Polymer compound and light emitting device using the same

Abstract

A polymer compound comprising a constitutional unit having a group represented by the formula (1): ##STR00001##
wherein Ring A.sup.1A and Ring R.sup.2A represent an aromatic hydrocarbon ring or a heterocyclic ring and these rings each optionally have a substituent, nA represents an integer of 0 to 5, nB represents an integer of 1 to 5, L.sup.A and L.sup.B represent an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic ring group, a group represented by NR, an oxygen atom or a sulfur atom, and R represents a hydrogen atom, an alkyl group or the like, and Q.sup.1 represents a crosslinkable group.

Claims

1. A polymer compound comprising a constitutional unit represented by the following formula (2): ##STR00172## wherein Ar.sup.1 represents an aromatic hydrocarbon group or a heterocyclic ring group and these groups each optionally have a substituent, n represents an integer of 1 to 4, and Q.sup.2 represents a group represented by the following formula and when a plurality of Q.sup.2 are present, they can be the same or different: ##STR00173## wherein Ring R.sup.1A and Ring R.sup.2A each independently represent an aromatic hydrocarbon ring or a heterocyclic ring, nA represents an integer of 0 to 5, and nB represents an integer of 1 to 5, L.sup.A and L.sup.B each independently represent an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic ring group, a group represented by NR, an oxygen atom or a sulfur atom and these groups each optionally have a substituent, and R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group and these groups each optionally have a substituent, and when a plurality of L.sup.A and L.sup.B are present, they may be the same or different at each occurrence, and Q.sup.1 represents a crosslinkable group selected from the following Group A, wherein Group A is a crosslinkable group selected from the group consisting of: ##STR00174## ##STR00175## wherein R.sup.XL represents a methylene group, an oxygen atom or a sulfur atom, n.sup.XL represents an integer of 0 to 5, and when a plurality of R.sup.XL, are present, they may be the same or different, and when a plurality of n.sup.XL are present, they may be the same or different, * represents a binding position, and these crosslinkable groups each optionally have a substituent.

2. The polymer compound according to claim 1, further comprising a constitutional unit represented by the following formula (X): ##STR00176## wherein a.sup.1 and a.sup.2 each independently represent an integer of 0 or more, Ar.sup.X1 and Ar.sup.X3 each independently represent an arylene group or a divalent heterocyclic ring group and these groups each optionally have a substituent, Ar.sup.X2 and Ar.sup.X4 each independently represent an arylene group, a divalent heterocyclic ring group or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other, and these groups each optionally have a substituent, and R.sup.X1, R.sup.X2 and R.sup.X3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group and these groups each optionally have a substituent.

3. The polymer compound according to claim 1, further comprising a constitutional unit represented by the following formula (Y):
Ar.sup.Y1(Y) wherein Ar.sup.Y1 represents an arylene group, a divalent heterocyclic group or a divalent group in which at least one arylene group and at least one divalent heterocyclic group are bonded directly to each other, and these groups each optionally have a substituent.

4. The polymer compound according to claim 1, wherein Ring R.sup.1A and Ring R.sup.2A are a benzene ring optionally having a substituent.

5. The polymer compound according to claim 1, wherein Ar.sup.1 is a group obtained by removing from a benzene ring optionally having a substituent, a fluorene ring optionally having a substituent, a naphthalene ring optionally having a substituent, a phenanthrene ring optionally having a substituent or a dihydrophenanthrene ring optionally having a substituent (2+n) hydrogen atoms linked directly to carbon atoms constituting the ring.

6. The polymer compound according to claim 3, wherein the constitutional unit represented by the formula (Y) is a constitutional unit represented by the following formula (Y-1) or a constitutional unit represented by the following formula (Y-2): ##STR00177## wherein R.sup.Y1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group and these groups each optionally have a substituent, and the plurality of R.sup.Y1 may be the same or different, and adjacent R.sup.Y1s may be combined together to form a ring together with the carbon atoms to which they are attached: ##STR00178## wherein R.sup.Y1 represents the same meaning as described above, X.sup.Y1 represents a group represented by C(R.sup.Y2).sub.2, C(R.sup.Y2)C(R.sup.Y2) or C(R.sup.Y2).sub.2C(R.sup.Y2).sub.2, and R.sup.Y2 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyl group, a cycloalkoxy group, an aryl group or a monovalent heterocyclic group and these groups each optionally have a substituent, and the plurality of R.sup.Y2 may be the same or different, and R.sup.Y2 s may be combined together to form a ring together with the carbon atoms to which they are attached.

7. The polymer compound according to claim 1, wherein the content of the constitutional unit represented by the formula (2) is 3 to 90 mol % with respect to the total content of constitutional units contained in the polymer compound.

