U.S. patent application number 11/779101 was filed with the patent office on 2007-11-22 for white electroluminescent polymeric material and preparation thereof.
This patent application is currently assigned to CHANGCHUN INSTITUTE OF APPLIED CHEMISTRY CHINES ACADEMY OF SCIENCE. Invention is credited to Jianxin Cao, Xiabin Jing, Jun Liu, Dongge Ma, Guoli Tu, Fosong Wang, Lixiang Wang.
Application Number | 20070270570 11/779101 |
Document ID | / |
Family ID | 34581635 |
Filed Date | 2007-11-22 |
United States Patent
Application |
20070270570 |
Kind Code |
A1 |
Wang; Lixiang ; et
al. |
November 22, 2007 |
WHITE ELECTROLUMINESCENT POLYMERIC MATERIAL AND PREPARATION
THEREOF
Abstract
This invention relates to a white electroluminescent polymeric
material and preparation thereof. Based on the physical idea that
white light emission can be achieved by regulating the relative
luminous intensities of blue- and orange-light emitting units
located in a single polymer molecule, the present invention
provides three types (main chain type, pendant chain type, and
terminal group type) of high efficiency and stable white
electroluminescent polymeric material systems.
Inventors: |
Wang; Lixiang; (Changchun
City, CN) ; Tu; Guoli; (Changchun City, CN) ;
Cao; Jianxin; (Changchun City, CN) ; Liu; Jun;
(Changchun City, CN) ; Ma; Dongge; (Changchun
City, CN) ; Jing; Xiabin; (Changchun City, CN)
; Wang; Fosong; (Jilin Province, CN) |
Correspondence
Address: |
DICKSTEIN SHAPIRO LLP
1177 AVENUE OF THE AMERICAS (6TH AVENUE)
NEW YORK
NY
10036-2714
US
|
Assignee: |
CHANGCHUN INSTITUTE OF APPLIED
CHEMISTRY CHINES ACADEMY OF SCIENCE
Changchun City
CN
|
Family ID: |
34581635 |
Appl. No.: |
11/779101 |
Filed: |
July 17, 2007 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
11042193 |
Jan 26, 2005 |
|
|
|
11779101 |
Jul 17, 2007 |
|
|
|
Current U.S.
Class: |
528/367 ;
257/E51.036; 313/504; 428/917; 528/368; 528/377; 528/380; 528/397;
528/422; 528/423 |
Current CPC
Class: |
H01L 51/0043 20130101;
C09K 11/06 20130101; C07D 401/04 20130101; C09K 2211/1416 20130101;
H01L 51/5036 20130101; Y10S 428/917 20130101; C09K 2211/1466
20130101; Y02B 20/181 20130101; Y02B 20/00 20130101; C09K 2211/1483
20130101; C07D 417/04 20130101; C09K 2211/1475 20130101; H01L
51/0039 20130101 |
Class at
Publication: |
528/367 ;
528/368; 428/917; 313/504; 257/E51.036; 528/423; 528/422; 528/377;
528/380; 528/397 |
International
Class: |
C08G 61/12 20060101
C08G061/12; C09K 11/06 20060101 C09K011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 29, 2004 |
CN |
200410010770.0 |
Claims
1. A white electroluminescent polymeric material, which comprising
a single white electroluminescent polymeric material selected from
a group consisting of: type (A): pendant chain type single white
electroluminescent polymeric material ##STR35## Wherein: R.sub.1 is
alkyl or aryl; R.sub.2 is selected from a group consisting of
alkyl, alkoxy, phenyl, and phenyl substituted by alkyl or alkoxy;
Ar1 is a naphthalimide derivative basic unit and has one or more
structures as listed below: ##STR36## ##STR37## ##STR38## ##STR39##
##STR40## wherein R.sub.6 is alkyl, phenyl, naphthyl, a phenyl or
naphthyl group substituted by alkyl or alkoxy, wherein the chain
lengths of the alkyl and the alkoxy are 1-18; and Ar2 is an
electron transport basic unit, a hole transport basic unit or a
luminescence basic unit and has one or more structural units
selected from the following units: ##STR41## ##STR42## ##STR43##
##STR44## wherein R.sub.5 is selected from a group consisting of
alkyl, phenyl, naphthyl, and phenyl or naphthyl substituted by
alkyl or alkoxy, m=0-20; wherein, the chain lengths of the alkyl
and the alkoxy are 1-18; each basic unit content--x, y and z
satisfy 0<x.ltoreq.1, 0<y<1, 0.ltoreq.z<1, x+y+z=1,
m=0-20, n=1-300; and the chain lengths of the alkyl and the alkoxy
are 1-18; and type (B): terminal group type single white
electroluminescent polymeric material ##STR45## wherein: R.sub.1 is
alkyl or aryl; Ar1 is a naphthalimide derivative basic unit and has
one or more structures as listed below: ##STR46## ##STR47##
##STR48## wherein R.sub.7 is alkyl, phenyl, naphthyl, or a phenyl
or naphthyl group substituted by alkyl or alkoxy; the structure of
Ar2 is the same as the Ar2 in the type (A) single white luminescent
polymeric material; x and y are basic unit contents and satisfy
0<x.ltoreq.1, 0<y<1, x+y=1; n=1-300; and the chain length
of alkyl and alkoxy is 1-18.
2. A method for preparing the white electroluminescent polymeric
material according to claim 1, the method comprising steps of: d.
providing a monomer selected from a group consisting of: (5)
monomers with a formula as follows: ##STR49## wherein, Ar1 is the
same as that in the main chain type single white luminescent
polymeric material according to claim 1; (6) monomers with a
formula as follows: ##STR50## wherein, Ar1 is the same as that in
the pendant chain type single white luminescent polymeric material
according to claim 1, m=0-20; (7) monomers with a formula as
follows: ##STR51## wherein, Ar1 is the same as that in the pendant
chain type single white luminescent polymeric material according to
claim 1, m=0-20; and (8) monomers with a formula as follows:
##STR52## wherein, Ar1 is the same as that in the pendant chain
type single white luminescent polymeric material according to claim
1, m=0-20; e. providing a monomer selected from a group consisting
of: ##STR53## wherein, Ar1 is the same as that in the terminal
group type single white luminescent polymeric material defined in
claim 1; and f. polymerizing a monomer obtained in step (a) and a
monomer obtained in step (b) using the Yamamoto polymerization
method or the Suzuki polymerization method.
3. The method according to claim 2, wherein the monomer (1) in step
a is prepared by a method comprising steps of: dissolving
naphthalimide derivative Ar1 and 2-4 mole equivalents of
tetrabutyltriammonium bromide in a dichloromethane; reacting the
resulting solution, preferably at room temperature, for 10-1200
min; and separating the reaction product.
4. The method according to claim 2, wherein the monomer (2) in step
a is prepared by a method comprising steps of: dissolving
4-amino-1,8-naphthalimide and 1-5 mole equivalents of
2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene in dimethyl
sulfoxide; adding 1-10 mole equivalents of MOH wherein M represents
Li, Na or K; reacting at 50-150.degree. C. for 1-120 hr; stopping
the reaction and separating the intermediate product; dissolving
the intermediate product, 2-20 mole equivalents of iodobenzene,
2-20 mole equivalents of carbonate, 1-5% mole equivalent of
18-crown-6 and 1-5% mole equivalent of cuprous iodide in a solvent;
heating to 140-200.degree. C. under N.sub.2 gas to react for 5-50
hr; and separating the product.
5. The method according to claim 2, wherein the monomer (3) in step
a is prepared by a method comprising steps of: contacting
N,N-diphenyl-1,8-naphthalimide derivative with 15-80 mole
equivalents of POCl.sub.3 in dimethyl formamide at
50.about.100.degree. C. for 20-100 hr to produce 4-aldo or
4,4'-dialdo-N,N-diphenyl-1,8-naphthalimide derivative; dissolving
the resulting product and 0.5-1 mole equivalents of
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluor-
ene or
9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene
in a chloroform solution; adding a solution of 4-10 mole
equivalents of sodium ethoxide; reacting at room temperature for
10-50 hr; and separating the reaction product.
6. The method according to claim 2, wherein the monomer (4) in step
a is prepared by a method comprising the steps of: dissolving
9,9-(m-bromoalkyl)-2,7-dibromofluorene and 2-3 mole equivalents of
4-amino-1,8-naphthalimide in a solvent; adding 2-20 mole
equivalents of MOH wherein M represents Li, Na or K; reacting at
50-150.degree. C. for 1-120 hr; separating the intermediate
product; dissolving the intermediate product, 4-20 mole equivalents
of iodobenzene, 6-20 mole equivalents of potassium carbonate, 2-10%
mole equivalents of 18-crown-6, 2-10% mole equivalent of cuprous
iodide in a solvent; heating the solution to 140-200.degree. C. to
react for 5-50 hr; and separating the product.
7. The method according to claim 2, wherein the monomer b in step b
is prepared using a method comprising steps of: dissolving
naphthalimide derivative Ar1H and 1-2 mole equivalents of
tetrabutyltriammonium bromide in a solvent, preferably,
dichloromethane; reacting for 10-1200 min; and separating the
product.
