JP5264682B2 - Twisted polymers, methods of use thereof, and methods of making random copolymers - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical device with a substrate and at least one semiconductor polymer sustained by the substrate. <P>SOLUTION: One of repeated units in the semiconductor polymer is the copolymer or the homopolymer of a group in formula (I). A conjunction unit X has at least a torsional angle of 5&deg; to a conjunction b-d between the conjunction a-b and the conjunction c-d. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an optical device comprising a substrate that supports at least one semiconductor polymer that emits blue-shifted light that is less likely to aggregate than conventional poly (fluorene) -based polymers. The invention also relates to novel homopolymers and copolymers for use in the devices, monomers for preparing the polymers, and methods for producing statistical copolymers particularly suitable for the preparation of the polymers of the invention.

  In recent years, interest in conjugated polymers has increased. These are polymers having a π-electron system delocalized along the polymer backbone. The delocalized π-electron system imparts semiconducting properties to the polymer and the ability to support positive and negative charge carriers with high mobility along the polymer chain. These conjugated polymer thin films are used in the manufacture of optical devices such as light emitting devices. These devices have many advantages over devices made using conventional semiconductor materials, including the potential for large area displays, low DC operating voltage and manufacturing simplicity. Yes. Devices of this type are described, for example, in WO-A-90 / 13148, US 5,512,654 and WO-A-95 / 06400.

The global market for displays based on organic and polymer light emitting materials has recently been estimated by Stanford Resources Inc. to grow to $ 200 million in 2002, stimulating high industrial interest in the field. (DE Mentley, "Flat Information Displays : Market and Technology Trends", 9 th edition, 1998). Efficient, high-stability, low-power consumption LED devices meet commercial demands, but have been manufactured by numerous companies and academic research organizations (eg, AC Grimsdale et al., Angew. Chem Int. Ed. 1998, 37, 402; see RH Friend et al., Nature 1999, 397,12). As a result of this rapid development of polymer-based LEDs (PLEDs) compared to the development of inorganic LEDs (Sheats et al., Science 1996,273,884), the first effective monochromatic active and passive addressing matrix display In 1999, Philips announced the start of a production line for PLED display components (eg, LEP backlights in the automotive and telecommunications industries).

  At present, great efforts are being made to achieve full color, all plastic screens. The main challenges to achieve this goal are (1) obtaining conjugated polymers that emit light of the three primary colors red, green and blue, and (2) processing and secondary processing of conjugated polymers to produce full color display structures. It must be easy to make. PLED devices show great promise to meet the first requirement. This is because the manipulation of the emission color can be achieved by changing the chemical structure of the conjugated polymer. However, adjusting the chemistry of the conjugated polymer is often easy and inexpensive on the laboratory scale, but can be an expensive and complex process on the industrial scale. The second requirement, ease of processing and manufacturing of full color matrix devices, raises the question of how to micropattern fine multicolor pixels and how to achieve full color emission . Inkjet printing and hybrid inkjet printing technologies have recently been of great interest for patterning PLED devices (eg RF Service, Science 1998,279, 1135; Wudl et al., Appl. Phys. Lett. 1998,73,2561). ; See J. Bharathan, Y. Yang, Appl. Phys. Lett. 1998, 72, 2660; and TR Hebner, CC Wu, D. Marcy, ML Lu, J. Sturm, Appl. Phys. Lett. 1998, 72, 519. )

In order to contribute to the development of full-color displays, there is a need for conjugated polymers that exhibit direct color adjustment, good processability and the possibility of inexpensive mass production. The step ladder polymer poly-2,7-fluorene has been the subject of much research into blue-emitting polymers (eg, AW Grice, DDC Bradley, MT Bernius, M. Inbasekaran, WW Wu, and EP). Woo, Appl. Phys. Lett. 1998, 73,629; JS Kim, RH Friend, and F. Cacialli, Appl. Phys. Lett. 1999,74,3084; WO-A-00 / 55927 and M. Bernius et al., Adv. Mater., 2000, 12, No. 23, 1737). This type of conjugated polymer has excellent processability, which is provided by the attachment of a soluble group at the remote C-9 position, but does not interfere with a wide range of conjugation and therefore is highly fluorescent in the solid state. It results in quantum yields (up to 79%) (see, for example, Q. Pei, Y. Yang, J Am. Chem. Soc. 1996, 118, 7416). Other advantages of poly-2,7-fluorene are excellent thermal stability (T _d > 400 ° C.) and chemical stability, and good film forming properties. However, the rigid nature of this polymer enhances interchain aggregation resulting in low luminescence efficiency due to undesired red color shifts and excimer formation (eg, VN Bliznyuk, SA Carter, JC Scott, G. Klarer, RD). Miller, and DC Miller, Macromolecules, 1999, 32, 361). Aggregation has been reduced to some extent by statistical copolymerization (statistical copolymerization) of 2,7-dibromofluorene with other halogenated monomers.

The process of making homopolymers and copolymers based on 9,9-disubstituted fluorene monomers is by metal-mediated cross coupling of both AA-BB and AB type monomers. There is currently considerable prior art in the field. Such copolymers can be made by cross-coupling by contacting a dibromo substituted monomer with a Ni (0) catalyst formed in situ from a Ni (II) salt (Yamamoto coupling, Progress in Polymer Science). , Vol. 17, p. 1153, 1992) (EP Woo et al., US 5,708,130; 5,962,631). Pd (0) mediated cross-coupling between aryl boronic acids and esters and aryl or vinyl halides (Suzuki coupling, A. Suzuki et al., Synth. Commun., 1981, 11, 513) is a phase transfer catalyst and Developed in the presence of inorganic bases, it produces relatively high quality poly (fluorene) derivatives for use as PLEDs (M. Inbasekaran, US 5,777,070). Extension to various comonomers with hole transport properties has also been realized (WO-A-99 / 54385). In further development, a combination of catalyst and base is selected to convert the boron functionality to —BX ₃ ^— (where X is F or OH).

  As mentioned above, the main drawback of poly (fluorene) -based homopolymers is that they tend to aggregate in the solid state, and the complex of excited states under fluorescent conditions via photoexcitation or stimulation by double charge injection (electroluminescence) It is well known to result in the formation of the body (excimer). One way to reduce this tendency is to use copolymers to eliminate aggregation (see US-A-5,777,070; D. Kim, et al., Macromolecules, 1999, 32, 1476). Alternative approaches include ladder-like planarized polymers (U. Scherf and K. Mullen, Adv. Polym. Sci., 1995, 123, 1), and poly (indenofluorene) (S. Setayesh et al., Macromolecules). , 2000, 33, 2016). As an end cap (G. Klaerner, RD Miller and CJ Hawker, Abstracts of Papers of the American Chemical Society, 216: 300-POLY, Part 3 Aug, 23 1998), 9th place in the fluorene building block (S. Setayesh et al , J Am. Chem. Soc., 2001, 123, 946) has been used to suppress aggregation. Also, end groups that trap holes enhance device performance, possibly by inhibiting aggregate formation (T. Miteva et al., Adv. Mater., 2001, 13, 565). It is noted that poly (1,4-phenylene vinylene) homopolymers and copolymers with 2,3-disubstituted patterns show a tendency to twist, and this strain has been used to improve the luminescence efficiency of polymer derivatives. (See WO-A-01 / 07052). The cause of broken conjugation in m-linked polyphenylenes has recently been discussed by S. Y. Hong et al., Macromolecules, 2001, 34, 6474.

