FLUORENE DERIVATIVES, POLYMERS OBTAINED FROM SAID FLUORENE DERIVATIVES AND METHOD FOR PREPARING THE SAME

Abstract

The present invention relates to a novel fluorene derivative having a structure of formula (I): wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; and R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative. The invention further relates to a polymer obtained from the said novel fluorene derivative and methods for preparing the same, as well as their uses as materials for an organic light-emitting diode device.

##STR00001##

Claims

1. A fluorene derivative having a structure of formula (I): ##STR00029## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole.

2-3. (canceled)

4. The fluorene derivative according to claim 1, wherein X is Br or I, Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10, and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical.

5. A method for preparing a fluorene derivative having a structure of formula (I): ##STR00030## the method comprising reacting a compound of formula (A) with a compound of formula (B) in an organic solvent in the presence of a strong base, ##STR00031## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; and wherein a mole ratio of the compound of formula (A) to the compound of formula (B) to the strong base ((A):(B):strong base) is in a range of 1:2.5-3:8-9.

6. (canceled)

7. The method according to claim 5, wherein the compound of formula (A) is prepared from steps comprising: reacting a fluorene compound with a halogenating agent or triflating agent in an organic solvent in the presence of a catalyst; and (ii) reacting the compound obtained from the step (i) with a C.sub.3-C.sub.12 alkyl halide in an organic solvent in the presence of the halogenating agent or triflating agent and a strong base wherein the step (i) is conducted at an ambient temperature for 3-5 hours and the step (ii) is conducted at a temperature of 70-80° C. for 4-5 hours; wherein a mole ratio of the fluorene compound to the halogenating agent or triflating agent to the catalyst in step (i) (fluorene compound:halogenating agent or triflating agent:catalyst) is in a range of 1:2-3:0.05-0.1, and a mole ratio of the compound obtained from step (i) to the C.sub.3-C.sub.12 alkyl halide to the halogenating agent or triflating agent to the strong base (compound obtained from step (i): alkyl halide:halogenating agent or triflating agent:strong base) is in a range of 1:3-5:0.1-0.3:8-15; and wherein the halogenating agent is dibromine (Br.sub.2) or tert-butyl ammonium bromide, the triflating agent is trifluoromethanesulfonate or 4-(trifluoromethyl) benzenesulfonate, the C.sub.3-C.sub.12 alkyl halide is selected from a group consisting of 1,3-dibromopropane, 1,6-dibromohexane, 1,8-dibromooctane and 1,10-dibromodecane, and the catalyst is metal halide.

8-14. (canceled)

15. The method according to claim 5, wherein the compound of formula (B) is prepared by reacting carbazole with a halogenating agent or triflating agent in a mixed organic solvent in the presence of a catalyst, and a mole ratio of carbazole to the halogenating agent or triflating agent to the catalyst (carbazole:halogenating agent or triflating agent:catalyst) is in a range of 1:2.5-3.5:2.5-3.5, preferably the halogenating agent is 2-chloro-2-methylpropane, the catalyst is metal halide, and the mixed organic solvent is a mixture of nitromethane and dichloromethane and a volume ratio of nitromethane and dichloromethane is 2 to 1.

16-19. (canceled)

20. The method according to claim 5, wherein the compound of formula (B) is prepared by steps of: (i) reacting 3,6-dihalo-N-tosyl carbazole with carbazole or carbazole derivative in an organic solvent in the presence of a catalyst and a strong base; and (ii) deprotecting a tosyl group of the compound obtained from step (i) in a mixed organic solvent in the presence of a strong base wherein the step (i) is conducted at a temperature of 110-120° C. under refluxing condition for 40-50 hours, the catalyst of step (i) is prepared from metal halide and diamine compound, a mole ratio of 3,6-dihalo-N-tosyl carbazole to carbazole or carbazole derivative to the catalyst (3,6-dihalo-N-tosyl carbazole:carbazole or carbazole derivative:the catalyst) is in a range of 1:2.2-2.5:0.5-0.8; and wherein the step (ii) is conducted at a temperature of 70-80° C. under refluxing condition for 3-5 hours, and the mixed organic solvent of step (ii) is a mixture of tetrahydrofuran and dimethyl sulfoxide.

21-25. (canceled)

26. A polymer comprising a repeating unit of a fluorene derivative having a structure of formula (I): ##STR00032## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; and R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from a group consisting of tert-butyl group, triphenylamine (TPA), and tert-butyl-substituted carbazole.

27. The polymer according to claim 26, wherein R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical X is Br or I, and Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10.

28-29. (canceled)

30. The polymer according to claim 26, comprising a repeating unit of fluorene derivatives of formulas (I) and (II): ##STR00033## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; Z is dioxaborolane; and R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

31. The polymer according to claim 30, wherein Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are identical, and R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

32-34. (canceled)

35. The polymer according to claim 30, having a weight average molecular weight (Mw) in a range of 6,000 to 60,000 g/mol, a number average molecular weight (Mn) in a range of 4,200 to 30,000 g/mol, and a polydispersity index (PDI) in a range of 1 to 5.

36. The polymer according to claim 30, having a mole ratio of formula (II) to formula (I) in a range of 1:0.3-1, preferably 1 to 1.

37-40. (canceled)

41. The polymer according to claim 30, having a peak wavelength of light emitted in a visible spectrum of 350 nm to 385 nm, and CIE coordinates of light emission of x=0.16 to 0.18, y=0.07 to 0.13.

42. The polymer according to claim 30 which is used as a blue electroluminescent material.

43. The polymer according to claim 26, comprising a repeating unit of fluorene derivatives of formulas (I) and (II) and a compound of formula (III): ##STR00034## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; Z is dioxaborolane; and R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

44. The polymer according to claim 43, wherein Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 are identical, and R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

45-47. (canceled)

48. The polymer according claim 43, having a weight average molecular weight (Mw) in a range of 10,000 to 100,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 35,000 g/mol, and a polydispersity index (PDI) in a range of 1 to 5.

49-50. (canceled)

51. The polymer according to claim 43, having a mole ratio of formula (II) to formula (I) to formula (III) in a range of 1:0.3-1:0.005-0.5.

52. The polymer according to claim 43, having a peak wavelength of light emitted in a visible spectrum of 370 to 390 nm and 540 nm to 560 nm, and CIE coordinates of light emission of x=0.68 to 0.72, y=0.28 to 0.31.

53. (canceled)

54. The polymer according to claim 43, which is used as a red electroluminescent material.

55. The polymer according to claim 26, comprising a repeating unit of fluorene derivatives of formulas (I) and (II) and a compound of formulas (IV) or (V): ##STR00035## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; Z is dioxaborolane; and R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

56. The polymer according to claim 55, wherein Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical, and R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

57-59. (canceled)

60. The polymer according to claim 55, having a weight average molecular weight (Mw) in a range of 10,000 to 50,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 30,000 g/mol, and a polydispersity index (PDI) in a range of 1 to 5.

61-62. (canceled)

63. The polymer according to claim 55, having a mole ratio of formula (II) to formula (I) to formula (IV) or (V) in a range of 1:0.3-1:0.008-0.7.

64. (canceled)

65. The polymer according to claim 55, having a peak wavelength of light emitted in a visible spectrum of 430 nm to 440 nm, and CIE coordinates of light emission of x=0.32 to 0.36, y=0.52 to 0.60.

66. (canceled)

67. The polymer according to claim 55, which is used as a green electroluminescent material.

68. The polymer according to claim 26, comprising a repeating unit of fluorene derivatives of formulas (I) and (II) and a compound of formula (III) and a compound of formulas (IV) or (V): ##STR00036## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; Z is dioxaborolane; and R.sup.5 and R.sup.6 are independently C.sub.3-C.sub.12 alkyl group.

69. The polymer according to claim 68, wherein Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical, and R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

70-72. (canceled)

73. The polymer according to claim 68, having a weight average molecular weight (Mw) in a range of 10,000 to 60,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 36,000 g/mol, and a polydispersity index (PDI) in a range of 1 to 5.

74-75. (canceled)

76. The polymer according to claim 68, having a mole ratio of formula (II) to formula (I) to formula (III) to formula (IV) or (V) in a range of 1:0.3-1:0.002-0.5:0.008-0.7.

77. (canceled)

78. The polymer according to claim 68, having a peak wavelength of light emitted in a visible spectrum of 360 nm to 380 nm, and CIE coordinates of light emission of x=0.27 to 0.35, y=0.20 to 0.33.

79. (canceled)

80. The polymer according to claim 68, which is used as a white electroluminescent material.

81. The polymer according to claim 26 which is used as a hole transport layer in electroluminescent device.

82. A light-emitting element comprising the polymer according to claim 26.

83. A method for preparing the polymer according to claim 26, comprising a polymerization of monomers comprising fluorene derivatives having structures of formulas (I) and (II): ##STR00037## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate; Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, and tert-butyl-substituted carbazole; Z is dioxaborolane; and R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

84. (canceled)

85. The method according to claim 83, wherein a mole ratio of the fluorene derivatives of formula (I) to formula (II) is in a range of 0.3-1:1.

86. The method according to claim 83, wherein the polymerization is conducted at a temperature of 70-80° C.

87. The method according to claim 83, wherein the monomers further comprising at least one compound having a structure of formulas (III), (VI) or (V): ##STR00038## wherein X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate.

