EP2328950A1

EP2328950A1 - Novel polymers having low polydispersity

Info

Publication number: EP2328950A1
Application number: EP09778281A
Authority: EP
Inventors: Frank Egon Meyer; Niels Schulte; Willi Kreuder
Original assignee: Merck Patent GmbH
Current assignee: Merck Patent GmbH
Priority date: 2008-09-25
Filing date: 2009-09-02
Publication date: 2011-06-08
Also published as: CN102076737A; US20110095280A1; JP2012503684A; DE102008049037A1; JP5710484B2; KR20110073387A; KR101660991B1; WO2010034393A1

Abstract

The present invention relates to novel polymers, comprising one or more recurrent units selected from the group consisting of spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene and dihydrobenzooxepine derivatives and having low polydispersity and a high molecular weight. The invention further relates to a method for the production thereof, to blends and to formulations comprising said polymers and to the use of said polymers in electronic devices, particularly in organic light emitting diodes, so-called OLEDs (OLED = Organic Light Emitting Diode).

Description

New polymers with low polydispersity

The present invention relates to novel polymers containing one or more repeating units selected from spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene and dihydrobenzooxepine derivatives and having low polydispersity and high molecular weight their preparation, blend and formulations containing these polymers and the use of these polymers in electronic devices, in particular in organic light emitting diodes, so-called OLEDs (OLED = Organic Light Emitting Diode). The polymers according to the invention show a longer service life, especially when used in OLEDs.

Conjugated polymers have long been studied intensively as promising materials in OLEDs. OLEDs that have polymers as organic materials are often referred to as PLEDs (PLED = Polymer Light Emitting Diode). Their simple production promises a cost-effective production of corresponding LEDs.

Since PLEDs usually consist of only one light-emitting layer, polymers are required which can combine as many functions as possible (charge injection, charge transport, recombination) of an OLED. In order to meet these requirements, different monomers are used during the polymerization, which take over the corresponding functions. Thus, for the production of all three emission colors, it is generally necessary to polymerize certain comonomers into the corresponding polymers (cf., for example, WO 00/046321 A1, WO 03/020790 A2 and WO 02/077060 A1). For example, starting from a blue emitting base polymer ("backbone") is the

Generation of the other two primary colors red and green possible. As polymers for full-color display elements, various classes of materials have already been proposed or developed, for example poly-para-phenylene (PPP) ₁ . Thus, for example, poly-fluorene derivatives (as disclosed, for example, in EP 0842208, WO 99/54385, WO 00/22027, WO 00/22026 and WO 00/46321), poly-spirobifluorene derivatives (such as for example in EP 0707020, EP 0894107 and WO 03/020790), poly-indenofluorene derivatives, poly-phenanthrene derivatives and poly-dihydro-phenanthrene derivatives (as disclosed, for example, in WO 2005/014689) , It is also possible to use a combination of two or more of these monomer units, as described for example in WO 02/077060.

The most important criteria of an OLED are efficiency, color and

Lifespan. Since these properties are largely determined by the polymer (s) used, improvements of these materials over those known in the art are reported

Materials still desired.

Starting from the known state of the art, it can be regarded as one of the objects of the present invention to provide novel polymers with improved properties, in particular a longer service life.

Surprisingly, it has now been found that polymers containing one or more repeat units selected from spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, dihydropyrene,

Tetrahydropyrene and Dihydrobenzooxepin derivatives containing and have a low polydispersity, ie a narrow molecular weight distribution, compared to the same materials having a broad molecular weight distribution, have a significantly higher life. The present invention thus relates to polymers which contain at least 1 to 100 mol% of one or more repeating units selected from spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene and dihydrobenzooxepine derivatives, which are characterized in that it has a polydispersity D (= MwZM _n ) of <2.0 and molecular weights M _w of ≥ 100,000 g / mol (determined by GPC against

Polystyrene standards).

The polydispersity D is understood to mean the quotient of the weight average molecular weight M _w and the number average molecular weight M _n : D = M _w / M _n .

Both the weight and the number average molecular weight of the polymers of the invention are determined by gel permeation chromatography (GPC).

Preferably, the polymers of the invention have a

Polydispersity of ≦ 1, 9, and more preferably ≦ 1.8.

In addition, the polymers according to the invention preferably have molecular weights M _w of ≥ 200,000 g / mol and more preferably of> 300,000 g / mol.