  It is highly desirable to develop electroluminescent polymers that reduce the aggregation found in poly (fluorene) based polymers. In the present invention, the design of electroluminescent polymers incorporating comonomers based on homologues of fluorene derivatives and optical devices incorporating such polymers are described.

Accordingly, in a first aspect of the present invention, the substrate comprises a substrate and at least one semiconductor polymer supported by the substrate, wherein one of the repeating units is a group of the following formula (I): An optical device is provided that is a copolymer or a homopolymer in which the repeating unit is a group of formula (I):

Here, A and B may be the same or different, and each contains an aryl group or heteroaryl group in whole or in part, the group of A is condensed to a bond ab, and the group of B is a bond condensed to cd, and X is a linking unit, wherein X has a torsion angle of at least 5 ° between bond ab and bond cd relative to bond bd .

  In the linking unit X, A and B are twisted around the bond bd, and the bond ab and bond cd are not coplanar, but instead the bond ab and bond c around the bond bd. A selection is made such that there is a twist angle of at least 5 ° between -d. Preferably, the twist angle is 5 ° to 75 °, more preferably the twist angle is 10 ° to 70 °, even more preferably the twist angle is 30 ° to 60 °, most preferably the twist angle. The angle is 40 ° to 55 °.

  Incorporating the repeating unit of formula (I) above results in the introduction of a twist angle into the polymer backbone. This has two effects. First, the overall extent of conjugation in the polymer is reduced, which has the effect of increasing the HOMO-LUMO band gap of these materials, resulting in blue-shifted emission. Second, the introduction of twist into the polymer backbone causes the reduction in aggregation experienced with existing poly (fluorene) based polymers.

  In the group of formula (I) above, the aryl group is, for example, an aromatic hydrocarbon group having 6 to 14 carbons in one or more rings, optionally substituted with at least one substituent. May be. For example, one or more substituents are a nitro group, a cyano group, an amino group, an alkyl group shown below, a haloalkyl group shown below, an alkoxyalkyl group shown below, an aryloxy group shown below, and an alkoxy group shown below. Selected from the group consisting of Examples of aryl groups include phenyl, naphthyl, phenanthryl, and anthracenyl groups.

  In the group of the above formula (I), the heteroaryl group is, for example, a 5- to 7-membered ring containing 1 to 3 heteroatoms selected from the group consisting of a sulfur atom, an oxygen atom and a nitrogen atom. Or an aromatic heterocyclic group of The group is optionally substituted with at least one substituent, for example one or more substituents are nitro, cyano, amino, alkyl group shown below, haloalkyl group shown below, alkoxyalkyl shown below A group, an aryloxy group shown below, and an alkoxy group shown below. Examples of such heteroaryl groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, tetrazolyl, thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl groups.

  The alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms.

  The haloalkyl group is an alkyl group as defined above substituted with at least one halogen atom.

  The alkoxy group is a linear or branched alkoxy group having 1 to 20 carbon atoms.

  The alkoxyalkyl group is an alkyl group as defined above substituted with at least one alkoxy group as defined above.

The aryl group of the aryloxy group is an aromatic hydrocarbon group having 6 to 14 carbon atoms in one or more rings, and optionally, a nitro group, a cyano group, an amino group, or an alkyl group as defined above Preferably, the substrate may be substituted with at least one substituent selected from the group consisting of a group, a haloalkyl group as defined above, an alkoxyalkyl group as defined above, and an alkoxy group as defined above. At least one semiconducting polymer supported by a substrate, wherein the semiconducting polymer is a copolymer in which one of the repeating units is a group of the following formula (II) or a repeating unit is a group of the following formula (II) Optical devices that are homopolymers are provided.

Here, Y ¹ and Y ² may be the same or different, and each represents a single bond or a linking unit conjugated with a bonded phenyl group,
X is a linking unit, and X has a twist angle of at least 5 ° between the two phenyl groups around the bond bd.

When Y ¹ or Y ² is a linking unit conjugated with a phenyl group to which it is bonded, the linking unit and the phenyl group to which it is bonded together form a unit of formula (II) Alternatively, it forms a conjugated group that is linked to the next unit in the homopolymer. Thus, for example, Y ¹ can be a phenyl group that condenses with a linking phenyl group to form a naphthylene linking unit, or an indenyl group that condenses with a linking phenyl group to form a fluorenyl linking unit.

More preferably, it comprises a substrate and at least one semiconducting polymer supported by said substrate, wherein said semiconducting polymer is a copolymer or repeating unit wherein one of the repeating units is a group of the following formula (III) An optical device is provided that is a homopolymer that is a group of formula (III).

  Here, m and n may be the same or different, and each is 0, an integer of 1, 2 or 3.

R ¹ and R ² may be the same or different, and each is an alkyl group as defined above, a haloalkyl group as defined above, an alkoxy group as defined above, an alkoxyalkyl group as defined above, an aryl group (1 The above ring has an aromatic hydrocarbon group having 6 to 14 carbon atoms, and may be optionally substituted with at least one substituent, the substituent being a nitro group, a cyano group, an amino group Selected from the group consisting of an alkyl group as defined above, a haloalkyl group as defined above, an alkoxyalkyl group as defined above, and an alkoxy group as defined above), an aryloxy group as defined above, and Selected from the group consisting of aralkyl groups containing an alkyl group as defined above substituted with at least one aryl group as defined.

X is a linking unit, and X has a twist angle of at least 5 ° between the two phenyl rings around the bond bd. When there are more than one R ¹ and / or R ² groups, each R ¹ or each R ² may be the same or different from the others.

In the optical device of the present invention, when the repeating unit in the copolymer or homopolymer is a group of the formula (III), X is preferably a group of the formula -ABC-, and A, B, and C are They may be the same or different, and each is O, S, SO, SO ₂ , NR ³ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ), C (R ⁴ ) (R ⁵ ), Si (R ^{4 '} ) (R ^5' ), and P (O) (OR ⁶ ).

Here, R ³ , R ^{3 ′} and R ^{3 ″} may be the same or different, and each is a hydrogen atom, an alkyl group as defined above, a haloalkyl group as defined above, an alkoxy group as defined above, An alkoxyalkyl group as defined above, an aryl group as defined above, an aryloxy group as defined above, an aralkyl group as defined above, and the above substituted with at least one group of formula -N ⁺ (R ⁷ ) ₃ (Wherein each R ⁷ group may be the same or different and is selected from the group consisting of a hydrogen atom, an alkyl group as defined above, and an aryl group as defined above). More selected.