88. The method according to claim 87, wherein a mole ratio of the fluorene derivatives of formula (I) to formula (II) to the compound of formula (III) is in a range of 0.3-1:1:0.005-0.5.

89. The method according to claim 87, wherein a mole ratio of the fluorene derivatives of formula (I) to formula (II) to the compound of formula (IV) or (V) is in a range of 0.3-1:1:0.008-0.7.

90. (canceled)

91. The method according to claim 87, wherein a mole ratio of the fluorene derivatives of formula (I) to formula (II) to the compound of formula (III) to the compound of formula (IV) or (V) is in a range of 0.3-1:1:0.002-0.5:0.008-0.7.

92. (canceled)

Description

DETAILED DESCRIPTION OF THE INVENTION

[0025] Unless otherwise indicated, any aspects shown herein shall encompass the application to other aspects of the present invention as well.

[0026] Unless otherwise specified, technical and scientific terms used herein have the definitions which are understood by a person skilled in the art.

[0027] Throughout the present invention, the term “about” is used to indicate that any values shown or presented herein may be varied or deviated. Such variation or deviation may be a result of an error of the equipment or method used to determine the values.

[0028] The terms “consist(s) of” and its variation such as “consisting of” and “consisted of”, “comprise(s)” and its variation such as “comprising” and “comprised”, “has/have/having”, “include(s)” and its variation such as “including” and “included” are open-ended verbs. For example, any methods which “consist of”, “comprise”, “have” or “include” one or more components or steps are not limited only to the one or more components or steps, but also cover the components or steps that are not mentioned.

[0029] The terms “a”, “an”, “the”, when used to refer to a singular noun, are intended to include a plural of that noun as well, unless otherwise specified.

[0030] Any tools, equipment, methods, materials or chemicals mentioned herein, unless otherwise indicated, mean the tool, equipment, methods, materials or chemicals generally used or practiced by a person skilled in the art.

Fluorene Derivatives of the Invention

[0031] According to the first aspect, the present invention provides a fluorene derivative having a structure of formula (I):

##STR00005##

wherein

[0032] X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0033] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12; and

[0034] R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative.

[0035] In a preferred embodiment, X is Br or I. Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10.

[0036] Preferably, carbazole derivative is tert-butyl-substituted carbazole.

[0037] More preferably, tert-butyl-substituted carbazole which can be used according to the present invention is selected from 3,6-di-tert-butylcarbazole and 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′: 6′,9″-tercarbazole.

[0038] Examples of fluorene derivatives according to the present invention have the following structures:

##STR00006## ##STR00007## ##STR00008## ##STR00009## ##STR00010##

Preparation of Fluorene Derivatives

[0039] According to the second aspect, the present invention also provides a method for preparing the fluorene derivative having the structure of formula (I), wherein the symbols X, Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meanings as defined above. The method according to this invention comprises reacting a compound of formula (A) with a compound of formula (B) in an organic solvent in the presence of a strong base,

##STR00011##

wherein

[0040] X is selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0041] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12;

[0042] Each R is independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative.

[0043] The preferred fluorene derivatives according to the present invention can be obtained by using an appropriate specific mole ratio and types of the reactants and reagents.

[0044] In a preferred embodiment, the mole ratio of the compound of formula (A) to the compound of formula (B) to the strong base ((A):(B):strong base) is in a range of 1:2.5-3:8-9.

[0045] The organic solvents for use in the reaction of the compound of formula (A) and the compound of formula (B) may be selected from a group consisting of dimethylformamide (DMF), hexane, toluene, dichloromethane and chloroform.

[0046] According to this invention, the compounds of formula (A) can be obtained by using a specific procedure as described below.

[0047] The compound of formula (A) is prepared from steps comprising:

[0048] (i) reacting a fluorene compound with a halogenating agent or triflating agent in an organic solvent in the presence of a catalyst; and

[0049] (ii) reacting the compound obtained from the step (i) with a C.sub.3-C.sub.12 alkyl halide in an organic solvent in the presence of the halogenating agent or triflating agent and a strong base.

[0050] In a preferred embodiment, the step (i) is conducted at an ambient temperature for 3-5 hours and the step (ii) is conducted at a temperature of 70-80° C. for 4-5 hours. Further, the step (i) is carried out by using a mole ratio of the fluorene compound to the halogenating agent or triflating agent to the catalyst (fluorene compound:halogenating agent or triflating agent:catalyst) is in a range of 1:2-3:0.05-0.1.

[0051] Preferably, the halogenating agent that can be used in the step (i) is selected from a group consisting of dibromine (Br.sub.2) and tert-butyl ammonium bromide.

[0052] Preferably, the triflating agent that can be used in the step (i) is selected from a group consisting of trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate.

[0053] The catalyst that can be used in step (i) is preferably selected from a group consisting of metal halide. For example, the metal halide catalyst is iron (III) chloride (FeCl.sub.3).

[0054] To obtain the desired compound of formula (A), an appropriate specific mole ratio and types of the reactants and reagents are used. In a preferred embodiment, the step (ii) is carried out by using a mole ratio of the compound obtained from step (i) to the C.sub.3-C.sub.12 alkyl halide to the halogenating agent or triflating agent to the strong base (compound obtained from step (i): C.sub.3-C.sub.12 alkyl halide:halogenating agent or triflating agent:strong base) in a range of 1:3-5:0.1-0.3:8-15.

[0055] Preferably, the C.sub.3-C.sub.12 alkyl halide that can be used in step (ii) is selected from a group consisting of 1,3-dibromopropane, 1,6-dibromohexane, 1,8-dibromooctane and 1,10-dibromodecane.

[0056] Preferably, the organic solvents that can be used to perform the reaction of step (i) and (ii) may be commercially available and selected from a group consisting of chloroform, tetrahydrofuran (THF), dichloromethane, toluene, and hexane.

[0057] Examples of the compounds of formula (A) have structures as shown below.

##STR00012## ##STR00013## ##STR00014##

[0058] According to this invention, the compounds of formula (B) can be obtained by using a procedure as described herein below.

[0059] The compound of formula (B) is prepared by reacting carbazole with a halogenated compound or triflating agent in a mixed organic solvent in the presence of a catalyst.

[0060] The reaction between the carbazole and the halogenated compound or triflating agent can be achieved by using an appropriate specific mole ratio of the reactants and catalyst. In a preferred embodiment, the preparation of the compound of formula (B) is carried out by using a mole ratio of carbazole to the halogenated compound or triflating agent to the catalyst (carbazole:halogenating compound or triflating agent:catalyst) in a range of 1:2.5-3.5:2.5-3.5.

[0061] Preferably, the halogenated compound is 2-chloro-2-methylpropane, the triflating agent is selected from a group consisting of trifluoromethanesulfonate and 4-(trifluoromethyl) benzenesulfonate. The catalyst is selected from a group of metal halide such as zinc (II) chloride.

[0062] The mixed organic solvent suitable for use in the reaction is a mixture of two or more organic solvents in an appropriate volume ratio that can at least partially dissolve the carbazole, halogenated compound and catalyst used in this invention. Preferably, the organic solvents may be any commercially available and selected from a group consisting of nitromethane (CH.sub.3NO.sub.2), dichloromethane, hexane and toluene.

[0063] In an embodiment, the mixed organic solvent is the mixture of nitromethane and dichloromethane and a volume ratio of nitromethane and dichloromethane is 2 to 1.

[0064] According to this invention, the compound of formula (B) is prepared by steps of:

[0065] (i) reacting 3,6-dihalo-N-tosyl carbazole with carbazole or carbazole derivative in an organic solvent in the presence of a catalyst and a strong base; and

[0066] (ii) deprotecting a tosyl group of the compound obtained from step (i) in a mixed organic solvent in the presence of a strong base.

[0067] Preferably, the step (i) is conducted at a temperature of 110-120° C. under refluxing condition for 40-50 hours. The step (ii) is conducted at a temperature of 70-80° C. under refluxing condition for 3-5 hours.

[0068] In a preferred embodiment, the step (i) is carried out by using a mole ratio of 3,6-dihalo-N-tosyl carbazole to carbazole or carbazole derivative to the catalyst (3,6-dihalo-N-tosyl carbazole:carbazole or carbazole derivative:catalyst) in a range of 1:2.2-2.5:0.5-0.8. The 3,6-dihalo-N-tosyl carbazole is preferably 3,6-diiodo-9-tosyl-9H-carbazole.

[0069] The catalyst used in the reaction between 3,6-dihalo-N-tosyl carbazole and carbazole, or 3,6-dihalo-N-tosyl carbazole and carbazole derivative according to the step (i) may be in a form of a transition metal-ligand complex, or a transition metal precursor/ligand mixture. In one embodiment, the catalyst can be provided by mixing a transition metal precursor and a ligand compound in an appropriate organic solvent. Preferably, the catalyst can be selected from a group consisting of metal halide and diamine compound.

[0070] In a preferred embodiment, the catalyst of step (i) is prepared from copper(I) iodide (CuI) and trans-diaminocyclohexane.