8. The method according to claim 2, wherein, for obtaining the main
chain type single white light polymeric material, the Yamamoto
polymerization method comprising steps of: dissolving
2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent
of dibromonaphthalimide derivative monomer and 0-30% mole
equivalent of dibromoaromatic monomer in a solvent, preferably
anhydrous toluene, under the protection of N.sub.2 gas; dropping
the resulting solution into a solution of 2-3 mole equivalents of
Ni (0) in a solvent; reacting at 50-100.degree. C. for 24-120 hr;
and separating the product.
9. The method according to claim 2, wherein, for obtaining the main
chain type single white light polymeric material, the Suzuki
polymerization method comprising steps of: dissolving 2,7-diborate
fluorene derivative monomer, 0.01-10% mole equivalent of
dibromonaphthalimide derivative monomer and 0-20% mole equivalent
of dibromoaromatic monomer in a solvent; adding 3 mole equivalents
of carbonate in a solution form; under the protection of inert gas
and at 50-100.degree. C., adding 0.05% mole equivalent of
tetra(triphenylphosphino) palladium (0); reacting for 1-200 hr; and
separating the product.
10. The method according to claim 2, wherein, for obtaining the
pendant chain type single white light polymeric material, the
Yamamoto polymerization method comprising steps of: dissolving
2,7-dibromofluorene derivative monomer, 0.01%-10% mole equivalent
of any one of monomers (2)-(4) in step a, and 0-30% mole equivalent
of dibromoaromatic monomer in a solvent; dropping the resulting
solution into a solution of 2-3 mole equivalents of Ni (0) in a
solvent; reacting at 50-100.degree. C. for 24-120 hr; and
separating the product.
11. The method according to claim 2, wherein, for obtaining the
pendant chain type single white light polymeric material, the
Suzuki polymerization method comprising steps of: dissolving
2,7-diborate fluorene derivative monomer, 0.01-10 mole equivalent
of any one of monomers (2)-(4) in step a, and 0-20% mole equivalent
of dibromoaromatic monomer in a solvent; adding 3 mole equivalents
of carbonate in a solution form; under the protection of inert gas
and at 50-100.degree. C., adding 0.05% mole equivalent of
tetra(triphenylphosphino) palladium (0); reacting for 1-200 hr; and
separating the product.
12. The method according to claim 2, wherein, for obtaining the
terminal group type single white light polymeric material, the
Yamamoto polymerization method comprising steps of: dissolving
2,7-dibromofluorene derivative monomer and 0-30% mole equivalent of
dibromoaromatic monomer in a solvent under the protection of an
inert gas; dropping the resulting solution into a solution of 2-3
mole equivalents of Ni (0) in a solvent; reacting at 50-100.degree.
C. for 24-120 hr; and separating the product.
13. The method according to claim 2, wherein, for obtaining the
terminal group type single white light polymeric material, the
Suzuki polymerization method comprising steps of: dissolving
2,7-diborate fluorene derivative monomer and 0-30% mole equivalent
of dibromoaromatic monomer in a solvent; adding 3 mole equivalents
of carbonate in a solution form; under the protection of N.sub.2
gas and at 50-100.degree. C., adding 0.050% mole equivalent of
tetra(triphenylphosphino) palladium (0); reacting for 24-120 hr;
adding 0.01-10% mole equivalent of monobromonaphthalimide
derivative monomer; reacting at 50-100.degree. C. for 1-48 hr; and
separating the product.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] The present application is a divisional of prior co-pending
application Ser. No. 11/042,193, filed on Jan. 26, 2005.
TECHNICAL FIELD
[0002] This invention relates to a white electroluminescent
polymeric material and preparation thereof.
BACKGROUND ART
[0003] Since the electroluminescence of poly(p-phenylene vinylene)
(PPV) was first reported by Burroughs et al, Cambridge Univ. U.K.
in 1990, the polymeric electroluminescent material and
manufacturing device thereof has been extensively concerned and
investigated by the research and industry circles due to its
prominent characteristics of simple process, easy to achieve large
screen display and flexible display etc. At present, some typical
blue-, green- and red-light polymeric luminescent material systems,
such as poly(p-phenylene) (PPP), poly(alkylfluorene) (PAF),
poly(phenylvinylene) (PPV), polythiophene (PTh) etc, have been
developed. All the performance indexes of the monochromatic light
polymeric electroluminescent device made of them can fulfill
practical requirements. By contrast, there is a larger gap between
every performance index of white light polymeric device and
practical requirement. It is necessary to research deeply the
material design and device structure separately so as to accelerate
the course of industrialization of white light polymeric device.
The means for achieving white light polymeric electroluminescent
device mainly include: (1) blending system of organic fluorescent
dye/polymer; (2) blending system of polymer/polymer; (3) single
white light polymeric system. For example, J. kido et al. disclosed
a method for obtaining white luminescence with a maximum luminance
of 3400 cd/m.sup.2 by dispersing three kinds of fluorescent dyes
(red, green and blue) in poly(vinylcarbazol) (PVK) and regulating
the contents of the three dyes, Appl. Phys. Lett., 64, 815, 1994;
Inganas et al. disclosed another method for obtaining a white light
emission (CIE 0.220, 0.466) by blending the polythiophene
derivatives (red, green and blue) with an inert polymer (such as
PMMA) under a high driving voltage (20V), Appl. Phys. Lett., 68,
147, 1996. But the system has the following disadvantages: the
obvious phase separation between polymer and polymer results in the
voltage-dependence of white light emission, and thus a stable white
light device is difficult to be obtained. Leising research group
disclosed a method for obtaining a white light polymeric device
having an external quantum efficiency of 1.2% by dispersing a trace
amount (0.66 wt %) of red light poly(perylene-co-diethynylbenzene)
(PPDB) in a high efficiency blue light laddertype
(polyparaphenylene) (m-LPPP), in which the voltage-dependence of
white color purity was improved to a certain extent due to the
formation of a homogeneous blending system of polymer/polymer, see
Appl. Phys. Lett., 71, 2883, 1997. For the single polymeric white
light system disclosed in "Appl. Phys. Lett., 79, 308, 2001" and
"Macromolecules, 35, 6782, 2002", it is obtained by forming an
exciplex during the electroluminescence of PPV polymer (blue or
blue-green), which can bring about a wide-band luminescence, so the
white light polymeric device made thereof has a sharp
voltage-dependence of color and relatively poor performances.
DISCLOSURE OF THE INVENTION
[0004] The object of this invention is to provide a white
electroluminescent polymeric material.
[0005] Another object of this invention is to provide a method for
preparing a white electroluminescent polymeric material.
[0006] The inventors of the present invention find that white light
emission can be achieved by regulating the relative luminous
intensities of blue- and orange-light emitting units located in a
single polymer molecule. Based on such a physical idea, the present
invention provides three types (main chain type, pendant chain
type, and terminal group type) of high efficiency and stable white
electroluminescent polymeric material systems.
[0007] The present invention provides the following aspects.
[0008] 1. A white electroluminescent polymeric material, which
comprising a single white electroluminescent polymeric material
selected from a group consisting of:
[0009] type (I): main chain type single white electroluminescent
polymeric material, ##STR1##
[0010] wherein: R.sub.1 is alkyl or aryl, Ar1 is a naphthalimide
derivative basic unit having one or more structures as listed
below: ##STR2## ##STR3## ##STR4## ##STR5## ##STR6## ##STR7##
##STR8##
[0011] wherein, Ar2 is an electron transport basic unit, a hole
transport basic unit or a luminescence basic unit; x, y, and z each
represents the content of one basic unit, satisfying
0<x.ltoreq.1, 0<y<1, 0.ltoreq.z<1, x+y+z=1, and
n=1-300, wherein, the chain lengths of the alkyl and the alkoxy are
1-18; the aryl is selected from a group consisting of phenyl,
naphthyl, fluorenyl, triphenylamino, oxadiazolyl, and phenyl or
naphthyl substituted by alkyl or alkoxy; R.sub.3 and R.sub.4
independently represent an alkyl having a chain length of 1-18 or
an aryl, wherein the aryl is selected from a group consisting of
phenyl, naphthyl, and phenyl or naphthyl substituted by alkyl or
alkoxy;
[0012] Ar2 has one or more structural units selected from the
following units: ##STR9## ##STR10## ##STR11## ##STR12##
[0013] wherein R.sub.5 is selected from a group consisting of
alkyl, phenyl, naphthyl, and phenyl or naphthyl substituted by
alkyl or alkoxy, m=0-20; wherein, the chain lengths of the alkyl
and the alkoxy are 1-18;
[0014] type (II): pendant chain type single white
electroluminescent polymeric material ##STR13## wherein: R.sub.2 is
selected from a group consisting of alkyl, alkoxy, phenyl, and
phenyl substituted by alkyl or alkoxy; Ar1 is a naphthalimide
derivative basic unit; The basic structure of Ar2 is the same as
the Ar2 of the main chain type single white luminescent polymeric
material; Each basic unit content--x, y and z satisfy
0<x.ltoreq.1, 0<y<1, 0.ltoreq.z<1, x+y+z=1, m=0-20,
n=1-300; wherein the chain lengths of the alkyl and the alkoxy are
1-18;
[0015] Ar1 has one or more structures as listed below: ##STR14##
##STR15## ##STR16## ##STR17## ##STR18## wherein R.sub.6 is alkyl,
phenyl, naphthyl, a phenyl or naphthyl group substituted by alkyl
or alkoxy, wherein the chain lengths of the alkyl and the alkoxy
are 1-18; and
[0016] type (III): terminal group type single white
electroluminescent polymeric material ##STR19## wherein: Ar1 is a
naphthalimide derivative basic unit; the structure of Ar2 is the
same as the Ar2 of the main chain type single white luminescent
polymeric material; x and y are basic unit contents and satisfy
0<x.ltoreq.1, 0<y<1, x+y=1; n=1-300;
[0017] Ar1 has one or more structures as listed below: ##STR20##
##STR21## ##STR22##
[0018] wherein R.sub.7 is alkyl, phenyl, naphthyl, or a phenyl or
naphthyl group substituted by alkyl or alkoxy; wherein the chain
length of alkyl and alkoxy is 1-18.
