 2005) (BASF, WO93 / 14079, 1993), McCullough's (EP1028136B1, US661 1172, US247420, WO2005 / 014691, US2006 / 0155105) and Rieke (US5756653) those used for the commercial production of polythiophenes.
  • 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 ).
  • a nickel catalyst preferably Ni (dppp) Cl 2
  • reaction conditions -5 ° C to 25 ° C in the first publications to polymerization under reflux conditions in today's publications. Except for possibly different reaction temperatures, this step is the same for the polymerization in all associated processes.
  • the catalyst selection eg alternative Ni (dppe) Cl 2
  • solvent eg THF, toluene ect.
  • magnesium Grignard compounds are the homogeneity of the reaction solution and the avoidance of purification steps between the individual stages (one-pot synthesis).
  • a disadvantage is the formation of methyl bromide, which is formed in the Grignard stage from the methylmagnesium bromide preferably used.
  • Methyl bromide is a above-4 ° C gaseous, harmful substance, which is difficult orAutozutute only with considerable technical effort from exhaust gases.
  • the polymers are generally obtained via Soxhlet purifications of the necessary purity.
  • the polymers described are first described as "normal" polymers of the respective thiophene moiety.Thus, the polymers should not bear any end group other than H. The idea was initially based on an early conception of the present catalytic cycle and lack of structure elucidation by NMR spectroscopy.
  • the object of the present invention was therefore to provide a process which allows the production of polythiophenes or oligothiophenes with defined average chain lengths and a narrow molecular weight distribution.
  • the necessary controlled conditions should be used optimally in the process.
  • a method should be found which allows the preparation of polymers and also of oligomers in the chain length range of 2 to 20 monomer units with very narrow molecular weight distributions without restrictions on the conversion or the need for purification of possible intermediates.
  • the process should provide advantages in terms of space / time yield, manageability, economy and ecology on an industrial scale.
  • the invention therefore provides a process for the preparation of oligo- or polythiophenes comprising the process steps:
  • reaction of at least one dissolved thiophene derivative having two leaving groups to form a polymerization-active monomer by a) mixing a solution of at least one dissolved thiophene derivative having two leaving groups with a solution of an organometallic compound or b) reacting a solution of at least one dissolved thiophene derivative with two leaving groups with elemental metal or c) reaction of a solution of at least one dissolved thiophene derivative with two leaving groups with elemental metal and at least one alkyl halide.
  • step Ia the solution of the at least one thiophene derivative with two leaving groups is reacted equimolar with the organometallic compound to the polymerization-active monomers.
  • the metal is in excess and can be provided in various ways.
  • the metal is present in excess and the reaction solution is added at least one alkyl halide.
  • step 1 a) or b) or c) are then added in step 2 catalyst and then polymerized.
  • the invention further provides a process for the preparation of oligo- or
  • Leaving groups to a polymerization-active monomer by a) mixing a solution of at least one dissolved thiophene derivative with two leaving groups with a solution of an organometallic compound or b) reacting a solution of at least one dissolved thiophene derivative with two leaving groups with elemental metal (2) polymerization of the product solution from 1 by the metered addition of a solution of at least one catalyst
  • the process of the invention surprisingly and advantageously achieves a lowering of the molecular weights achieved by the two-stage metering strategy of the intermediately formed polymerization-active organometallic thiophene derivatives.
  • this process reduces the average molecular weight (M n ) of the polymer and results in narrower molecular weight distributions.
  • M n average molecular weight
  • the two-stage monomer dosing allows a technically simple way to defined block copolymers or mixed copolymers.
  • the dosage of the educts can be different.
  • One possibility consists in preparing the polymerization-active monomers from the thiophene derivatives provided with two leaving groups in the initial charge and subsequently metering in the dissolved catalyst, polymerizing in the batch and subsequently metering in additional polymerization-active monomer.
  • Another conceivable variant is the mixing of catalyst and the polymerization-active monomer mixture in the template at low temperatures (about 15-25 ° C), the subsequent polymerization by heating to polymerization and subsequent addition of further polymerization-active monomer. Also conceivable is the simultaneous metered addition of polymerization-active monomer mixture solution and catalyst solution, their rapid and complete mixing and subsequent heating and thus polymerization and subsequent addition of further polymerization-active monomer.
  • the reaction of the catalyst according to step 2 in the first metering step with 1-3 molar equivalents, preferably 1.5 to 2.5 molar equivalents, more preferably 1, 8 to 2.2 molar equivalents, particularly preferably 2 molar equivalents polymerization-active monomer according to step 1 and in the second dosing step according to step 3, the remaining, depending on the target molecular weight amount of polymerization-active monomer added.