R ⁴ , R ⁵ , R ^{4 ′} and R ^{5 ′} may be the same or different and each is a hydrogen atom, an alkyl group as defined above, a haloalkyl group as defined above, an alkoxy group as defined above, or a halogen atom. , A nitro group, a cyano group, an alkoxyalkyl group as defined above, an aryl group as defined above, an aryloxy group as defined above, an aralkyl group as defined above, and an alkyl group as defined above substituted with a substituent. [The substituent is selected from the group consisting of the aryl group defined above, the heteroaryl group defined below, the fluorenyl group, and the spirobifluorenyl group (the aryl, heteroaryl , Fluorenyl, and spirobifluorenyl groups are substituted with disubstituted amino groups, which may be the same or different Ku, an aryl group as defined above, heteroaryl groups as defined below, fluorenyl groups, and is selected from the group consisting of spirobifluorenyl group)], or R ⁴ and R ⁵ they are joined together A carbonyl group is shown together with the carbon atom.

R ⁶ represents a hydrogen atom, an alkyl group as defined above, a haloalkyl group as defined above, an alkoxyalkyl group as defined above, an aryl group as defined above, an aryloxy group as defined above, and an aralkyl as defined above. Selected from the group consisting of groups.

  The heteroaryl group is a 5-membered to 7-membered aromatic heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom. The aryl group is optionally a nitro group, a cyano group, an amino group, an alkyl group as defined above, a haloalkyl group as defined above, an alkoxyalkyl group as defined above, an aryloxy group as defined above, and as defined above. Substitution with at least one substituent selected from the group consisting of alkoxy groups.

Preferably, R ³ , R ^{3 ′} and R ^{3 ″} may be the same or different, each selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, The group is optionally substituted with a group of formula —N ⁺ (R ⁷ ) ₃ where each R ⁷ may be the same or different and consists of a hydrogen atom and an alkyl group having 1 to 6 carbon atoms. Selected from the group. More preferably, R ³ , R ^{3 ′} and R ^{3 ″} may be the same or different, each representing an alkyl group having 1 to 3 carbon atoms, said alkyl group optionally having the formula —N ⁺ (R ⁷ ) ₃ substituted with groups, wherein each R ⁷ group may be the same or different and is an alkyl group having 1 to 3 carbon atoms.

Preferably, R ⁴ , R ⁵ , R ^{4 ′} and R ^{5 ′} may be the same or different, each of which is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 1 to 10 carbons. Selected from the group consisting of an alkoxy group having an atom and an alkyl group having 1 to 10 carbon atoms (eg, a methyl group) substituted with a substituent, wherein the substituent is an aryl group, heteroaryl group, fluorenyl And the aryl, heteroaryl, fluorenyl and spirobifluorenyl groups (preferably in the para position relative to the alkyl group) are substituted with a disubstituted amino group selected from the group consisting of a group and a spirobifluorenyl group And the substituents may be the same or different and consist of aryl, heteroaryl, fluorenyl and spirobifluorenyl groups. It is selected from the group. More preferably, R ⁴ , R ⁵ , R ^{4 ′} and R ^{5 ′} may be the same or different and each is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, and 5 to 10 Selected from the group consisting of alkoxy groups having the following carbon atoms. And most ^preferably, R 4, or each or R ⁴ of ^{R 5 'and} R ^5' is a hydrogen atom, or ^{R 4} or R ^{4 'represents} a hydrogen atom, ^{R 5} or R ^5' is 7 Or an alkoxy group having 10 carbon atoms.

Preferably, R ⁶ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and most preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Preferred examples of the repeating unit of formula (III) are those in which m and n are each 0 and X is a linking unit of formula -ABC-. here,
(I) A and C each represent a methylene group, B represents from O, S, SO ₂ , NR ³ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ), and C (R ⁴ ) (R ⁵ ) Wherein R ³ , R ^{3 ′} , R ^{3 ″} , R ⁴ , R ⁵ and R ⁶ are as defined in the above definition of the repeating unit of formula (III).

(Ii) A and C each represent a methylene group, B is selected from the group consisting of O, S, SO ₂ , NR ³ , where R ³ is a hydrogen atom and an alkyl having 1 to 6 carbon atoms Selected from the group consisting of groups, wherein said alkyl group is optionally of formula —N ⁺ (R ⁷ ) ₃ {wherein each R ⁷ group may be the same or different and is a hydrogen atom and 1 to 6 carbon atoms Selected from the group consisting of alkyl groups having N}, N ⁺ (R ^{3 ′} ) (R ^{3 ″} ) {wherein R ^{3 ′} and R ^{3 ″} may be the same or different, each one Represents an alkyl group having 6 to 6 carbon atoms, said alkyl group being optionally substituted with the formula -N ⁺ (R ⁷ ) ₃ , wherein each R ⁷ group may be the same or different, and may be a hydrogen atom and Consists of alkyl groups having 1 to 6 carbon atoms It is selected from the group}, and ^{C (R 4) (R 5} ) { wherein R ⁴ and R ⁵ may be the same or different, each represents a hydrogen atom, an alkyl having 1 to 10 carbon atoms Selected from the group consisting of a group, an alkoxy group having 1 to 10 carbon atoms, and an alkyl group having 1 to 10 carbon atoms substituted with a substituent (for example, a methyl group), Is selected from the group consisting of an aryl group, a heteroaryl group, a fluorenyl group, and a spirobifluorenyl group, wherein the aryl, heteroaryl, fluorenyl, and spirobifluorenyl group (preferably in a position para to the alkyl group). Substituted with a disubstituted amino group, which substituents may be the same or different and are aryl, heteroaryl, fluorenyl and Substituted with a group selected from the group consisting of a lobifluorenyl group.

(Iii) A and C each represent a methylene group, B is O, S, SO ₂ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ) {where R ^{3 ′} and R ^{3 ″} are the same or different Each representing an alkyl group with 1 to 3 carbon atoms, said alkyl group optionally substituted with a group of formula -N ⁺ (R ⁷ ) ₃ , wherein each R ⁷ group is It may be the same or different and is an alkyl group having 1 to 3 carbon atoms. }, And C (R ⁴ ) (R ⁵ ) {wherein R ⁴ and R ⁵ may be the same or different and each is a hydrogen atom, 1 to 3 carbon atoms, and 5 to 10 carbon atoms. Selected from the group consisting of alkoxy groups having carbon atoms, wherein in particular each of R ⁴ and R ⁵ is a hydrogen atom, or R ⁴ represents a hydrogen atom and R ⁵ is from 7 to 10 carbon atoms Is selected from the group consisting of:

(Iv) A and C each represent O or S, and B is from O, S, SO ₂ , NR ₃ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ) and C (R ⁴ ) (R ⁵ ) Wherein R ³ , R ^{3 ′} , R ^{3 ″} , R ⁴ , R ⁵ and R ⁶ are as defined in the above definition of the repeating unit of formula (III).

(V) A and C each represent O or S and B is a group of formula C (R ⁴ ) (R ⁵ ), where R ⁴ and R ⁵ may be the same or different, each of which is hydrogen Represents an atom or an alkyl group having 1 to 10 carbon atoms. Or
(Vi) A and C each represent O and B is of the formula C (R ⁴ ) (R ⁵ ), wherein R ⁴ and R ⁵ may be the same or different, each of 1 to 3 Represents an alkyl group having one carbon atom.

Particularly preferred repeating units are selected from the following group.

