EP2121799A1 - Procédé de préparation d'oligomères thiophèniques - Google Patents

Procédé de préparation d'oligomères thiophèniques

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Publication number
EP2121799A1
EP2121799A1 EP07856487A EP07856487A EP2121799A1 EP 2121799 A1 EP2121799 A1 EP 2121799A1 EP 07856487 A EP07856487 A EP 07856487A EP 07856487 A EP07856487 A EP 07856487A EP 2121799 A1 EP2121799 A1 EP 2121799A1
Authority
EP
European Patent Office
Prior art keywords
thiophene derivative
polymerization
thiophene
leaving groups
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.)
Withdrawn
Application number
EP07856487A
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German (de)
English (en)
Inventor
Björn HENNINGER
Frank Rauscher
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
Application filed by Bayer Technology Services GmbH filed Critical Bayer Technology Services GmbH
Publication of EP2121799A1 publication Critical patent/EP2121799A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes

Definitions

  • the invention relates to a process for the preparation of Ohgothiophenen.
  • 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 in integrated organic semiconductor circuits enables low-cost solutions for smart cards or price tags, which hitherto can not be realized with the help of silicon technology due to the price and the lack of flexibility of the silicon structures. 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 Ohgomere of polymers in that Ohgomers 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.
  • oligomers and polymers 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) quaterthiophene.
  • 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.
  • EP 402 269 describes the preparation of oligothiophenes by oxidative coupling, for example using iron chloride (page 7, lines 20-30, page 9, lines 45-55).
  • the synthesis method leads to oligothiophenes, which are in the cationic form and thus in a conductive form and no longer in the neutral, semiconducting form (EP 402 269, 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.
  • oligothiophenes Due to the higher temperature side reactions are often favored, so that high-quality oligothiophenes are no longer accessible even through intensive purification operations (Chem. Mater., 1995, 7, 2235).
  • Another possibility for the preparation of oligothiophenes is described in the literature as the oxidative coupling by copper salts, in particular by copper ( ⁇ ) chloride (Kagan, Heterocycles, 1983, 20, 1937).
  • 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 based on the fact that the organolithium intermediate to be coupled is present in dissolved form prior to the addition of the catalyst.
  • Stille and Suzuki methods are more commonly used in the stepwise synthesis of oligomers, in particular from different building blocks (HCStarck, DE 10 353 094, 2005) (BASF, WO93 / 14079, 1993), the methods according to McCullough ( EP 1 028 136 Bl, US 6 611 172, US 247 420, WO 2005/014691, US 2006/0155105) and Rieke (US 5 756 653) those which are used for the commercial production of polythiophenes in a single synthesis step.
  • regioselective chain growth reaction starting from an organometallic compound (Sn, Mg, Zn) or a borane compound as a monomer with the aid of a catalyst (nickel (eg Ni (dppp) Cl 2 ), palladium (eg Pd ( PPh 3 ) 4 )) a polymer is formed regio- selectively. Differences are often in the synthesis of the actual monomer, any purification steps and purities of the monomers, the nature of the catalyst and the solvent used. In addition, the degree of regioselectivity serves as a distinguishing feature between the possible syntheses.
  • 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
  • the reaction conditions are -5 ° C to 25 ° C in the first publications to the polymerization under reflux conditions in today's publications called. 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, etc.
  • the advantages are in particular the price of magnesium compared to Alkymagnesiumreagenzien and the avoidance of alkyl halides in the by-products mentioned.
  • Advantages of using 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 notion of the present catalytic cycle and the lack of structure elucidation by NMR spectroscopy.
  • McCullough describes in his patent a synthesis variation in which a base (eg LDA) and a metal dihalide (eg ZnCl 2 ) must be used, so that a polymer which carries a halogen atom as an end group, can be prepared.
  • a base eg LDA
  • a metal dihalide eg ZnCl 2
  • the object of the present invention was therefore to provide a simplified process which enables the production of oligothiophenes having a defined average chain length and a narrow molecular weight distribution.
  • a method should be found which allows the preparation of low molecular weight polymers or oligomers in the chain length range of 2 to 20 monomer units with the narrowest possible molecular weight distribution 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 oligothiophenes comprising the steps:
  • the invention likewise relates to a process of oligothiophenes comprising the steps:
  • the solution of at least one thiophene derivative having a leaving group and at least one thiophene derivative having two leaving groups is reacted equimolar with the organometallic compound or by providing the metal or at least one alkyl halide with elemental metal to the polymerization-active monomer mixture and then metered in catalyst, which then allows the polymerization.
