Patent Application
20100090177
The invention relates to a process for preparing oligothiophenes. It is the aim of the process to prepare semiconductive polymers or semiconductive oligomers having a defined mean molecular weight and a narrow molecular weight distribution.
The field of molecular electronics has developed rapidly in the last 15 years with the discovery of organic conductive and semiconductive compounds. In this time, a multitude of compounds which have semiconductive or electrooptical properties have been found. It is generally understood that molecular electronics will not displace conventional semiconductor units based on silicon. Instead, it is assumed that molecular electronic components will open up new fields of application in which suitability for coating large surfaces, structural flexibility, processability at low temperatures and low costs are required. Semiconductive organic compounds are currently being developed for fields of use such as organic field-effect transistors (OFETs), organic luminescent diodes (OLEDs), sensors and photovoltaic elements. As a result of simple structuring and integration of OFETs into integrated organic semiconductor circuits, inexpensive solutions for smart cards or price tags, which have not been realizable to date with the aid of silicon technology owing to the cost and the lack of flexibility of the silicon units, are becoming possible. It would likewise be possible to use OFETs as switching elements in large-area, flexible matrix displays.
All compounds have continuous conjugated units and are, according to molecular weight and structure, divided into conjugated polymers and conjugated oligomers. Oligomers are generally distinguished from polymers in that oligomers usually have a narrow molecular weight distribution and a molecular weight up to about 10 000 g/mol (Da), whereas polymers generally have a correspondingly higher molecular weight and a broader molecular weight distribution. However, it is more sensible to distinguish between oligomers and polymers on the basis of the number of repeat units, since one monomer unit can quite possibly achieve a molecular weight of 300 to 500 g/mol, as, for example, in the case of (3,3″″-dihexyl)quaterthiophene. In the case of distinction according to the number of repeat units, molecules are still referred to as oligomers in the range of 2 to about 20 repeat units. However, a fluid transition exists between oligomers and polymers. Often, the distinction between oligomers and polymers is used to express the difference in the processing of these compounds. Oligomers are frequently evaporable and can be applied to substrates by means of vapour deposition processes. Polymers frequently refer to compounds—irrespective of their molecular structure—that are not evaporable and are therefore generally applied by means of other processes.
An important prerequisite for the production of high-value organic semiconductor circuits is compounds of extremely high purity. In semiconductors, order phenomena play an important role. Hindrance of uniform alignment of the compounds and development of particle interfaces leads to a dramatic decline in the semiconductor properties, such that organic semiconductor circuits which have been built using compounds not of extremely high purity are generally unusable. Remaining impurities can, for example, inject charges into the semiconductive compound (“doping”) and hence reduce the on/off ratio or serve as charge traps and hence drastically lower the mobility. Moreover, impurities can initiate the reaction of the semiconductive compounds with oxygen and oxidizing compounds can oxidize the semiconductive compounds and hence shorten possible storage, processing and operating times.
The most important semiconductive polymers and oligomers include the poly/oligothiophenes whose monomer unit is, for example, 3-hexylthiophene. In the case of linkage of individual or a plurality of thiophene units to give a polymer or oligomer, it is necessary in principle to distinguish between two processes—the simple coupling reaction and the multiple coupling reaction in the sense of a polymerization mechanism.
In the case of the simple coupling reaction, generally two thiophene derivatives with identical or different structure are coupled to one another in one step so as to form a molecule which then consists of one unit of the two monomers in each case. After a removal, purification and refunctionalization, this new molecule can in turn serve as the monomer and thus open up access to longer-chain molecules. This process leads generally to exactly one oligomer, the target molecule, and hence to a product without molar mass distribution, and few by-products. They also offer the possibility to build up very defined block copolymers by the use of different monomers. A disadvantage here is that molecules which consist of more than two monomer units, even owing to the purification steps, can be prepared only with very great difficulty, and the economic investment can be justified only in the case of processes with very high quality demands on the product.
For instance, 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). However, the synthesis method leads to oligothiophenes which are present in the cationic form and hence in a conductive form and no longer in the neutral semiconductive form (EP 402 269, page 8, lines 28-29). These oligothiophenes are thus unusable for application in semiconductor electronics, since the oligothiophenes do conduct electrical current efficiently in the cationic form but do not have a semiconductor effect. It is possible to reduce cationic oligothiophenes, for example, by electrochemical or chemical reaction, but this is complicated and does not always lead to the desired result.