Many of the semiconducting polymers used in the optical devices of the present invention are novel. Accordingly, in a further aspect of the invention, there is provided a semiconductor copolymer in which one of the repeating units is a group of formula (II) as defined above, or a semiconductor homopolymer in which the repeating unit is a group of formula (II) as defined above. Provided. However, in the case ^{where Y 1} and ^{Y 2} each represent a single bond, X is -CO-O-CO -, - CO-NH-CO- and -O-P (O) (OH ) consisting -O- Must not represent a linking unit selected from the group, Y ¹ represents a phenyl group that forms a naphthalenyl group by condensing with the bonded phenyl group, and Y ² is condensed with the bonded phenyl group. X represents a group of the formula —O—CH ₂ —O— when it represents a phenyl group forming a naphthalenyl group.

Preferably, the semiconducting polymer of the invention is a copolymer in which one of the repeating units is a group of formula (III) as defined above or a homopolymer in which the repeating unit is a group of formula (III) as defined above. However, in the case ^{where Y 1} and ^{Y 2} each represent a single bond, X is -CO-O-CO -, - CO-NH-CO- and -O-P (O) (OH ) consisting -O- It must not represent a linking unit selected from the group.

Substituents R ³ , R ^{3 ′} , R ^{3 ″} , R ⁴ , R ⁵ , R ⁶ , and R ⁷ and the linking unit —A—B in the repeating unit of formula (III) of the copolymers and homopolymers of the invention Preferred, more preferred and most preferred options for -C- are as described above for the optical device of the present invention.

Preferably, the polymer used in the optical device of the present invention is a copolymer or terpolymer. These copolymers include alternating AB copolymers and alternating terpolymers as well as statistical copolymers and statistical terpolymers. These can be represented by the following general formulas (IV), (V), (VI) and (VII).

Where (I) is a repeating unit as defined above, D ¹ , D ² and D ³ are repeating units conjugated to adjacent units in the polymer chain, n ¹ is an integer greater than 3, x : Y ratio is 99: 1 to 1:99, and x: (y + z) ratio is 99: 1 to 1:99.

The repeating units D ¹ , D ² and D ³ are all conjugated units commonly used in electroluminescent polymers, for example Burroughes et al., Nature, 1990,347, 539; WO-A-93 / 14177; WO -A-94 / 29883; US-A-5,514,878; WO-A-99 / 54385; US-A5,672,678; WO-A-00 / 55927; EP-A-0707020; and co-pending PCT / GB00 This is disclosed in / 04594. Specific examples include conjugated units of the following formulas (VIII), (IX), (X), (XI), (XII), (XIII), (XIV) and (XV).

Here, each of R ⁸ to R ¹⁵ and R ¹⁷ to R ³³ is the same or different, and is an alkyl group as defined above, a haloalkyl group as defined above, an alkoxy group as defined above, an alkoxyalkyl as defined above. Selected from the group consisting of a group, an aryl group as defined above, an aryloxy group as defined above, an aralkyl group as defined above, and a formula —COR ¹⁶ wherein R ¹⁶ is a hydroxy group, an alkyl group as defined above. A haloalkyl group as defined above, an alkoxy group as defined above, an alkoxyalkyl group as defined above, an aryl group as defined above, an aryloxy group as defined above, an aralkyl group as defined above, an amino group, its alkyl An alkylamino group, a dialkylamino group (wherein each alkyl group is as defined above) The groups may be the same or different and are as defined above), an aralkyloxy group whose aralkyl group is as defined above, and an alkoxy group as defined above substituted with at least one halogen atom Selected from the group consisting of haloalkoxy groups having

Each of Z ¹ , Z ² and Z ³ may be the same or different, and O, S, SO, SO ₂ , NR ³ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ), C (R ⁴ ) (R ⁵ ), Si (R ^{4 ′} ) (R ^{5 ′} ), and P (O) (OR ⁶ ), wherein R ³ , R ^{3 ′} , R ^{3 ″} , R ⁴ , R ⁵ , R ^{4 ′} , R ^{5 ′} and R ⁶ are as defined above.

Each of X ¹ , X ² , X ³ and X ⁴ may be the same or different;
An aryl group as defined above,
A linear or branched alkylene group having 1 to 6 carbon atoms,
Selected from linear or branched alkenylene groups having 2 to 6 carbon atoms and linear or branched alkynylene groups having 1 to 6 carbon atoms, or X Both ¹ and X ² and / or X ³ and X ⁴ may represent a linking group of the following formula (V).

Here, X ⁵ represents an aryl group as defined above,
Each of e1, e2, f1 and f2 may be the same or different and is 0 or an integer of 1 to 3,
each of g, q1, q2, q3 and q4 may be the same or different and is 0, 1 or 2;
each of h1, h2, j1, j2, j3, l1, l2, l3, l4, r and s may be the same or different and is 0 or an integer from 1 to 4;
Each of i, k1, k2, o1, and o2 may be the same or different, and is 0 or an integer of 1 to 5, and each of p1, p2, p3, and p4 is 0 or 1.

  In the alternating AB copolymers and terpolymers and statistical copolymers and terpolymers of the above general formulas (IV), (V), (VI) and (VII), the following are preferred.

  (A) The repeating unit (I) is a repeating unit of the formula (II) defined above.

  (B) The repeating unit (I) is a repeating unit of the formula (III) defined above.

  (C) The repeating unit (I) is one of the preferred, more preferred and most preferred units of formula (III) as defined above.

(D) The repeating units D ¹ , D ² and D ³ are selected from the group consisting of formulas (VIII), (IX), (XIV) and (XV) as defined above.

(E) The repeating unit D ¹ , D ² or D ³ is a unit of the formula (VIII), wherein Z ¹ , Z ² and Z ³ are O, S and C (R ⁴ ) (R ⁵ ) And wherein R ⁴ and R ⁵ are as defined above.

(F) The repeating unit D ¹ , D ² or D ³ is a unit of formula (VIII), wherein each of e1 and e2 is 0 and Z ¹ , Z ² or Z ³ is of formula C (R ⁴ ) A group of (R ⁵ ), wherein R ⁴ and R ⁵ may be the same or different and are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (eg n-hexyl, n-octyl, 2-ethylhexyl and 3,7-dimethylloctyl group), and an alkyl group having 1 to 10 carbon atoms substituted with a substituent (eg, a methyl group), wherein the substituent is aryl Selected from the group consisting of a group, a heteroaryl group, a fluorenyl group and a spirobifluorenyl group, wherein the aryl, heteroaryl, fluorenyl and spirobifluorenyl groups are (preferably Substituted by La position in) disubstituted amino group, the substituents may be the same or different, aryl group, heteroaryl group, those selected from the group consisting of fluorenyl groups and spirobifluorenyl groups.

(G) The repeating unit D ¹ , D ² or D ³ is a unit of the formula (XV) having the following formula.

Here, R ³⁴ and R ³⁵ may be the same or different, and each is an alkyl group as defined above.

  (H) A statistical copolymer of formula (VI) wherein the ratio of x: y is 10:90 to 50:50.

  (I) A statistical copolymer of formula (VI) wherein the ratio of x: y is 10:90 to 45:55.