Preference is given to spirobifluorene derivatives of the formula (I):

- A - wherein V = C, Si or Ge, preferably C;

Particularly preferred are 9,9'-spirobifluorene derivatives of the formula (Ia):

Preferred indenofluorene derivatives are both trans-indenofluorene derivatives of the formula (II) and cis-indenofluorene derivatives of the formula (III):

Also preferred are phenanthrene derivatives of the formula (IV) and 9,10-dihydrophenanthrene derivatives of the formula (V):

Also preferred are 4,5-dihydropyrene derivatives of the formula (VI) and 4,5,9,10-tetrahydropyrene derivatives of the formula (VII):

wherein W = CR ₂ , O, S or Se, preferably CR ₂ .

Particularly preferred are 4,5-dihydropyrene derivatives of the formula (VIa) and 4,5,9,10-tetrahydropyrene derivatives of the formula (VIIa):

Also preferred are 5,7-dihydrodibenzooxepin derivatives of the formula ( ^v "):

wherein W = CR ₂ , O, S or Se, preferably CR ₂ .

Particularly preferred are 5,7-dihydrodibenzooxepin derivatives of the formula (Villa):

(Villa)

The various formulas (I) to (VIII) and (Ia), (VIa) to (Villa) can also be substituted at the free positions by one or more substituents R ¹ .

R and R ¹ are the same or different at each occurrence H, a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 carbon atoms, in which also one or more non-adjacent C atoms by O, S, CR ² = CR ² , C≡C, CO ₁ O-CO, CO-O or O-CO-O may be replaced, wherein also one or more H atoms may be replaced by fluorine, an aryl or aryloxy group having 5 to 40 C. -Atomen, in which also one or more C atoms may be replaced by O, S or N, which may also be substituted by one or more non-aromatic radicals R ¹ , or F, CN, N (R ² ) ₂ or B (R ² ) ₂ ; and

R ² is the same or different at each occurrence H, a straight-chain, branched or cyclic alkyl chain having 1 to 22 carbon atoms, in which one or more non-adjacent C atoms by O, S, CO, O-CO, CO- O or O-CO-O may be replaced, it also being possible for one or more H atoms to be replaced by fluorine, or an optionally substituted aryl group having 5 to 40 C atoms, in which one or more C atoms are also replaced by O, S or N can be replaced. Preferred alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl , n-heptyl, cycloheptyl, n-octyl, cyclooctyl, dodecanyl, trifluoromethyl, perfluoro-n-butyl, 2,2,2-trifluoroethyl, perfluorooctyl and perfluorohexyl.

Preferred alkenyl groups are ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl and cyclooctenyl.

Preferred alkynyl groups are ethynyl, propynyl, butynyl, pentynyl, hexynyl and octynyl.

Preferred alkoxy groups are methoxy, ethoxy, 2-methoxyethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2-methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy and n-octoxy.

Preferred aryl groups are phenyl, biphenyl, triphenyl, [i Naphthyl, anthracene, binaphthyl, phenanthrene, dihydrophenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene and spirobifluorene.

Preferred heteroaryl groups are 5-membered rings such as e.g. pyrrole,

Pyrazole, imidazole, 1, 2,3-triazole, 1, 2,4-triazole, tetrazole, furan, thiophene, selenophene, oxazole, isoxazole, 1, 2-thiazole, 1, 3-thiazole, 1, 2,3- Oxadiazole, 1, 2,4-oxadiazole, 1, 2,5-oxadiazole, 1, 3,4-oxadiazole, 1, 2,3-thiadiazole, 1, 2,4-thiadiazole, 1, 2,5-thiadiazole, 1, 3,4-thiadiazole, 6-membered rings such as pyridine, pyridazine, pyrimidine, pyrazine, 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,3-triazine, 1, 2, 4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensed groups such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, Pyridimidazole, pyrazine imidazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7, 8-quinoline, benzoisoquinoline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, Dibenzothiophene, benzothiadiazothiophene or combinations of these groups.

The aryl and heteroaryl groups may also be substituted by alkyl, alkoxy, thioalkyl, fluoro, fluoroalkyl or other aryl or heteroaryl groups.

In a preferred embodiment, the polymer according to the invention contains 10 to 99 mol%, and particularly preferably 30 to 98 mol%, of one or more structural units selected from the formulas (I) to (VIII).

The polymers according to the invention are conjugated, partially conjugated or non-conjugated polymers. However, preferred are conjugated and partially conjugated polymers, more preferably conjugated polymers.