[0071] The organic solvent that can be used in the preparation of the compound of formula (B) may be commercially available and selected from toluene, dichloromethane, hexane, dimethyl sulfoxide and THF. Preferably, the organic solvent of step (i) is toluene and the mixed organic solvent step (ii) is a mixture of tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO).

[0072] Examples of the compounds of formula (B) have structures as shown below.

##STR00015##

Polymers of the Invention

[0073] According to the third aspect, the present invention provides a polymer comprising a repeating unit derived from a fluorene derivative having a structure of formula (I), wherein the symbols X, Y, R.sup.1, R.sup.2, R.sup.3 and R.sup.4 have the same meanings as defined above.

[0074] In a preferred embodiment, X is Br or I. Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10.

[0075] The carbazole derivative according to the present invention is preferably Cert-butyl-substituted carbazole.

[0076] The tert-butyl-substituted carbazole according to the present invention is preferably 3,6-di-tert-butylcarbazole.

[0077] According to specific embodiments of the present invention, the polymer is provided in which the fluorene derivative unit of the invention is incorporated into a backbone of the polymer as described in detail below.

Blue Light-Emitting Polymer

[0078] An embodiment of a blue light-emitting polymer of the present invention comprises a repeating unit derived from fluorene derivatives of formulas (I) and (II):

##STR00016##

[0079] wherein

[0080] X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0081] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12;

[0082] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative;

[0083] Z is dioxaborolane; and

[0084] R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

[0085] In a preferred embodiment, Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical. The carbazole derivative is tert-butyl-substituted carbazole. The preferred carbazole derivative can be selected from a group consisting of 3,6-di-tert-butylcarbazole and 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′:6′,9″-tercarbazole. R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

[0086] The compounds having structures of formulas (I) and (II) which are used as monomers for preparing the blue light-emitting polymer according to the present invention can have any sequence of arrangement within the polymer chain.

[0087] Examples of the blue light-emitting polymers according to the present invention have structures as shown below.

##STR00017##

[0088] It is preferable that the blue light-emitting polymer according to the present invention has a weight average molecular weight (Mw) in a range of 6,000 to 60,000 g/mol, a number average molecular weight (Mn) in a range of 4,200 to 30,000 g/mol and a polydispersity index (PDI) in a range of 1 to 5.

[0089] In a preferred embodiment, the blue light-emitting polymer according the present invention has a mole ratio of formula (II) to formula (I) in a range of 1:0.3-1, preferably 1 to 1.

[0090] In one embodiment, the blue light-emitting polymer has a peak wavelength of light emitted in a visible spectrum of 350 nm to 385 nm.

[0091] In further embodiment, the blue light-emitting polymer has CIE coordinates of light emission of x=0.16 to 0.18, y=0.07 to 0.13.

[0092] It is preferable that the polymer is used as a blue electroluminescent material.

Red Light-Emitting Polymer

[0093] An embodiment of a red light-emitting polymer of the present invention comprises a repeating unit derived from fluorene derivatives of formulas (I) and (II) and a compound of formula (III):

##STR00018##

[0094] wherein

[0095] X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0096] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12;

[0097] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative;

[0098] Z is dioxaborolane; and

[0099] R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

[0100] In a preferred embodiment, Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical. The carbazole derivative is tert-butyl-substituted carbazole. The preferred carbazole derivative can be selected from a group consisting of 3,6-di-tert-butylcarbazole and 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′:6′,9″-tercarbazole. R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

[0101] The derivatives and compounds having structures of formulas (I), (II) and (III) which are used as monomers for preparing the red light-emitting polymer according to the present invention can have any sequence of arrangement within the polymer chain. For example, the monomer sequences for the red light-emitting polymer can be (I)-(II)-(III), (I)-(III)-(II), (II)-(I)-(III), (II)-(III)-(I), (III)-(I)-(II) or (III)-(II)-(I).

[0102] Examples of the red light-emitting polymers according to the present invention have structures as shown below.

##STR00019## ##STR00020##

[0103] It is preferable that the red light-emitting polymer according to the present invention has a weight average molecular weight (Mw) in a range of 10,000 to 100,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 35,000 g/mol and a polydispersity index (PDI) in a range of 1 to 5.

[0104] In a preferred embodiment, the red light-emitting polymer according to the present invention has a mole ratio of formula (II) to formula (I) to formula (III) in a range of 1:0.3-1:0.005-0.5.

[0105] In one embodiment, the red light-emitting polymer has a peak wavelength of light emitted in a visible spectrum of 370 nm to 390 nm and 540 nm to 560 nm.

[0106] In further embodiment, the red light-emitting polymer has CIE coordinates of light emission of x=0.68 to 0.72, y=0.28 to 0.31

[0107] It is preferable that the polymer is used as a red electroluminescent material.

Green Light-Emitting Polymer

[0108] An embodiment of a green light-emitting polymer of the present invention comprises a repeating unit derived from fluorene derivatives of formulas (I) and (II) and a compound of formulas (IV) or (V):

##STR00021##

[0109] wherein

[0110] X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0111] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12;

[0112] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative;

[0113] Z is dioxaborolane; and

[0114] R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

[0115] In a preferred embodiment, Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical. The carbazole derivative is tert-butyl-substituted carbazole. The preferred carbazole derivative can be selected from a group consisting of 3,6-di-tert-butylcarbazole and 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′:6′,9″-tercarbazole. R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

[0116] The compounds having structures of formulas (I), (II), (IV) or (V) which are used as monomers for preparing the green light-emitting polymer according to the present invention can have any sequence of arrangement within the polymer chain. For example, the monomer sequences for the green light-emitting polymer can be (I)-(II)-(IV), (I)-(IV)-(II), (II)-(I)-(IV), (II)-(IV)-(I), (I)-(II)-(V), (I)-(V)-(II), (II)-(I)-(V) or (II)-(V)-(I).

[0117] Examples of the green light-emitting polymer according to the present invention have structures as shown below.

##STR00022## ##STR00023## ##STR00024##

[0118] It is preferable that the green light-emitting polymer according to the present invention has a weight average molecular weight (Mw) in a range of 10,000 to 50,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 30,000 g/mol and a polydispersity index (PDI) in a range of 1 to 5.

[0119] In a preferred embodiment, the green light-emitting polymer according to the present invention has a mole ratio of formula (II) to formula (I) to formula (IV) in a range of 1:0.3-1:0.008-0.7.

[0120] In a preferred embodiment, the green light-emitting polymer according to the present invention has a mole ratio of formula (II) to formula (I) to formula (V) in a range of 1:0.3-1:0.008-0.7.

[0121] In one embodiment, the green light-emitting polymer has a peak wavelength of light emitted in a visible spectrum of 430 nm to 440 nm.

[0122] In further embodiment, the green light-emitting polymer has CIE coordinates of light emission of x=0.32 to 0.36, y=0.52 to 0.60.

[0123] It is preferable that the polymer is used as a green electroluminescent material.

White Light-Emitting Polymer

[0124] An embodiment of a white light-emitting polymer of the present invention comprises a repeating unit derived from fluorene derivatives of formulas (I) and (II) and a compound of formula (III) and a compound of formulas (IV) or (V):

##STR00025##

[0125] wherein

[0126] X is independently selected from a group consisting of Cl, Br, I, trifluoromethanesulfonate and 4-(trifluoromethyl)benzenesulfonate;

[0127] Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 12;

[0128] R.sup.1, R.sup.2, R.sup.3, and R.sup.4, are independently selected from a group consisting of tert-butyl group, triphenylamine, carbazole and carbazole derivative;

[0129] Z is dioxaborolane; and

[0130] R.sup.5 and R.sup.6 are independently selected from C.sub.3-C.sub.12 alkyl group.

[0131] In a preferred embodiment, Y is a group of formula —(CH.sub.2).sub.n— where n is an integer ranging from 3 to 10. R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are identical. The carbazole derivative is tert-butyl-substituted carbazole. The preferred carbazole derivative can be selected from a group consisting of 3,6-di-tert-butylcarbazole and 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′:6′,9″-tercarbazole. R.sup.5 and R.sup.6 are identical and are C.sub.6-C.sub.10 alkyl group.

[0132] The compounds having structures of formulas (I), (II), (III), (IV) or (V) which are used as monomers for preparing the white light-emitting polymer according to the present invention can have any sequence of arrangement within the polymer chain. For example, the monomer sequences for the white light-emitting polymer can be (I)-(II)-(III)-(IV), (I)-(II)-(IV)-(III), (I)-(III)-(IV)-(II), (I)-(III)-(II)-(IV), (I)-(IV)-(II)-(III), (I)-(IV)-(III)-(II), (II)-(I)-(III)-(IV), (II)-(I)-(IV)-(III), (II)-(III)-(IV)-(I), (II)-(III)-(I)-(IV), (II)-(IV)-(III)-(I), (II)-(IV)-(I)-(III), (III)-(I)-(II)-(IV), (III)-(I)-(IV)-(II), (III)-(II)-(I)-(IV), (III)-(II)-(IV)-(I), (III)-(IV)-(I)-(II), (III)-(IV)-(II)-(I), (IV)-(I)-(II)-(III), (IV)-(I)-(III)-(II), (IV)-(II)-(I)-(III), (IV)-(II)-(III)-(I), (IV)-(III)-(II)-(I), (IV)-(III)-(I)-(II), (I)-(II)-(III)-(V), (I)-(II)-(V)-(III), (I)-(III)-(V)-(II), (I)-(III)-(II)-(V), (I)-(V)-(II)-(III), (I)-(V)-(III)-(II), (II)-(I)-(III)-(V), (II)-(I)-(V)-(III), (II)-(III)-(V)-(I), (II)-(III)-(I)-(V), (II)-(V)-(III)-(I), (II)-(V)-(I)-(III), (III)-(I)-(II)-(V), (III)-(I)-(V)-(II), (III)-(II)-(I)-(V), (III)-(II)-(V)-(I), (III)-(V)-(I)-(II), (III)-(V)-(II)-(I), (V)-(I)-(II)-(III), (V)-(I)-(III)-(II), (V)-(II)-(I)-(III), (V)-(II)-(III)-(I), (V)-(III)-(II)-(I), (V)-(III)-(I)-(II).