One alternative is the coupling of organolithium compounds with iron(III) salts, for example iron(III) chloride. This reaction affords generally undoped, i.e. neutral, oligothiophenes, but side reactions in this reaction also lead to products highly contaminated with iron and chlorine. Instead of iron(III) chloride, other iron(III) compounds, for example iron(III) acetylacetonate, have been proposed as coupling reagents (J. Am. Chem. Soc., 1993, 115, 12214). Owing to the relatively low reactivity of this coupling reagent, this variant, however, has the disadvantage that the reaction has to be performed at elevated temperature. The relatively high temperature frequently promotes side reactions, so that qualitatively high-value oligothiophenes are not obtainable even by intensive purifying operations (Chem. Mater., 1995, 7, 2235). A further method of preparing oligothiophenes described in the literature is the oxidative coupling by copper salts, especially by copper(II) chloride (Kagan, Heterocycles, 1983, 20, 1937). However, in the preparation of, for example, sexithiophene, it was found that the product, after purification by recrystallization, still contains chlorine and copper, of which at least the chlorine is present at least partly in chemically bound form to the oligothiophene and cannot be removed any further even by further complicated purification (Katz et al., Chem. Mater., 1995, 7, 2235). An improvement to this method is described in DE10248876 and is based on the presence of the oligolithium intermediate to be coupled in dissolved form before the addition of the catalyst.
Further processes are based on coupling reactions of Grignard compounds (JP 02 250 881) or organozinc compounds (U.S. Pat. No. 5,546,889) in the presence of nickel catalysts. In this case, for example proceeding from halogenated thiophenes, a portion of this compound is converted to the organometallic intermediate with the aid of magnesium or of an alkylmagnesium halide and then coupled to the unconverted portion by addition of a nickel catalyst. This coupling method has been described, inter alia, as the Kumada method (Kumada, Pure Appl. Chem, 1980, 52, 669-679) (Tamao, Sumitani, Mumada, J. Am. Chem. Soc., 1972, 94, 4374-4376). The coupling of two organometallic intermediates to one dihalogenated derivative, in which a trimer is formed, is considered to be a variation thereon.
However, what is common to all processes is that several synthesis steps are always necessary for the selective preparation of an oligomer proceeding from the corresponding thiophene base unit. At the same time, it is unimportant whether the monomer used, for example a terthiophene for the synthesis of a hexathiophene, has to be prepared in several stages, or else the hexathiophene is obtained by a multistage coupling of a thiophene. There is thus the need to be able to prepare oligomers directly from a monomer, as is the case for the polymerization of thiophenes to prepare polythiophenes.
In the polymerization of thiophenes, several monomer units are coupled to one another within one reaction stage. This usually forms polymers having mean molar masses greater than 10 000 g/mol. Differences in the products are made predominantly on the basis of their molecular weight, their distribution and the properties, especially with regard to their conductivity. With regard to the multitude of processes, reference is made to the description in the relevant sources (R. D. McCullough, Advanced Materials, 1998, 10(2), 93-116) (D. Fichon, Handbook of Oligo- and Polythiophenes, 1999, Wiley-VCH).
While electrochemical polymerizations and iron salt-supported polymerizations lead to already doped and hence conductive polymers and are therefore not amenable to use in semiconductor electronics without complicated purification, the methods described below are suitable for preparing the semiconductive polymers. In principle, the most important synthetic routes for the preparation of semiconductive thiophene polymers can be divided into four methods: the McCullough, Rieke, Stille and Suzuki methods. In all methods, polymers can be prepared with high regioregularity, i.e., in the case of unsymmetrically substituted thiophene derivatives, a head-to-tail coupling proceeds predominantly, for example a 2,5′-coupling of 3-hexylthiophene. While the Stille and Suzuki methods are, however, employed more commonly in the stepwise synthesis of oligomers, especially from different units (H. C. Starck, DE 10 353 094, 2005) (BASF, WO93/14079, 1993), the McCullough (EP 1 028 136 B1, U.S. Pat. No. 6,611,172, U.S. Pat. No. 247,420, WO 2005/014691, US 2006/0155105) and Rieke (U.S. Pat. No. 5,756,653) methods are those which are employed for the commercial preparation of polythiophenes in a single synthesis step.