Conjugated polymers in the context of the present application are polymers which contain in the main chain mainly sp ² -hybridized carbon atoms, which may also be replaced by corresponding heteroatoms. This means alternating in the simplest case

Presence of double and single bonds in the main chain. Mainly, of course, suggests that naturally occurring defects that lead to conjugation disruptions do not invalidate the term "conjugated polymer". Furthermore, in this application text also For example, arylamine units and / or certain heterocycles (ie conjugation via N, O or S atoms) and / or organometallic complexes (ie conjugation via the metal atom) are referred to as conjugated in the main chain. In contrast, units such as simple alkyl bridges, (thio) ether, ester, amide or imide linkages are clearly defined as non-conjugated segments. By a partially conjugated polymer is meant a polymer in which longer conjugated portions in the main chain are interrupted by non-conjugated portions or which contain longer conjugated portions in the side chains of a non-conjugated polymer in the main chain.

The polymers according to the invention are either homopolymers selected from structural units of the formulas (I) to (VIII) or

Copolymers. The polymers according to the invention can be linear, branched or crosslinked.

The copolymers according to the invention may have random, alternating or block-like structures or alternatively have several of these structures in turn. How copolymers having block-like structures can be obtained and which further structural elements are particularly preferred for this purpose are described in detail, for example, in WO 2005/014688 A2. It should also be emphasized at this point that the polymer, in addition to linear, can also have dendritic structures.

The polymers of the invention may in addition to one or more

Structural units of the formulas (I) to (VIII) contain further structural elements. These include those as disclosed in WO 02/077060 A1 and DE 10337346 A1 and are listed extensively. The further structural units can come, for example, from the following classes: Group 1: units containing the hole injection and / or

-transport properties of the polymers influence;

Group 2: units which influence the electron injection and / or transport properties of the polymers;

Group 3: units comprising combinations of Group 1 and Group 2 individual units;

Group 4: units which change the emission characteristics to the extent that electrophosphorescence can be obtained instead of electro-fluorescence;

Group 5: units that improve the transition from the so-called singlet to triplet state;

Group 6: Units which have the morphology and / or the

Influence emission color of the resulting polymers;

Group 7: units that emit light.

Preferred polymers of this invention are those in which at least one structural element has charge transport properties, i. contain the units from groups 1 and / or 2.

Structural elements from group 1 which have hole transport properties are, for example, triarylamine, benzidine, tetraaryl-para-phenylenediamine, triarylphosphine, phenothiazine, phenoxazine, dihydrophenazine, thianthrene, dibenzo-para-dioxin, phenoxathiin, Carbazole, azulene, thiophene, pyrrole and furan derivatives and other O-, S- or N-containing heterocycles with high-lying HOMO (HOMO = highest occupied molecular orbital). Preferably, these arylamines and heterocycles lead to a HOMO in the polymer of greater than -5.8 eV (at vacuum level), more preferably greater than -5.5 eV.

Structural elements from group 2 which have electron transport properties are, for example, pyridine, pyrimidine, pyridazine, pyrazine, oxadiazole, quinoline, quinoxaline and phenazine derivatives, but also triarylboranes and further O, S or N-containing heterocycles with low lying LUMO (LUMO = lowest unoccupied molecular orbital). Preferably, these units in the polymer result in a LUMO of less than -1.5 eV (vs. vacuum level), more preferably less than -2.0 eV.

It may be preferred if in the polymers of the invention

Group 3 units are included in which structures that increase hole mobility and which increase electron mobility (that is, units from groups 1 and 2) are directly bound together. Some of these units can serve as emitters and move the

Emission color to the green, yellow or red. Their use is thus suitable, for example, for the production of other emission colors from originally blue-emitting polymers.

Structural units according to group 4 are those which can emit light from the triplet state even at room temperature with high efficiency, ie show electrophosphorescence instead of electrofluorescence, which frequently causes an increase in energy efficiency. For this purpose, compounds which are heavy atoms with a first

Ordinal number of more than 36 included. Preference is given to compounds which contain d- or f-transition metals which fulfill the abovementioned condition. Particular preference is given here to corresponding structural units which contain elements of group 8 to 10 (Ru, Os, Rh, Ir ₁ Pd, Pt).

As structural units for the polymers of the invention come here z. B. various complexes in question, as described for example in WO 02/068435 A1, DE 10116962 A1, EP 1239526 A2 and DE 10238903 A1. Corresponding monomers are described in WO 02/068435 A1 and in DE 10350606 A1.

Structural elements of group 5 are those which are the transition from the

Improve singlet to triplet state and which, used in support of the group 4 structural elements, improve the phosphorescence properties of these structural elements. In particular, carbazole and bridged carbazole dimer units are suitable for this purpose, as described in DE 10304819 A1 and DE 10328627 A1. Also suitable for this purpose are ketones, phosphine oxides, sulfoxides and similar compounds, as described in DE 10349033 A1.