[0019] 2. A process for preparing the white electroluminescent
polymeric material according to aspect 1, comprising steps of:
[0020] a. providing a monomer selected from a group consisting of:
[0021] (1) monomers with a formula as follows: ##STR23## [0022]
wherein, Ar1 is the same as that in the main chain type single
white luminescent polymeric material according to aspect 1; [0023]
(2) monomers with a formula as follows: ##STR24## [0024] wherein,
Ar1 is the same as that in the pendant chain type single white
luminescent polymeric material according to aspect 1, m=0-20,
preferably 1-20; [0025] (3) monomers with a formula as follows:
##STR25## [0026] wherein, Ar1 is the same as that in the pendant
chain type single white luminescent polymeric material according to
aspect 1, m=0-20, preferably 1-20; and [0027] (4) monomers with a
formula as follows: ##STR26## [0028] wherein, Ar1 is the same as
that in the pendant chain type single white luminescent polymeric
material according to aspect 1, m=0-20, preferably 1-20; [0029] b.
providing a monomer selected from a group consisting of: ##STR27##
[0030] wherein, Ar1 is the same as that in the terminal group type
single white luminescent polymeric material defined in aspect 1;
and [0031] c. polymerizing a monomer obtained in step (a) and a
monomer obtained in step (b) using the Yamamoto polymerization
method or the Suzuki polymerization method.
[0032] 3. The method according to aspect 2, wherein the monomer (1)
in step a is prepared by a method comprising steps of: dissolving
naphthalimide derivative Ar1 and 2-4 mole equivalents of
tetrabutyltriammonium bromide in dichloromethane; reacting the
resulting solution, preferably at room temperature, for 10-1200
min; and separating the reaction product.
[0033] 4. The method according to aspect 2, wherein the monomer (2)
in step a is prepared by a method comprising steps of: dissolving
4-amino-1,8-naphthalimide and 1-5 mole equivalents of
2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene in dimethyl
sulfoxide; adding 1-10 mole equivalents of MOH wherein M represents
Li, Na or K; reacting at 50-150.degree. C. for 1-120 hr; stopping
the reaction and separating the intermediate product; dissolving
the intermediate product, 2-20 mole equivalents of iodobenzene,
2-20 mole equivalents of carbonate, preferably, sodium carbonate or
potassium carbonate, 1-5% mole equivalent of 18-crown-6 and 1-5%
mole equivalent of cuprous iodide in a solvent, preferably DMPU
(1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-primidinone); heating to
140-200.degree. C. under an inert gas, preferably N.sub.2 gas, to
react for 5-50 hr; and separating the product.
[0034] 5. The method according to aspect 2, wherein the monomer (3)
in step a is prepared by a method comprising steps of: contacting
N,N-diphenyl-1,8-naphthalimide derivative with 15-80 mole
equivalents of POCl.sub.3 in dimethyl formamide at
50.about.100.degree. C. for 20-100 hr to produce 4-aldo or
4,4'-dialdo-N,N-diphenyl-1,8-naphthalimide derivative; dissolving
the resulting product and 0.5-1 mole equivalents of
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluor-
ene or
9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene
in a chloroform solution; adding a solution of 4-10 mole
equivalents of sodium ethoxide; reacting at room temperature for
10-50 hr; and separated the reaction product.
[0035] 6. The method according to aspect 2, wherein the monomer (4)
in step a is prepared by a method comprising the steps of:
dissolving 9,9-(m-bromoalkyl)-2,7-dibromofluorene and 2-3 mole
equivalents of 4-amino-1,8-naphthalimide in a solvent, preferably,
DMSO; adding 2-20 mole equivalents of MOH wherein M represents Li,
Na or K; reacting at 50-150.degree. C. for 1-120 hr; separating the
intermediate product; dissolving the intermediate product, 4-20
mole equivalents of iodobenzene, 6-20 mole equivalents of potassium
carbonate, 2-10% mole equivalents of 18-crown-6, 2-10% mole
equivalent of cuprous iodide in a solvent such as DMPU; heating the
solution to 140-200.degree. C. to react for 5-50 hr; and separated
the product.
[0036] 7. The method according to aspect 2, wherein the monomer b
in step b is prepared using a method comprising steps of:
dissolving naphthalimide derivative Ar1H and 1-2 mole equivalents
of tetrabutyltriammonium bromide in a solvent, preferably,
dichloromethane; reacting, preferably at room temperature, for
10-1200 min; and separated the product.
[0037] 8. The method according to aspect 2, wherein, for obtaining
the main chain type single white light polymeric material, the
Yamamoto polymerization method comprising steps of:
[0038] dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10%
mole equivalent of dibromonaphthalimide derivative monomer and
0-30% mole equivalent of dibromoaromatic monomer in a solvent,
preferably anhydrous toluene, under the protection of an inert gas,
preferably N.sub.2 gas;
[0039] dropping the resulting solution into a solution of 2-3 mole
equivalents of Ni (0) in a solvent, preferably dimethyl
formamide;
[0040] reacting at 50-100.degree. C. for 24-120 hr; and
[0041] separating the product.
[0042] 9. The method according to aspect 2, wherein, for obtaining
the main chain type single white light polymeric material, the
Suzuki polymerization method comprising steps of:
[0043] dissolving 2,7-diborate fluorene derivative monomer,
0.01-10% mole equivalent of dibromonaphthalimide derivative monomer
and 0-20% mole equivalent of dibromoaromatic monomer in a solvent,
preferably toluene;
[0044] adding 3 mole equivalents of carbonate, preferably potassium
carbonate or sodium carbonate, in a solution form;
[0045] under the protection of an inert gas, preferably N.sub.2 gas
and at 50-100.degree. C., adding 0.05% mole equivalent of
tetra(triphenylphosphino) palladium (0);
[0046] reacting for 1-200 hr; and
[0047] separating the product.
[0048] 10. The method according to aspect 2, wherein, for obtaining
the pendant chain type single white light polymeric material, the
Yamamoto polymerization method comprising steps of:
[0049] dissolving 2,7-dibromofluorene derivative monomer, 0.01%-10%
mole equivalent of any one of monomers (2)-(4) in step a, and 0-30%
mole equivalent of dibromoaromatic monomer in a solvent, preferably
anhydrous toluene, under the protection of an inert gas, preferably
N.sub.2 gas;
[0050] dropping the resulting solution into a solution of 2-3 mole
equivalents of Ni (0) in a solvent, preferably dimethyl
formamide;
[0051] reacting at 50-100.degree. C. for 24-120 hr; and
[0052] separating the product.
[0053] 11. The method according to aspect 2, wherein, for obtaining
the pendant chain type single white light polymeric material, the
Suzuki polymerization method comprising steps of:
[0054] dissolving 2,7-diborate fluorene derivative monomer, 0.01-10
mole equivalent of any one of monomers (2)-(4) in step a, and 0-20%
mole equivalent of dibromoaromatic monomer in a solvent, preferably
toluene;
[0055] adding 3 mole equivalents of carbonate, preferably potassium
carbonate or sodium carbonate, in a solution form;
[0056] under the protection of an inert gas, preferably N.sub.2 gas
and at 50-100.degree. C., adding 0.05% mole equivalent of
tetra(triphenylphosphino) palladium (0);
[0057] reacting for 1-200 hr; and
[0058] separating the product.
[0059] 12. The method according to aspect 2, wherein, for obtaining
the terminal group type single white light polymeric material, the
Yamamoto polymerization method comprising steps of:
[0060] dissolving 2,7-dibromofluorene derivative monomer and 0-30%
mole equivalent of dibromoaromatic monomer in a solvent, preferably
anhydrous toluene, under the protection of N.sub.2 gas;
[0061] dropping the resulting solution into a solution of 2-3 mole
equivalents of Ni (0) in a solvent, preferably dimethyl
formamide;
[0062] reacting at 50-100.degree. C. for 24-120 hr; and
[0063] separating the product.