  • the reaction according to the invention surprisingly and advantageously achieves a lowering of the molecular weights by the addition of thiophene monomers having only one leaving group.
  • the dosage of the reactants can be different.
  • One possibility is to prepare the polymerization-active monomer mixture from the thiophene derivatives having one or two leaving groups in the template by adding an organometallic compound, or by providing a metal or at least one alkyl halide with an elemental metal, and then metering in the dissolved catalyst and to polymerize in batch.
  • Another conceivable variant is the mixing of the polymerization-active monomer mixture solution in the template with the catalyst solution at low temperatures (about 15-25 ° C) and the subsequent polymerization by heating to polymerization.
  • 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 at least one thiophene derivative having a leaving group is one of the general formula (1)
  • R. in formula (1) at position 3, 4 or 5 and / or in formula (2) at position 3 or 4 for H or preferably for an organic group, particularly preferably for a non-reactive or a protective group, preferably 5 or more C atoms is
  • 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. Particularly preferred are thiophene derivative according to formula (1) and / or (2) in which
  • R.sup.1 represents an organic group, preferably represents an alkyl group containing 5 or more carbon atoms,
  • R is an un branched alkyl chain having 1 to 20, preferably 5 to 12 carbon atoms
  • R is n-hexyl
  • R is selected from Ci to C20 alkyl, Ci-C 2O alkenyl, C] -C 2 O alkynyl, Ci-C20 alkoxy, Q-
  • Ci-C 20 silyl Ci-C 20 ester
  • Ci-C 2O amino optionally substituted aryl or heteroaryl, in particular Ci-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, likewise comprising fused ring systems which may optionally be substituted by one or more groups L, where L is an alkyl, alkoxy, Alkylcarbonyl or alkoxycarbonyl group having 1 to 20 C atoms may be.
  • 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 a leaving group can be used.
  • mixtures of two or more thiophene derivatives having two leaving groups can be used.
  • the at least one thiophene derivative having a leaving group and the at least one thiophene derivative having two leaving groups are erf ⁇ ndungshiel in solution.
  • 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.
  • organometallic Sn compounds for example tributyltin chloride, or Zn compounds, for example activated zinc (Zn *) or borane.
  • Compounds such as 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,
  • R is 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 1 , C 12 alkyl, more preferably C 2 , C 3 , C 4 , C 5 , C 6 , C 7 , C 9 -alkyl, very particularly preferably C 2 -alkyl,
  • X is halogen, particularly preferably Cl, Br or I and particularly preferably Br.
  • a metal or at least one alkyl halide is provided with an elemental metal, with the aid of the thiophene derivatives with one or two leaving groups by providing a metal or at least one alkyl halide with the elemental Metal are reacted to the polymerizable monomer mixture.
  • the metal can be added, for example in the form of chips, grains, particles or feeds and subsequently separated for example by filtration or the reaction space in a rigid form available, such as by temporary immersion of wires, grids, nets or comparable in the Reaction solution or in the form of an interior equipped with metal flowable cartridge or as a fixed bed in a column in which the metal is sufficiently finely divided (eg in chips) and is covered with solvent, wherein the thiophene derivatives with one or two Leaving groups when flowing through the cartridge or the column is implemented.
  • the at least one 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 11 , C 12 -alkyl, particularly preferably C 2 , C 3 , C 4 , C 5 , C 6 , 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, most 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.
  • the at least one catalyst used in the process according to the invention is one which is preferably used for regioselective polymerization, as described, for example, in RD McCullough, Adv. Mater., 1998, 70 (2), 93-116 and those listed therein References cited, for example, palladium or nickel catalysts, such as bis (triphenylphosphino) palladium (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 H-acetylacetonate Ni (acac) 2 , dichloro (2,2'-bipyridine) nickel, dibromobis (triphenylphosphine) nickel ( Ni (PPh 3 ) 2 Br
  • the catalyst can be prepared "in situ" and reacted with the polymerization-active monomer mixture.
  • mixtures of two or more catalysts can be used.
  • the at least one catalyst according to the invention is present in solution during the polymerization.
  • the thiophene derivatives having one or 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.
  • Suitable organic solvents for use in the process according to the invention are, in principle, all solvents or solvent mixtures which do not react with organometallic compounds, such as, for example, alkylmagnesium bromides or other compounds listed in this application, under polymerization conditions. These 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. For the workup are also suitable halogenated aliphatic hydrocarbons such as methylene chloride and chloroform.