[0133] Examples of the white light-emitting polymer according to the present invention have structures as shown below.

##STR00026## ##STR00027## ##STR00028##

[0134] It is preferable that the white light-emitting polymer according to the present invention has a weight average molecular weight (Mw) in a range of 10,000 to 60,000 g/mol, a number average molecular weight (Mn) in a range of 10,000 to 36,000 g/mol and a polydispersity index (PDI) in a range of 1 to 5.

[0135] In a preferred embodiment, the white light-emitting polymer according to the present invention has a mole ratio of formula (II) to formula (I) to formula (III) to formula (IV) in a range of 1:0.3-1:0.002-0.5:0.008-0.7.

[0136] In a preferred embodiment, the white light-emitting polymer according to the present invention has a mole ratio of formula (II) to formula (I) to formula (III) to formula (V) in a range of 1:0.3-1:0.002-0.5:0.008-0.7.

[0137] In one embodiment, the white light-emitting polymer has a peak wavelength of light emitted in a visible spectrum of 360 nm to 380 nm.

[0138] In further embodiment, the white light-emitting polymer has CIE coordinates of light emission of x=0.27 to 0.35, y=0.20 to 0.33.

[0139] It is preferable that the polymer is used as a white electroluminescent material.

Preparation of Polymer

[0140] In the present invention, the direct synthesis of small conjugated polymer nanoparticles (<30 nm) under mini-emulsion conditions via Glaser coupling reactions has been developed. The advantages of emulsion polymerization over the post-polymerization are scalable, which can obtain the concentration of polymer as 11 mg/ml, size controllable, and the uniform of particles. Due to the high stability of each droplet, evaporation of the solvent does not lead to any change of the droplet number. Therefore, using this mini-emulsion polymerization method in preparation of light-emitting conjugated polymer nanoparticles (NP) dispersion or light-emitting NP inks (EL inks) is attractive alternatives for commercial production of OLED devices by printing. The use of NPs dispersion in OLED fabrication promises of low temperature processing techniques and gives much lower viscosities than the equivalent loadings of high molar mass conjugated polymer dissolved in organic solvents.

[0141] The fourth aspect of the present invention relates to a method for preparing the polymers of the invention. The method comprises a polymerization of monomers comprising fluorene derivatives having structures of formulas (I) and (II) as described above.

[0142] In one embodiment, the monomers further comprise at least one compound having a structure of formulas (III), (IV) or (V) as described above.

[0143] In a preferred embodiment, the present invention provides a polymerization of monomers comprising the fluorene derivatives of formulas (I) and (II) and the compound of formula (III).

[0144] More preferably, the polymerization is conducted by using a mole ratio of the fluorene derivatives of formula (I):formula (II):the compound of formula (III) in a range of 0.3-1:1:0.005-0.5.

[0145] In one embodiment, the present invention provides a polymerization of monomers comprising the fluorene derivatives of formulas (I) and (II) and the compound of formula (IV).

[0146] More preferably, the polymerization is conducted by using a mole ratio of the fluorene derivatives of formula (I):formula (II):the compound of formula (IV) in a range of 0.3-1:1:0.008-0.7.

[0147] In one embodiment, the present invention provides a polymerization of monomers comprising the fluorene derivatives of formulas (I) and (II) and the compound of formula (V).

[0148] More preferably, the polymerization is conducted by using a mole ratio of the fluorene derivatives of formula (I):formula (II):the compound of formula (V) in a range of 0.3-1:1:0.008-0.7.

[0149] In one embodiment, the present invention provides a polymerization of monomers comprising the fluorene derivatives of formulas (I) and (II) and the compound of formulas (III) and (IV).

[0150] More preferably, the polymerization is conducted by using a mole ratio of the fluorene derivatives of formula (I):formula (II):the compound of formula (III):the compound of formula (IV) in a range of 0.3-1:1:0.002-0.5:0.008-0.7.

[0151] In one embodiment, the present invention provides a polymerization of monomers comprising the fluorene derivatives of formulas (I) and (II) and the compound of formulas (III) and (V).

[0152] More preferably, the polymerization is conducted by using a mole ratio of the fluorene derivatives of formula (I):formula (II):the compound of formula (III):the compound of formula (V) in a range of 0.3-1:1:0.002-0.5:0.008-0.7.

Examples

[0153] The invention will now be described further by way of the following examples. The examples are for illustrative purposes and are not intended to limit the scope of the invention.

1. Preparation of Fluorene Derivatives

[0154] Examples of fluorene derivatives of formula (I) according to this invention are prepared by reacting the compound of formula (A) with the compound of formula (B). The compound (A) and (B) were prepared according to the following procedure.

1.1 Synthesis of Compound (A): 2,7-disubstituted-9,9-dihaloalkylfluorene

Step 1: Synthesis of 2,7-dibromo-9H-fluorene

[0155] Fluorene (50 g) was dissolved in chloroform and then added FeCl.sub.3 (0.3 g). After that, the solution of bromine 10% v/v chloroform was dropped at lower 10° C. and then the reaction mixture was stirred at room temperature for 3-5 hours. When the reaction completed, the reaction mixture was extracted with dichloromethane and brine solution. The resultant product was then dried over sodium sulfate (Na.sub.2SO.sub.4), concentrated on a rotary evaporator and recrystallized to give more than 70% yield of 2,7-dibromo-9H-fluorene.

Step 2: Alkylation of 2,7-dibromo-9H-fluorene

[0156] 2,7-dibromo-9H-fluorene (2 g) and tert-butylammonium bromide (0.1 g) were dissolved in 30 mL tetrahydrofuran and then the solution of KOH solution was added. The reaction mixture was stirred at room temperature for half an hour. After that, an alkylating agent (2 mL) was added and then stirred at 60-70° C. for 4-5 hours. The reaction was cooled to room temperature and the reaction mixture was poured in water, extracted with dichloromethane 3 times and brine solution. The resultant product was dried over sodium sulfate (Na.sub.2SO.sub.4) and concentrated on a rotary evaporator prior to purify by column chromatography to give 2,7-disubstituted-9,9-dihaloalkylfluorene.

[0157] The alkylating agents used in the step 2 above were varied resulting in different reaction products of the compound (A). Those different compounds A5-A8 obtained from using various alkylating agents are shown in Table 1 below.

TABLE-US-00001 TABLE 1 Compound Alkylating agent Reaction Product A5 1,3-dibromopropane 2,7-dibromo-9,9-bis (3-bromopropyl)-9H-fluorene A6 1,6-dibromohexane 2,7-dibromo-9,9-bis (6-bromohexyl)-9H-fluorene A7 1,8-dibromooctane 2,7-dibromo-9,9-bis (8-bromooctyl)-9H-fluorene A8 1,10-dibromodecane 2,7-dibromo-9,9-bis (10-bromodecyl)-9H-fluorene

1.2 Synthesis of Compound (B): 3,6-disubstituted 9H-carbazole

[0158] Examples of compound (B) obtained from the analogous manner with a variety of substituting groups are shown in Table 2 below.

TABLE-US-00002 TABLE 2 Com- Substituting pound group Reaction Product B1 tert-butyl 3,6-di-tert-butyl-9H-carbazole B2 carbazole 9′H-9,3′:6′,9″-tercarbazole B3 3,6-di-tert-butyl- 3,3″,6,6″-tetra-tert-butyl-9′H- carbazole 9,3′:6′,9″-tercarbazole B4 TPA 4,4′-(9H-carbazole-3,6- diyl)bis(N,N-diphenylaniline)

[0159] The synthesis of compounds B1-B4 are as described below.

Synthesis of Compound B1: 3,6-di-tert-butyl-9H-carbazole

[0160] Carbazole (10 g) was dissolved in the mixed solvent of nitromethane and dichloromethane. ZnCl.sub.2 (25 g) was added to the mixture solution, followed by dropwise addition of 2-chloro-2-methylpropane (20 mL) The reaction mixture was sonicated in an ultrasonic bath for at least 30 minutes. After that, the reaction mixture was poured into water, extracted with dichloromethane and brine solution. The resultant product was dried over sodium sulfate (Na.sub.2SO.sub.4) and concentrated on a rotary evaporator prior to purify by crystallization to give 3,6-di-tert-butyl-9H-carbazole.