Of these, preferred are alternating AB copolymers and alternating terpolymers of the general formulas (IV), (V), (VI) and (VII), as well as statistical copolymers and statistical terpolymers, which are repeating units. (I) is defined in (A), and repeating units D ¹ , D ² and D ³ are defined in (D). More preferred are alternating AB copolymers and alternating terpolymers of the general formulas (IV), (V), (VI) and (VII), as well as statistical copolymers and statistical terpolymers, wherein the repeating unit (I) Are defined in (B), and repeating units D ¹ , D ² and D ³ are defined in (E) or (G). Further preferred are alternating AB copolymers and alternating terpolymers of the general formulas (IV), (V), (VI) and (VII), as well as statistical copolymers and statistical terpolymers, wherein the repeating unit (I) Is defined in (C), and repeating units D ¹ , D ² and D ³ are defined in (E) or (G). Particularly preferred are alternating AB copolymers and alternating terpolymers of the general formulas (IV), (V), (VI) and (VII), as well as statistical copolymers and statistical terpolymers, wherein the repeating unit (I) Is defined in (C), and the repeating units D ¹ , D ² and D ³ are defined in (F) or (G). Most preferred is a statistical copolymer of formula (VI) as defined in (H) wherein the repeat unit (I) is defined in (C) and the repeat unit D ¹ is (F) or ( G).

  The optical device of the present invention may comprise only the semiconducting polymer according to the present invention supported on a substrate, the semiconducting polymer of the present invention being disclosed in other semiconducting polymers such as WO-A-99 / 48160. May be blended with things.

  The semiconducting polymers used in the manufacture of optical devices according to the present invention can be manufactured using any of a standard group of polycondensation methods (for example, Heck, Suzuki, Yamamoto, Horner, Wessling and Gilch US-A-5,777,070 and review article “Electroluminescent Conjugated Polymers-Seeing Polymers in a New Light”, A. Kraft, AC Grimsdale and AB Holmes, Angew. Chem. Int. Ed. Engl., 1998, 37, 402-428 (The contents of which are incorporated herein by reference). One skilled in the art can select the desired monomer and a suitable polycondensation method depending on the properties of the targeted semiconductor polymer of the present invention.

One method that is preferred for its simplicity and flexibility is the Suzuki reaction. That is, the polymer of the present invention can be synthesized according to the following scheme 1.

Where E is a repeating unit of formula (I), (II) or (III) as defined above,
D is a repeating unit of formula D ¹ , D ² or D ³ as defined above;
Y ³ and Y ⁴ are leaving groups,
W ¹ and W ² are boronic acid groups [B (OH) ₂ ], boronate ester groups of formula B (OR ³⁵ ) ₂ (where R ³⁵ is an alkyl group as defined above and an aryl group as defined above) Or two R ³⁵ groups together represent a linear or branched alkylene group having 2 to 10 carbon atoms), and a borane of formula B ( R ³⁶ ) ₂ ( Wherein R ³⁶ is selected from the group consisting of an alkyl group as defined above, an aryl group as defined above, and an aralkyl group as defined above.
n ¹ is an integer greater than 3.

Typically, in the above, the leaving groups Y ³ and Y ⁴ may be bromine or iodine. Substituents W ¹ and W ² may be boronate ester groups of formula B (OR ³⁵ ) ₂ where the two R ³⁵ groups are both alkylene groups having 2 to 6 carbon atoms, such as 2,3- Represents a dimethylbutylene group. The palladium catalyst may be tetrakis (triphenylphosphine) palladium (0). The base may be tetraalkylammonium hydroxide, most preferably tetraethylammonium hydroxide as disclosed in WO 00/53656, PCT / GB00 / 00771. This reaction can be carried out in toluene containing sodium carbonate as the required base and Aliquat® as the phase transfer catalyst.

Scheme 2 below shows two specific examples belonging to the general type Suzuki polymer presented in Scheme 1 above.

As already mentioned above, we are especially thought Sita infantis Pharmaceutical semiconductor copolymer comprising a recurring unit of the formula (I) and D ¹ is good. We have discovered a preferred method for synthesizing such statistical copolymers, which is a modification of the Suzuki polymerization method. This method makes it possible to introduce the exact amount of repeating units of formula (I) in a very random way along the polymer backbone. This method not only applies to the present invention, but also applies to the synthesis of other random statistical conjugated polymers.

Accordingly, in a further aspect of the present invention, a method for producing a random statistical conjugated polymer is provided. In this method, in the presence of a palladium (0) or palladium (II) catalyst and a base, x ¹ mol of a monomer of formula W ³ -F ¹ -W ⁴ , y ¹ mol of Y ⁵ -F ¹ -Y ⁶ , And z ¹ mol of monomer of formula Y ⁵ -G ¹ -Y ⁶ is reacted,
(Where Y ⁵ and Y ⁶ are leaving groups,
W ³ and W ⁴ are boronic acid groups [B (OH) ₂ ], boronate ester groups of formula B (OR ³⁵ ) ₂ , where R ³⁵ is as defined above, and formula B ( R ³⁶ ) selected from the group consisting of ₂ boranes, wherein R ³⁶ is as defined above;
F ¹ and G ¹ are radicals whose properties are such that the groups F ¹ and G ¹ in the polymerization product obtained during polymerization are conjugated, and x ¹ : (y ¹ + z ¹ ) (Molar ratio is 1: 1)
A random statistical conjugated polymer of formula (XVI) is given below, where F ¹ , G ¹ , x ¹ , y ¹ and z ¹ are as defined above: (x ¹ + y ¹ ): z molar ratio of ¹ is greater than 1).

Typically, in the above, the leaving groups Y ⁵ and Y ⁶ may be bromine or iodine. Substituents W ³ and W ⁴ each represent a boronate ester group of formula B (OR ³⁵ ) ₂ , where two R ³⁵ groups in each boronate ester group contain 2 to 6 carbon atoms. Represents an alkylene group, for example, a 2,3-dimethylbutylene group. The palladium catalyst may be tetrakis (triphenylphosphine) palladium (0). This reaction can be carried out in toluene containing sodium carbonate as the required base and Aliquat® as the phase transfer catalyst. Preferably, the palladium catalyst is combined with a tetraalkylammonium hydroxide base.

  Surprisingly, tricyclohexylphosphine has been found to yield very rapid polymerization and high molecular weight polymers when combined in palladium (II) acetate and tetraethylammonium hydroxide in toluene. For poly (9,9-dialkylfluorene-2,7-diyl) homopolymer, typical Mp (measured by GPC) was obtained in the range of 200,000-350,000. Tri (tert-butylphosphine) could also be used. These specific phosphines are suitable for effective Suzuki coupling catalysts by AF Littke and GC Fu, J. Am. Chem. Soc., 2001, 123, 6989 (and references cited therein). It is surprising that high molecular weight polymers are also obtained. Preferred stoichiometry includes 1 mol% palladium acetate, 3 mol% phosphine, and 5 equivalents of tetraethylammonium hydroxide per mole of dibromoallene.

This modification of the Suzuki polymerisation process is particularly useful because very random statistical copolymers are produced and small amounts of the desired monomer units can be incorporated into the polymer backbone containing large amounts of comonomer units. In an embodiment of the copolymers of the present invention, the copolymers of formula (VI) as defined above in the can [the method be synthesized using the above method, the monomer Y ⁵ -G ¹ - G ¹ in the Y ⁶ are is a repeating unit of formula (I) as defined above, wherein said copolymer of (VI) is has a mole fraction of large repeat units D ¹ than repeating units having the formula (I), the polymer a small twist It is introduced along the main chain. This random introduction of small amounts of repeating units (I) allows control over the degree of conjugation reduction in the polymer produced by the introduction of said repeating units of formula (I). As a result, changes in the HOMO-LUMO bandgap can be adjusted as required to produce the desired blue shift in polymer emission, and the degree to which polymer aggregation is reduced can be adjusted as well.