  • 3-alkylthiophene is oligomerized by the regioselective reaction of a solution of mono- and dihalogenated 3-alkylthiophene using a Grignard reagent or by temporary provision of Mg or Mg in the presence of an alkyl halide to give a corresponding polymerization-active organomagnesium bromide Compound and its subsequent polymerization in the presence of a Ni catalyst.
  • the amount of catalyst added depends on the average molecular weight (M n ) to be achieved and is usually in the range from 0.1 to 20 mol%, preferably in the range from 10 to 20 mol%, particularly preferably in the range from 10 to 15 mol%, in each case based on the amount of thiophene derivative used with 2 leaving groups
  • PDI polydispersity index
  • the average molecular weight can be adjusted by the use of a polymerization-active monomer mixture of at least one thiophene derivative having a leaving group and at least one thiophene derivative with two leaving groups on addition of an appropriate amount of at least one catalyst.
  • the oligomer prepared according to the method is also distinguished, according to the thiophene derivatives used, 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.
  • Suitable temperatures for carrying out the inventive method are 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.
  • the polymerization is preferably carried out at atmospheric pressure and under reflux, however, is possible due to the low boiling points of the solvents used and a reaction is conducted at elevated pressures, preferably at from 1-30 bar, in particular 2- and 8 bar more preferably in the range of 4-7 bar.
  • the erf ⁇ ndungswashe process 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 monomer mixture by mixing an organometallic reagent with the thiophene derivative (s) having one or two leaving groups or by reacting the thiophene derivative (s) with one or two leaving groups with metal on a column as described in DE 10 304 006 B3 and in an apparatus as described by Reimschüssel, Journal of Organic Chemistry, 1960, 25, 2256-7, in a corresponding cartridge or in a tubular reactor provided with static mixers as described in DD 260 276 , DD 260 277 and DD 260 278 in a first module.
  • the at least one catalyst to the polymerization-active monomer mixture and mixing at Room temperature or at a lower temperature (about 15-25 ° C) in a second module is then followed by the continuous polymerization in a third module at the reaction temperature and under controlled conditions.
  • a fourth module further - same or different - monomer can be added.
  • the educt streams are rapidly mixed by a mixer.
  • 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, more preferably in the range of 20-40 minutes.
  • microreactor used here is representative of microstructured, preferably continuously operating reactors, which are known under the name microreactor, mini-reactor, micro-heat exchanger, mini mixer or micromixer.
  • microreactors examples are microreactors, micro-heat exchangers, T and Y mixers and micromixers from a wide variety of companies (eg Ehrfeld Mikrotechnik BTS GmbH, Institute for Microtechnology Mainz GmbH, Siemens AG, CPC-Cellular Process Chemistry Systems GmbH), and others as are generally known to the person skilled in the art
  • a "microreactor” usually has characteristic / determining internal dimensions of up to 1 mm and may contain static mixing internals
  • a preferred microreactor for the method according to the invention has internal dimensions of 100 ⁇ m to 1 mm.
  • ⁇ -mixer By using a micromixer ( ⁇ -mixer), the reaction solutions are mixed together very quickly, whereby a broadening of the molecular weight distribution due to possible radial concentration gradients is avoided. Furthermore, the ⁇ -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 polymerization is started in all cases by increasing the temperature. In this case too, the use of a micro heat exchanger ( ⁇ 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.
  • ⁇ heat exchanger a micro heat exchanger
  • reaction solution is conveyed through a residence section and reacted under pressure and at higher temperatures than previously described in the literature.
  • the erf ⁇ ndungswashe 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 the at least one thiophene derivative having a leaving group in addition to the at least one thiophene derivative having two leaving groups makes it possible to reduce very significantly the necessary amounts of the catalyst with regard to the desired average chain length or average molecular weights or the average molecular weight. significantly lower weights for a given amount of catalyst.
  • oligothiophenes obtainable by the process according to the invention.
  • Fig. 1 gelpimeationschromatogramrne (GPC) of the product of Example 2 (monomer ratio 1: 4) and an analog prepared oligothiophene (monomer ratio 1: 1).
  • GPC chromatogram of a product which, according to Example 2, however, has a monomer ratio "monomer ratio" of thiophene derivative having a leaving group to give thiophene derivative is also shown two leaving groups of 1: 1 was prepared.
  • the chromatograms show a peak in the low molecular weight region which can be assigned to the dimer 3-hexylthiophene.
  • the syntheses are carried out under protective gas.
  • reaction mixture was then pumped continuously at 120 0 C and below 5 bar through a reaction capillary.
  • the residence time was 40 min. After about 4 residence times, a sample was taken.
  • the product prepared was precipitated in methanol, separated, washed with methanol and taken up in THF. The conversion was 75 - 80%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