Synthesis of Compound B2: 9′H-9,3′:6′,9″-tercarbazole

[0161] —Ullmann Coupling Reaction of 3,6-diiodo-9-tosyl-9H-carbazole

[0162] 3,6-diiodo-9-tosyl-9H-carbazole (1 g), carbazole (0.6 g), copper(I) iodide (0.1 g) and Potassium phosphate (K.sub.3PO.sub.4) (4.36 mmol) were dissolved in toluene. The mixture solution was added by trans-1,2-diaminocyclohexane (0.92 mmol), stirred at 110-120° C. and then refluxed for 40-50 hours. After the reaction completed, the reaction was cooled to room temperature and the reaction mixture was evaporated by using a rotary evaporator. Finally, the crude product was purified by crystallization with mixed solvent of dichloromethane and methanol.

[0163] —Deprotection of Tosyl Group

[0164] The deprotection of tosyl group was conducted by using potassium hydroxide as base and a mixture of tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) as solvent. The reaction mixture was added with small amount of water, stirred at 70-80° C. and then refluxed for 3-5 hours. After the reaction completed, the reaction mixture was poured in water, extracted with dichloromethane and brine solution. The resultant product was dried over sodium sulfate and concentrated by a rotary evaporator.

Synthesis of Compound B3: 3,3″,6,6″-tetra-tert-butyl-9′H-9,3′:6′,9″-tercarbazole

[0165] —Ullmann Coupling Reaction of 3,6-diiodo-9-tosyl-9H-carbazole

[0166] 3,6-diiodo-9-tosyl-9H-carbazole (1 g), 3,6-di-tert-butyl-9H-carbazole (0.6 g), copper(I) iodide (0.1 g) and Potassium phosphate (K.sub.3PO.sub.4) (4.36 mmol) were dissolved in toluene. The mixture solution was added by trans-1,2-diaminocyclohexane (0.92 mmol), stirred at 110-120° C. and then refluxed for 40-50 hours. After the reaction completed, the reaction was cooled to room temperature and the reaction mixture was evaporated by using a rotary evaporator. Finally, the crude product was purified by crystallization with mixed solvent of dichloromethane and methanol.

[0167] —Deprotection of Tosyl Group

[0168] The deprotection of tosyl group was conducted by using potassium hydroxide as base and a mixture of tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) as solvent. The reaction mixture was added with small amount of water, stirred at 70-80° C. and then refluxed for 3-5 hours. After the reaction completed, the reaction mixture was poured in water, extracted with dichloromethane and brine solution. The resultant product was dried over sodium sulfate and concentrated by a rotary evaporator.

Synthesis of Compound B4: 4,4′-(9H-carbazole-3,6-diyl)bis(N,N-diphenylaniline)

[0169] 3,6-diiodo-9H-carbazole (1 g) and 4-(Diphenylamino)phenylboronic acid (1.7 g) was dissolve in THF (30 mL). 2M Na.sub.2CO.sub.3 and Pd(PPh.sub.3).sub.4 were added into the solution. The mixture was stirred and reflux at 75° C. for 18 h. After cool to room temperature, the mixture was poured in water and then extracted with dichloromethane (DCM, 3×50 mL) and brine solution (100 mL), dried over Na.sub.2SO.sub.4 and concentrated on a rotary evaporator. Finally, the residue was purified by column chromatography eluting with DCM/hexane to give white solid of 4,4′-(9H-carbazole-3,6-diyl)bis(N,N-diphenylaniline).

[0170] 1.3 Synthesis of Fluorene Derivatives of the Invention

[0171] The fluorene derivatives of this invention were obtained by reacting the fluorene compounds A5-A8 with the carbazole compounds B1-B4. The synthesis follows the procedure as specified below.

[0172] The carbazole compound and potassium hydroxide were dissolved in dimethylformamide (DMF) and then added the fluorene compound. The reaction mixtures were stirred at room temperature for 4-5 hours. After the reaction completed, the reaction mixtures were poured in water and extracted with dichloromethane and brine solution. The resultant products were dried over sodium sulfate (Na.sub.2SO.sub.4) and evaporated by a rotary evaporator. Finally, the resultant products were purified by column chromatography to give fluorene derivatives

[0173] Various compounds of fluorene derivatives (I1-I16) obtained from the analogous manner using different fluorene compounds (A5-A8) and carbazole compounds (B1-B4) are shown in Table 3 below.

TABLE-US-00003 TABLE 3 Fluorene derivative Fluorene Carbazole Example compound compound No. Chemical name A5 B1 I1 9,9′-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(propane-3,1-diyl))bis(3,6-di-tert- butyl-9H-carbazole) A6 B1 I2 9,9′-((2,7-dibromo-9H-fluorene-9,9-diyl)bis(hexane- 6,1-diyl))bis(3,6-di-tert-butyl-9H-carbazole) A7 B1 I3 9,9′-((2,7-dibromo-9H-fluorene-9,9-diyl)bis(octane- 8,1-diyl))bis(3,6-di-tert-butyl-9H-carbazole) A8 B1 I4 9,9′-((2,7-dibromo-9H-fluorene-9,9-diyl)bis(decane- 10,1-diyl))bis(3,6-di-tert-butyl-9H-carbazole) A5 B2 I5 9′,9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(propane 3,1-diyl))bis(9′H-9,3′:6,9″- tercarbazole) A6 B2 I6 9′,9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(hexane-6,1-diyl))bis(9′H-9,3′:6′,9″- tercarbazole) A7 B2 I7 9′9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(octane-8,1-diyl))bis(9′H-9,3′:6′,9″- tercarbazole) A8 B2 I8 9′9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(decane-10,1-diyl))bis(9′H-9,3′: 6′,9″- tercarbazole) A5 B3 I9 9′,9″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(propane-3,1-diyl))bis(3,3″,6,6″-tetra-tert- butyl-9′H-9,3′:6,9″-tercarbazole) A6 B3 I10 9′,9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(hexane-6,1-diyl))bis(3,3″,6,6″-tetra-tert- butyl-9′H-9,3′:6,9″-tercarbazole) A7 B3 I11 9′,9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(octane-8,1-diyl))bis(3,3″,6,6″-tetra-tert- butyl-9′H-9,3′:6,9″-tercarbazole) A8 B3 I12 9′,9″″-((2,7-dibromo-9H-fluorene-9,9- diyl)bis(decane-10,1-diyl))bis(3,3″,6,6″-tetra-tert- butyl-9′H-9,3′:6,9″-tercarbazole) A5 B4 I13 4,4′,4″,4′″-(((2,7-dibromo-9H-fluorene-9,9- diyl)bis(propane-3,1-diyl))bis(9H-carbazole-9,3,6- triyl))tetrakis(N,N-diphenylaniline) A6 B4 I14 4,4′4″,4″′-(((2,7-dibromo-9H-fluorene-9,9- diyl)bis(hexane-6,1-diyl))bis(9H-carbazole-9,3,6- triyl))tetrakis(N,N-diphenylaniline) A7 B4 I15 4,4′4″,4″′-(((2,7-dibromo-9H-fluorene-9,9- diyl)bis(octane-8,1-diyl))bis(9H-carbazole-9,3,6- triyl))tetrakis(N,N-diphenylaniline) A8 B4 I16 4,4′,4″,4″′-(((2,7-dibromo-9H-fluorene-9,9- diyl)bis(decane-10,1-diyl))bis(9H-carbazole-9, 3,6- triyl))tetrakis(N,N-diphenylaniline)

[0174] The fluorene derivatives I1-I16 were characterized by .sup.1H NMR and Atmospheric pressure chemical ionization-Mass Spectrometry (APCI-MS) analysis. The exemplary characterization results for the fluorene derivatives I1-I4 of the present invention are shown below.

[0175] Compound I1

[0176] .sup.1H NMR (600 MHz, CDCl.sub.3): δ=8.03 (s, 4H), 7.46 (d, 2H, J=7.98 Hz), 7.43-7.40 (m, 6H), 7.26 (s, 4H), 6.94 (d, 4H, J=8.52 Hz), 3.88 (t, 4H, J=7.26, 7.32 Hz), 1.46 (s, 37H), 1.17-1.12 (m, 4H) ppm. APCI (m/z) calcd for C.sub.65H.sub.78Br.sub.2N.sub.2 [M.sup.+]: 962.3572; found 963.4061.

[0177] Compound I2

[0178] .sup.1H NMR (600 MHz, CDCl.sub.3): δ=8.07 (s, 4H), 7.48-7.47 (m, 6H), 7.43 (d, 2H, J=8.04 Hz), 7.38 (s, 2H), 7.21 (s, 2H), 7.19 (s, 2H), 4.11 (t, 4H J=7.02, 7.08 Hz), 1.85-1.83 (m, 4H), 1.66 (t, 4H, J=7.14, 7.14), 1.53 (s, 8H), 1.45 (s, 38H), 1.37-1.15 (m, 4H), 1.10-1.06 (m, 4H), 0.56-0.55 (m, 4H) ppm, APCI (m/z) calcd for C.sub.6H.sub.78Br.sub.2N.sub.2 [M.sup.+]:: 1046.4511; found 1047.5145.