What is common to all is the regioselective chain growth reaction, in which, proceeding from an organometallic compound (Sn, Mg, Zn) or a borane compound as a monomer with the aid of a catalyst (Nickel (e.g. Ni(dppp)Cl2), palladium (e.g. Pd(PPh3)4), a polymer is formed regioselectively. Differences are frequently made in the synthesis of the actual monomer, possible purification steps and purities of the monomers, the type of catalyst and the solvent used. In addition, the degree of regioselectivity serves as a distinguishing feature between the possible syntheses.
In the McCullough method, a regioselectively prepared Grignard compound is used as the monomer in the actual polymerization (X=halogen, R=substituent):
For the polymerization, in the Kumada method (cross-coupling metathesis reaction), the polymerization in a catalyst cycle is commenced with the aid of a nickel catalyst (preferably Ni(dppp)Cl2). In this case, the reaction conditions specified are −5° C. to 25° C. in the first publications up to polymerization under reflux conditions in recent publications. Apart from different reaction temperatures in some cases, this step in the polymerization is the same in all corresponding processes. For all processes, the same possibilities in the catalyst selection (for example alternatively Ni(dppe)Cl2) and in the solvent selection (for example THF, toluene, etc.) apply, provided that a homogeneous solution is obtained. What is likewise common to all processes is that exclusively batchwise processes are described.
Crucial differences are described in the preparation of the abovementioned Grignard compound. According to commonly known syntheses, it is possible to use alkylmagnesium halides (trans-metallization) or elemental magnesium (Grignard synthesis) in order to convert an initially charged dihalogen compound of the alkylthiophene (even with different halogens as X and X′) to the desired intermediate. Both methods have their advantages and disadvantages. In the case of synthesis with elemental magnesium, a removal of unconverted magnesium before the addition of the catalyst is recommended. At the same time, this is a heterogeneous mixture (“slurry”) and an activation of the magnesium additionally has to be effected by suitable measures (for example addition of Br2). Advantages are especially the price of magnesium compared to alkylmagnesium reagents and the avoidance of alkyl halides in the by-products. Advantages in the case of use of 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 from the methylmagnesium bromide used with preference in the Grignard stage. Methyl bromide is a substance which is gaseous above −4° C., is harmful to health, and can be removed from offgases with difficulty or only with a considerable level of technical complexity.
In addition to the methods, it is also possible to obtain the corresponding Grignard compound of the alkylthiophene by reacting the dihalogen compound of the alkylthiophene with magnesium and a small amount of alkyl halide, for example ethyl bromide (Khimiga Geterotsiklicheskikh Soedinenii, (4), 468-70; 1981).
The polymers are generally obtained in the necessary purity via Soxhlet extractions.
Interestingly, the prior art initially describes the polymers prepared as “normal” polymers of the particular thiophene unit. The polymers should thus not bear any end group other than H. The perception was based initially on an early perception with regard to the catalyst cycle present and lack of means of structural elucidation by means of NMR spectroscopy. Only more recent studies regarding the possible reaction mechanism (R. D. McCullough, Macromolecules, 2004, 37, 3526-3528 and Macromolecules, 2005, 38, 8649-8656) show that at least one end group of the polymer must be a halogen. For the second end group, it is assumed that a complex of nickel(II) and the polymer is initially present, and the complexed group is hydrolysed by the workup with methanol/water. This is certainly correct in the respect that the nickel catalyst must be present in equimolar ratio to the polymer. Otherwise, some polymer chains should bear a halide at both ends. In the course of these studies, the synthesis of end group-functionalized polymers was also combined with the actual polymerization, so that relatively easy access to these terminally functionalized polymers is enabled (R. D. McCullough, Macromolecules, 2005, 38, 10346-10352) (US 2005/0080219) (U.S. Pat. No. 6,602,974, 2003).
Other processes for the preparation of end-capped oligomers, in contrast, use staged reactions in which controlled chain formation results from the individual addition steps (DE 10 248 876 and DE 10 353 094).
While Koller (US 2005/0080219) in his patent assumes that the polymer prepared bears at least one end group other than H, McCullough in his patent describes a synthesis variation in which a base (e.g. LDA) and a metal dihalide (e.g. ZnCl2) have to be used in order that a polymer which bears a halogen atom as an end group can be prepared.
No application of the typical polymerization techniques for polythiophenes to a process for preparing oligomers, i.e. specifically low molecular weight polymers, can be found in the literature.