L'invention concerne un procédé de préparation d'oligothiophènes. Ce procédé vise à obtenir des polymères semiconducteurs ou des oligomères semiconducteurs ayant un poids moléculaire moyen défini et une étroite distribution du poids moléculaire.
EP07856487A 2006-12-21 2007-12-08 Procédé de préparation d'oligomères thiophèniques Withdrawn EP2121799A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006061967A DE102006061967A1 (de) 2006-12-21 2006-12-21 Verfahren zur Darstellung von oligomeren Thiophenen
PCT/EP2007/010711 WO2008080513A1 (fr) 2006-12-21 2007-12-08 Procédé de préparation d'oligomères thiophèniques

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EP2121799A1 true EP2121799A1 (fr) 2009-11-25

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US (1) US20100090177A1 (fr)
EP (1) EP2121799A1 (fr)
JP (1) JP2010513613A (fr)
KR (1) KR20090100397A (fr)
CN (1) CN101616950B (fr)
CA (1) CA2673605A1 (fr)
DE (1) DE102006061967A1 (fr)
TW (1) TWI427097B (fr)
WO (1) WO2008080513A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010062961A1 (de) 2010-12-13 2012-06-14 Bayer Technology Services Gmbh Carboxylierung von Poly-/Oligothiophenen

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007038449A1 (de) 2007-08-14 2009-02-19 Bayer Technology Services Gmbh Verfahren zur Herstellung von Thiophenoligomeren
JP2009209259A (ja) * 2008-03-04 2009-09-17 Nec Tokin Corp 導電性高分子およびそれを用いた固体電解コンデンサ
DE102008053589A1 (de) 2008-10-28 2010-04-29 Bayer Technology Services Gmbh Verfahren zur Reinigung halbleitender Polymere
EP2904381B1 (fr) 2012-10-08 2019-02-06 University Of Washington Through Its Center For Commercialization Points de polymère semi-conducteur contenant du métal et leurs procédés de fabrication et d'utilisation
US9481764B1 (en) * 2015-10-13 2016-11-01 The Boeing Company Flow reactor synthesis of polymers
CN107325202B (zh) * 2017-07-06 2019-09-17 淄博千汇生物科技有限公司 舒更葡萄糖钠的精制方法
CN109651600A (zh) * 2018-11-12 2019-04-19 深圳烯湾科技有限公司 一种聚3-己基噻吩的制备方法
CN113929881A (zh) * 2021-11-08 2022-01-14 上海交通大学 一种基于连续流微反应器合成共轭光电高分子的制备方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02250881A (ja) * 1989-03-24 1990-10-08 Matsushita Electric Ind Co Ltd チオフェンオリゴマー及びその製造方法
US5556706A (en) * 1993-10-06 1996-09-17 Matsushita Electric Industrial Co., Ltd. Conductive layered product and method of manufacturing the same
US6072027A (en) * 1997-11-18 2000-06-06 The Dow Chemical Company Process for preparing an electrically conductive polymer