[0179] Compound I3

[0180] .sup.1H NMR (600 MHz, CDCl.sub.3): δ=8.08 (s, 4H), 7.48-7.45 (m, 6H), 7.41 (d, 4H, J=7.5 Hz), 7.24 (s, 4H), 4.16 (t, 4H, J=6.96, 6.90 Hz), 1.89-1.86 (m, 4H), 1.76-1.74 (m, 4H), 1.45 (s, 36H), 1.29-1.25 (m, 5H), 1.12 (m, 4H), 1.01 (s, 8H), 0.55 (br. s, 4H), APCI (m/z) calcd for C.sub.69H.sub.86Br.sub.2N.sub.2 [M.sup.+]: 1102.5564; found 1103.5642.

[0181] Compound I4

[0182] .sup.1H NMR (600 MHz, CDCl.sub.3): δ=8.09 (br. d, 4H), 7.49 (br. d, 2H), 7.48 (br. d, 2H), 7.47-7.45 (m, 2H), 7.42-7.41 (m, 4H), 4.20 (t, 4H, J=6, 12 Hz), 1.90-1.88 (m, 4H), 1.83-1.73 (m, 4H), 1.46 (s, 36H) 1.36-1.30 (m, 4H), 1.15-1.11 (m, 4H), 1.06-1.02 (m, 12H) 0.56 (br. s, 4H) ppm.

[0183] 1.4 Synthesis of Comparative Examples of Fluorene Derivatives

[0184] The comparative examples of fluorene derivatives were synthesized by the same procedure as specified in 1.3 using the fluorene compound A5-A8 but using 9H-carbazole as the carbazole compound. The obtained comparative fluorene derivatives are shown in Table 4 below.

TABLE-US-00004 TABLE 4 Fluorene Carbazole Comparative fluorene derivative compound compound Example No. Chemical name A5 9H-carbazole C1 9,9′-((2,7-dibromo-9H-fluorene- 9,9-diyl)bis(propane-3,1- diyl))bis(9H-carbazole) A6 9H-carbazole C2 9,9′-((2,7-dibromo-9H-fluorene- 9,9-diyl)bis(hexane-6,1- diyl))bis(9H-carbazole) A7 9H-carbazole C3 9,9′-((2,7-dibromo-9H-fluorene- 9,9-diyl)bis(octane-8,1- diyl))bis(9H-carbazole) A8 9H-carbazole C4 9,9′-((2,7-dibromo-9H-fluorene- 9,9-diyl)bis(decane-10,1- diyl))bis(9H-carbazole)

[0185] The comparative fluorene compounds C.sub.1-C.sub.4 were characterized by .sup.1H NMR and Atmospheric pressure chemical ionization-Mass Spectrometry (APCI-MS) analysis. The characterization results for such comparative fluorene compounds are shown below.

[0186] Comparative C1

[0187] .sup.1H-NMR (600 MHz, CDCl.sub.3): δ=8.07 (d, 4H, J=12 Hz), 7.49-7.44 (m, 4H), 7.40 (t, 4H, J=12, 6 Hz), 7.29 (s, 2H), 7.20 (t, 4H, J=6, 6 Hz), 7.05 (d, 4H, J=12 Hz), 3.97 (t, 4H, J=12, 6 Hz), 2.00 (t, 4H, J=12, 6 Hz), 1.20-1.15 (m, 4H) ppm. APCI (m/z) calc for C.sub.43H.sub.34Br.sub.2N.sub.2 [M.sup.+]: 738.1068; found 739.1790.

[0188] Comparative C2

[0189] .sup.1H-NMR (600 MHz, CDCl.sub.3): δ=8.09-8.07 (m, 5H), 7.48 (d, 2H, J=12 Hz), 7.44-7.42 (m, 7H), 7.36 (s, 2H), 7.33-7.30 (m, 5H), 7.22-7.19 (m, 5H), 4.18 (t, 4H, J=6, 6 Hz), 1.82-1.80 (m, 5H), 1.72-1.67 (m, 4H), 1.16-1.06 (m, 8H), 0.53 (br. s, 4H) ppm. APCI (m/z) calc for C.sub.49H.sub.46Br.sub.2N.sub.2 [M.sup.+]: 822.2007; found 823.2857

[0190] Comparative C3

[0191] .sup.1H-NMR (600 MHz, CDCl.sub.3): δ=8.09 (d, 4H, J=6 Hz), 7.48-7.40 (m, 10H), 7.36 (d, 4H, J=12 Hz), 7.21 (t, 4H, J=6, 6 Hz), 4.24 (t, 4H, J=6, 6 Hz), 1.86 (t, 4H, J=6, 6 Hz), 1.81-1.76 (m, 4H), 1.86 (t, 4H, J=6, 6 Hz), 1.14-1.12 (m, 4H), 1.01 (s, 8H), 0.54 (brs, 4H) ppm. APCI (m/z) calc for C.sub.53H.sub.54Br.sub.2N.sub.2 [M.sup.+]: 878.2633; found 879.3067.

[0192] Comparative C4

[0193] .sup.1H NMR (600 MHz, CDCl.sub.3): δ=7.97 (d, 4H, J=6 Hz), 7.34-7.28 (m, 10H), 7.26 (d, 4H, J=12 Hz), 7.11-7.08 (m, 4H), 4.13 (t, 4H, J=12, 6 Hz), 1.76 (t, 4H, J=6, 12 Hz), 1.72-1.67 (m, 4H), 1.22-1.17 (m, 4H), 1.14-1.08 (m, 4H), 0.99-0.97 (m, 4H), 0.92-0.88 (m, 12H), 0.44 (br. s, 4H) ppm.

2. Preparation of Polymer

[0194] The polymers according to this invention were synthesized by mini-emulsion polymerization via Suzuki Miyaura cross-coupling of fluorene derivative monomers of the invention and at least one other monomer as described in detailed description of the invention. The examples and comparative examples were synthesized by following procedure.

[0195] The solution of tetraethylammonium hydroxide (Et.sub.4NOH) (0.2 ml) was added to a three-neck flask containing 0.5 g of sodium dodecyl sulfate (SDS) and 50 mL of deionized water. The mixture solution was degassed by bubbling with nitrogen for 30-40 minutes. Monomers were dissolved in toluene, to which 100 uL of hexadecane was also added. The monomer solution was degassed by bubbling with nitrogen for 5-10 minutes. [1,1′-Bis(diphenylphosphino) ferrocene]palladium(II) dichloride (Pd(dppf)Cl.sub.2) was added into the monomer solution, which then was transferred to the reaction vessel. The reaction mixture was emulsified by ultrasonication for 15-20 minutes while cooling with an ice bath. The three-neck flask was resealed, and the mini-emulsion polymerization was performed at 70-80° C. for 24-30 hours. After the polymerization completed, the reaction mixture was cooled to room temperature and precipitated in methanol. The reaction product was filtered and dried in an oven.

[0196] The resultant polymers obtained from the polymerization may be further purified to remove residue Pd catalyst which is the cause of dark spot in OLED device. The obtained polymers were extracted with Et.sub.4NOH solution under reflux at 70-80° C. for 3-5 hours, two times.

[0197] In addition, the comparative polymers were obtained by the same procedure as specified in the method of polymerization but using the comparative fluorene derivatives C1-C4 instead of fluorene derivatives of the present invention.

[0198] The preparation of polymers with different color properties are specified below.

[0199] 2.1 Blue Light-Emitting Polymer

[0200] Examples of blue light-emitting polymers are prepared from variations of substituents of the monomers as shown in Table 5 below.

TABLE-US-00005 TABLE 5 Functional Mole ratio group of of fluorene Functional group of fluorene fluorene deriv- derivative of formula (I) derivative of atives of Example R.sup.1, R.sup.2, R.sup.3 n of Y group formula (II) formulas No. and R.sup.4 groups (—CH.sub.2).sub.n) R.sup.5 and R.sup.6 group (I):(II) Compar- H 3 C.sub.8 alkyl 1:1 ative 1 Compar- H 6 C.sub.8 alkyl 1:1 ative 2 Compar- H 8 C.sub.8 alkyl 1:1 ative 3 Compar- H 10 C.sub.8 alkyl 1:1 ative 4  1 Tert-butyl 3 C.sub.8 alkyl 1:1  2 Tert-butyl 6 C.sub.8 alkyl 1:1  3 Tert-butyl 8 C.sub.8 alkyl 1:1  4 Tert-butyl 10 C.sub.8 alkyl 1:1  5 Carbazole 3 C.sub.8 alkyl 1:1  6 Carbazole 6 C.sub.8 alkyl 1:1  7 Carbazole 8 C.sub.8 alkyl 1:1  8 Carbazole 10 C.sub.8 alkyl 1:1  9 3,6-di-tert-butyl 3 C.sub.8 alkyl 1:1 carbazole 10 3,6-di-tert-butyl 6 C.sub.8 alkyl 1:1 carbazole 11 3,6-di-tert-butyl 8 C.sub.8 alkyl 1:1 carbazole 12 3,6-di-tert-butyl 10 C.sub.8 alkyl 1:1 carbazole 13 TPA 3 C.sub.8 alkyl 1:1 14 TPA 6 C.sub.8 alkyl 1:1 15 TPA 8 C.sub.8 alkyl 1:1 16 TPA 10 C.sub.8 alkyl 1:1

[0201] 2.2 Red Light-Emitting Polymer

[0202] Examples of red light-emitting polymers are prepared from variations of substituents of the monomers as shown in Table 6 below.