[0064] 13. The method according to aspect 2, wherein, for obtaining
the terminal group type single white light polymeric material, the
Suzuki polymerization method comprising steps of:
[0065] dissolving 2,7-diborate fluorene derivative monomer and
0-30% mole equivalent of dibromoaromatic monomer in a solvent,
preferably toluene;
[0066] adding 3 mole equivalents of carbonate, preferably potassium
carbonate or sodium carbonate, in a solution form;
[0067] under the protection of N.sub.2 gas and at 50-100.degree.
C., adding 0.050% mole equivalent of tetra(triphenylphosphino)
palladium (0);
[0068] reacting for 24-120 hr;
[0069] adding 0.01-10% mole equivalent of monobromonaphthalimide
derivative monomer;
[0070] reacting at 50-100.degree. C. for 1-48 hr; and
[0071] separating the product.
PREFERRED EMBODIMENTS OF THE INVENTION
[0072] In this invention, polyfluorene and its derivative are used
as the structural unit for blue light, naphthalimide derivative as
that for orange light.
[0073] In the present invention, otherwise indicated, the term
"alkyl" means a straight or branched alkyl having 1-18, preferably
1-10, more preferably 1-6 carbon atoms, the term "alkoxy group"
means a straight or branched alkoxy group having 1-18, preferably
1-10, more preferably 1-6 carbon atoms, and the term "aryl" means
an aryl optionally substituted by an alkyl or aryl, more
preferably, having 6-18 carbon atoms.
[0074] The preparation methods for the three types of white
electroluminescent polymeric material mainly relates to five types
of monomers and two types of copolymerization reactions.
[0075] Examples of the preparations methods are provided as
follows:
[0076] 1. Preparation of 2,7-Dibromofluorene and the Monomer
Derived Therefrom
[0077] The general structural formulas of 2,7-dibromofluorene and
the monomer derived therefrom are as follows: ##STR28##
[0078] That is, 2,7-dibromofluorene and the monomer derived
therefrom can be classified as 9,9-dialkyl-2,7-dibromofluorene
monomer and 9,9-diaryl-2,7-dibromofluorene. Their preparation
methods are respectively described as follows:
a) Preparation of 9,9-dialkyl-2,7-dibromofluorene monomer
[0079] 2,7-dibromofluorene and 2-6 mole equivalents of excessive
bromoalkane are dissolved in toluene, then 2-50 mole equivalents of
10-70% NaOH aqueous solution was added. After reacting under the
protection of N.sub.2 gas for 1-24 hr at 30-100.degree. C., the
reaction product was poured into water, and then the organic phase
was separated, washed repeatedly with water, dried, concentrated
and recrystallized to obtain 9,9-dialkyl-2,7-dibromofluorene.
b) Preparation of 9,9-diaryl-2,7-dibromofluorene monomer
[0080] First, 2,7-dibromofluorene ketone is dissolved in ethyl
ether, under the protection of N.sub.2 gas, 1-4 mole equivalents of
an aryl Grignard reagent is then added. After reacting under reflux
for 1-24 hr, 9-hydroxy-9-aryl-2,7-dibromofluorene is obtained.
9-hydroxy-9-aryl-2,7-dibromofluorene is then dropped slowly into an
aryl hydrocarbon sulfuric acid solution in a mole ratio of 1:1-5.
After refluxing for 1-24 hr, the reaction product is poured into
water. The resulting organic phase is separated, washed repeatedly
with water, dried, concentrated and recrystallized to obtain
9,9-diaryl-2,7-dibromofluorene.
[0081] 2. Preparation of 9,9-Disubstituted-2,7-Biborate and Monomer
Derived Therefrom ##STR29##
[0082] The general structural formula of
9,9-disubstituted-2,7-biborate and monomer derived therefrom is one
of the following formulas:
[0083] The preparation method for 9,9-dialkylfluorene-2,7-biborate,
9,9-spirobifluorene-2,7-biborate and monomer derived therefrom is
as follows:
[0084] 1-4 mole equivalents of n-butyllithium is added at
-100.about.0.degree. C. into a solution of 2,7-dibromofluorene and
monomer derived therefrom in THF. After stirring for 1-10 hr, 2-10
mole equivalents of trimethyl borate is then added at
-100.about.0.degree. C. After stirring at room temperature for 1-48
hr, the reaction product is poured into water. Then the organic
phase is separated, washed repeatedly with water, dried,
concentrated, and dissolved in toluene. 2-10 mole equivalents of
1,3-propylene glycol is added. After refluxing for 1-72 hr, the
reaction product is poured into water. The organic phase is
separated, washed repeatedly with water, dried, concentrated and
finally separated by column chromatography to produce
9,9-dialkylfluorene-2,7-biborate or
9,9-spirobifluorene-2,7-biborate and their derivatives.
[0085] 3. Preparation of Dibromonaphthalimide Derivative
Monomer
[0086] dibromonaphthalimide derivative monomer mainly includes:
main chain type dibromonaphthalimide derivative monomers, pendant
chain type dibromonaphthalimide derivative monomers and pendant
chain type 9,9-disubstituted dibromofluorene naphthalimide
derivative monomers;
[0087] 1) The general structural formula of the main chain type
dibromonaphthalimide derivative monomers is as follows: ##STR30##
wherein Ar1 is the same as the Ar1 in the main chain type single
white light polymeric material.
[0088] The preparation method for the main chain type
dibromonaphthalimide derivative monomers is as follows:
[0089] Naphthalimide derivative Ar1 and 2-10 mole equivalents of
tetra-n-butylammonium tribromide are dissolved in dichloromethane.
After reacting at 0-40.degree. C. for 10-1200 min, the reaction
product is poured into water, and the organic phase is separated,
washed repeatedly with water, dried, concentrated and
recrystallized to obtain a main chain type dibromonaphthalimide
derivative monomer.
[0090] 2) Pendant chain type dibromonaphthalimide derivative
monomer: ##STR31## wherein Ar1 is the same as the Ar1 in the
pendant chain type single white light polymeric material.
[0091] The preparation method for the pendant chain type
dibromonaphthalimide derivative monomer is as follows:
[0092] First, 2-hydroxy-5-substituted-1,4-dibromobenzene and 1-3
mole equivalents of dibromoalkane with a chain segment number of m
are dissolved in anhydrous ethanol, and refluxed in the presence of
a solution of 1-10 mole equivalents of KOH for 2-10 hr to obtain
2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene as above.
Naphthalimide derivative Ar1 and 1-5 mole equivalents of
2-(m-bromoalkoxy)-5-substituted-1,4-dibromobenzene are dissolved in
dimethyl sulfoxide. A solution of 1-10 mole equivalents of NaOH is
added. After reacting at 20-150.degree. C. for 1-5 days, the
reaction is stopped with water. The organic phase is separated,
washed repeatedly with water, dried, concentrated and separated by
column chromatography to obtain a pendant chain type
dibromonaphthalimide derivative monomer.
[0093] 3) Pendant chain type 9,9-disubstituted dibromofluorene
naphthalimide derivative monomer. ##STR32## wherein Ar1 is the Ar1
in the pendant chain type single white light polymeric
material.
[0094] Pendant chain type 9,9-disubstituted dibromofluorene
naphthalimide derivative monomer mainly includes: (1) pendant chain
type 9,9-dialkyl substituted dibromofluorene naphthalimide
derivative monomer, and (2) pendant chain type 9,9-diaryl
substituted dibromofluorene naphthalimide derivative monomer.
[0095] (1) The preparation method for pendant chain type
9,9-dialkyl substituted dibromofluorene naphthalimide derivative
monomer is as follows:
[0096] First, 2,7-dibromofluorene and 2-6 mole equivalents of
dibromoalkane with a chain segment of (CH.sub.2)m are dissolved in
toluene, and 10-70% aqueous solution of 2-50 mole equivalents of
NaOH is then added. The reaction system reacted at 30-100.degree.
C. under the protection of N.sub.2 gas for 1-24 hr to obtain
9,9-(m-bromoalkyl)-2,7-dibromofluorene with the above structure.
Then, naphthalimide derivative Ar1 and 1-5 mole equivalents of
9,9-(m-bromoalkyl)-2,7-dibromofluorene are dissolved in DMSO. After
adding a solution of 1-10 mole equivalents of NaOH and reacting at
20-150.degree. C. for 1-5 days, the reaction is stopped with water,
the organic phase is separated, washed repeatedly with water,
dried, concentrated, and separated by column chromatography to
obtain pendant chain type 9,9-dialkyl substituted dibromofluorene
naphthalimide derivative monomer.