  • a hydrolyzing solvent is added to the polymerization solution to terminate the reaction, preferably an alkyl alcohol, more preferably ethanol or methanol, most preferably methanol.
  • the precipitated product is filtered off, washed with the precipitant and then taken up in a solvent.
  • purification may be carried out in soxhlet, preferably using nonpolar solvents such as e.g. Hexane can be used as extractant.
  • the process according to the invention is carried out continuously.
  • the dosage or the preparation of the reactants can be done differently.
  • a preferred embodiment of the process according to the invention is the continuous preparation of the polymerization-active monomers by mixing an organometallic reagent with the at least one thiophene derivative having two leaving groups according to step 1 a) or by reacting the thiophene derivative with two leaving groups with metal according to step 1 b). or lc) on a column as described in DE 10304006 B3 or Reimschüssel, Journal of Organic Chemistry, 1960, 25, 2256-7, in a corresponding cartridge or in a static mixer-equipped tubular reactor as described in DD260276, DD260277 and DD260278 in one first module.
  • the continuous polymerization according to step 2 is then carried out in a third module at reaction temperature and under controlled conditions.
  • a fourth module at least once more - same or at least one different - monomer is added in accordance with step 3.
  • the educt streams are rapidly mixed by a mixer. After thorough mixing and polymerization in one module, in a further module at least once more - same or at least one different monomer - is metered in according to step 3 and polymerized.
  • the invention likewise relates to a continuous process for the preparation of oligo- or polythiophenes comprising the process steps:
  • Leaving groups to a polymerization-active monomer by a) mixing a solution of at least one dissolved thiophene derivative with two leaving groups with a solution of an organometallic Compound or b) Passage or overflow of elemental metal initially introduced in the apparatus with a solution of at least one dissolved thiophene derivative having two leaving groups c) Passage or overflow of elemental metal introduced into the apparatus with a solution at least a dissolved thiophene derivative having two leaving groups and at least one alkyl halide II. Continuous polymerization of the product solution from I after addition of a
  • step Ia the solution of the at least one thiophene derivative with two leaving groups is reacted equimolar with the organometallic compound to the polymerization-active monomers.
  • step Ib) or Ic the degree of reacted thiophene leaving group bonds to the corresponding polymerization-active bonds by the residence time to an equimolar conversion (metal: thiophene derivative) to adjust.
  • step II The polymerization-active monomer prepared according to step I a) or b) or c) is subsequently added in step II catalyst and polymerized continuously.
  • the invention furthermore relates to a continuous process for the preparation of oligo- or polythiophenes comprising the process steps:
  • Leaving groups to a polymerization-active monomer by a) mixing a solution of at least one dissolved thiophene derivative with two leaving groups with a solution of an organometallic compound or b) passing or overflow of elemental, submitted in the apparatus metal with a solution of at least one dissolved thiophene - derivative with two leaving groups
  • step Ia the solution of the at least one thiophene derivative with two leaving groups equimolar with the organometallic compound to the polymerization Monomers reacted.
  • step Ib the degree of reacted thiophene leaving group bonds to the corresponding polymerization-active bonds by the residence time to an equimolar conversion (metal: thiophene derivative) to adjust.
  • the polymerization-active monomer prepared according to step I a) or b) is subsequently metered into catalyst in step II and polymerized continuously.
  • the continuous reaction procedure is of particular advantage since, compared to the batchwise reaction procedure of the prior art, it allows higher space-time yields and leads to defined poly- and oligothiophenes with a narrow molecular weight distribution. Thus, inexpensive well-defined poly- and oligothiophenes become accessible in a surprisingly simple manner.
  • step II subsequent to step II in a step HI, the continuous polymerization of the product solution from II by the addition of at least one further solution prepared according to I with the purpose of chain extension based on the same thiophene derivative and / or at least one other thiophene derivative.
  • the at least one thiophene derivative having two leaving groups is one of the general formula:
  • X or X 'independently of one another are a leaving group, preferably halogen, particularly preferably Cl, Br or I and particularly preferably Br.
  • R 'and R "independently of one another represent H or alkyl having 1 to 12 C atoms
  • Y 1 and Y 2 independently represent H or CN
  • Terminal CH 3 groups are understood as CH 2 groups in the sense of CH 2 -H.