TABLE-US-00006 TABLE 6 Functional Mole group ratio of Functional group of fluorene of fluorene fluorene derivative of formula (I) derivative of derivatives Example R.sup.1, R.sup.2, R.sup.3 n of Y group formula (II) of formulas No. and R.sup.4 (—CH.sub.2).sub.n) R.sup.5 and R.sup.6 (I):(II):(III) Compar- H 3 C.sub.8 alkyl 0.5:1:0.5 ative 5 Compar- H 6 C.sub.8 alkyl 0.5:1:0.5 ative 6 Compar- H 8 C.sub.8 alkyl 0.5:1:0.5 ative 7 Compar- H 10 C.sub.8 alkyl 0.5:1:0.5 ative 8 17 Tert-butyl 3 C.sub.8 alkyl 0.5:1:0.5 18 Tert-butyl 6 C.sub.8 alkyl 0.5:1:0.5 19 Tert-butyl 8 C.sub.8 alkyl 0.5:1:0.5 20 Tert-butyl 10 C.sub.8 alkyl 0.5:1:0.5 21 Carbazole 3 C.sub.8 alkyl 0.5:1:0.5 22 Carbazole 6 C.sub.8 alkyl 0.5:1:0.5 23 Carbazole 8 C.sub.8 alkyl 0.5:1:0.5 24 Carbazole 10 C.sub.8 alkyl 0.5:1:0.5 25 3,6-di-tert-butyl 3 C.sub.8 alkyl 0.5:1:0.5 carbazole 26 3,6-di-tert-butyl 6 C.sub.8 alkyl 0.5:1:0.5 carbazole 27 3,6-di-tert-butyl 8 C.sub.8 alkyl 0.5:1:0.5 carbazole 28 3,6-di-tert-butyl 10 C.sub.8 alkyl 0.5:1:0.5 carbazole 29 TPA 3 C.sub.8 alkyl 0.5:1:0.5 30 TPA 6 C.sub.8 alkyl 0.5:1:0.5 31 TPA 8 C.sub.8 alkyl 0.5:1:0.5 32 TPA 10 C.sub.8 alkyl 0.5:1:0.5

[0203] 2.3 Green Light-Emitting Polymer

[0204] Examples of green light-emitting polymers are prepared from variations of substituents of the monomers as shown in Table 7 below.

TABLE-US-00007 TABLE 7 Functional Functional Mole group of fluorene group ratio of derivative of formula (I) of fluorene Fluorene n of Y derivative of derivative R.sup.1, R.sup.2, R.sup.3 group formula (II) of formulas Example No. and R.sup.4 (—CH.sub.2).sub.n) R.sup.5 and R.sup.6 (I):(II):(V) Comparative 9 H 3 C.sub.8 alkyl 0.5:1:0.5 Comparative 10 H 6 C.sub.8 alkyl 0.5:1:0.5 Comparative 11 H 8 C.sub.8 alkyl 0.5:1:0.5 Comparative 12 H 10 C.sub.8 alkyl 0.5:1:0.5 33 Tert-butyl 3 C.sub.8 alkyl 0.5:1:0.5 34 Tert-butyl 6 C.sub.8 alkyl 0.5:1:0.5 35 Tert-butyl 8 C.sub.8 alkyl 0.5:1:0.5 36 Tert-butyl 10 C.sub.8 alkyl 0.5:1:0.5 37 Carbazole 3 C.sub.8 alkyl 0.5:1:0.5 38 Carbazole 6 C.sub.8 alkyl 0.5:1:0.5 39 Carbazole 8 C.sub.8 alkyl 0.5:1:0.5 40 Carbazole 10 C.sub.8 alkyl 0.5:1:0.5 41 3,6-di-tert-butyl 3 C.sub.8 alkyl 0.5:1:0.5 carbazole 42 3,6-di-tert-butyl 6 C.sub.8 alkyl 0.5:1:0.5 carbazole 43 3,6-di-tert-butyl 8 C.sub.8 alkyl 0.5:1:0.5 carbazole 44 3,6-di-tert-butyl 10 C.sub.8 alkyl 0.5:1:0.5 carbazole 45 TPA 3 C.sub.8 alkyl 0.5:1:0.5 46 TPA 6 C.sub.8 alkyl 0.5:1:0.5 47 TPA 8 C.sub.8 alkyl 0.5:1:0.5 48 TPA 10 C.sub.8 alkyl 0.5:1:0.5

[0205] 2.4 White Light-Emitting Polymer

[0206] Examples of white light-emitting polymers are prepared from variations of substituents of the monomers as shown in Table 8 below.

TABLE-US-00008 TABLE 8 Functional Mole Functional group ratio of group of fluorene of fluorene Fluorene derivative of formula (I) derivative of derivative Example R.sup.1, R.sup.2, R.sup.3 n of Y group formula (II) of formulas No. and R.sup.4 (—CH.sub.2).sub.n) R.sup.5 and R.sup.6 (I):(II):(III):(V) Compar- H 3 C.sub.8 alkyl 0.96:1:0.002:0.038 ative 13 Compar- H 6 C.sub.8 alkyl 0.96:1:0.002:0.038 ative 14 Compar- H 8 C.sub.8 alkyl 0.96:1:0.002:0.038 ative 15 Compar- H 10 C.sub.8 alkyl 0.96:1:0.002:0.038 ative 16 49 Tert-butyl 3 C.sub.8 alkyl 0.96:1:0.002:0.038 50 Tert-butyl 6 C.sub.8 alkyl 0.96:1:0.002:0.038 51 Tert-butyl 8 C.sub.8 alkyl 0.96:1:0.002:0.038 52 Tert-butyl 10 C.sub.8 alkyl 0.96:1:0.002:0.038 53 Carbazole 3 C.sub.8 alkyl 0.96:1:0.002:0.038 54 Carbazole 6 C.sub.8 alkyl 0.96:1:0.002:0.038 55 Carbazole 8 C.sub.8 alkyl 0.96:1:0.002:0.038 56 Carbazole 10 C.sub.8 alkyl 0.96:1:0.002:0.038 57 3,6-di-tert- 3 C.sub.8 alkyl 0.96:1:0.002:0.038 butyl carbazole 58 3,6-di-tert- 6 C.sub.8 alkyl 0.96:1:0.002:0.038 butyl carbazole 59 3,6-di-tert- 8 C.sub.8 alkyl 0.96:1:0.002:0.038 butyl carbazole 60 3,6-di-tert- 10 C.sub.8 alkyl 0.96:1:0.002:0.038 butyl carbazole 61 TPA 3 C.sub.8 alkyl 0.96:1:0.002:0.038 62 TPA 6 C.sub.8 alkyl 0.96:1:0.002:0.038 63 TPA 8 C.sub.8 alkyl 0.96:1:0.002:0.038 64 TPA 10 C.sub.8 alkyl 0.96:1:0.002:0.038

3. Determination of Characteristics of the Polymers

[0207] The examples of polymers from the above-described Tables 5-8 were further characterized by using various techniques.

[0208] 3.1 Determination of Molecular Weight and Molecular Weight Distribution of Polymers

[0209] The weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (PD) of the polymers were measured by Gel Permeation Chromatography (GPC), relative to a polystyrene standard.

[0210] 5 mg of polymer example was dissolved in 2 mL of tetrahydrofuran (THF) at 35° C. for 45 minutes. X μL of the sample solution was injected into the GPC with RI detector (Malvern, United Kingdom) with flow rate of 1 mL/min at 35° C. in column zone and 35° C. in detector zone. The data was processed by Malvern Omnisec software, Malvern Viscotek TDAmax, country.

[0211] 3.2 Determination of Shading and Optical Properties of Polymers

[0212] Color of the polymer was measured by using the coordinates of CIE 1931 XYZ color space chromaticity diagram.

[0213] Optical properties of the polymer were measured by Photoluminescence Spectroscopy and UV-Visible Spectroscopy in both diluted solution and film of samples.

[0214] UV-visible absorption of the polymer was detected by using Perkin-Elmer Lambda 1050 spectrometer.

[0215] Photoluminescence of the polymer was detected by using Edinburgh Instruments FLS 980 spectrometer. The samples were prepared by coating 2% w/v of the synthesized polymers in toluene on a glass substrate at 3000 rpm.

4. Results

[0216] 4.1 Blue Light-Emitting Polymer

[0217] —Molecular Weight and Molecular Weight Distribution

[0218] The results of measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (PDI) obtained by GPC technique are shown in Table 9 below.

TABLE-US-00009 TABLE 9 Example Mn (g/mol) Mw (g/mol) PDI Comparative 1 8,721 18,315 2.100 Comparative 2 21,611 45,615 2.111 Comparative 3 20,121 33,278 1.654 Comparative 4 19,057 39,039 2.049  1 11,045 23,794 2.154  2 4,258 6,086 1.429  3 29,233 56,937 1.938  4 19,750 41,769 2.115  5 11,092 20,293 1.829  6 11,995 26,818 2.236  7 19,899 36,461 1.832  8 13,190 20,938 1.587  9 9,331 12,554 1.344 10 12,547 18,872 1.504 11 11,703 16,904 1.444 12 13,533 18,310 1.353 13 9,259 14,657 1.583 14 16,932 30,846 1.822 15 9,393 11,916 1.268 16 13,562 22,607 1.667

[0219] —Optical Properties

[0220] The photoluminescence, UV-visible absorption and CIE coordinates results of obtained polymers from the polymerization according to the present are shown in Table 10 below.