[0097] (2) The preparation method for the pendant chain type
9,9-diaryl substituted dibromofluorene naphthalimide derivative
monomer is as follows:
[0098] First, N,N-diphenyl-1,8-naphthalimide derivative reacted
with a solution of 2-40 mole equivalents of phosphorus oxychloride
(POCl.sub.3) in dimethyl formamide
[0099] (DMF) at -50.about.0.degree. C. (low-temperature) for 2-10
hr to produce 4-aldo or 4,4'-dialdo-N,N-diphenyl-1,8-naphthalimide
derivative. Then, the resulting product and 1-4 mole equivalents of
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene
or
9,9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene
are dissolved in a chloroform solution. And a solution of 1-10 mole
equivalents of sodium ethoxide is then added. After reacting at
0-60.degree. C. for 1-120 hr, the reaction product is poured into
water, and the organic phase is separated, washed repeatedly with
water, dried, concentrated, and finally separated by column
chromatography to obtain pendant chain type 9,9-diaryl substituted
dibromofluorene naphthalimide derivative monomer.
[0100] 4. Preparation of Monobromonaphthalimide Derivative
Monomer
[0101] The general structural formula of monobromonaphthalimide
derivative monomer is as follows: ##STR33## wherein Ar1 is the same
as the Ar1 in the terminal group type single white light polymeric
material.
[0102] The preparation method for monobromonaphthalimide derivative
monomer is as follows:
[0103] Naphthalimide derivative Ar1H and 1-5 mole equivalents of
tetra-n-butylammonium tribromide are dissolved in dichloromethane.
After reacting at 0-40.degree. C. for 10-1200 min, the reaction
product is poured into water, and the organic phase is separated,
washed repeatedly with water, dried, concentrated and
recrystallized to obtain monobromonaphthalimide derivative
monomer.
[0104] 5. Preparation of Dibromoaromatic Monomer and Oligomer
[0105] The general structural formula of dibromoaromatic monomer
and oligomer is as follows: ##STR34## wherein Ar2 is the same as
the Ar2 in the main chain type, pendant chain type and terminal
group type polymeric structures.
[0106] The preparation method and reaction conditions are the same
as those of 2,7-dibromofluorene and its derivative monomer.
[0107] 6. Preparation of White Electroluminescent Polymeric
Material
[0108] 1) Preparation of Main Chain Type White Light Polymeric
Material
[0109] The main chain type white light polymeric material is
prepared using Yamamoto or Suzuki polymerizations.
[0110] (1) Yamamoto Polymerization
[0111] Under the protection of N.sub.2 gas, 1 mol of
2,7-dibromofluorene derivative monomer, 0.01-50 mol % of
dibromonaphthalimide derivative monomer and 0-50 mol % of
dibromoaromatic monomer are dissolved in anhydrous toluene. Then
the resulted solution is dropped into a DMF solution of 1-5 mole
equivalents of Ni (0). After reacting at 50-100.degree. C. for
20-200 hr, the reaction is stopped with a mixed solution of
methanol and concentrated HCl, and the reaction product is
extraction-separated, concentration precipitated, extracted by
solvent and vacuum-dried to produce a fibrous polymeric luminescent
material.
[0112] (2) Suzuki Polymerization
[0113] 1 mol of 9,9-disubstituted-2,7-biborate derivative monomer,
0.01-50 mol % of dibromonaphthalimide derivative monomer and 0-50
mol % of dibromoaromatic monomer were dissolved in toluene, then
2.0M solution of 5-20 mole equivalents of potassium carbonate is
added. Under the protection of N.sub.2 gas and at 50-100.degree.
C., 0.05-10 mol % of tetrakis(triphenylphosphine) palladium (0) is
added. After reacting for 20-200 hr, the reaction is stopped with
0.1M diluted HCl solution. And the reaction product is
chloroform-extracted, methanol-settled, solvent-extracted and
vacuum-dried to obtain a fibrous polymeric material.
[0114] 2) Preparation of Pendant Chain Type White Light Polymeric
Material
[0115] The preparation methods for pendant chain type white light
polymeric material using Yamamoto and Suzuki polymerizations
separately are the same as those of the main chain type white tight
polymeric material, except that dibromonaphthalimide derivative
monomer is substituted by pendant chain type dibromonaphthalimide
derivative monomer or pendant chain type 9,9-disubstituted
dibromofluorene naphthalimide derivative monomer.
[0116] 3) Preparation of Terminal Group Type White Light Polymeric
Material
[0117] The terminal group type white light polymeric material is
prepared using Yamamoto or Suzuki polymerizations.
[0118] (1) Yamamoto Polymerization
[0119] Under the protection of N.sub.2 gas, 2,7-dibromofluorene
derivative monomer and 0-50 mol % of dibromoaromatic monomer Ar2
are dissolved in anhydrous toluene, then the resulting solution is
dropped into a DMF solution of 1-5 mole equivalents of Ni (0).
After reacting at 50-100.degree. C. for 20-200 hr, 0.01-10 mol % of
monobromonaphthalimide derivative monomer is added. After reacting
at 50-100.degree. C. for further 1-50 hr, the reaction is stopped
with a mixed solution of methanol and concentrated HCl, and the
reaction product is extraction-separated,
concentration-precipitated, solvent-extracted and vacuum-dried to
obtain a fibrous polymeric luminescent material.
[0120] (2) Suzuki Polymerization
[0121] 1 mol of 9,9-disubstituted-2,7-biborate derivative monomer
and 0-50 mol % of dibromoaromatic monomer Ar2 are dissolved in
toluene, then 2.0M solution of 5-20 mole equivalents of potassium
carbonate is added. Under the protection of N.sub.2 gas and at
50-100.degree. C., 0.05-10 mol % of tetrakis(triphenylphosphine)
palladium (0) is added. After reaction for 1-200 hr, 0.01-10 mol %
of monobromonaphthalimide derivative monomer Ar1 is added, and
reacted at 50-100.degree. C. for further 1-50 hr. The reaction is
terminated with 0.1M diluted HCl solution, then the reaction
product is chloroform-extracted, methanol-settled,
solvent-extracted, and vacuum-dried to obtain a fibrous polymeric
material.
EXAMPLES
Example 1
Synthesizing of 4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide
[0122] Under the protection of N.sub.2 gas, 4-bromo-1,8-naphthalic
anhydride (10.0 g, 36.2 mmol), p-t-butyl aniline (6.0 g, 40.1 mmol)
were added into a reacting flask containing 120 ml of acetic acid
as a solvent. After reacting while magnetic stirring at 130.degree.
C. for 10 hr, the reaction product was poured into water, filtered,
washed repeatedly, and separated by column chromatography. 8.10 g
(yield 55%) of a white solid
4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide was obtained. .sup.1H
NMR (CDCl.sub.3, 300 MHz) .delta. 8.68 (d, 1H), 8.59 (d, 1H), 8.43
(d, 1H), 8.04 (d, 1H), 7.86 (t, 1H), 7.56 (d, 2H), 7.23 (d, 2H),
1.38 (s, 9H).
Example 2
Synthesizing of
4-N,N-diphenyl-9-(4-t-butylphenyl)-1,8-naphthalimide
[0123] Under the protection of N.sub.2 gas, 3 ml of DMPU solvent
was added into a mixture of
4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide (4.48 g, 11.0 mmol),
diphenylamine (1.69 g, 10.0 mmol), anhydrous potassium carbonate
(1.53 g, 1.0 mmol), cuprous iodide (0.096 g, 0.50 mmol), and
18-crown-6 (0.13 g, 0.50 mmol). After reacting while magnetic
stirring at 190.degree. C. for 20 hr, the reaction product was
extracted with dichloromethane, acid washed, ammonia liquor washed,
water washed repeatedly, and separated by column chromatography.
1.74 g (yield 35%) of an orange red solid
4-N,N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide was obtained.
.sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.61 (d, 1H), 8.54 (d,
1H), 8.22 (d, 1H), 7.57-7.50 (m, 3H), 7.40 (d, 1H). 7.30-7.22 (d,
6H), 7.11-7.04 (m, 6H), 1.38 (s, 9H).
Example 3
Synthesizing of
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
[0124] 4-N,N-diphenyl-9-(4-t-butylphenyl)-1,8-naphthalimide (1.49
g, 3.0 mmol), tetra-n-butylammonium tribromide (3.16 g, 6.6 mmol)
were dissolved in 50 ml of dichloromethane. After reacting at room
temperature for 10 min, the reaction product was poured into water.
The organic layer, after washing repeatedly, was separated by
column chromatography. 1.91 g (yield 97%) of an orange red solid
(pure intermediate
product)-4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
was obtained. .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.60 (d,
1H), 8.55 (t, 1H), 8.16 (d, 1H), 7.60 (d, 1H), 7.56 (d, 2H),
7.42-7.37 (m, 5H). 7.22 (d, 2H), 6.90 (d, 4H), 1.38 (s, 9H).
Example 4
Synthesizing of
4-carbazolyl-9-(4-t-butylphenyl)-1,8-naphthalimide
[0125] Under the protection of N.sub.2 gas, 3 ml of DMPU solvent
was added into a mixture of
4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide (4.48 g, 11.0 mmol),
carbazole (1.67 g, 10.0 mmol), anhydrous potassium carbonate (1.53
g, 11.0 mmol), cuprous iodide (0.096 g, 0.50 mmol) and 18-crown-6
(0.13 g, 0.50 mmol). After reacting while magnetic stirring at
190.degree. C. for 20 hr, the reaction product was extracted with
dichloromethane, washed with acid, washed with ammonia liquor,
washed with water repeatedly, and separated by column
chromatography. 1.22 g (yield 25%) of a yellow solid pure
4-carbazolyl-9-(4-t-butylphenyl)-1,8-naphthalimide was obtained.