Proceeding from the prior art mentioned, it was an object of the present invention to provide a simplified process which enables the preparation of oligothiophenes with a defined mean chain length and a narrow molecular weight distribution. In particular, a method should be found which enables the preparation of low molecular weight polymers or oligomers in the chain length range from 2 to 20 monomer units with a very narrow molecular weight distribution without restrictions in the conversion or the need for purifications of possible intermediates. At the same time, the process should include advantages with regard to the space-time yield, handling, economy and ecology on the industrial scale.
The invention likewise provides a process of oligothiophenes comprising the steps of:
The invention likewise provides a process of oligothiophenes comprising the steps of:
In this process, the solution of at least one thiophene derivative having one leaving group and at least one thiophene derivative having two leaving groups is reacted in an equimolar amount 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 catalyst is subsequently metered in, which then enables the polymerization.
Surprisingly and advantageously, it has now been found that, in the case of use of a monomer mixture of a thiophene derivative having one leaving group and a thiophene derivative having two leaving groups, the molecular weight can be adjusted by a smaller amount of the catalyst in relation to the amount of the thiophene derivatives used compared to the sole polymerization of thiophene derivatives. In fact, nearly 100% catalyst efficiency from a statistical point of view is observed, such that the molecular weight and the number of repeat units in the chain can be adjusted via the ratio of [thiophene derivative having two leaving groups]/[catalyst]. What is particularly surprising here is that the mean molecular weight achieved in the case of use of 3-substituted thiophene derivatives having one and two leaving groups is very substantially independent of the amount of the thiophene derivative having one leaving group. An increase in the proportion of the thiophene derivative having one leaving group mentioned leads unexpectedly to a rise in one dimer component, as can be seen from
It is known from the prior art that, in the conventional preparation of polythiophenes, the catalyst is initially charged in different concentrations depending on the target molecular weight. For instance, amounts in the range of 1 to 0.5 mol % are usually used, based on the monomer used. In general, in the polymerization of thiophenes having two active leaving groups, polymers with mean molecular weights (Mn) in the range of 20 000 to 40 000 g/mol are then obtained. Taking account of the amount used, this indicates, viewed in statistical terms, effective utilization of the catalyst in the range of 60 to 80% of the amount used.
Surprisingly and advantageously, in contrast, the inventive reaction succeeds in lowering the molecular weights by the addition of thiophene monomers having only one leaving group. For example, even a proportion of 20% of 2-bromo-3-hexylthiophene in the monomer mixture reduces the mean molecular weight of the polymer from Mn=3040 g/mol to Mn=1850 g/mol with the same amount of catalyst (10 mol %) and the same procedure (see Examples 1 and 2). Viewed in statistical terms, this leads to the assumption that virtually 100% of the catalytic sites are active. This succeeds even in the case of use of relative low amounts of thiophene derivatives having one leaving group in the range of 10-20% of the amount of monomer used. In this case, narrow molecular weight distributions with a polydispersity index PDI of 1.1-1.7 are achieved.
In preferred embodiments of the process according to the invention, the reactants can be metered in differently. One possibility consists in preparing the polymerization-active monomer mixture from the thiophene groups provided with one or two leaving groups in the initial charge 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 polymerizing it in the batch.
A further conceivable variant is the mixing of the polymerization-active monomer mixture solution in the initial charge with the catalyst solution at low temperatures (approx. 15-25° C.) and subsequent polymerization by heating to polymerization temperature.
Also conceivable is the simultaneous metered addition of polymerization-active monomer mixture solution and catalyst solution and its rapid and complete mixing and subsequent heating.
In a preferred embodiment of the process according to the invention, the reaction is ended by adding a hydrolysing solvent to the polymerization solution, 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. Alternatively, purification can be effected in Soxhlet apparatus, in which case preference is given to using nonpolar solvents, for example hexane, as the extractant.
In a preferred embodiment of the invention, the at least one thiophene derivative having one leaving group is one of the general formula (1)
and
the at least one inventive thiophene derivative having two leaving groups is one of the general formula (2)
where
and
Especially preferably, R is CN or a straight chain, branched or cyclic alkyl having one or more, preferably 5 or more, more preferably 1 to 20 atoms, which are unsubstituted or mono- or polysubstituted by CN, where one or more nonadjacent CH2 groups may be replaced independently by —O—, —S—, —NH—, —NR′—, —SiR′R″—, —CO—, —COO—, —OCO—, —OCO—O—, —SO2—, —S—CO—, —CO—S—, —CY1═CY2 or —C≡C—, and in such a way that oxygen and/or sulphur atoms are not bonded directly to one another, and are likewise optionally replaced by aryl or heteroaryl preferably containing 1 to 30 carbon atoms, where
Terminal CH3 groups are understood to be CH2 groups in the sense of CH2—H.