A further example of a suitable polymerization method is Horner-Emmons polycondensation of phosphonate and aldehyde, as illustrated in Scheme 3 below.

  In the polymerization method shown above, an end capping unit can be introduced if necessary. For example, addition of aryl bromide or aryl boronate after a predetermined time prevents further chain extension of the polymer.

The twisted monomers of the present invention of the formulas Y ³ -EY ⁴ and W ¹ -EW ² defined above can be synthesized by standard methods well known in the field of synthetic organic chemistry. Examples of such methods are illustrated in Schemes 4-7 below.

Many of the monomers used in the condensation polymerization reaction are novel. In a further aspect of the invention, of the formulas Y ³ -E-Y ⁴ and W ¹ -E-W ² (E, W ¹ , W ² , Y ³ and Y ⁴ are as defined above). Monomers are provided. Provided that when each of Y ³ and Y ⁴ is a bromine atom, E is dibenzoxepinyl, dibenzothiepinyl, dibenzothiepinyl S-oxide, or Does not represent a dibenzothiepinyl S, S-dioxide group.

The optical device of the present invention can be manufactured based on any known method in the field relating to the manufacture of optical devices. Suitable production methods are disclosed, for example, in the following references, the contents of which are hereby incorporated by reference: WO-A-90 / 13148; US-A-5,512,654; WO-A- 95/06400; RF Service, Science 1998,279, 1135; Wudl et al., Appl. Phys. Lett. 1998, 73, 2561; J. Bharathan, Y. Yang, Appl. Phys. Lett. 1998, 72, 2660 and TR Hebner, CC Wu, D. Marcy, ML Lu, J. Sturm, Appl. Phys. Lett. 1998, 72, 519).
For example, a typical thin film LED optical device according to the present invention is made of an O ₂ plasma treated ITO coated glass, poly (3,4-ethylenedioxythiophene) doped with poly (styrene sulfonate) (PEDOT: PSS). It comprises a hole injection layer, a thin film of the inventive semiconductor copolymer, and a Ca—Al cathode. A PEDOT: PSS film (typically approximately 70 nm thick) can be spun from the filtered H ₂ O solution before heating to 100 ° C. under N _{2 for} 30 minutes. Spin coating can also be used to deposit the luminescent copolymer film of the present invention (typically approximately 100 nm thick) from a xylene solution in a nitrogen filled glove box. The Ca cathode (typically about 500 mm thick) and the Al protective layer (typically about 150 mm thick) are deposited by thermal evaporation in a vacuum (eg, base pressure about 5 × 10 ⁻⁶ mbar). The film can be formed by patterning with a shadow mask.

  Water-soluble polyelectrolyte copolymers according to the present invention can be prepared by copolymerization of an ammonium salt and a suitable fluorene monomer. Selection of a suitable polymer can favor inkjet printing and layer-by-layer deposition of luminescent polyelectrolytes.

The X-ray crystal structure of the twisted monomer 12 prepared in Example 1. UV / VIS solution spectra of various semiconducting polymers of general formula 33 prepared in Example 2. Thin film photoluminescence spectra for the semiconducting polymer of general formula 33 prepared in Example 2 and two prior art copolymers. FIG. 4 is a current-voltage photoluminescence curve of a bilayer electroluminescent device incorporating the semiconductor statistical copolymer of Formula 36 prepared in Example 3. FIG. The schematic diagram of the electroluminescent device of this invention. Thin film photoluminescence spectrum of the designated copolymer (excitation wavelength 360 nm). Thin film photoluminescence spectrum of the designated copolymer (excitation wavelength 360 nm). Thin film photoluminescence spectrum of the designated copolymer (excitation wavelength 360 nm). Thin film photoluminescence spectrum of the designated copolymer (excitation wavelength 360 nm). Electroluminescence spectrum of PF6 copolymer 36 (m = 75; n = 25). Device construction was according to the procedure outlined herein.

  The invention can be further understood by consideration of the following examples of the invention with reference to the drawings.

Example 1
Synthesis of 3,9-dibromo-5,7-dihydro-dibenzo [c, e] oxepin (7)

4,4′-Dibromo-2,2′-bis-hydroxymethylbiphenyl 23 (its structure is shown in Scheme 4 above) (5 g, 0.013 mol, “DM Hall, F. Minhaj, J Chem. Soc. , 1957,4584 ") was dissolved in THF (50 ml). HBr (48% wt / wt aqueous solution, 40 ml) was added and the solution was refluxed overnight. After this period, THF was removed under reduced pressure and the yellow oil was extracted between DCM / H ₂ O (DCM is dichloromethane). The combined organic layers were dried (MgSO ₄ ), reduced and recrystallized from acetone (100 ml) to give 3,9-dibromo-5,7-dihydro-dibenzo [c, e] oxepin (12) finely divided. Obtained as white crystals (1 g). Additional product was obtained by repeated recrystallization of the mother liquor. Total yield after 3 recrystallizations (2.2 g, 0.0062 mol, 48% yield), fine white crystals.

¹ H-NMR (400 MHz, CDCl ₃ ): 4.30 (4H, s, CH ₂ ), 7.39 (2H, d, ArH, J 8), 7.58-7.63 (4H, m, ArH); ¹³ C-NMR ( _{100 MHz, CDCl 3) 67.0,} 122.4, 128.9, 132.1, 132.7, 136.8, 139.0; Elemental analysis (calculated for C 14 H lO Br 2 O, C 47.50, H 2.85%); found: C 47.44, H 2.94%;
mp. 129-131 ° C.

  The X-ray crystal structure of 3,9-dibromo-5,7-dihydro-dibenzo [c, e] oxepin (12) prepared in this way was obtained using single crystal X-ray crystallography. This is shown in FIG. From this, it was possible to measure that there was a 41.25 ° twist angle between the phenyl rings around the biphenyl bond.

Using the same synthetic method as described above for the preparation of 3,9-dibromo-5,7-dihydro-dibenzo [c, e] oxepin, the torsion monomers 15, 17, 25-32 shown below Was prepared. The twist angle of many monomers was measured as for 3,9-dibromo-5,7-dihydrodibenzo [c, e] oxepin. The number of twist angles is shown in parentheses after each number. It should be noted that 29, 30, and 32 are not converted to dibromo derivatives, but the potential for use in cross-coupling reactions is clear.