Group 6 structural elements which influence the morphology and / or the emission color of the polymers are, besides those mentioned above, those which have at least one further aromatic or another conjugated structure which does not fall under the abovementioned groups, ie which has little charge carrier mobilities which are not organometallic complexes or have no effect on the singlet-triplet transition. Such structural elements may affect the morphology and / or the emission color of the resulting polymers. Depending on the unit, they can therefore also be used as emitters. Preference is given to aromatic structures having 6 to 40 carbon atoms or else toluenes, stilbene or bisstyrylarylene derivatives which may each be substituted by one or more radicals R ¹ .

Particularly preferred is the incorporation of 1, 4-phenylene, 1, 4-naphthlenylene, 1, 4 or 9,10-anthrylene, 1, 6, 2,7- or 4,9-pyrenylene , 3,9- or 3,10-perylenylene, 4,4'-biphenylylene, 4,4 "-terphenyl, 4,4'-bi- _{1 1-} naphthylylene, 4,4'-tolanylene , 4,4'-stilbenylene or 4,4 "-bityryl-arylene derivatives. Group 7 structural elements that emit light are preferably units that emit blue, green, or red.

As blue-emitting units, units are generally suitable, which are generally used as a polymer backbone. These are generally those having at least one aromatic or other conjugated structure, but not the emission color in the

Green or move to red.

Preferred are aromatic structures having 4 to 40 carbon atoms, but also stilbene and tolane derivatives and bis (styryl) arylene derivatives. These are, for example, the following structural elements which may be substituted or unsubstituted: 1, 4-phenylene, 1, 4-naphthylene, 1, 4 or

9,10-Anthracenylene, 2,7 or 3,6-phenanthrenylene, 4,4'-biphenylylene, 4,4 "-terphenyl, 4,4'-bi-1, 1'-naphthylylene, 4,4'-stilbene derivatives, 9,10-dihydropyrene derivatives, 4,5,9,10-tetrahydropyrene derivatives (for example according to EP-A-699699), fluorene derivatives (for example according to EP-A-0 842 208, WO 99 / 54385, WO 00/22027, WO 00/22026, WO 00/46321), spirobifluorene derivatives (for example according to EP-AO 707 020, EP-A-0 894 107, WO 03/020790, WO 02/077060), 5 , 7-Dihydrodibenzoxepinderivate, cis and trans Indenofluorenderivate (eg, according to GB 0226010 and EP 03014042) and 9,10-Dihydrophenanthrenderivate (eg according to DE 10337346) .Besides these classes, for example, the so-called ladder PPPs ("ladder PPPs" = LPPP) (eg according to WO 92/18552), but also ansa structures containing PPPs (eg according to EP-A-690086) Also bis (styryl) arylene Derivatives that are not electron-rich can be used for this purpose.

It may also be preferred if more than one such blue-emitting structural unit is used in the polymer according to the invention. If the polymer according to the invention contains green-emitting structural units, preference is given to structural units which have at least one aromatic or other conjugated structure and shift the emission color into the green. Preferred structures for green emitting units are selected from the groups of the electron-rich bis-styrylarylenes and derivatives of these structures.

Further preferred green-emitting structural units are selected from the groups of the benzothiadiazoles and corresponding oxygen derivatives, the quinoxalines, the phenothiazines, the phenoxazines, the dihydrophenazines, the bis (thiophenyl) arylenes, the oligo (thiophenylenes) and the phenazines. It is also permissible that instead of a green-emitting structural unit several different such units are used, in which case the total proportion of green-emitting units is not more than 20 mol%, preferably not more than 10 mol% and more preferably not more than 3 mol%.

As red-emitting structural units are preferably units in

Question, which have at least one aromatic or other conjugated structure and shift the emission color to the red. Preferred structures for red emitting moieties are those in which electron-rich moieties, such as thiophene, are combined with green-emitting electron-deficient moieties, such as quinoxaline or benzothiadiazole. Other preferred red-emitting moieties are systems of at least four fused aromatic moieties, such as rubrene, pentacene or perylenes, which are preferably substituted, or preferably conjugated push-pull systems (systems substituted with donor and acceptor substituents) or systems such as Squarins or quinacridones, which are preferably substituted. It is also permissible for a plurality of such units to be used instead of a red-emitting unit, in which case the total proportion of the red-emitting units is not more than 10 mol%, preferably at most 5 mol% and particularly preferably at most 1 mol%.

In principle, units which emit light from the triplet state, that is to say electrophosphorescence instead of electrofluorescence, are also suitable as blue, green and red emitting structural units, which frequently leads to an increase in energy efficiency. These units are referred to below as the triplet emitter. The use of such metal complexes in low molecular weight OLEDs is described, for example, in M.A. Baldo et al. {Appl. Phys. Lett. 1999, 75, 4-6).