8. A compound represented by the following formula (2M): ##STR00179## wherein Ring R.sup.1A and Ring R.sup.2A each independently represent an aromatic hydrocarbon ring or a heterocyclic ring and these rings each optionally have a substituent, nA represents an integer of 0 to 5, and nB represents an integer of 1 to 5, L.sup.A and L.sup.B each independently represent an alkylene group, a cycloalkylene group, an arylene group, a divalent heterocyclic ring group, a group represented by NR, an oxygen atom or a sulfur atom and these groups each optionally have a substituent, and R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a monovalent heterocyclic group and these groups each optionally have a substituent, and when a plurality of L.sup.A and L.sup.B are present, they may be the same or different at each occurrence, Q.sup.1 represents a crosslinkable group selected from the following Group A of crosslinkable group, Ar.sup.1 represents an aromatic hydrocarbon group or a heterocyclic ring group and these groups each optionally have a substituent, n represents an integer of 1 to 4, and Z.sup.1 and Z.sup.2 each independently represent a group selected from the following Group A of substituent or Group B of substituent: wherein Group A is a crosslinkable group selected from the group consisting of: ##STR00180## ##STR00181## wherein R.sup.X1 represents a methylene group, an oxygen atom or a sulfur atom, n.sup.XL represents an integer of 0 to 5, and when a plurality of R.sup.XL are present, they may be the same or different, and when a plurality of n.sup.X1 are present, they may be the same or different, * represents a binding position, and these crosslinkable groups each optionally have a substituent: wherein Group A is a substituent selected from the group consisting of: a chlorine atom, a bromine atom, an iodine atom, and a group represented by OS(O).sub.2R.sup.C1, wherein R.sup.C1 represents an alkyl group, a cycloalkyl group or an aryl group and these groups each optionally have a substituent, wherein Group B is a substituent selected from the group consisting of: a group represented by B(OR.sup.C2).sub.2, wherein R.sup.C2 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group and these groups each optionally have a substituent, and the plurality of R.sup.C2 may be the same or different and may be combined together to form a cyclic structure together with the oxygen atoms to which they are attached; a group represented by BF.sub.3Q, wherein Q represents a lithium atom, a sodium atom, a potassium atom, a rubidium atom or a cesium atom; a group represented by MgY, wherein Y represents a chlorine atom, a bromine atom or an iodine atom; a group represented by ZnY, wherein Y represents a chlorine atom, a bromine atom or an iodine atom; and a group represented by Sn(R.sup.C3).sub.3, wherein R.sup.C3 represents a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group and these groups each optionally have a substituent, and the plurality of R.sup.C3 may be the same or different and may be combined together to form a cyclic structure together with the tin atom to which they are attached.

9. A composition comprising the polymer compound according to claim 1, and at least one material selected from the group consisting of a hole transporting material, a hole injection material, an electron transporting material, an electron injection material, a light emitting material, an antioxidant and a solvent.

10. A light emitting device produced by using the polymer compound according to claim 1.

Description

EXAMPLES

(1) The present invention will be illustrated further in detail by examples below, but the present invention is not limited to these examples.

(2) In the present examples, the polystyrene-equivalent number average molecular weight (Mn) and the polystyrene-equivalent weight average molecular weight (Mw) of a polymer compound were measured by size exclusion chromatography (SEC) (manufactured by Shimadzu Corp., trade name; LC-10Avp). SEC measurement conditions are as described below.

(3) [Measurement Condition]

(4) The polymer compound to be measured was dissolved in THF at a concentration of about 0.05 wt %, and 10 L of the solution was injected into SEC. As the mobile phase of SEC, tetrahydrofuran was used and allowed to flow at a flow rate of 2.0 mL/min. As the column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. As the detector, UV-VIS detector (manufactured by Shimadzu Corp., trade name: SPD-10Avp) was used.

(5) Measurement of liquid cbromatograph mass spectrometry (LC-MS) was carried out according to the following method.

(6) A measurement sample was dissolved in chloroform or THF so as to give a concentration of about 2 mg/mL, and about 1 L of the solution was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). As the mobile phase of LC-MS, acetonitrile and THF were used while changing the ratio thereof and allowed to flow at a flow rate of 0.2 mL/min. As the column, L-column 2 ODS (3 m) (manufactured by Chemicals Evaluation and Research Institute, internal diameter: 2.1 mm, length: 100 mm, particle size: 3 m) was used.

(7) Measurement of NMR was carried out according to the following method.

(8) 5 to 10 mg of a measurement sample was dissolved in about 0.5 mL of deuterated chloroform (CDCl.sub.3), deuterated tetrahydrofuran (THF-d.sub.8) or deuterated methylene chloride (CD.sub.2Cl.sub.2), and measurement was performed using an NMR apparatus (manufactured by Varian, Inc., trade name: MERCURY 300).