.sup.1H NMR (CDCl.sub.3, 300 MHz): .delta. 8.85 (d, 1H), 8.7 (d,
1H), 8.45 (d, 1H), 7.57-7.50 (m, 3H), 7.40 (d, 1H), 7.30-7.22 (d,
6H), 7.00 (m, 4H), 1.38 (s, 9H).
Example 5
Synthesizing of
4-(4,4'-dibromocarbazolyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
[0126] 4-carbazolyl-9-(4-t-butylphenyl)-1,8-naphthalimide (0.99 g,
2.0 mmol) and tetra-n-butylammonium tribromide (2.10 g, 4.4 mmol)
were dissolved in 30 ml of dichloromethane. After reacting at room
temperature for 20 hr, the reaction product was poured into water.
The organic layer, after washing repeatedly, was separated by
column chromatography (dichloromethane). 1.24 g (yield 95%) of a
yellow solid (pure intermediate product)
4-(4,4'-dibromocarbazolyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
was obtained. .sup.1H NMR (CDCl3, 300 MHz): .delta. 8.85 (d, 1H),
8.72 (d, 1H), 8.28 (d, 1H), 7.91 (d, 1H), 7.68 (m, 2H), 7.60 (m,
2H), 7.50 (d, 2H), 7.25 (d, 1H), 6.90 (d, 2H), 1.38 (s, 9H).
Example 6
Synthesizing of
4-N,N-di(4-aldophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
[0127] In a cryohydric bath, POCl.sub.3 (32.8 g, 214 mmol) was
dropped in DMF (15.6 g, 214 mmol). After stirring for 30 min, a
solution of
4-N-(4-aldophenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide
(1.40 g, 2.67 mmol) in DMF was then dropped in. After reacting for
82 hr at the temperature increased gradually to 97.degree. C., the
reaction product was washed with water, extracted by
dichloromethane, cleaned repeatedly, dried, filtered, and separated
by column chromatography. 0.34 g (yield 23%) of a product was
obtained. .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 9.93 (s, 2H),
8.67 (m, 2H), 8.11 (d, 1H), 7.82 (d, 4H), 7.74-7.52 (m, 6H). 7.19
(d, 4H), 1.38 (s, 9H).
Example 7
Synthesizing of
4-N,N-di(4-bromostyryl)phenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
[0128] 4-N,N-di(4-aldophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.34 g, 0.62 mmol) and 4-bromo-tributylphosphine bromide methylene
benzene (0.62 g, 1.37 mmol) were dissolved in chloroform (20 ml),
then a solution (5 ml) of metallic sodium (0.091 g, 3.91 mmol) in
ethanol was dropped in. After reacting at room temperature for 10
hr, diluted HCl solution was added to stop the reaction. The
reaction product was extracted by chloroform, washed repeatedly,
dried, filtered, and separated by column chromatography. 0.37 g
(yield 69%) of a product was obtained. .sup.1H NMR (CDCl.sub.3, 300
MHz) .delta. 8.59 (d, 1H), 8.54 (t, 1H), 8.20 (d, 1H), 7.58-7.53
(m, 3H), 7.48-7.34 (m, 11H), 7.24-6.88 (m, 11H), 6.58-6.47 (m, 1H),
1.38 (s, 9H).
Example 8
Synthesizing of
4-N,N-(4,4'-di(4-p-tolylphenylamino)phenyl)-9-(4-t-butylphenyl)-1,8-napht-
halimide
[0129] Under the protection of N.sub.2 gas,
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide (0.65
g, 0.99 mmol), 4-N,N-p-tolylphenyl aminophenyl pinacolyl borate
(0.85 g, 2.2 mmol), anhydrous potassium carbonate (1.60 g, 0.9
mmol), toluene (10 ml), and a mixture of water (10 ml) and Pd
catalyst (30 mg) were added into a reacting flask. After reacting
while magnetic stirring at 80.degree. C. for 48 hr, the reaction
product was extracted with dichloromethane, washed once with 1N HCl
solution, washed with ammonia liquor till the water layer became
colorless, washed repeatedly with water, dried with anhydrous
Na.sub.2SO.sub.4, concentrated, and separated by silica gel column
chromatography. 0.69 g (yield 69%) of a red solid was obtained.
.sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.58 (m, 2H), 8.29 (d,
1H), 7.59-7.43 (m, 12H), 7.28-7.23 (m, 7H), 7.15-7.01 (m, 21H),
2.87 (s, 6H), 1.40 (s, 9H).
Example 9
Synthesizing of
4-N,N-(4,4'-di(4-p-tolyl-4-bromophenylamino)phenyl)-9-(4-t-butylphenyl)-1-
,8-naphthalimide
[0130]
4-N,N-(4,4'-di(4-p-tolylphenylamino)phenyl)-9-(4-t-butylphenyl)-1,-
8-naphthalimide (0.51 g, 0.50 mmol) and tetra-n-butylammonium
tribromide (0.53 g, 1.1 mmol) were dissolved in dichloromethane (10
ml). After reacting at room temperature for 10 min, the reaction
product was poured into water. The organic layer, after washed with
water repeatedly, was separated by column chromatography. 0.55 g
(yield 95%) of an orange red solid was obtained. .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta. 8.57 (m, 2H), 8.27 (d, 1H), 7.56-7.40
(m, 12H), 7.25-7.20 (m, 7H), 7.14-7.01 (m, 19H), 2.87 (s, 6H), 1.39
(s, 9H).
Example 10
Synthesis of
9-phenyl-9-(4-bromomethylphenyl)-2,7-dibromofluorene
[0131] Into a flask,
9-phenyl-9-(4-methylphenyl)-2,7-dibromofluorene (0.90 g, 1.84
mmol), NBS (0.33 g, 1.84 mmol), BPO (0.044 g, 0.184 mmol) and
CCl.sub.4 (10 ml) were added and reacted under reflux for 2 hr.
Then, the reaction system was cooled and filtered. After removing
the filtrate, a gray solid of
9-phenyl-9-(4-bromomethylphenyl)-2,7-dibromofluorene (0.94 g) was
obtained as a pure intermediate product (yield, 90%). .sup.1HNMR
(300 MHz, CDCl.sub.3): .delta. 7.51-7.48 (m, 6H), 7.26-7.00 (M,
9H), 4.46 (s, 2H).
Example 11
Synthesis of
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromofluorene
[0132] Into a flask, tributyl phosphorous (0.65 ml, 2.55 mmol) was
heated to 100.degree. C. under N2 gas, then a mixture solution of
9-phenyl-9-(4-bromomethylphenyl)-2,7-dibromofluorene (1.00 g, 1.76
mmol) and DMF (15 ml) was dropwisely added. The reaction system was
heated to 140.degree. C. to react for 24 hr, then cooled to room
temperature, poured into ethyl ether and stirred. Repeated for
three times. A gray powder of
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibro-
mofluorene (0.89 g) was obtained as a pure intermediate product
(yield, 64%). .sup.1HNMR (300 MHz, CDCl.sub.3): .delta. 7.50-7.47
(m, 6H), 7.24-6.98 (M, 9H), 4.26-4.21 (d, 2H), 2.34 (t, 6H), 1.45
(m, 12H), 0.98-0.94 (t, 18H).
Example 12
Synthesis of
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-phenyl-9-(4-tributylphenyl)-1,-
8-naphthalimide
[0133]
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromof-
luorene (0.49 g, 0.64 mmol) and
4-N-(4-aldophenyl)-4-N-phenyl-9-(4-tributylphenyl)-1,8-naphthalimide
(0.34 g, 0.64 mmol) was dissolved in chloroform (15 ml). And then a
solution of metal sodium (0.058 g, 2.560 mmol) in ethanol (5 ml)
was dropwisely added. Reacted for 10 hr at room temperature. Then a
dilute hydrochloride solution is added to terminate the reaction.
After extracted with chloroform, the product was washed repeatedly,
dried, filtered and separated by column chromatography to obtain a
red solid of
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl-4-N-phenyl-9-(4-tributylphenyl)-1,8-
-naphthalimide)-2,7-dibromofluorene (0.46 g, yield, 72%) as a pure
intermediate product. .sup.1HNMR (300 MHz, CDCl.sub.3): .delta.
8.57 (d, 1H), 8.52 (d, 1H), 8.20 (d, 1H), 7.58-6.50 (M, 32H), 1.38
(s, 9H).
Example 13
Synthesis of
4-N-(4-aldophenyl)-4-N-(4-(4'-styryl)phenyl)-9-(4-tributylphenyl)-1,8-nap-
hthalimide
[0134] bromotributylphosphinomethylenephenyl (0.37 g, 1.00 mmol)
and 4-N,N-di(4-aldophenyl)-9-(4-tributylphenyl)-1,8-naphthalimide
(0.55 g, 1.00 mmol) was dissolved in chloroform (25 ml). And then a
solution of metal sodium (0.092 g, 4.000 mmol) in ethanol (5 ml)
was dropwisely added. Reacted for 20 hr at room temperature. Then a
dilute hydrochloride solution is added to terminate the reaction.