• For this purpose, compounds that are heavy atoms, d. H. Atoms from the periodic table of elements with an atomic number greater than 36, included.

• Particularly suitable for this purpose are compounds containing d and f transition metals, which are the o. Fulfill condition. Very particular preference is given here to corresponding structural units which contain elements of group 8 to 10 (i.e., Ru, Os, Rh, Ir, Pd, Pt).

As structural units for the polymers according to the invention are e.g. various complexes in question, which, for example, in WO 02/068435, DE 10116962 A1, EP 1239526 and DE 10238903

A1 are described.

Corresponding compounds are described in WO 02/068435.

The colors of the complexes are determined primarily by the metal used, by the exact ligand structure and by the substituents on the ligand. Both green and red emitting complexes are known. For example, an unsubstituted tris (phenylpyridyl) iridium (III) emits green light, while electron-donating substituents in the para position to the coordinating carbon atom (e.g. Diarylamino substituents) shift the emission to orange-red. Furthermore, derivatives of this complex with varied ligand structure are known, which lead directly (without further substitutions) to orange or deep red emission. Examples of such ligands are 2-phenylisoquinoline, 2-benzothiophenylpyridine or 2-naphthylpyridine.

Blue-emitting complexes are obtained, for example, by substituting the tris (phenyl-pyridyl) -iridium (III) base with electron-withdrawing substituents such as multiple fluoro and / or cyano groups.

Preferred fluorescent emitters of the present invention are selected from the class of monostyrylamines, distyrylamines, tristyrylamines, tetrastyrylamines, and the arylamines, each substituted with a fluoro radical. By a monostyrylamine is meant a compound containing a styryl group and at least one amine, which is preferably aromatic. By a distyrylamine is meant a compound containing two styryl groups and at least one amine, which is preferably aromatic. By a tristyrylamine is meant a compound containing three styryl groups and at least one amine, which is preferably aromatic. By a tetrastyrylamine is meant a compound containing four styryl groups and at least one amine, which is preferably aromatic. An arylamine or an aromatic amine in the context of the present invention is understood as meaning a compound which contains three aromatic or heteroaromatic ring systems bonded directly to the nitrogen, of which at least one condensed ring system having at least 14 aromatic ring atoms is preferred. The styryl groups are particularly preferably stilbenes, which may also be further substituted on the double bond or on the aromatic. Examples of such compounds are substituted or unsubstituted tristilbeneamines or others

Compounds which, for example, in WO 06/000388, the WO 06/058737, WO 06/000389, DE 102005058543 A1 and DE 102006015183 A1 are described. Furthermore, compounds according to WO 06/122630 and according to DE 102006025846 A1 are preferred as emitters.

A phosphorescent emitter compound is preferably selected from the class of metal complexes containing at least one element of atomic number greater than 20, preferably greater than 38 and less than 84, particularly preferably greater than 56 and less than 80. Preference is given to using metal complexes ^{ι υ} , the copper, molybdenum, tungsten, Rhenium, ruthenium,

Osmium, rhodium, iridium, palladium, platinum, silver, gold or europium, in particular iridium. Generally suitable for this purpose are phosphorescent materials, as used in the prior art 5.

By using several different structural elements, properties such as solubility, solid phase morphology, color, charge injection and transport properties, temperature stability, electro-optical characteristics, etc. can be adjusted.

The necessary solubility of the polymers is ensured above all by the substituents on the various repeat units. 5

The polymers according to the invention are generally prepared by polycondensation of one or more types of monomer of which at least one monomer in the polymer results in structural units O selected from the formulas (I) to (VIII). Suitable polycondensation reactions are known to the person skilled in the art and described in the literature. Particularly suitable and preferred polycondensation reactions which lead to C-C or C-N linkages are: 5

(A) polycondensation according to SUZUKI; (B) polycondensation according to YAMAMOTO;

(C) polycondensation according to SILENCE;

(D) polycondensation according to HECK;

(E) polycondensation according to NEGISHI;

(F) polycondensation according to SONOGASHIRA;

(G) polycondensation according to HIYAMA; and

(H) polycondensation according to HARTWIG-BUCHWALD.

How the polycondensation can be carried out by these methods and how the polymers can then be separated off from the reaction medium and purified is known to the person skilled in the art and in the literature, for example in WO 03/048225 A2, WO 2004/037887 A2 and WO 2004 / 037887 A2 described in detail.

The C-C linkages are preferably selected from the groups of SUZUKI coupling, YAMAMOTO coupling and STILLE coupling; the C-N linkage is preferably a coupling according to

HARTWIG-Buchenwald.

In order to obtain the desired polydispersities, it is generally necessary to subject the polymers prepared by the processes described above to a separation process. All separation methods known to those skilled in the art can be used for this purpose.