(9) As the index of the purity of a compound, a value of the high performance liquid chromatography (HPLC) area percentage was used. This value is a value in high performance liquid chromatography (HPLC, manufactured by Shimadzu Corp., trade name: LC-20A) at 254 nm, unless otherwise state. In this operation, the compound to be measured was dissolved in THF or chloroform so as to give a concentration of 0.01 to 0.2 wt %, and depending on the concentration, 1 to 10 L of the solution was injected into HPLC. As the mobile phase of HPLC, acetonitrile and THF were used and allowed to flow at a flow rate of 1 mL/min as gradient analysis of acetonitrile/THF=100/0 to 0/100 (volume ratio). As the column, Kaseisorb LC ODS 2000 (manufactured by Tokyo Chemical Industry Co., Ltd.) or an ODS column having an equivalent performance was used. As the detector, a photo diode array detector (manufactured by Shimadzu Corp., trade name: SPD-M20A) was used.

Synthesis Example 1

Synthesis of Compound Ma3

(10) ##STR00157##

(11) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, a compound Ma2 (64.6 g) and tetrahydrofuran (615 mL) were added, and the mixture was cooled down to 70 C. Into this, a n-butyllithium hexane solution (1.6 M, 218 mL) was dropped over a period of 1 hour, then, the mixture was stirred at 70 C. for 2 hours. To this, a compound Ma1 (42.1 g) was added in several batches, then, the mixture was stirred at 70 C. for 2 hours. Into this, methanol (40 mL) was dropped over a period of 1 hour, then, the mixture was heated up to room temperature. Thereafter, the solvent was distilled off by concentrating under reduced pressure, and toluene and water were added. Thereafter, an aqueous layer was separated and the resultant organic layer was washed with water. The resultant organic layer was concentrated under reduced pressure, and the resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and ethyl acetate), thereby obtaining 71 g of a compound Ma3 as a colorless oil. The compound Ma3 had an HPLC area percentage value (UV: 254 nm) of 97.5%. This operation was repeated, thereby obtaining a necessary amount of the compound Ma3.

(12) .sup.1H-NMR (CDCl.sub.3, 300 MHz): (ppm): 2.43 (1H, s), 3.07-3.13 (4H, m), 6.95 (1H, d), 7.07 (1H, s), 7.18-7.28 (3H, m), 7.28-7.40 (4H, m), 7.66 (2H, s).

Synthesis Example 2

Synthesis of Compound Ma4

(13) ##STR00158##

(14) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Ma3 (72.3 g), toluene (723 mL) and triethylsilane (118.0 g) were added, and the mixture was heated up to 70 C. Into this, methanesulfonic acid (97.7 g) was dropped over a period of 1.5 hours, then, the mixture was stirred at 70 C. for 0.5 hours. Thereafter, the mixture was cooled down to room temperature, and toluene (1 L) and water (1 L) were added, then, an aqueous layer was separated. The resultant organic layer was washed with water, a 5 wt % sodium hydrogen carbonate aqueous solution and water in this order. The resultant organic layer was concentrated under reduced pressure, and the resultant coarse product was recrystallized from a mixed solvent of toluene and ethanol, thereby obtaining 51.8 g of a compound Ma4 as a white solid. The compound Ma4 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more. This operation was repeated, thereby obtaining a necessary amount of the compound Ma4.

(15) .sup.1H-NMR (CDCl.sub.3, 300 MHz): (ppm): 3.03-3.14 (4H, m), 4.99 (1H, s), 6.68 (1H, s), 6.92-7.01 (2H, m), 7.20-7.28 (2H, m), 7.29-7.38 (4H, m), 7.78 (2H, d).

Synthesis Example 3

Synthesis of Compound Mb3

(16) ##STR00159##

(17) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, a compound Mb1 (185.0 g), a compound Mb2 (121.1 g), copper(I) iodide (3.2 g), dichloromethane (185 mL) and triethylamine (2.59 L) were added, and the mixture was heated up to the reflux temperature. Thereafter, the mixture was stirred at the reflux temperature for 0.5 hours, and cooled down to room temperature. To this was added dichloromethane (1.85 L), then, the mixture was filtrated through a filter paved with celite. To the resultant filtrate was added a 10 wt % sodium hydrogen carbonate aqueous solution, then, an aqueous layer was separated. The resultant organic layer was washed with water twice, washed with a saturated sodium chloride aqueous solution, then, magnesium sulfate was added. The resultant mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of chloroform and ethyl acetate), thereby obtaining a coarse product. The resultant coarse product was dissolved in ethanol (1.4 L), then, activated carbon (5 g) was added, and the mixture was filtrated. The resultant filtrate was concentrated under reduced pressure, and the resultant residue was recrystallized from hexane, thereby obtaining 99.0 g of a compound Mb3 as a white solid. The compound Mb3 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more. This operation was repeated, thereby obtaining a necessary amount of the compound Mb3.

(18) .sup.1H-NMR (DMSO-d6, 300 MHz) (ppm): 1.52-1.55 (8H, m), 2.42 (4H, t), 3.38-3.44 (4H, m), 4.39-4.43 (2H, m), 7.31 (4H, s).