  • R is an organic group, preferably one for an alkyl group, which is 5 or more
  • R is an unbranched alkyl chain having 1 to 20, preferably 5 to 12 carbon atoms
  • R is n-hexyl
  • R is selected from Ci to C 20 alkyl, C 20 alkenyl, C] -C 20 alkynyl, C 20 alkoxy, Q- C 20 thioalkyl, C 20 silyl, Ci-C 20 esters, Ci- C 20 amino, optionally substituted aryl or heteroaryl, in particular C) -C 20 alkyl, preferably unbranched chains
  • R is selected from pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl or dodecyl
  • Aryl and heteroaryl preferably denote a mono-, bi- or tricyclic aromatic or heteroaromatic group having up to 25 C atoms, wherein likewise fused ring systems which may optionally be substituted with one or more groups L, wherein L may be an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group having 1 to 20 C atoms.
  • aryl or heteroaryl groups are phenyl in which, in addition, one or more CH groups are replaced by N, naphthalene, thiophene, thienothiophene, dithienothiophene, alkylfluorene and oxazole, all of which may be unsubstituted, mono- or polysubstituted with L.
  • L is as defined above.
  • mixtures of two or more thiophene derivatives having two leaving groups can be used.
  • the at least one thiophene derivative having two leaving groups is present in solution according to the invention.
  • organometallic compounds which are used in the process according to the invention are preferably organometallic Sn compounds, for example tributyltin chloride, or Zn compounds, for example activated zinc (Zn *) or borane compounds, for example B ( OMe) 3 or B (OH) 3 , or Mg compounds, particularly preferably organometallic Mg compounds, particularly preferably Grignard compounds of the formula R-Mg-X, where R is alkyl and in particular C ( , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , Cn, C ⁇ -alkyl, particularly preferably C 2 , C 3 , C 4 , C 5 , C O , C 7 , Cs Alkyl, most preferably C 2 -
  • X is halogen, particularly preferably Cl, Br or I and particularly preferably Br.
  • a metal or at least one alkyl halide with an elemental metal is provided, with the aid of which the at least one thiophene derivative having two leaving groups is provided by providing a metal or at least one alkyl halide with an elemental metal be converted to the polymerizable monomers.
  • the metal can be added, for example, in the form of chips, grains, particles or feeds and subsequently separated, for example, by filtration or be made available to the reaction space in a rigid form, such.
  • the continuous reaction to the Grignard reagent can also be carried out under high turbulence in tubular reactors equipped with static mixers, wherein the liquid column is exposed to pulsations, as is known from the patents DD260276, DD260277 and DD260278.
  • the embodiments preferred therein for the preparation of the Grignard reagents also apply to the method according to the invention described here.
  • the metals are preferably magnesium or zinc, more preferably magnesium.
  • the alkyl halide is one of the formula R-X,
  • R represents alkyl and in particular C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 8 , C 9 , C 10 , C n , C 12 -alkyl, particularly preferably C 2 , C 3 , C 4 , C 5 , Ce, C 7 , C 8 -alkyl, very particularly preferably C 2 -alkyl,
  • X is halogen, particularly preferably Cl, Br or I and particularly preferably Br.
  • the alkyl halide with the elemental metal is an ethyl halide and magnesium or zinc, more preferably ethyl bromide with magnesium.
  • the alkyl halide is used in catalytic amounts, i. > 0 to 0.5, preferably 0.001 to 0.1, particularly preferably 0.01 to 0.05, equivalents relative to the total amount of thiophene derivative used.
  • organometallic Mg compounds When using organometallic Mg compounds, the dosing of a solution of this compound takes place, wherein the solvent does not have to correspond to that in the further process.
  • elemental magnesium or elemental magnesium with at least one Alkyl halide for the preparation of the intermediate organometallic thiophene compound, the reaction is carried out with magnesium provided within the process. A separation of unreacted magnesium is usually carried out by suitable retention devices such as metal or glass frits.
  • the at least one catalyst used in the process according to the invention is one which is preferably used for regioselective polymerization, as described in RD McCullough, Adv. Mater., 1998, 10 (2), 93-1 16 and those listed therein References cited, for example, to palladium or nickel catalysts, for example bis (triphenylphosphino) palladium dichloride (Pd (PPh 3 ) Cl 2 ), palladium (II) acetate (Pd (OAc) 2 ) or tetrakis (triphenylphosphine) palladium (Pd ( PPh 3 ) 4 ) or tetrakis (triphenylphosphine) nickel (Ni (PPh 3 ) 4 ), nickel ⁇ -acetylacetonate Ni (acac) 2 , dichloro (2,2'-bipyridine) nickel, dibromobis (triphenylphosphine) nickel (Ni (PPh 3
  • mixtures of two or more catalysts can be used.
  • the at least one catalyst is present in solution according to the invention.
  • thiophene derivatives having two leaving groups to be used according to the invention and also the corresponding catalysts are usually commercially available or else preparable by methods familiar to the person skilled in the art.