However, fractionation of the resulting polymers is preferred by a process as disclosed, for example, in DE 102 02 591 A1. This application discloses a process for the fractionation of polymers which is characterized in that a polymer solution (delivery phase) passes through a spinneret or through several spinnerets into a mixing zone containing a vigorously agitated precipitation bath

(Pickup phase) is pressed, with a two-phase

Mixture of a sol phase and a gel phase is formed, and the Solphase and the gel phase are separated. The corresponding device for carrying out this method is likewise disclosed in DE 102 02 591 A1.

Preferred embodiments of this method are characterized by:

that the sol phase and gel phase separate in a quiet zone adjoining the mixing zone,

- That from the rest zone Solphase and gel phase continuously ^{ι υ are} removed;

- That within the rest zone in the area of the brine withdrawal and the gel removal different temperatures are set;

- That the precipitation bath is a solvent or solvent mixture, the 5 preferably the more soluble components of the fraction to be fractionated

Absorbs polymers;

- That the donor phase is a concentrated, homogeneous solution of the polymer to be fractionated;

- That the polymer solution by means of a pump through the spinneret (s) is pressed;

- That the Aufnehmerphase contains a homopolymer as an auxiliary polymer;

- and / or that the fractionation takes place according to the molecular weight. 5

The present invention thus also provides a process for the preparation of the polymers according to the invention which is prepared by polycondensation according to SUZUKI, polycondensation according to YAMAMOTO, polycondensation according to STILLE or polycondensation according to HARTWIG-BUCHWALD and then fractionated.

To synthesize the polymers according to the invention, the corresponding monomers are required. The synthesis of the monomers in leading polymers of the invention to units of the formulas (I) to (VIII) and to the units described in groups 1 to 7 is known in the art and in the literature, for example in WO 2005/014689 A2, WO 2005/030827 A1 and WO 2005/030828 A1.

It may also be preferred that the polymers according to the invention are not pure, but blend (blend) together with any other polymeric, oligomeric, dendritic or low molecular weight

To use substances. These can, for example, improve the electronic properties, influence the transfer from the singlet to the triplet state or even emit light from the singlet or from the triplet state. But also electronically inert substances may be useful to influence, for example, the morphology of the polymer film formed or the viscosity of polymer solutions. As "blend" above and below a mixture containing at least one polymeric component is referred to.

Another object of the present invention is thus a polymer blend containing one or more polymers of the invention, and one or more other polymeric, oligomeric, dendritic or low molecular weight substances.

The present invention furthermore relates to solutions and

Formulations of one or more polymers of the invention or blends in one or more solvents. How such solutions can be prepared is known to the person skilled in the art and described, for example, in WO 02/072714 A1, in WO 03/019694 A2 and in the literature cited therein. These solutions can be used to prepare thin polymer layers, for example, by area coating methods (eg, spin coating) or printing methods (eg, ink jet printing). Polymers comprising structural units selected from the formulas (I) to (VIII) which contain one or more polymerizable groups and thus crosslinkable are particularly suitable for the production of films or coatings, in particular for the production of structured coatings, for example by thermal or light-induced In situ polymerization and in situ crosslinking, such as in situ UV photopolymerization or photopatterning. Particularly preferred for such applications are polymers according to the invention having one or more polymerisable groups, for example selected from acrylate, methacrylate, vinyl, epoxy and oxetane. In this case, both corresponding polymers can be used in pure substance, but it can also be used formulations or blends of these polymers as described above. These can be used with or without the addition of solvents and / or binders. Suitable materials, methods and devices for the methods described above are described, for example, in WO 2005/083812 A2. Possible binders are, for example, polystyrene, polycarbonate, polyacrylates, polyvinyl butyral and similar, optoelectronically neutral polymers.

Suitable and preferred solvents are, for example, toluene, anisole, xylene, methyl benzoate, dimethylanisole, mesitylene, tetralin, veratrole and tetrahydrofuran.

The polymers, blends and formulations according to the invention can be used in electronic or optoelectronic devices or for their preparation.

Another object of the present invention is thus the use of the polymers, blends and

Formulations in electronic or optoelectronic devices, preferably in organic or polymeric organic light-emitting diodes (OLED, PLED), organic field effect transistors (OFETs) ₁ organic integrated circuits (O-ICs), organic thin film transistors (TFTs), organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic ( OPV) elements or devices or organic photoreceptors (OPCs), particularly preferably in organic or polymeric organic light-emitting diodes

(OLED ₁ PLED), especially in polymeric organic light-emitting diodes (PLED).