Synthesis Example 4

Synthesis of Compound Mb4

(19) ##STR00160##

(20) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb3 (110.0 g), ethanol (1.65 L) and palladium/carbon (palladium weight: 10%) (11.0 g) were added, and the mixture was heated up to 30 C. Thereafter, a gas in the flask was purged with a hydrogen gas. Thereafter, the mixture was stirred at 30 C. for 3 hours while feeding a hydrogen gas into the flask. Thereafter, a gas in the flask was purged with a nitrogen gas. The resultant mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of chloroform and ethyl acetate), thereby obtaining a coarse product. The resultant coarse product was recrystallized from hexane, thereby obtaining 93.4 g of a compound Mb4 as a white solid. The compound Mb4 had an HPLC area percentage value (UV: 254 nm) of 98.3%.

(21) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 1.30-1.40 (8H, m), 1.55-1.65 (8H, m), 2.58 (4H, t), 3.64 (4H, t), 7.09 (4H, s).

(22) .sup.13C-NMR (CDCl.sub.3, 75 MHz) (ppm): 25.53, 28.99, 31.39, 32.62, 35.37, 62.90, 128.18, 139.85.

Synthesis Example 5

Synthesis of Compound Mb5

(23) ##STR00161##

(24) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb4 (61.0 g), pyridine (0.9 g) and toluene (732 mL) were added, and the mixture was heated up to 60 C. Into this, thionyl chloride (91.4 g) was dropped over a period of 1.5 hours, then, the mixture was stirred at 60 C. for 5 hours. The resultant mixture was cooled down to room temperature, then, concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and ethyl acetate), thereby obtaining 64.3 g of a compound Mb5 as a colorless oil. The compound Mb5 had an HPLC area percentage value (UV: 254 nm) of 97.2%.

(25) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 1.35-1.40 (4H, m), 1.41-1.50 (4H, m), 1.60-1.68 (4H, m), 1.75-1.82 (4H, m), 2.60 (4H, t), 3.55 (4H, t), 7.11 (4H, s).

Synthesis Example 6

Synthesis of Compound Mb6

(26) ##STR00162##

(27) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb5 (42.0 g), an iron powder (1.7 g), iodine (0.3 g) and dichloromethane (800 mL) were added. Thereafter, the whole flask was light-shielded, and cooled at 0 to 5 C. Into this, a mixed liquid of bromine (44.7 g) and dichloromethane (200 mL) was dropped over a period of 1 hour, then, the mixture was stirred at 0 to 5 C. overnight. The resultant mixed liquid was added to water (1.2 L) cooled at 0 to 5 C., then, an organic layer was separated. The resultant organic layer was washed with a 10 wt % sodium thiosulfate aqueous solution, and further, washed with a saturated sodium chloride aqueous solution and water in this order. To the resultant organic layer was added sodium sulfate, then, the mixture was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was purified by using a silica gel column (developing solvent; hexane), thereby obtaining a coarse product. The resultant coarse product was recrystallized from hexane, thereby obtaining 47.0 g of a compound Mb6 as a white solid. The compound Mb6 had an HPLC area percentage value (UV: 254 nm) of 98.3%.

(28) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 1.38-1.45 (4H, m), 1.47-1.55 (4H, m), 1.57-1.67 (4H, m), 1.77-1.84 (4H, m), 2.66 (4H, t), 3.55 (4H, t), 7.36 (2H, s).

Synthesis Example 7

Synthesis Oil Compound Mb7

(29) ##STR00163##

(30) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium iodide (152.1 g) and acetone (600 mL) were added, and the mixture was stirred at room temperature for 0.5 hours. To this was added the compound Mb6 (40.0 g), then, the mixture was heated up to the reflux temperature, and stirred at the reflux temperature for 24 hours. Thereafter, the mixture was cooled down to room temperature, and the resultant mixed liquid was added to water (1.2 L). The deposited solid was separated by filtration, then, washed with water, thereby obtaining a coarse product. The resultant coarse product was recrystallized from a mixed liquid of toluene and methanol, thereby obtaining 46.0 g of a compound Mb7 as a white solid. The compound Mb7 had an HPLC area percentage value (UV: 254 nm) of 99.4%. This operation was repeated, thereby obtaining a necessary amount of the compound Mb7.

(31) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 1.35-1.50 (8H, m), 1.57-1.65 (4H, m), 1.80-1.89 (4H, m), 2.65 (4H, t), 3.20 (4H, t), 7.36 (2H, s).

Example 1

Synthesis of Compound Mb8

(32) ##STR00164##

(33) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium hydride (60 wt %, dispersed in liquid paraffin) (9.4 g), tetrahydrofuran (110 mL) and the compound Mb7 (63.2 g) were added. To this, a compound Ma4 (55.0 g) was added in several batches, then, the mixture was stirred for 12 hours. To this were added toluene (440 mL) and water (220 mL), then, an aqueous layer was separated. The resultant organic layer was washed with water, then, magnesium sulfate was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and toluene). Thereafter, the product was recrystallized from hexane, thereby obtaining 84.1 g of a compound Mb8 as a white solid. The compound Mb8 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more.