Particularly preferred thiophene derivatives of the formula (1) and/or (2) are those in which
Aryl and heteroaryl preferably refer to a mono-, bi- or tricyclic aromatic or heteroaromatic group having up to 25 carbon atoms, likewise including fused ring systems which may optionally be substituted by one or more L groups where L may be an alkyl, alkoxy, alkylcarbonyl or alkoxycarbonyl group having 1 to 20 carbon atoms.
Particularly preferred aryl or heteroaryl groups are phenyl in which one or more CH groups have additionally been replaced by N, naphthalene, thiophene, thienothiophene, dithienothiophene, alkylfluorene and oxazole, each of which may be unsubstituted, monosubstituted or polysubstituted by L, where L is as defined above.
In a preferred embodiment of the process according to the invention, mixtures of two or more thiophene derivatives having one leaving group may be used.
In a preferred embodiment of the process according to the invention, mixtures of two or more thiophene derivatives having two leaving groups may be used.
The at least one thiophene derivative having one leaving group and the at least one thiophene derivative having two leaving groups are, in accordance with the invention, present in solution.
The organometallic compounds which are used in the process according to the invention are preferably organometallic tin compounds, for example tributyltin chloride, or zinc compounds, for example activated zinc (Zn*), or borane compounds, for example B(OMe)3 or B(OH)3, or magnesium compounds, more preferably organometallic magnesium compounds, more preferably Grignard compounds of the formula R—Mg—X
where
and
In a further preferred embodiment of the process according to the invention, instead of adding an organometallic compound, a metal or at least one alkyl halide with an elemental metal is provided, with whose aid the thiophene derivatives having one or two leaving groups can be converted to the polymerizable monomer mixture by providing a metal or at least one alkyl halide with the elemental metal. In this case, the metal can be added, for example, in the form of turnings, grains, particles or flakes, and can then be removed, for example, by filtration, or else provided to the reaction space in rigid form, for example by temporarily immersing wires, grilles, meshes or comparable materials into the reaction solution, or else in the form of a metal-equipped cartridge which can be flowed through in the interior or else as a fixed bed in a column in which the metal is present in sufficiently finely distributed form (for example in turnings) and is blanketed with solvent, in which case the thiophene derivatives having one or two leaving groups are converted as they flow through the cartridge or the column. Corresponding details for the continuous conduct of the reaction through columns and preferred apparatus can be taken from the patent DE 10 304 006 B3 or else the publication of Reimschüssel, Journal of Organic Chemistry, 1960, 25, 2256-7, whose embodiments or preferred embodiments for the preparation of the Grignard reagents also apply to the process according to the invention described here. Alternatively, the continuous conversion to the Grignard reagent can also be effected with high turbulence in tubular reactors equipped with static mixers, in which case the liquid column is subjected to pulses, as is known from the patents DD 260 276, DD 260 277 and DD 260 278. The embodiments for the preparation of the Grignard reagents preferred therein also apply to the process according to the invention described here. The metals are preferably magnesium or zinc, more preferably magnesium.
The at least one alkyl halide which is used in one of the formula R—X
where
R is alkyl and especially C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12-alkyl, more preferably C2, C3, C4, C5, C6, C7, C8-alkyl, most preferably C2-alkyl,
and
X is halogen, more preferably Cl, Br or I and especially preferably Br.
The alkyl halide with the elemental metal is particularly an ethyl halide and magnesium or zinc, more preferably ethyl bromide with magnesium.