Example 2
3,9-Dibromo-5,7-dihydro-dibenzo [c, e] oxepin (12) and 9,9-di-n-hexylfluorene-2,7-bis- (isopropoxy-4,4,5 , 5-tetra-methyl-1,3,2-dioxaboronate) 13 and 2,7-dibromo-9,9-di-n-hexylfluorene, statistical polymerization 9,9-di-n- Hexylfluorene-2,7-bis- (isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaboronate) (Structure 13 below) (1.84 g, 3.13 mmol) , 2,7-Dibromo-9,9-di-n-hexylfluorene (154 mg, 0.313 mmol) and 3,9-dibromo-5,7-dihydro-dibenzo [c, e] oxepin 12 (1 g, 2. 82 mmol) ( Prepared as described in Example 1 above) was placed in a Schlenk tube frame-dried under nitrogen. Tetrakis (triphenylphosphine) palladium (0) (40 mg, 0.03 mmol), toluene (40 ml), aqueous sodium carbonate (6 ml, 2M), and Aliquat® (120 mg) were then added to remove the solution. I worried. The resulting mixture was heated at 100 ° C. for 48 hours under nitrogen. The resulting viscous liquid was then precipitated into methanol to give an off-white solid. Finally, the polymer was reprecipitated from the filtered toluene solution into methanol and poly (9,9-dialkylfluorene) -co- (5,7-dihydrodibenzo [c, e] oxepin) (structure 33:55 below). % Of fluorene and 45% of structural units derived from 12).

Normal calibration GPC (PS standard, 30 ° C.) Mn12K, MWD5, bimodal);
¹ H-NMR (250 MHz, CDCl ₃ ) 0.80 (br, 10H, CH ₃ + CH ₂ ), 1.12 (br, 12H, CH ₂ ), 2.12 (br, 4H, CH ₂ ), 4.50 (br, 3.6H , CH ₂ , 45% 4H CH ₂ signal Methylene group adjacent to aromatic ring in hexyl substituent, correlated with 4H signal at 2.12 ppm), 7.50-7.87 (12H, Ar-H);
Solution UV (methylene chloride, RT) λ _max 366 nm;
Thin film UV λ _max 372 nm;
Cyclic voltammetry (Ag / AgCl corrected with iron (II) ferrocene) E _ox 1.46 V, E _red -0.84 V E _ox -E _red 2.3 eV;
PL spectrum (methylene chloride) λ _max 412 nm, λ _max (shoulder) 445 nm;
PL spectrum λ _max 418 nm, λ _max (shoulder) 450 nm.

9,9-di-n-hexylfluorene-2- (isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaboronate), 2,7 used in the above polymerization method By varying the relative amounts of -dibromo-9,9-di-n-hexylfluorene and 3,9-dibromo-5,7-dihydrodibenzo [c, e] oxepin, the series shown in Table 1 below [The polymer with 0% B is, of course, a homopolymer poly (di-n-hexylfluorene)].

  Solution UV / VIS absorption spectra of these polymers 33 were obtained and shown in FIG. 2 (in this figure, the term “ether” refers to the twisted monomer unit of structure B in 33). As can be seen, the copolymer of the present invention gives a blue-shifted emission, the shift increasing with increasing amount of twisted monomer units in structure B.

The UV / VIS absorption spectrum of the statistical copolymer of formula 33 having 25% units B and 75% units A is shown to be poly (di-n-hexylfluorene) having the following structure 34 and 75% 9,9: Comparison was made with the spectrum of a copolymer having the following structure 35 containing di-n-hexylfluorenyl groups and 25% phenyl groups (see FIG. 3). As can be seen, the random copolymers of the present invention have significantly reduced long wavelength tails in the visible region when compared to the two prior art polymers.

The photoluminescence spectrum of the copolymer of this example was measured and shown in FIG. 4 (in dichloromethane) and FIG. 5 (thin film). As the amount of 5,7-dihydrodibenzo [c, e] oxepin decreases, the emission shifts to longer wavelengths. Furthermore, cyclic voltammetry data of the copolymer was measured and the results are shown below.

Example 3
3,9-Dibromo-5,7-dihydro-dibenzo [c, e] thiepine (15) and 9,9-di-n-hexylfluorene-2,7-bis- (isopropoxy-4,4,5 , 5-tetramethyl-1,3,2-dioxaboronate) 13, 9,9-dibromo-5,7-dihydro-dibenzo [c, e] thiepine 15 (0.37 g, 1 .00 mmol, 1 equivalent) and 9,9-di-n-hexylfluorene-2,7-bis- (isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaboronate) 13 (0.50 g, 1.00 mmol, 1 eq) in a solution of dry degassed tetrahydrofuran (30 ml) (degassed by 3 cycles of pump-freeze-thaw) was dissolved in Cs ₂ CO ₃ (5 ml H ₂ O in 3.3 g, 2M) and tetrakis (triphenylphosphine) palladium (0) (0.021g, 0.02mmol, 0.02 eq) was added under a nitrogen atmosphere. After heating to reflux for 4 days, the concentrated polymer solution was filtered through a short silica plug (Pasteur pipette) and then precipitated from methanol (500 ml). After drying, the title polymer 36 was obtained as a white solid (0.18 g) in 32% yield.

ν _max (CHClg) / cm ⁻¹ 3037, 2931, 2860, 2393, 1605, 1465, 1262, 1003, 820;
δ _H (500 MHz; CDC13): 7.85-7.38 (12 H, m, ArH), 3.76 (2 H, br s, SCH2), 3.52 (2 H, br s, SCH2), 2.10 (4 H, br s , ArC (CH ₂ C ₅ H ₁₁ ) ₂ ), 1.22-1.05 (12 H, br s, alkyl), 0.83-0.64 (10 H, m, alkyl); GPC (CHCl ₃ ) M _w 1.4-10 ⁴ , M _n 4.3 · 10 ³ , M _w / M _n 3.3; TGA: 391 C (5% weight loss); λ _max (CHCl ₃ ) / nm 356.

Example 4
Manufacture of electroluminescent device A glass substrate coated with indium-tin oxide (ITO) was patterned into stripes (3 mm wide) and washed with water, acetone and ethanol. A hole injection layer, poly (3,4-ethylene-dioxythiophene): poly (styrenesulfonic acid) (PEDT: PSS) was spin coated on ITO (2000 rpm, 30 seconds). The PEDT: PSS layer was dried on a hot plate (130 ° C.) for 5 minutes. Next, the light emitting polymer F prepared in Example 3 was spin-coated on the PEDT: PSS layer. Thereafter, the device was introduced into a high vacuum coating unit, and a shadow mask (2 mm stripe) was set. The cathode metal calcium was deposited on the organic layer through a shadow mask, followed by aluminum. The size of each pixel is 3 mm × 2 mm. Finally, the device was sealed to block moisture. The film formation was performed under high vacuum (1 × 10 ⁻⁵ mbar). In general, PEDT: PSS is provided as an aqueous solution, and the light emitting polymer is prepared as a solution in an organic solvent. A metal having a low work function is usually used as the cathode. Typical thickness of the layer is as follows: ITO (190 nm) / PEDT: PSS (50 nm) / luminescent polymer (60 nm) / Ca (40 nm) / Al (200 nm). The device was examined by applying a direct current bias (0-30V) to the electrode. Electroluminescence properties were measured with a Hewlett-Packard E3631A DC power supply, a Keithley 2000 digital multimeter, a Topcon BM-8 luminance meter, and Aminco-Bowman. A schematic diagram illustrating the structure of the device is shown in FIG. 7 (PF in this figure refers to copolymer F of Example 3). Moreover, although manufactured almost the same as the above, another device was manufactured except for the Ca layer.