(34) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 0.70-0.76 (4H, m), 1.10-1.21 (8H, m), 1.32-1.44 (4H, m), 2.39-2.58 (8H, m), 3.00-3.12 (8H, m), 6.82-6.94 (4H, m), 7.00-7.05 (2H, m), 7.17-7.28 (10H, m), 7.30-7.38 (4H, m), 7.71-7.77 (4H, m).

Example 2

Synthesis of Compound MM1

(35) ##STR00165##

(36) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mb8 (84.0 g), [1,1-bis(diphenylphosphino)ferrocene]palladium(II) dichloride dichloromethane adduct (PdCl.sub.2(dppf).CH.sub.2Cl.sub.2, 2.2 g), bispinacolatodiboron (68.3 g), potassium acetate (52.8 g) and cyclopentyl methyl ether (840 mL) were added, and the mixture was heated up to the reflux temperature, then, stirred at the reflux temperature for 5 hours. Thereafter, the mixture was cooled down to room temperature, and toluene (500 mL) and water (300 mL) were added, then, an aqueous layer was separated. The resultant organic layer was washed with water, then, activated carbon (18.5 g) was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was purified by using a silica gel column (developing solvent: a mixed solvent of hexane and toluene). Thereafter, an operation of recrystallizing from a mixed liquid of toluene and acetonitrile was repeated, thereby obtaining 45.8 g of a compound MM1 as a white solid. The compound MM1 had an HPLC area percentage value (UV: 254 nm) of 99.4%.

(37) .sup.1H-NMR (CDCl.sub.3, 300 MHz) (ppm): 0.70-0.76 (4H, m), 1.24-1.40 (36H, m), 2.39-2.48 (4H, m), 2.66-2.75 (4H, m), 3.00-3.10 (8H, m), 6.76-6.90 (4H, m), 7.00-7.05 (2H, m), 7.19-7.30 (8H, m), 7.30-7.36 (4H, m), 7.43 (2H, s), 7.72 (4H, d).

Synthesis Example 8

Synthesis of Compound Mc1

(38) ##STR00166##

(39) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium hydride (60 wt %, dispersed in liquid paraffin) (10.9 g), tetrahydrofuran (268 mL) and 1-bromo-6-chlorohexane (198.3 g) were added. Thereafter, the whole flask was light-shielded, and cooled at 0 to 5 C. To this, a mixed liquid of a compound Ma4 (67.0 g) and tetrahydrofuran (330 mL) was added over a period of 2.5 hours, then, the mixture was heated up to 50 C., and stirred at 50 C. for 6 hours. To this were added heptane (536 mL) and water (268 mL), and an aqueous layer was separated. The resultant organic layer was washed with water, then, magnesium sulfate was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was recrystallized from isopropanol, then, the resultant crystal was dissolved in a mixed liquid of toluene and heptane, and activated carbon (9.6 g) was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure. The resultant residue was recrystallized from a mixed liquid of toluene and heptane, thereby obtaining 81.0 g of a compound Mc1 as a white solid. The compound Mc1 had an HPLC area percentage value (UV: 254 nm) of 99.5%. This operation was repeated, thereby obtaining a necessary amount of the compound Mc1.

(40) .sup.1H-NMR (CD.sub.2Cl.sub.2, 300 MHz) (ppm): 0.71-0.83 (2H, m), 1.27 (4H, t), 1.58-1.68 (2H, m), 2.49-2.54 (2H, m), 3.08-3.19 (4H, m), 3.49 (2H, t), 6.89 (1H, s), 6.94 (1H, d), 7.07 (1H, d), 7.25-7.44 (6H, m), 7.33 (2H, d).

Synthesis Example 3

Synthesis of Compound Mc2

(41) ##STR00167##

(42) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, the compound Mc1 (124.4 g), sodium iodide (385.5 g) and acetone (786 mL) were added, then, the mixture was heated up to the reflux temperature, and stirred at the reflux temperature for 34 hours. Thereafter, the mixture was cooled down to room temperature, and to the resultant mixed liquid were added heptane, toluene and water, then, an aqueous layer was separated. The resultant organic layer was washed with water, then, magnesium sulfate was added. The resultant mixed liquid was filtrated, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. The resultant coarse product was recrystallized from a mixed liquid of heptane and isopropanol, thereby obtaining 143 g of a compound Mc2 as a white solid. The compound Mc2 had an HPLC area percentage value (UV: 254 nm) of 99.4%.

(43) .sup.1H-NMR (CD.sub.2Cl.sub.2, 300 MHz) (ppm): 0.71-0.83, (2H, m), 1.20-1.36 (4H, m), 1.60-1.70 (2H, m), 2.48-2.54 (2H, m), 3.13-3.18 (6H, m), 6.89 (1H, s), 6.94 (1H, d), 7.07 (1H, d), 7.25-7.43 (6H, m), 7.83 (2H, d).