  • organometallic compounds such as alkylmagnesium bromides or other listed in this application, which do not react under polymerization. This are usually compounds which have no halogen atoms or, compared to organometallic compounds under polymerization, no reactive hydrogen atoms.
  • Suitable solvents are, for example, aliphatic hydrocarbons, e.g. Alkanes, especially pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons, e.g. 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, such. a mixture of THF and toluene.
  • aliphatic hydrocarbons e.g. Alkanes, especially pentane, hexane, cyclohexane or heptane
  • unsubstituted or substituted aromatic hydrocarbons e.g. Benzene, tolu
  • Solvents containing ether groups are preferably used in the process according to the invention. Very particular preference is tetrahydrofuran. However, it is also possible to use as solvent mixtures of two or more of these solvents. For example, mixtures of the preferred solvent may be tetrahydrofuran and alkanes, e.g. Hexane (e.g., contained in commercially available solutions of starting products such as organometallic compounds). It is important in the context of the invention that the solvent, the solvents or their mixtures are chosen such that the thiophene derivatives or the polymerization-active monomers are present in dissolved form before the addition of the catalyst. Also suitable for the workup are halogenated aliphatic hydrocarbons, such as methylene chloride and chloroform.
  • 3-alkylthiophene is polymerized by the regioselective reaction of a solution of dihalogenated 3-alkylthiophene with the use of a Grignard reagent or elemental magnesium to form a corresponding polymerization-active organomagnesium bromide compound and its subsequent polymerization in the presence of a Ni - Catalyst.
  • a Grignard reagent or elemental magnesium to form a corresponding polymerization-active organomagnesium bromide compound and its subsequent polymerization in the presence of a Ni - Catalyst.
  • equimolar reaction of 2,5-dibromo-3-hexylthiophenes in THF solution with ethylmagnesium bromide and their subsequent polymerization in the presence of Ni (dppp) Cl 2 is especially preferred.
  • the amount of added catalyst is dependent on the target molecular weight and is usually in the range of 0.1 to 20 mol%, preferably in the range of 10-20 mol%, particularly preferably in the range of 10-15 mol%, in each case based on the molar amount of used thiophene derivative.
  • Ni (dppp) Cl 2 catalyst concentrations of 0.1 to 20 mol% based on the amount of monomers used, depending on the target molecular weight, has proven useful.
  • the preparation according to the invention serves to prepare poly- and oligothiophenes. Preference is given to the preparation of degrees of polymerization or number of repeating units n in the chain of from 2 to 5000, in particular from 10 to 5000 or from 10 to 5000, particularly preferably from 50 to 1000 , very particularly preferably from 100 to 1000.
  • the molecular weight is dependent on the molecular weight of the monomeric thiophene derivative of 5000 to 300,000, preferably from 10,000 to 100,000, more preferably from 15,000 to 100,000, particularly preferably from 20,000 to 60,000.
  • the average molecular weight or the mean chain length can be set by the two-stage metering strategy with activation of the catalyst in the first metering stage and the continued polymerization within the second metering precisely defined by the amount of catalyst according to [Thiophene
  • the continuous conduct of the reaction leads to higher space-time yields than comparable prior art batch-wise polymerizations.
  • costly purification of any intermediate stages are not necessary increases the economic attractiveness of the process considerably and also facilitates the technical implementation.
  • poly- and oligomers prepared according to the method are 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.
  • a preferred embodiment of the process according to the invention is the continuous preparation of the polymerization-active monomer mixture by mixing an organometallic reagent with the thiophene derivatives having two leaving groups or by reacting the thiophene derivatives with two leaving groups with metal or by reacting the thiophene derivatives with two leaving groups and at least an alkyl halide with metal on a column as described in DE 10304006 B3 and in an apparatus as described by Reimschüssel, Journal of Organic Chemistry, 1960, 25, 2256-7, in a corresponding cartridge or in a static mixer-equipped tubular reactor as described in DD260276 , DD260277 and DD260278 in a first module.
  • a primary activation of the catalyst by the preceding optionally continuously carried out reaction with 1-3 molar equivalents, preferably 1.5 to 2.5 molar equivalents, more preferably 1, 8 to 2.2 molar equivalents, particularly preferably 2 molar equivalents of polymerization-active monomers Thiophene derivative with two leaving groups.
  • the educt streams are rapidly mixed by a mixer.
  • suitable temperatures are generally in the range of +20 to +200 0 C, preferably in the range of +80 to +160 0 C and in particular at +100 to +140 0 C. Due to the low boiling temperatures used Solvent, the reaction is carried out at elevated pressures, preferably at 1-30 bar, especially at 2-8 bar and more preferably in the range of 4-7 bar.