The alkyl halide is preferably used in catalytic amounts, i.e. >0 to 0.5, preferably 0.001 to 0.1 and more preferably 0.01 to 0.05 equivalent in relation 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 cited in, for example, R. D. McCullough, Adv. Mater., 1998, 10(2), 93-116 and the references cited there, for example palladium or nickel catalysts, for example bis(triphenylphosphino)palladium dichloride (Pd(PPh3)Cl2), palladium(II) acetate (Pd(OAc)2) or tetrakis(triphenylphosphine)palladium (Pd(PPh3)4) or tetrakis(triphenyl-phosphine)nickel (Ni(PPh3)4), nickel(II) acetylacetonate Ni(acac)2, dichloro(2,2′-bipyridine)nickel, dibromobis(triphenylphosphine)nickel (Ni(PPh3)2Br2), and nickel and palladium catalysts having ligands, for example tri-tert-butylphosphine, triadamantylphosphine, 1,3-bis(2,4,6-trimethylphenyl)imidazolidinium chloride, 1,3-bis(2,6-diisopropylphenyl)imidazolidinium chloride or 1,3-diadamantylimidazolidinium chloride, more preferably nickel catalysts and especially preferably bis(diphenylphosphino)propane nickel dichloride (Ni(dppp)Cl2) or bis(diphenyl-phosphino)ethane nickel dichloride Ni(dppe)Cl2. Likewise conceivable are those catalysts of palladium and nickel whose ligands consist of combinations of those mentioned above. In addition, in a preferred embodiment of the invention, the catalyst can be prepared and reacted with the polymerization-active monomer mixture “in situ”.
In a preferred embodiment of the process according to the invention, mixtures of two or more catalysts may be used.
According to the invention, the at least one catalyst is present in solution during the polymerization. The thiophene derivatives having one or two leaving groups to be used in accordance with the invention and also the corresponding catalysts are typically commercially available or can be prepared by methods familiar to those skilled in the art.
Useful organic solvents for use in the process according to the invention include in principle all solvents or solvent mixtures which do not react under polymerization conditions with organometallic compounds, for example alkylmagnesium bromides or further organometallic compounds listed in this application. These are generally compounds which do not have any halogen atoms or any hydrogen atoms reactive toward organometallic compounds under polymerization conditions.
Suitable solvents are, for example, aliphatic hydrocarbons, for example alkanes, especially pentane, hexane, cyclohexane or heptane, unsubstituted or substituted aromatic hydrocarbons, for example benzene, toluene and xylenes, and compounds containing ether groups, for example diethyl ether, tert-butyl methyl ether, dibutyl ether, amyl ether, dioxane and tetrahydrofuran (THF), and also solvent mixtures of the aforementioned groups, for example a mixture of THF and toluene. In the process according to the invention, preference is given to using solvents which contain ether groups. Very particular preference is given to tetrahydrofuran. However, it is also possible to use, as solvents, mixtures of two or more of these solvents. For example, it is possible to use mixtures of tetrahydrofuran, the solvent used with preference, and alkanes, e.g. hexane (for example present in commercially available solutions of starting materials such as organometallic compounds). What is important in the context of the invention is that the solvent, the solvents or mixtures thereof are selected such that, before addition of the catalyst, the thiophene derivatives used or the polymerization-active monomers are present in dissolved form. For the workup, halogenated aliphatic hydrocarbons such as methylene chloride and chloroform are also suitable.
In a particularly preferred embodiment of the process according to the invention, 3-alkylthiophene is oligomerized by the regioselective reaction of a solution of mono- and dihalogenated 3-alkylthiophene using a Grignard reagent or by temporarily providing Mg or Mg in the presence of an alkyl halide to give a corresponding polymerization-active organomagnesium bromide compound and the subsequent polymerization thereof in the presence of a nickel catalyst. Especially preferred is the reaction of 2-bromo-3-hexylthiophene and 2,5-dibromo-3-hexylthiophene in THF solution with equimolar amounts of ethylmagnesium bromide or with magnesium or with magnesium in the presence of ethyl bromide and the subsequent polymerization thereof in the presence of Ni(dppp)Cl2.
It has been found to be useful to use mono- and dibromo-3-hexylthiophenes in a ratio of 0.2 to 4 and in the case of use of Ni(dppp)Cl2 catalyst concentrations of 0.1 to 20 mol % based on the amount of monomers used. Particularly suitable monomer ratios (thiophene derivative having one leaving group to thiophene derivative having two leaving groups) are in the range of 0 to 1, especially in the range of 0 to 0.8, more preferably in the range of 0.1 to 0.4.