Example: 3

Synthesis of Compound MM2

(44) ##STR00168##

(45) A gas in a flask equipped with a stirrer was purged with a nitrogen gas, then, sodium hydride (60 wt %, dispersed in liquid paraffin) (1.0 g), tetrahydrofuran (42.5 mL), N,N-dimethylformamide (42.5 mL) and the compound Mc2 (10.8 g) were added. Thereafter, the whole flask was light-shielded, and cooled at 0 to 5 C. To this, a mixed liquid of a compound Mc3 (10.6 g) synthesized according to a synthesis method described in Japanese Patent Application National Publication No. 2014-506609 and tetrahydrofuran (42.5 mL) was added over a period of 1 hour, then, the mixture was stirred at 0 to 5 C. for 4 hours. The resultant reaction mixture wan heated up to room temperature, then, toluene (106 mL) and water (106 mL) were added, and an aqueous layer was separated. The resultant organic layer was washed with water, then, sodium sulfate was added. The resultant mixed liquid was filtrated through a filter paved with silica gel, and the resultant filtrate was concentrated under reduced pressure, thereby obtaining a coarse product. An operation of recrystallizing the resultant coarse product from a mixed liquid of ethyl acetate and acetonitrile was repeated, thereby obtaining 14.3 g of a compound MM2 as a white solid. The compound MM2 had an HPLC area percentage value (UV: 254 nm) of 99.5% or more.

(46) LC-MS (positive): m/z: 955 ([M+K].sup.+)

(47) .sup.1H-NMR (CD.sub.2Cl.sub.2, 300 MHz) (ppm): 0.56-0.65 (4H, m), 0.90-1.32 (22H, m), 1.54-1.58 (4H, m), 2.34-2.42 (4H, m), 2.52 (4H, t), 3.12 (4H, d), 6.74 (2H, s), 6.85 (1H, s), 6.92 (2H, d), 7.00-7.05 (1H, m), 7.19 (2H, d), 7.26-7.41 (6H, m), 7.53 (2H, d), 7.65 (2H, d), 7.80 (2H, d).

Synthesis Example 10

Synthesis of Compounds MM10 to MM17

(48) A compound MM10 was synthesized according to a synthesis method described in International Publication WO2005/049546.

(49) A compound MM11 was synthesized according to a synthesis method described in JP-A No. 2010-189630.

(50) A compound MM12 was synthesized according to a synthesis method described in JP-A No. 2010-215886.

(51) A compound MM13 was synthesized according to a synthesis method described in International Publication WO2013/191088.

(52) A compound MM14 was synthesized according to a synthesis method described in JP-A 2010-189630.

(53) A compound MM15 was synthesized according to a synthesis method described in International Publication WO2009/131255.

(54) A compound MM16 was synthesized according to a synthesis method described in International Publication WO2013/146806.

(55) A compound MM17 was synthesized according to a synthesis method described in Japanese Patent Application National Publication No. 2007-528916.

(56) ##STR00169## ##STR00170##

Synthesis Example 11

Synthesis of Metal Complex Ca1

(57) A metal complex Ca1 was synthesized according to a synthesis method described in International Publication WO2009/131255.

(58) ##STR00171##

Example 4

Synthesis of Polymer Compound 1

(59) (Step 1) An inert gas atmosphere was prepared in a reaction vessel, then, the compound MM10 (918.4 mg), the compound MM11 (493.3 mg), the compound MM12 (115.6 mg), the compound MM1 (257.8 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were added, and the mixture was heated at 105 C.

(60) (Step 2) Into the reaction liquid, a 20 wt % tetraethylammonium hydroxide aqueous solution (10 mL) was dropped, and the mixture was refluxed for 5 hours.

(61) (Step 3) After the reaction, to this were added phenylboronic acid (36.6 mg) and dichlorobis(triso-O-methoxyphenylphosphine)palladium (2.6 mg), and the mixture was refluxed for 16.5 hours.

(62) (Step 4) After the reaction, to this was added a sodium diethyldithiacarbamate aqueous solution, and the mixture was stirred at 80 C. for 2 hours. After cooling, the reaction liquid was washed with water twice, with a 3 wt % acetic acid aqueous solution twice, and with water twice, and the resultant solution was dropped into methanol, to observe precipitation. The precipitate was dissolved in toluene, and the solution was purified by passing through an alumina column and a silica gel column in this order. The resultant solution was dropped into methanol, the mixture was stirred, then, the resultant precipitate was isolated by filtration, and dried, thereby obtaining 1.10 g of a polymer compound 1. The polymer compound 1 had a Mn of 3.310.sup.4 and a Mw of 3.210.sup.5.

(63) The polymer compound 1 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM11, a constitutional unit derived from the compound MM12 and a constitutional unit derived from the compound MM1 at molar ratios of 40:40:10:10, according to theoretical values calculated from the amounts of charged raw materials.