Various physical properties of the device thus manufactured were measured and presented in Table 2 below.

  The current-voltage luminescence curve of the above fcm01 device is shown in FIG.

Claims (5)

In the presence of a palladium (0) or palladium (II) catalyst and a base, x ¹ mol of the monomer of formula W ³ -F ¹ -W ⁴ , y ¹ mol of Y ⁵ -F ¹ -Y ⁶ , and z ¹ mol A method for producing a polymer comprising reacting a monomer of formula Y ⁵ -G ¹ -Y ⁶ of formula (XVI) to give a polymer of formula (XVI):

[Wherein Y ⁵ and Y ⁶ are leaving groups,
W ³ and W ⁴ are selected from the group consisting of a boronic acid group [B (OH) ₂ ], a boronate ester group of formula B (OR ³⁵ ) ₂ and a borane of formula B (R ³⁶ ) ₂ ;
R ³⁵ is 1) selected from the group consisting of a) and b) below, or a) a linear or branched alkyl group having 1 to 20 carbon atoms,
b) a straight or branched chain having an aromatic hydrocarbon group with 6 to 14 carbon atoms in one or more rings and having a nitro group, cyano group, amino group, 1 to 20 carbon atoms A chain alkyl group, a haloalkyl group in which the alkyl group is substituted with at least one halogen atom, a linear or branched alkoxy group having 1 to 20 carbon atoms, and the alkyl group is at least 1 An aryl group optionally substituted with at least one substituent selected from the group consisting of alkoxyalkyl groups substituted with two alkoxy groups,
2) Two R ³⁵ represent a linear or branched alkylene group having 2 to 10 carbon atoms forming one ring ,
R ³⁶ is selected from the group consisting of a), b) and c) below:
a) a straight-chain or branched alkyl group having 1 to 20 carbon atoms,
b) a straight or branched chain having an aromatic hydrocarbon group with 6 to 14 carbon atoms in one or more rings and having a nitro group, cyano group, amino group, 1 to 20 carbon atoms A chain alkyl group, a haloalkyl group in which the alkyl group is substituted with at least one halogen atom, a linear or branched alkoxy group having 1 to 20 carbon atoms, and the alkyl group is at least 1 An aryl group optionally substituted with at least one substituent selected from the group consisting of alkoxyalkyl groups substituted with two alkoxy groups,
c) an aralkyl group in which a linear or branched alkyl group having 1 to 20 carbon atoms is substituted with at least one aryl group),
G ¹ is a repeating unit represented by the following formula (I):

Here, A and B may be the same or different, and each or all or part thereof includes an aryl group shown below or a heteroaryl group shown below, and the group of A is condensed to a bond ab; The B group is fused to the bond cd, and X is a linking unit having the formula -A'-B'-C'-, and A ', B' and C 'may be the same or different. , O, S, SO, SO ₂ , NR ³ , N ⁺ (R ^{3 ′} ) (R ^{3 ″} ), C (R ⁴ ) (R ⁵ ), Si (R ^{4 ′} ) (R ^{5 ′} ), respectively. And P (O) (OR ⁶ ), wherein X has a twist angle of at least 5 ° between bond ab and bond cd with respect to bond bd And
R ³ , R ^{3 ′} and R ^{3 ″} may be the same or different and are each a hydrogen atom, an alkyl group shown below, a haloalkyl group shown below, an alkoxy group shown below, an alkoxyalkyl group shown below, Selected from the group consisting of an aryl group shown below, an aryloxy group shown below, an aralkyl group shown below, and an alkyl group shown below substituted with at least one group having the formula —N ⁺ (R ⁷ ) _3. ,
R ⁴ , R ⁵ , R ^{4 ′} and R ^{5 ′} may be the same or different and are each a hydrogen atom, an alkyl group shown below, a haloalkyl group shown below, an alkoxy group shown below, a halogen atom, or a nitro group. , A cyano group, an alkoxyalkyl group shown below, an aryl group shown below, an aryloxy group shown below, an aralkyl group shown below, an aryl group shown below, a heteroaryl group shown below, a fluorenyl group, and a spirobi Fluorenyl group (These aryl, heteroaryl, fluorenyl, and spirobifluorenyl groups are substituted with a disubstituted amino group, and the substituents may be the same or different. Selected from the group consisting of heteroaryl groups, fluorenyl groups, and spirobifluorenyl groups Or is selected from the group consisting of alkyl groups shown below which is substituted with more selected substituents, or R ⁴ and R ⁵ is a carbonyl group together with the carbon atoms to which they are attached,
R ⁶ is selected from the group consisting of a hydrogen atom, an alkyl group shown below, a haloalkyl group shown below, an alkoxyalkyl group shown below, an aryl group shown below, an aryloxy group shown below, and an aralkyl group shown below. And
The R ⁷ groups may be the same or different and are each selected from the group consisting of a hydrogen atom, an alkyl group shown below, and an aryl group shown below;
The heteroaryl group is a 5-membered to 7-membered aromatic heterocyclic group containing 1 to 3 heteroatoms selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom. The aryl group is selected from the group consisting of a nitro group, a cyano group, an amino group, an alkyl group shown below, a haloalkyl group shown below, an alkoxyalkyl group shown below, an aryloxy group shown below, and an alkoxy group shown below. Substituted with at least one substituent
The aryl group is an aromatic hydrocarbon group having 6 to 14 carbons in one or more rings, and includes a nitro group, a cyano group, an amino group, an alkyl group shown below, a haloalkyl group shown below, May be substituted with at least one substituent selected from the group consisting of an alkoxyalkyl group shown below, an aryloxy group shown below, and an alkoxy group shown below,
The alkyl group is a linear or branched alkyl group having 1 to 20 carbon atoms;
The haloalkyl group is the alkyl group substituted with at least one halogen atom;
The alkoxy group is a linear or branched alkoxy group having 1 to 20 carbon atoms;
The alkoxyalkyl group is the alkyl group substituted with at least one alkoxy group;
The aryl group of the aryloxy group is an aromatic hydrocarbon group having 6 to 14 carbon atoms in one or more rings, and includes a nitro group, a cyano group, an amino group, the alkyl group, the haloalkyl group, The alkoxyalkyl group may be substituted with at least one substituent selected from the group consisting of the alkoxy group,
The aralkyl group is an aralkyl group containing the alkyl group substituted with at least one aryl group,
F ¹ is a repeating unit conjugated with an adjacent unit in the polymer chain,
The molar ratio of x ¹ : (y ¹ + z ¹ ) is 1: 1 and the molar ratio of (x ¹ + y ¹ ): z ¹ is greater than 1] The method of claim 1, wherein the palladium (II) catalyst comprises a combination of tricyclohexylphosphine and palladium (II) acetate. The method of claim 2, wherein the base is tetraethylammonium hydroxide. The method according to any one of claims 1 to 3, characterized in that the leaving groups Y ⁵ and Y ⁶ are bromine or iodine. Substituents W ³ and W ⁴ each represent a boronate ester group of formula B (OR ³⁵ ) ₂ , and two R ³⁵ groups in each boronate ester group form two to two forming one ring. 5. A process according to any one of claims 1 to 4, characterized in that it represents an alkylene group with 6 carbon atoms.

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