The amount of the catalyst added depends on the mean molecular weight (Mn) to be achieved and is typically in the range of 0.1-20 mol %, preferably in the range of 10-20 mol %, more preferably in the range of 10-15 mol %, based in each case on the amount of the thiophene derivative having two leaving groups used. The process according to the invention serves to prepare oligomers in the chain length range of 2 to 20 monomer units, preferably of 2 to 10, more preferably of 4 to 8, and of 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. It is notable in that the mean molecular weight, as a result of the use of a polymerization-active monomer mixture composed of at least one thiophene derivative having one leaving group and at least one thiophene derivative having two leaving groups, can be adjusted in a controlled manner in the case of addition of a corresponding amount of at least one catalyst. The oligomer prepared by the process is additionally notable, according to the thiophene derivatives used, by the presence of one or two leaving groups at the chain ends, which can later serve as substitution sites for functionalizations or end-capping reactions. The reaction of the thiophene derivatives having one or two leaving groups to give the polymerization-active Grignard intermediate using alkylmagnesium bromides or temporary provision of magnesium or with magnesium in the presence of ethyl bromide and the directly subsequent polymerization by the addition of the catalyst makes it possible to obtain oligomers by a direct route without complicated purifications of any intermediates being necessary. This increases the economic attractiveness of the process considerably, and also facilitates industrial performance.
Temperatures suitable for the performance of the process according to the invention are in the range of +20 to +200° C., preferably in the range of +80 to +160° C. and especially +100 to +140° C. The polymerization is performed preferably at standard pressure and under reflux, but, owing to the low boiling points of the solvents used, a reaction at elevated pressures is also possible, preferably at 1-30 bar, especially at 2-8 bar and more preferably in the range of 4-7 bar.
In a particularly preferred embodiment, the process according to the invention is performed continuously. In this, the metered addition and the preparation of the reactants can be effected differently.
Possible process steps to be conducted continuously are
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) having 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 an appropriate 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 addition of the at least one catalyst to the polymerization-active monomer mixture and mixing at room temperature or at lower temperature (approx. 15-25° C.) in a second module subsequently results in the continuous polymerization in a third module at reaction temperature and under controlled conditions. Optionally, in a fourth module, further—identical or different—monomer can be metered in. However, preference is given to conveying two dosage streams, in each case one for the polymerization-active monomer solution optionally to be prepared continuously and one for the catalyst solution. The reactant streams are mixed rapidly by a mixer.
For instance, the continuous polymerization, in a preferred embodiment using a mixer unit and a delay zone, is performed under pressure of 1-30 bar, preferably of 2-8 bar, more preferably in the range of 4-7 bar, and temperatures of +20 to +200° C., preferably in the range of +80 to +160° C. and especially at +100 to +140° C.
The metering rates depend primarily on the residence times desired and conversions to be achieved.
Typical residence times are in the range of 5 min to 120 min. The residence time is preferably between 10 and 40 min, more preferably in the range of 20-40 min.
It has been found in this context that the use of microreaction technology (μ-reaction technology) using microreactors is particularly advantageous. The term “microreactor” used represents microstructured, preferably continuous reactors, which are known under the name microreactor, minireactor, micro-heat exchanger, minimixer or micromixer. Examples are microreactors, micro-heat exchangers, T and Y mixers and also micromixers from a wide variety of different companies (e.g. Ehrfeld Mikrotechnik BTS GmbH, Institut für Mikrotechnik Mainz GmbH, Siemens AG, CPC-Cellulare Process Chemistry Systems GmbH), and others as generally known to those skilled in the art, and a “microreactor” in the context of the present invention typically has characteristic/determining internal dimensions of up to 1 mm and static mixing internals. A preferred microreactor for the process according to the invention has internal dimensions of 100 μm to 1 mm.
As a result of the use of a micromixer (μ-mixer), the reaction solutions are mixed with one another very rapidly, as a result of which a broadening of the molecular weight distribution owing to possible radial concentration gradients is prevented. Furthermore, μ-reaction technology in a microreactor (μ-reactor) enables a usually significantly narrower residence time distribution than in conventional continuous apparatus, which likewise prevents broadening of the molecular weight distribution.
In all cases, the polymerization is started by the increase in the temperature. In this context too, one possibility in particular is to use a micro-heat exchanger (μ-heat exchanger), which enables rapid and controlled temperature increase of the reaction solution, which is advantageous for a narrow molecular weight distribution.
For the increase in the conversion, the reaction solution is conveyed through a delay zone and converted under pressure and at higher temperatures than described to date in the literature.
The process according to the invention features in particular the controlled establishment of a desired mean chain length, and also the preparation of products having a narrow molecular weight distribution. In addition, the continuous conduction of the polymerization enables a significant increase in the space-time yield.