Polymeric organic light emitting diodes include cathode, anode, emission layer, and optionally further layers, such as e.g. preferably a hole injection layer and optionally an intermediate layer between the hole injection and the emission layer.

How OLEDs or PLEDs can be produced is known to the person skilled in the art and is described in detail, for example, as a general method in WO 2004/070772 A2, which is to be adapted accordingly for the individual case.

As described above, the polymers according to the invention are very particularly suitable as electroluminescent materials in PLEDs or displays produced in this way.

As electroluminescent materials in the context of the present invention are materials that can be used as the active layer. Active layer means that the layer is able to emit light upon application of an electric field (light-emitting layer) and / or that it improves the injection and / or transport of the positive and / or negative charges (charge injection or charge transport layer). It may also be an intermediate layer between a hole injection layer and an emission layer. A preferred subject of the present invention is therefore also the use of the polymers or blends according to the invention in a PLED, in particular as electroluminescent material.

The present invention also relates to electronic or

D optoelectronic components, preferably organic or polymeric organic light emitting diodes (OLED, PLED), organic field effect transistors (OFETs), organic integrated circuits (O-ICs), organic thin film transistors (TFTs), organic solar cells (O-SCs),

¹⁰ organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPCs), more preferably organic or polymeric organic light-emitting diodes, in particular polymeric organic light-emitting diodes, with one or more

15 active layers, wherein at least one of these active layers contains one or more polymers according to the invention. The active layer can be, for example, a light-emitting layer, a charge-transport layer, a charge-injection layer and / or an intermediate layer

20 ^Seia

In the present application text and also in the examples below, the main focus is on the use of the polymers according to the invention in relation to PLEDs and corresponding displays. Despite this limitation of the description, it is possible for the skilled person without further inventive step, the polymers of the invention as semiconductors also for the other uses described above in other electronic devices

30 use.

The invention will be described in more detail below with reference to embodiments, without, however, being limited thereby. In particular, the features, properties and advantages described therein are the defined compounds underlying the respective example also apply to other compounds not mentioned in detail but within the scope of the claims, unless otherwise stated elsewhere.

Examples

A) Preparation of the polymers

Examples 1 to 3

First, three polymers 1 to 3 are prepared by using the following monomers (percentages = mol%) by SUZUKI coupling according to WO 03/048225 A2.

Polymer 1

2% 2% Polymer 2

Polymer 3

50% 10%

29.88%

10% 0.02% 0.1% B) Fractionation of the polymers obtained

Examples 4 to 6

The polymers 1 to 3 are fractionated according to the method described in WO 03/062282 A1. In all experiments, a 1% solution of the polymer in toluene is used as the "delivery phase." Ethanol is used as the "receiving phase" in all examples. The results of the fractionation of the polymers 1 to 3 are summarized in the following Table 1. From polymer 1, fractions 1.1 and 1.2 are recovered, from polymer 2 fraction 2.1 and from polymer 3 corresponding to fractions 3.1 and 3.2.

Table 1

Description of the measuring method (s):

The molecular weights M _w and M _n were determined by GPC (Model: Agilent HPLC System Series 1100) (column: PL-RapidH from Polymer Laboratories, solvent: THF with 0.12% by volume o-dichlorobenzene, detection: UV and refractive index, temperature : 4O ⁰ C). Calibrated with polystyrene standards.

C) OLED devices with the fractionated polymers

Examples 7 to 14: Production of a PLED

The preparation of a polymeric organic light-emitting diode has already been described many times in the literature (for example in WO 2004/037887 A2). To illustrate the present invention by way of example, PLEDs with the fractionated polymers 1.1 and 1.2, 2.1 and 3.1 and 3.2 are prepared by spin coating on previously coated with PEDOT and a hole-injecting interlayer ITO substrates. (PEDOT is a polythiophene derivative (Baytron P, by H. C. Starck, Goslar)). The layer thickness of the polymer layer is about 80 nm. Thereafter, a Ba / Al cathode (metals from Aldrich) is evaporated, the PLED encapsulated and characterized electro-optically.

The results which are obtained in PLEDs using polymers 1, 2 and 3 and the fractionated polymers 1.1 and 1.2, 2.1 and 3.1 and 3.2 prepared from these polymers are summarized in Table 2 below.

Table 2

As can be seen from the results, the lifetime of the polymeric light-emitting materials of the present invention is better than that of the comparative materials. The emission color and the efficiency are comparable. This shows that the polymeric, light-emitting materials according to the invention are better suited for use in displays than polymers according to the prior art.