  • the metering rates depend primarily on the desired residence times or sales to be achieved.
  • Typical residence times are in the range of 5 minutes to 120 minutes.
  • the residence time is between 10 and 40 minutes, preferably in the range of 20-40 minutes.
  • microreactor used here is representative of microstructured, preferably continuously operating
  • Micro-heat exchangers, T and Y mixers as well as micromixers of various companies for example Ehrfeld Mikrotechnik BTS GmbH, Institute for Microtechnology Mainz GmbH, Siemens AG, CPC-
  • a "microreactor" in the sense of the present invention usually has characteristic / determining internal dimensions of up to 1 mm and static
  • a preferred microreactor for the inventive method has internal dimensions of 100 .mu.m to 1 mm.
  • ⁇ -mixer a micromixer
  • the reaction solutions are mixed together very quickly, whereby a broadening of the molecular weight distribution due to possible radial concentration gradients is avoided.
  • the microreaction technique ( ⁇ -reaction technique) in a microreactor ( ⁇ -reactor) allows a usually much narrower residence time distribution than in conventional continuously guided apparatus, which also prevents broadening of the molecular weight distribution.
  • the process according to the invention is carried out continuously using ⁇ -reaction apparatuses.
  • the metered addition of a catalyst solution via a ⁇ -mixer takes place in a suitable, temperature-controlled residence section.
  • the polymerization is started in all cases by increasing the temperature.
  • the use of a micro heat exchanger which allows a rapid and controlled increase in the temperature of the reaction solution, which is advantageous for a narrow molecular weight distribution, is particularly suitable.
  • reaction solution is conveyed through a residence section and reacted under pressure and at higher temperatures than previously described in the literature.
  • the inventive method is characterized in particular by the targeted adjustment of a desired average chain length as well as by the production of products with a narrow molecular weight distribution.
  • the continuous conduct of the polymerization allows a significant increase in the space-time yield.
  • the use according to the invention of a two-stage metering strategy for the polymerization of the organometallic thiophene derivative makes it possible to very clearly reduce the necessary amounts of the catalyst with respect to the desired mean chain length or molecular weights or to markedly lower the average molecular weights for a given amount of catalyst.
  • oligothiophenes obtainable by the process according to the invention.
  • the invention is explained in more detail below by means of examples without, however, limiting them to these.
  • the syntheses are carried out under protective gas.
  • Dosing stream E Dosing flow from catalyst activation, 5.9 ml / h
  • Dosing flow F 0.23 M 2-bromo-5-bromouragnesium-3-hexylthiophene, 6.2 ml / h
  • Mixer ⁇ -structured cascade mixer
  • Flask A 2,5-dibromo-3-hexylthiophene (4 mmol) in 10 ml of THF is introduced under protective gas determinations into a 50 ml three-necked flask equipped with a reflux condenser, nitrogen inlet and thermometer and heated to reflux. After adding 1M solution of methylmagnesium bromide in hexane (4 mL, 4 mmol), the reaction solution is refluxed for one hour.
  • Flask B 2,5-Dibromo-3-hexylthiophene (1 mmol) in 10 ml of THF is introduced under protective gas determinations into a 50 ml three-necked flask equipped with a reflux condenser, nitrogen inlet and thermometer and heated to reflux. After adding 1M solution of methylmagnesium bromide in hexane (ImI, 1 mmol), the reaction solution is refluxed for one hour. Subsequently, 0.5 mmol of Ni (dppp) Cl 2 are added as catalyst to the reaction solution and heated for 1 hour under reflux.

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EP07856486A 2006-12-21 2007-12-08 Verfahren zur darstellung von thiophenen Withdrawn EP2121798A1 (de)

Applications Claiming Priority (2)

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DE102006061966A DE102006061966A1 (de) 2006-12-21 2006-12-21 Verfahren zur Darstellung von Thiophenen
PCT/EP2007/010710 WO2008080512A1 (de) 2006-12-21 2007-12-08 Verfahren zur darstellung von thiophenen

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US (1) US20110105717A1 (ko)
EP (1) EP2121798A1 (ko)
JP (1) JP2010513612A (ko)
KR (1) KR20090101919A (ko)
CN (1) CN101563390A (ko)
CA (1) CA2673415A1 (ko)
DE (1) DE102006061966A1 (ko)
TW (1) TW200835773A (ko)
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DE102010062961A1 (de) 2010-12-13 2012-06-14 Bayer Technology Services Gmbh Carboxylierung von Poly-/Oligothiophenen

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CA2673415A1 (en) 2008-07-10
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