US6166653A (en) * 1998-08-13 2000-12-26 Motorola Inc System for address initialization of generic nodes in a distributed command and control system and method therefor
US6166172A (en) * 1999-02-10 2000-12-26 Carnegie Mellon University Method of forming poly-(3-substituted) thiophenes
US6602974B1 (en) * 2001-12-04 2003-08-05 Carnegie Mellon University Polythiophenes, block copolymers made therefrom, and methods of forming the same
CN1400210A (zh) * 2002-09-06 2003-03-05 华南理工大学 新型低聚噻吩衍生物及其制备方法和应用
DE602004016858D1 (de) * 2003-08-06 2008-11-13 Merck Patent Gmbh Verfahren zur herstellung von regioregulären polymeren
JP4125658B2 (ja) * 2003-09-30 2008-07-30 Ｊｆｅケミカル株式会社 炭化水素の製造方法
CN1253448C (zh) * 2004-09-29 2006-04-26 徐良衡 一种噻吩类聚合物单体的制备及其聚合方法
US7321133B2 (en) * 2004-11-17 2008-01-22 Plextronics, Inc. Heteroatomic regioregular poly(3-substitutedthiophenes) as thin film conductors in diodes which are not light emitting or photovoltaic
US7262264B2 (en) * 2005-01-12 2007-08-28 Honeywell International Inc. Halogenated thiophene monomer for the preparation of regioregular polythiophenes
US7795359B2 (en) * 2005-03-04 2010-09-14 Novartis Ag Continuous process for production of polymeric materials
ES2400513T3 (es) * 2005-03-07 2013-04-10 Arkema Inc. Copolímeros de bloque conductores, métodos y artículos
CN101213234B (zh) * 2005-04-01 2011-12-07 卡内基·梅隆大学 包括立体规则性聚合物、聚噻吩和嵌段共聚物的导电聚合物的活性合成
CA2615489C (fr) * 2005-07-18 2013-04-09 Rieke Metals Inc. Processus ameliore de polymeres polythiophenes substitues
CN1730477A (zh) * 2005-08-30 2006-02-08 华南理工大学 低聚噻吩衍生物及其制备方法和应用
JP2007116115A (ja) * 2005-09-21 2007-05-10 Mitsubishi Chemicals Corp 有機半導体材料及び有機電界効果トランジスタ
WO2007034841A1 (fr) * 2005-09-21 2007-03-29 Mitsubishi Chemical Corporation Matériau semi-conducteur organique et transistor organique à effet de champ

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008080513A1 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010062961A1 (de) 2010-12-13 2012-06-14 Bayer Technology Services Gmbh Carboxylierung von Poly-/Oligothiophenen
WO2012080074A1 (fr) 2010-12-13 2012-06-21 Bayer Technology Services Gmbh Carboxylation de polythiophènes/oligothiophènes

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US20100090177A1 (en) 2010-04-15
KR20090100397A (ko) 2009-09-23
CN101616950B (zh) 2012-05-23
CN101616950A (zh) 2009-12-30
TW200902584A (en) 2009-01-16
WO2008080513A1 (fr) 2008-07-10
DE102006061967A1 (de) 2008-06-26
CA2673605A1 (fr) 2008-07-10
JP2010513613A (ja) 2010-04-30
TWI427097B (zh) 2014-02-21

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