Synthesis Example 12

Synthesis of Polymer Compound 2

(64) A nitrogen atmosphere was prepared in a reaction vessel, then, the compound MM11 (822.2 mg), the compound MM15 (850.7 mg), the compound MM14 (209.7 mg) and toluene (37 mL) were added, and the mixture was heated at 80 C., Thereafter, to this were added palladium acetate (0.41 mg), tris(2-methoxyphenyl)phosphine (2.30 mg) and a 20 wt % tetraethylammonium hydroxide aqueous solution (5.8 g), and the mixture was stirred for 4 hours under reflux. Thereafter, to this was added phenylboronic acid (40.6 mg), and the mixture was stirred for 2 hours under reflux. Thereafter, to this was added a solution prepared by dissolving sodium N,N-diethyldithiocarbamate trihydrate (0.46 g) in ion-exchanged water (9 mL), and the mixture was stirred at 85 C. for 2 hours. The resultant organic layer was washed with 3.6 wt % hydrochloric acid twice, with a 2.5 wt % ammonia aqueous solution twice and with ion-exchanged water five times, in series. The resultant organic layer was dropped into methanol, to observe precipitation. The resultant precipitate was isolated by filtration, and dried. The resultant solid was dissolved in toluene, and the solution was allowed to pass through a silica gel column and an alumina column through which toluene had passed previously. The resultant solution was dropped into methanol, to observe precipitation. The resultant precipitate was isolated by filtration, and dried, thereby obtaining a polymer compound 2 (1.11 g). The polymer compound 2 had a Mn of 8.710.sup.4 and a Mw of 2.310.sup.5.

(65) The polymer compound 2 is a copolymer having a constitutional unit derived from the compound MM11, a constitutional unit derived from the compound MM14 and a constitutional unit derived from the compound MM15 at molar ratios of 50:10:40, according to theoretical values calculated from the amounts of charged raw materials.

Comparative Example C1

Synthesis of Polymer Compound 3

(66) A polymer compound 3 (0.95 g) was obtained in the same manner as for synthesis of the polymer compound 1 excepting that (Step 1) in synthesis of the polymer compound 1 was changed to An inert gas atmosphere was prepared in a reaction vessel, then, the compound MM10 (918.4 mg), the compound MM11 (491.4 mg), the compound MM12 (115.6 mg), the compound MM13 (156.9 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were mixed, and heated at 105 C.. The polymer compound 3 had a Mn of 3.510.sup.4 and a Mw of 3.410.sup.5.

(67) The polymer compound 3 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM11, a constitutional unit derived from the compound MM12 and a constitutional unit derived from the compound MM13 at molar ratios of 40:40:10:10, according to theoretical values calculated from the amounts of charged raw materials.

Example 5

Synthesis of Polymer Compound 4

(68) A polymer compound 4 (1.05 g) was obtained in the same manner as for synthesis of the polymer compound 1 excepting that (Step 1) in synthesis of the polymer compound 1 was changed to An inert gas atmosphere was prepared in a reaction vessel, then, the compound MM10 (917.2 mg), the compound MM11 (499.6 mg), the compound MM1 (259.2 mg), the compound MM2 (230.1 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were mixed, and heated at 105 C.. The polymer compound 4 had a Mn of 4.010.sup.4 and a Mw of 2.810.sup.5.

(69) The polymer compound 4 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM11, a constitutional unit derived from the compound MM1 and a constitutional unit derived from the compound MM2 at molar ratios of 40:40:10:10, according to theoretical values calculated from the amounts of charged raw materials.

Example 6

Synthesis of Polymer Compound 5

(70) A polymer compound 5 (1.23 g) was obtained in the same manner as for synthesis of the polymer compound 1 excepting that (Step 1) in synthesis of the polymer compound 1 was changed to An inert gas atmosphere was prepared in a reaction vessel, then, the compound MM10 (917.2 mg), the compound MM16 (49.6 mg), the compound MM1 (923.0 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were mixed, and heated at 105 C.. The polymer compound 5 had a Mn of 2.310.sup.4 and a Mw of 1.210.sup.5.

(71) The polymer compound 5 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM16 and a constitutional unit derived from the compound MM1 at molar ratios of 50:5:45, according to theoretical values calculated from the amounts of charged raw materials.

Example 7

Synthesis of Polymer Compound 6

(72) A polymer compound 6 (1.23 g) was obtained in the same manner as for synthesis of the polymer compound 1 excepting that (Step 1) in synthesis of the polymer compound 1 was changed to An inert gas atmosphere prepared in a reaction vessel, then, the compound MM10 (917.2 mg), the compound MM16 (49.6 mg), the compound MM11 (194.8 mg), the compound MM1 (518.5 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were mixed, and heated at 105 C.. The polymer compound 6 had a Mn of 2.510.sup.4 and a Mw of 3.010.sup.5.