After extracted with chloroform, the product was washed repeatedly,
dried, filtered and separated by column chromatography to obtain a
red solid of
4-N-(4-aldophenyl)-4-N-(4-(4'-styryl)phenyl)-9-(4-tributylphenyl)-1,8-nap-
hthalimide (0.41 g, yield, 65%) as a pure intermediate product.
.sup.1HNMR (300 MHz, CDCl.sub.3): .delta. 8.57 (d, 1H), 8.52 (d,
1H), 8.20 (d, 1H), 7.58-6.50 (M, 32H), 1.38 (s, 9H).
Example 14
Synthesis of
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-((4'-styryl)phenyl)-9-(4-tribu-
tylphenyl)-1,8-naphthalimide)-2,7-dibromofluorene
[0135]
9-phenyl-9-(4-bromotributylphosphino-methylenephenyl)-2,7-dibromof-
luorene (0.61 g, 0.80 mmol) and
4-N-(4-aldophenyl)-4-N-(4-(4-styryl)phenyl)-9-(4-tributylphenyl)-1,8-naph-
thalimide (1.00 g, 1.60 mmol) was dissolved in chloroform (20 ml).
And then a solution of metal sodium (0.185 g, 8.0 mmol) in ethanol
(5 ml) was dropwisely added. Reacted for 50 hr at room temperature.
Then a dilute hydrochloride solution is added to terminate the
reaction. After extracted with chloroform, the product was washed
repeatedly, dried, filtered and separated by column chromatography
to obtain a red solid of
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-((4'-styryl)phenyl)-9-(4-tribu-
tylphenyl)-1,8-naphthalimide)-2,7-dibromofluorene (0.62 g, yield,
70%) as a pure intermediate product. .sup.1HNMR (300 MHz,
CDCl.sub.3): .delta. 8.57 (d, 1H), 8.52 (d, 1H), 8.20 (d, 1H),
7.58-6.50 (m, 38H), 1.38 (s, 9H).
Example 15
Synthesis of
2-(2'-(4'-amino-1',8'-naphthalimide-9'-alkyl)ethoxyl)-5-hexoxyl-1,4-dibro-
mobenzene
[0136] Under protection of N2 gas, 4-amino-1,8-naphthalimide (1.06
g, 5 mmol) was dissolved in dimethyl sulfoxide (60 ml). Into the
resulting solution, powdered KOH (2.8 g, 50 mmol) was added. The
reaction was carried out at 150.degree. C. for 10 min while
magnetic stirring, and then
2-(2-bromoethoxyl)-5-hexoxyl-1,4-dibromobenzene (2.31 g, 5 mmol)
was added stepwisely. After reacting for 1 hr, the resulting
product was extracted with chloroform, washed repeatedly, dried,
filtered, and separated by column chromatograph to obtain a pure
intermediate product (2.06 g, yield, 70%). .sup.1H NMR (CDCl.sub.3,
300 MHz) .delta. 8.63 (d, 1H), 8.44 (d, 1H), 8.12 (d, 1H), 7.67 (t,
1H), 7.20 (s, 1H), 7.01 (s, 1H), 6.90 (d, 1H), 4.65 (t, 2H), 4.29
(t, 2H), 3.90 (t, 2H), 1.81-1.29 (m, 8H), 0.87 (t, 3H).
Example 16
Synthesis of
2-(2'-(4'-dianilino-1',8'-naphthalimide-9'-alkyl)ethoxyl)-5-hexoxyl-1,4-d-
ibromo benzene
[0137] Under protection of N2 gas,
2-(2'-(4'-amino-1',8'-naphthalimide-9'-alkyl)ethoxyl)-5-hexoxyl-1,4-dibro-
mobenzene (0.589 g, 1.0 mmol), iodobenzene (0.41 g, 2.0 mmol),
potassium carbonate (0.28 g, 2.0 mmol), 18-crown-6 (0.003 g, 0.01
mmol), cuprous iodide (0.002 g, 0.01 mmol) and DMPU (0.30 ml) were
heated to 200.degree. C. and reacted for 5 hr. After extracted with
chloroform, the product was washed repeatedly, dried, filtered, and
separated by column chromatography to obtain a red solid (0.33 g,
yield, 45%). .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.54 (d,
1H), 8.51 (d, 1H), 7.50 (t, 1H), 7.37 (d, 1H), 7.25-6.90 (m, 13H),
4.68 (t, 2H), 4.30 (t, 2H), 3.90 (t, 2H), 1.77 (m, 2H), 1.47-1.25
(m, 6H), 0.87 (t, 3H).
Example 17
Synthesis of
2-(12'-(4'-amino-1',8'-naphthalimide-9'-alkyl)dodecoxyl-5-hexoxyl-1,4-dib-
romo benzene
[0138] Under protection of N2 gas, 4-amino-1,8-naphthalimide (1.06
g, 5 mmol) was dissolved in dimethyl sulfoxide (60 ml). Into the
resulting solution, powdered KOH (0.28 g, 5 mmol) was added. The
reaction was carried out at 50.degree. C. for 10 min while magnetic
stirring, and then
2-(12-bromododecoxyl)-5-hexoxyl-1,4-dibromobenzene (30.0 g, 50
mmol) was added stepwisely. After reacting for 120 hr, the
resulting product was extracted with chloroform, washed repeatedly,
dried, filtered, and separated by column chromatograph to obtain a
pure intermediate product (2.906 g, yield, 81%). .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta. 8.60 (d, 1H), 8.42 (d, 1H), 8.10 (d,
1H), 7.66 (t, 1H), 7.06 (s, 2H), 6.89 (d, 1H), 4.93 (s, 2H), 4.18
(t, 2H), 3.94 (t, 4H), 1.80-1.25 (m, 28H), 0.92 (t, 3H).
Example 18
Synthesis of
2-(12'-(4'-dianilino-1',8'-naphthalimide-9-alkyl)dodecoxyl)-5-hexoxyl-1,4-
-dibromobenzene
[0139] Under protection of N.sub.2 gas,
2-(12'-(4'-amino-1',8'-naphthalimide-9'-alkyl)dodecoxyl)-5-hexoxyl-1,4-di-
bromobenzene (0.7369 g, 1.0 mmol), iodobenzene (4.08 g, 10.0 mmol),
potassium carbonate (2.8 g, 20.0 mmol), 18-crown-6 (0.015 g, 0.05
mmol), cuprous iodide (0.0095 g, 0.05 mmol) and DMPU (0.30 ml) were
heated to 140.degree. C. and reacted for 50 hr. After extracted
with chloroform, the product was washed repeatedly, dried,
filtered, and separated by column chromatography to obtain a red
solid (0.283 g, yield, 33%). .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta. 8.57 (d, 1H), 8.48 (d, 1H), 8.44 (d, 1H), 7.66 (t, 1H),
7.28-7.01 (m, 13H), 4.18 (t, 2H), 3.94 (t, 4H), 1.79-1.25 (m, 28H),
0.91 (t, 3H).
Example 19
Synthesis of
9,9-di(2-(4-amino-1,8-naphthalimide-9)-ethyl)-2,7-dibromofluorene
[0140] Under protection of N.sub.2 gas, 4-amino-1,8-naphthalimide
(1.06 g, 5 mmol) was dissolved in dimethyl sulfoxide (60 ml). Into
the resulting solution, powdered KOH (2.8 g, 50 mmol) was added.
The reaction was carried out at 150.degree. C. for 10 min while
magnetic stirring, and then
9,9-di(2-bromoethyl)-2,7-dibromofluorene (1.34 g, 2.5 mmol) was
added stepwisely. After reacting for 1 hr, the resulting product
was extracted with chloroform, washed repeatedly, dried, filtered,
and separated by column chromatograph to obtain a pure intermediate
product (1.40 g, yield, 70%). .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta. 8.59 (d, 2H), 8.39 (d, 2H), 8.09 (d, 2H), 7.65 (t, 2H),
7.52-7.04 (m, 6H), 6.90 (d, 2H), 3.90 (t, 4H), 2.17 (t, 4H).
Example 20
Synthesis of
9,9-di(2-(4-dianilino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene
[0141] Under protection of N.sub.2 gas,
9,9-di(2-(4-amino-1,8-naphthalimide-9-)ethyl)-2,7-dibromofluorene
(0.400 g, 0.5 mmol), iodobenzene (0.41 g, 2.0 mmol), potassium
carbonate (0.414 g, 3.0 mmol), 18-crown-6 (0.015 g, 0.05 mmol),
cuprous iodide (0.0095 g, 0.05 mmol) and DMPU (0.30 ml) were heated
to 200.degree. C. and reacted for 5 hr. After extracted with
chloroform, the product was washed repeatedly, dried, filtered, and
separated by column chromatography to obtain a red solid (0.138 g,
yield, 25%). .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.48 (t,
4H), 8.15 (d, 2H), 7.65 (d, 2H), 7.57 (s, 2H), 7.50-7.00 (m, 16H),
3.90 (t, 4H), 2.17 (t, 4H).