TABLE-US-00010 TABLE 10 Maximum Maximum absorption absorption Photo- peak peak of lumin- of UV- photo- escence CIE Visible luminescence quantum Example coordinates spectrum spectrum yield No. (x, y) (nm) (nm) (Φ, %) Compar- (0.17, 0.11) 378 420 13 ative 1 Compar- (0.17, 0.09) 383 434 16 ative 2 Compar- (0.17, 0.10) 385 423 16 ative 3 Compar- (0.17, 0.10) 379 419 16 ative 4 1 (0.17, 0.10) 377 417 22 2 (0.18, 0.13) 355 416 25 3 (0.17, 0.07) 384 417 16 4 (0.17, 0.09) 354 416 17 5 (0.17, 0.09) 374 423 15 6 (0.16, 0.08) 376 421 16 7 (0.16, 0.08) 383 422 21 8 (0.17, 0.09) 377 422 19

[0221] 4.2 Red Light-Emitting Polymer

[0222] —Molecular Weight and Molecular Weight Distribution

[0223] The results of measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (PDI) obtained by GPC technique are shown in Table 11 below.

TABLE-US-00011 TABLE 11 Example Mn (g/mol) Mw (g/mol) PDI Comparative 5 21,400 28,900 1.35 Comparative 6 21,957 29,345 1.34 Comparative 7 23,876 29,877 1.25 Comparative 8 23,368 28,497 1.22 17 18,344 31,400 1.71 18 19,456 31,675 1.62 19 19,432 30,966 1.594 20 20,554 31,868 1.55 21 22,600 32,899 1.45 22 25,744 35,233 1.37 23 26,877 33,856 1.25 24 27,655 35,899 1.29 25 23,987 33,125 1.38 26 24,777 32,658 1.32 27 28,976 31,455 1.08 28 26,588 32,635 1.23 29 24,567 33,555 1.36 30 26,678 31,699 1.18 31 26,788 35,899 1.34 32 29,743 35,134 1.18

[0224] —Optical Properties

[0225] The photoluminescence, UV-visible absorption and CIE coordinates results of obtained polymers from the polymerization according to the present are shown in Table 12 below.

TABLE-US-00012 TABLE 12 Maximum Maximum absorption absorption Photo- peak peak of lumin- of UV- photo- escence Visible luminescence quantum CIE spectrum spectrum yield Example coordinates (nm) (nm) (Φ, %) Compar- (0.69, 0.30) 380, 544 680 8.55 ative 5 Compar- (0.69, 0.29) 381, 545 677 9.64 ative 6 Compar- (0.72, 0.31) 382, 544 676 13.44 ative 7 Compar- (0.70, 0.30) 380, 545 680 14.78 ative 8 17 (0.71, 0.29) 381, 550 678 15.66 18 (0.72, 0.29) 382, 551 678 15.66 19 (0.70, 0.30) 383, 546 686 19.31 20 (0.71, 0.29) 381, 550 678 15.66 21 (0.70, 0.30) 370, 546 674 9.55 22 (0.72, 0.29) 372, 551 680 14.73 23 (0.68, 0.29) 376, 545 677 13.55 24 (0.70, 0.30) 377, 550 675 14.51 25 (0.71, 0.30) 380, 548 687 16.78 26 (0.70, 0.28) 381, 546 675 16.22 27 (0.70, 0.29) 382, 549 685 22.56 28 (0.72, 0.31) 388, 550 680 15.46 29 (0.71, 0.30) 375, 543 677 11.12 30 (0.70, 0.31) 380, 550 680 15.44 31 (0.70, 0.29) 376, 544 670 14.56 32 (0.72, 0.30) 380, 552 669 16.78

[0226] 4.3 Green Light-Emitting Polymer

[0227] —Molecular Weight and Molecular Weight Distribution

[0228] The results of measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (PDI) obtained by GPC technique are shown in Table 13.

TABLE-US-00013 TABLE 13 Example Mn (g/mol) Mw (g/mol) PDI Comparative 9 16,342 46,789 2.86 Comparative 10 16,360 40,233 2.45 Comparative 11 17,865 47,854 2.67 Comparative 12 18,112 46,890 2.58 33 18,289 46,556 2.54 34 19,553 47,885 2.44 35 19,723 48,903 2.479 36 19,966 48,775 2.44 37 18,211 45,877 2.54 38 19,456 40,764 2.09 39 19,254 46,213 2.479 40 19,369 45,786 2.36 41 16,654 43,765 2.62 42 17,854 42,800 2.39 43 18,236 45,600 2.50 44 18,657 41,671 2.23 45 17,890 47,901 2.67 46 18,354 42,890 2.33 47 19,432 48,300 2.48 48 19,800 41,543 2.09

[0229] —Optical Properties

[0230] The photoluminescence, UV-visible absorption and CIE coordinates results of obtained polymers from the polymerization according to the present are shown in Table 14 below.

TABLE-US-00014 TABLE 14 Maximum Maximum absorption absorption Photo- peak peak of lumin- of UV- photo- escence Visible luminescence quantum CIE spectrum spectrum yield Example coordinates (nm) (nm) (Φ, %) Compar- (0.34, 0.55) 434 532 6.75 ative 9 Compar- (0.33, 0.54) 430 531 6.80 ative 10 Compar- (0.36, 0.55) 436 532 6.76 ative 11 Compar- (0.36, 0.56) 435 533 6.70 ative 12 41 (0.35, 0.52) 435 533 10.78 42 (0.36, 0.54) 436 534 14.55 43 (0.35, 0.60) 430 535 16.89 44 (0.33, 0.55) 434 536 17.66 45 (0.34, 0.55) 437 535 10.88 46 (0.34, 0.54) 440 535 11.88 47 (0.33, 0.58) 432 532 14.55 48 (0.35, 0.55) 435 536 16.49

[0231] 4.4 White Light-Emitting Polymer

[0232] —Molecular Weight and Molecular Weight Distribution

[0233] The results of measurement of weight average molecular weight (Mw), number average molecular weight (Mn) and polydispersity (PDI) obtained by GPC technique are shown in Table 15 below.

TABLE-US-00015 TABLE 15 Example Mn (g/mol) Mw (g/mol) PDI Comparative 13 13,480 46,789 3.47 Comparative 14 15,467 45,765 2.96 Comparative 15 13,935 43,566 3.12 Comparative 16 24,577 48,534 1.97 49 21,333 45,677 2.14 50 24,756 38,344 1.55 51 23,935 46,724 1.95 52 29,788 36,456 1.22 53 23,455 38,765 1.65 54 21,674 41,234 1.90 55 25,678 39,675 1.53 56 28,980 43,567 1.50 57 24,455 48,970 2.00 58 27,865 41,235 1.47 59 25,654 41,896 1.63 60 24,788 43,688 1.76 61 29,876 42,990 1.43 62 28,987 39,888 1.38 63 31,467 41,907 1.33 64 35,678 57,890 1.62

[0234] —Optical Properties

[0235] The photoluminescence, UV-visible absorption and CIE coordinates results of obtained polymers from the polymerization according to the present are shown in Table 16.

TABLE-US-00016 TABLE 16 Maximum Maximum absorption absorption peak peak of UV- of photo- CIE Visible luminescence Example coordinates spectrum (nm) spectrum (nm) Compar- (0.30, 0.31) 367 445, 615 ative 13 Compar- (0.29, 0.28) 370 451, 616 ative 14 Compar- (0.30, 0.31) 371 450, 620 ative 15 Compar- (0.30, 0.28) 372 451, 619 ative 16 49 (0.33, 0.30) 370 450, 620 50 (0.28, 0.29) 368 449, 618 51 (0.32, 0.26) 371 451, 618 52 (0.28, 0.29) 369 450, 617 53 (0.33,0.20) 372 451, 620 54 (0.30, 0.28) 370 451, 615 55 (0.31,0.27) 365 450, 620 56 (0.33, 0.29) 375 455, 619 57 (0.35, 0.33) 371 450, 622 58 (0.31,0.33) 370 451, 623 59 (0.33, 0.30) 371 450, 621 60 (0.29, 0.30) 370 451, 620 61 (0.30, 0.31) 369 450, 615 62 (0.27, 0.30) 371 451, 620 63 (0.28, 0.30) 367 450, 617 64 (0.31,0.33) 371 445, 615

[0236] The synthesized white light-emitting polymers were further measured photoluminescence quantum yield (Φ) to compare with the comparative examples 13-16. From the experimental results, it shows that the obtained polymers of the present invention provide higher photoluminescence quantum yields than that of the comparative examples when compared with the same number of carbon atoms of —(CH.sub.2).sub.n— group of the fluorene derivatives of formula (I). For example, when n is 3 the photoluminescence quantum yield of the comparative example 13 is 20% while that of white polymer of the present invention is 30% (example 57) and when n is 8 the photoluminescence quantum yield of the comparative example 15 is 31% while that of the white polymers of the present invention are 48% (examples 51) and 40% (example 59).