Claims

claims

1. Polymers containing 1 to 100 mo!% Of one or more repeating units selected from spirobifluorene, indenofluorene, phenanthrene, dihydrophenanthrene, dihydropyrene, tetrahydropyrene and Dihydrobenzooxepin derivatives, characterized in that they have a polydispersity D (= MwZM _n ) of <2.0 and molecular weights M _w of> 100,000 g / mol.

2. Polymers according to claim 1, characterized in that the repeating units are selected from

Spirobifluorene derivatives of the formula (I):

wherein V = C, Si or Ge;

trans-indenofluorene derivatives of the formula (II) and cis-indenofluorene derivatives of the formula (III):

(III) Phenanthrene derivatives of the formula (IV) and 9,10-dihydrophenanthrene derivatives of the formula (V):

4,5-dihydropyrene derivatives of the formula (VI) and 4,5,9,10-tetrahydropyrene derivatives of the formula (VII):

wherein W = CR ₂ , O is ₁ S or Se, as well as

5,7-Dihydrodibenzooxepin derivatives of the formula (VIII):

wherein W = CR ₂ , O, S or Se, where R is the same or different at each occurrence H, a straight-chain, branched or cyclic alkyl or alkoxy chain having 1 to 22 C atoms, in which also one or more non-adjacent C atoms by O, S, CR ² = CR ² , C ,C, CO, O-CO, CO-O or O-CO-O may be replaced, it also being possible for one or more H atoms to be replaced by fluorine, an aryl or aryloxy group having 5 to 40 C atoms also one or more C atoms may be replaced by O, S or N, which may also be substituted by one or more non-aromatic radicals R, or F, CN, N (R ² ) ₂ or B (R ² ) ₂ , and

R ^{2 is the} same or different at each occurrence H _{1 is} a straight-chain, branched or cyclic alkyl chain having 1 to 22 C atoms, in which also one or more non-adjacent C atoms by O, S, CO, O-CO, CO-O or O-CO-O may be replaced, wherein one or more H atoms may be replaced by fluorine, or an optionally substituted aryl group having 5 to 40 carbon atoms, in which also one or more C atoms by O, S or N can be replaced is.

3. Polymers according to claim 1 or 2, characterized in that they are conjugated or partially conjugated.

4. Polymers according to claim 2 or 3, characterized in that they contain structural elements in addition to one or more structural units of the formulas (I) to (VIII), which increase the Lochinjektions- and / or -transporteigenschaften the polymers.

5. Polymers according to one or more of claims 2 to 4, characterized in that they contain structural elements in addition to one or more structural units of the formulas (I) to (VIII), which increase the electron injection and / or transport properties of the polymers.

6. Polymers according to one or more of claims 2 to 5, characterized in that they contain, in addition to one or more structural units of the formulas (I) to (VIII) or structural elements which change the emission characteristics to the extent that Elektrophosphores- cence be obtained instead of electro-fluorescence can. 5

7. Polymers according to one or more of claims 2 to 6, characterized in that they contain, in addition to one or more structural units of the formulas (I) to (VIII) or structural elements which the

^ Improve transition from so-called singlet to triplet state.

8. Polymers according to one or more of claims 2 to 7, characterized

15 characterized in that they contain structural elements in addition to one or more structural units of the formulas (I) to (VIII), which influence the morphology and / or the emission color of the resulting polymers.

20

9. Polymers according to one or more of claims 2 to 8, characterized in that they contain, in addition to one or more structural units of the formulas (I) to (VIII) or structural elements which emit light. 25

10. A process for the preparation of polymers according to one or more of claims 1 to 9, characterized in that they are prepared by polycondensation according to SUZUKI, polycondensation according to

30 YAMAMOTO, polycondensation according to SILENCE or

Polycondensation according to HARTWIG-BUCHWALD are produced and then fractionated.

11. A polymer blend comprising one or more polymers according to one or more of claims 1 to 9, and one or more further polymeric, oligomeric, dendritic or low molecular weight substances.

12. Solutions and formulations of one or more polymers according to one or more of claims 1 to 9 or blends

Claim 11 in one or more solvents.

13. Use of the polymers according to one or more of claims 1 to 9, blends according to claim 11 and formulations according to claim

12 in electronic or optoelectronic devices.

14. Electronic or optoelectronic components having one or more active layers, wherein at least one of these active layers contains one or more polymers according to one or more of claims 1 to 9.

15. Electronic or optoelectronic components according to claim 14, characterized in that the components are organic or polymeric organic light-emitting diodes (OLED, PLED), organic field-effect transistors (OFETs), ₁ organic integrated circuits (O-ICs), organic thin-film transistors ( TFTs) ₁ organic solar cells (O-SCs), organic laser diodes (O-lasers), organic photovoltaic (OPV) elements or devices or organic photoreceptors (OPCs) are.