(73) The polymer compound 6 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM16, a constitutional unit derived from the compound MM11 and a constitutional unit derived from the compound MM1 at molar ratios of 50:5:20:25, according to theoretical values calculated from the amounts of charged raw materials.

Comparative Example C2

Synthesis of Polymer Compound 7

(74) A polymer compound 7 (0.92 g) was obtained in the same manner as for synthesis of the polymer compound 1 excepting that (Step 1) in synthesis of the polymer compound 1 was changed to An inert gas atmosphere was prepared in a reaction vessel, then, the compound MM10 (918.4 mg), the compound MM11 (502.3 mg), the compound MM12 (116.0 mg), the compound MM17 (163.9 mg), dichlorobis(tris-o-methoxyphenylphosphine)palladium (2.6 mg) and toluene (71 mL) were mixed, and heated at 105 C.. The polymer compound 7 had a Mn of 3.310.sup.4 and a Mw of 2.210.sup.5.

(75) The polymer compound 7 is a copolymer having a constitutional unit derived from the compound MM10, a constitutional unit derived from the compound MM11, a constitutional unit derived from the compound MM12 and a constitutional unit derived from the compound MM17 at molar ratios of 40:40:10:10, according to theoretical values calculated from the amounts of charged raw materials.

Example D1

Fabrication and Evaluation of Light Emitting Device D1

(76) On a glass substrate carrying thereon an ITO film having a thickness of 45 nm formed by a sputtering method, a polythiophene.sulfonic acid type hole injecting agent AQ-1200 (manufactured by Plextronics) was spin-coated as a hole injection material to form a film with a thickness of 65 nm, and this was heated on a hot plate at 170 C. for 15 minutes in an air atmosphere.

(77) Next, the polymer compound 1 was dissolved in xylene to prepare a 0.7 wt % xylene solution. This xylene solution was spin-coated to form a film with a thickness of 20 nm, and this was heated on a hot plate at 180 C. for 60 minutes in a nitrogen gas atmosphere.

(78) Next, the polymer compound 2 and the metal complex Ca1 were respectively dissolved in xylene, to prepare 1.8 wt % xylene solutions. Next, the xylene solution of the polymer compound 2 and the xylene solution of the metal complex Ca1 were mixed so that the weight ratio of solid components of the polymer compound 2 and the metal complex Ca1 was 70:30. This xylene solution was spin-coated to form a film with a thickness of 80 nm, and this was heated on a hot plate at 150 C. for 10 minutes in a nitrogen gas atmosphere. Thereafter, as a cathode, sodium fluoride was vapor-deposited with a thickness of about 7 nm, then, aluminum was vapor-deposited with a thickness of about 120 nm, to fabricate a light emitting device D1. After the degree of vacuum reached 110.sup.4 Pa or lower, vapor-deposition of a metal was initiated.

(79) When voltage was applied to the light emitting device D1, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 81.2 cd/A.

Example D2

Fabrication and Evaluation of Light Emitting Device D2

(80) A light emitting device D2 was fabricated in the same manner as in Example D1 excepting that a 0.7 wt % xylene solution was prepared using the polymer compound 4 instead of the polymer compound 1 in Example D1.

(81) When voltage was applied to the light emitting device D2, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 83.2 cd/A.

Example D3

Fabrication and Evaluation of Light Emitting Device D3

(82) A light emitting device D3 was fabricated in the same manner as in Example D1 excepting that a 0.7 wt % xylene solution was prepared using the polymer compound 5 instead of the polymer compound 1 in Example D1.

(83) When voltage was applied to the light emitting device D3, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 77.0 cd/A.

Example D4

Fabrication and Evaluation of Light Emitting Device D4

(84) A light emitting device D4 was fabricated in the same manner as in Example D1 excepting that a 0.7 wt % xylene solution was prepared using the polymer compound 6 instead of the polymer compound 1 in Example D1.

(85) When voltage was applied to the light emitting device D4, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 74.9 cd/A.

Comparative Example CD1

Fabrication and Evaluation of Light Emitting Device CD1

(86) A light emitting device CD1 was fabricated in the same manner as in Example D1 excepting that a 0.7 wt % xylene solution was prepared using the polymer compound 3 instead of the polymer compound 1 in Example D1.

(87) When voltage was applied to the light emitting device CD1, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 66.0 cd/A.

Comparative Example CD2

Fabrication and Evaluation of Light Emitting Device CD2

(88) A light emitting device CD2 was fabricated in the same manner as in Example D1 excepting that a 0.7 wt % xylene solution was prepared using the polymer compound 7 instead of the polymer compound 1 in Example D1.

(89) When voltage was applied to the light emitting device CD2, EL emission having a peak at 520 nm was obtained from this device, and the maximum light emission efficiency was 60.3 cd/A.

INDUSTRIAL APPLICABILITY

(90) The light emitting device of the present invention is excellent in light emission efficiency. The polymer compound and the composition of the present invention are useful for production of the light emitting device.