The inventive use of the at least one thiophene derivative having one leaving group in addition to the at least one thiophene derivative having two leaving groups allows, with regard to the desired mean chain length or mean molecular weights, the necessary amounts of catalyst to be reduced very significantly or the mean molecular weights for a given amount of catalyst to be lowered significantly.
The invention likewise provides the oligothiophenes obtainable by the process according to the invention.
The invention will be illustrated in detail hereinafter with reference to the figures and examples which follow, but without restricting it to them.
The figure shows:
In the low molecular weight range, the chromatograms exhibit a peak attributable to the dimer 3-hexylthiophene.
In all examples, the syntheses are performed under protective gas.
2,5-Dibromo-3-hexylthiophene (4 mmol) was initially charged in 20 ml of THF under protective gas in a 50 ml three-neck flask equipped with a reflux condenser, nitrogen connection and thermometer, and heated under reflux. After the addition of 1 M solution of methylmagnesium bromide in hexane, (4 ml, 4 mmol), the reaction solution was heated under reflux for one hour. Subsequently, 0 4 mmol of Ni(dppp)Cl2 as a catalyst was added to the reaction solution which was heated under reflux for a further 2 hours. To end the reaction, 40 ml of methanol were added to the solution. The product precipitated in methanol was filtered off, washed with methanol and then taken up in THF. 676 mg of product (yield approx. 80%) were obtained. GPC analysis: Mw=6990 g/mol, Mn=3040 g/mol, PDI=2.3 (measured against polystyrene standards, THF as the eluent (0.6 ml/min)).
2,5-Dibromo-3-hexylthiophene (3.2 mmol) and 2-bromo-3-hexylthiophene (0.8 mmol) was initially charged in 20 ml of THF under protective gas in a 50 ml three-neck flask equipped with a reflux condenser, nitrogen connection and thermometer, and heated under reflux. After the addition of 1 M solution of ethylmagnesium bromide in hexane, (4 ml, 4 mmol), the reaction solution was heated under reflux for one hour. Subsequently, 0.4 mmol of Ni(dppp)Cl2 as a catalyst was added to the reaction solution which was heated under reflux for a further 2 hours. To end the reaction, 40 ml of methanol were added to the solution. The product precipitated in methanol was filtered off, washed with methanol and then taken up in THF. 543 mg of product (yield approx. 75%) were obtained. GPC analysis: Mw=2450 g/mol, Mn=1850 g/mol, PDI=1.3.
2,5-Dibromo-3-hexylthiophene (4 mmol) was initially charged in 20 ml of THF under protective gas in a 50 ml three-neck flask equipped with a reflux condenser, nitrogen connection and thermometer, and heated under reflux. After the addition of 1 M solution of ethylmagnesium bromide in hexane, (4 ml, 4 mmol), the reaction solution was heated under reflux for one hour. The solution was then cooled to approx. 15° C. Subsequently, 0 4 mmol of Ni(dppp)Cl2 as a catalyst was added to the reaction solution. The reaction mixture was subsequently pumped through a reaction capillary continuously at 100° C. and under 5 bar. The residence time was 40 min. After about 4 residence times, a sample was taken. The product prepared was precipitated in methanol, removed, washed with methanol and taken up in THF. The conversion was 75-80%. GPC analysis: Mw=7760 g/mol, Mn=2700 g/mol, PDI=2.8.
2,5-Dibromo-3-hexylthiophene (3.6 mmol) and 2-bromo-3-hexylthiophene (0.4 mmol) was initially charged in 30 ml of THF under protective gas in a 50 ml three-neck flask equipped with a reflux condenser, nitrogen connection and thermometer, and heated under reflux. After the addition of 1 M solution of ethylmagnesium bromide in hexane, (4 ml, 4 mmol), the reaction solution was heated under reflux for one hour. The solution was then cooled to approx. 15° C. Subsequently, 0.4 mmol of Ni(dppp)Cl2 as a catalyst was added to the reaction solution. The reaction mixture was subsequently pumped through a reaction capillary continuously at 120° C. and under 5 bar. The residence time was 40 min After about 4 residence times, a sample was taken. The product prepared was precipitated in methanol, removed, washed with methanol and taken up in THF. The conversion was 75-80%. GPC analysis: Mw=2380 g/mol, Mn=1420 g/mol, PDI=1.7.
| Number | Date | Country | Kind |
|---|---|---|---|
| 102006061967.6 | Dec 2006 | DE | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/EP2007/010711 | 12/8/2007 | WO | 00 | 7/8/2009 |