Example 21
Synthesis of
9,9-di(12-(4-amino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene
[0142] Under protection of N.sub.2 gas, 4-amino-1,8-naphthalimide
(1.6 g, 7.5 mmol) was dissolved in dimethyl sulfoxide (60 ml). Into
the resulting solution, powdered KOH (0.28 g, 5 mmol) was added.
The reaction was carried out at 50.degree. C. for 10 min while
magnetic stirring, and then
9,9-di(12-bromododecyl)-2,7-dibromofluorene (2.04 g, 2.5 mmol) was
added stepwisely. After reacting for 120 hr, the resulting product
was extracted with chloroform, washed repeatedly, dried, filtered,
and separated by column chromatograph to obtain a pure intermediate
product (2.00 g, yield, 74%). .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta. 8.58 (d, 2H), 8.38 (d, 2H), 8.07 (d, 2H), 7.63 (t, 2H),
7.50-7.00 (m, 6H), 6.90 (d, 2H), 4.07 (t, 4H), 1.92 (t, 4H),
1.77-1.20 (m, 16H).
Example 22
Synthesis of
9,9-di(12-(4-dianilino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene
[0143] Under protection of N.sub.2 gas,
9,9-di(2-(4-amino-1,8-naphthalimide-9-)dodecyl)-2,7-dibromofluorene
(0.540 g, 0.5 mmol), iodobenzene (2.04 g, 10 mmol), potassium
carbonate (1.38 g, 10 mmol), 18-crown-6 (0.003 g, 0.01 mmol),
cuprous iodide (0.002 g, 0.01 mmol) and DMPU (0.30 ml) were heated
to 140.degree. C. and reacted for 50 hr. After extracted with
chloroform, the product was washed repeatedly, dried, filtered, and
separated by column chromatography to obtain a red solid (0.221 g,
yield, 32%). .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.47 (t,
4H), 8.14 (d, 2H), 7.63 (d, 2H), 7.55 (s, 2H), 7.50-7.00 (m, 16H),
4.07 (t, 4H), 1.92 (t, 4H), 1.77-1.20 (m, 16H).
Example 23
Synthesis of
2-(6'-(4'-amino-1',8'-naphthalimide-9'-alkyl)hexoxyl)-5-hexoxyl-1,4-dibro-
mobenzene
[0144] Under protection of N.sub.2 gas, 4-amino-1,8-naphthalimide
(2.02 g, 10 mmol) was dissolved in dimethyl sulfoxide (60 ml). Into
the resulting solution, powdered KOH (0.56 g, 10 mmol) was added.
The reaction was carried out at 120.degree. C. for 10 min while
magnetic stirring, and then
2-(6-bromohexoxyl)-5-hexoxyl-1,4-dibromobenzene was added
stepwisely. After reacting for 14 hr, the resulting product was
extracted with chloroform, washed repeatedly, dried, filtered, and
separated by column chromatograph to obtain a pure intermediate
product (3.94 g, yield, 61%). .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta. 8.63 (d, 1H), 8.44 (d, 1H), 8.12 (d, 1H), 7.67 (t, 1H),
7.20 (s, 1H), 7.01 (s, 1H), 6.90 (d, 1H), 4.18 (t, 2H), 3.94 (t,
4H), 1.81-1.29 (m, 16H), 0.87 (t, 3H)
Example 24
Synthesis of
2-(6'-(4'-dianilino-1',8'-naphthalimide-9'-alkyl)hexoxyl)-5-hexoxyl-1,4-d-
ibromo benzene
[0145] Under protection of N.sub.2 gas,
2-(6'-(4'-amino-1',8'-naphthalimide-9'-alkyl)hexoxyl)-5-hexoxyl-1,4-dibro-
mobenzene (0.618 g, 1.0 mmol), iodobenzene (1.020 g, 5.0 mmol),
potassium carbonate (0.414 g, 3.0 mmol), 18-crown-6 (0.015 g, 0.05
mmol), cuprous iodide (0.0095 g, 0.05 mmol) and DMPU (0.30 ml) were
heated to 190.degree. C. and reacted for 48 hr. After extracted
with chloroform, the product was washed repeatedly, dried,
filtered, and separated by column chromatography to obtain a red
solid (0.45 g, yield, 57%). .sup.1H NMR (CDCl.sub.3, 300 MHz)
.delta. 8.55 (d, 1H), 8.46 (d, 1H), 8.44 (d, 1H), 7.63 (t, 1H),
7.30-7.01 (m, 13H), 4.19 (t, 2H), 3.90 (t, 4H), 1.79-1.25 (m, 16H),
0.91 (t, 3H).
Example 25
Synthesis of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-iodophenyl-1-)amino-1,8-naphthalimide--
9-)-hexoxyl)benzene
[0146]
1,4-dibromo-2-hexoxyl-5-(6-(4-dianilino-1,8-naphthalimide-9-)-hexo-
xyl)benzene (3.99 g, 5 mmol) was dissolved in ethanol (30 ml).
While stirring, iodine (3.05 g, 12 mmol) was added into the flask
in batches. Reacted for 30 min. Then the reaction mixture was
poured into water, extracted with chloroform, washed with water,
dried, and separated by column chromatography to produce an
orange-red solid (4.35 g, yield, 82%). .sup.1H NMR (CDCl.sub.3, 300
MHz) .delta. 8.55 (d, 1H), 8.46 (d, 1H), 8.44 (d, 1H), 7.45 (m,
5H), 7.30-7.01 (m, 7H), 4.19 (t, 2H), 3.90 (t, 4H), 1.79-1.25 (m,
16H), 0.91 (t, 3H).
Example 26
Synthesis of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4'-dianilino-biphenyl-4-)amino-1,8-napht-
halimide-9-)-hexoxyl)benzene
[0147] A mixture of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-iodophenyl-1-)amino-1,8-naphthalimide--
9-)-hexoxyl)benzene (2.10 g, 2 mmol), triarylamine borate (0.89 g,
2.4 mmol), KF (0.232 g, 4 mmol), tetra(triphenyl
phosphino)palladium (23 mg, 0.02 mmol), DMF (10 ml), and water (2
ml) was heated to 100.degree. C. to react for 6 hr under N2 gas.
The product was extracted with chloroform, water washed, dried, and
separated by column chromatography to obtain a red solid (2.31 g,
yield, 90%). .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.55 (d,
1H), 8.46 (d, 1H), 8.44 (d, 1H), 7.41 (d, 1H), 7.30-7.01 (m, 21H),
4.00 (t, 2H), 3.69 (t, 4H), 1.79-1.25 (m, 16H), 0.91 (t, 3H).
Example 27
Synthesis of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-aldophenyl-1-)amino-1,8-naphthalimide--
9-)-hexoxyl)benzene
[0148]
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-iodophenyl-1-)amino-1,8-naphtha-
limide-9-)-hexoxyl)benzene (3.20 g, 4 mmol) was dissolved in DMF
(20 ml). Then POCl3 (1.38 g, 9 mmol) was added and the mixture was
heated up to 120.degree. C. to react for 10 hr. The product was
extracted with chloroform, washed with water, dried, and separated
by column chromatography to obtain an orange-red solid (1.81 g,
yield, 53%). .sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.90 (s,
2H), 8.55 (d, 1H), 8.46 (d, 1H), 8.44 (d, 1H), 7.85 (d, 4H), 7.63
(t, 1H), 7.38-7.01 (m, 7H), 4.19 (t, 2H), 3.90 (t, 4H), 1.79-1.25
(m, 16H), 0.91 (t, 3H).
Example 28
Synthesis of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-styrylphenyl-1-)amino-1,8-naphthalimid-
e-9-)-hexoxyl)benzene
[0149] A mixture of
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-aldophenyl-1-)amino-1,8-naphthalimide--
9-)-hexoxyl)benzene (1.71 g, 2 mmol),
bromotributylphosphinomethylenebenzene (1.69 g, 4.5 mmol), sodium
(0.192 g, 8 mmol), ethanol (10 ml) and chloroform (10 ml) was
stirred at room temperature for 3 hr. The product was extracted
with chloroform, washed with water, dried, and separated by column
chromatography to obtain an orange-red solid (1.30 g, yield 65%).
.sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.55 (d, 1H), 8.46 (d,
1H), 8.44 (d, 1H), 7.63 (t, 1H), 7.38-6.87 (m, 17H), 4.19 (t, 2H),
3.90 (t, 4H), 1.79-1.25 (m, 16H), 0.91 (t, 3H).
Example 29
Synthesizing of
4-N-(4-aldophenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide
[0150] In a cryohydric bath, POCl.sub.3 (15.40 g, 100 mmol) was
dropped in DMF (7.30 g, 100 mmol). After stirring under the
protection of N.sub.2 gas for 30 min, a solution of
4-N,N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide (3.30 g, 6.65
mmol) in DMF was then dropped in. After reacting for 26 hr at the
temperature increased gradually to 97.degree. C., the reaction
product was washed with water, extracted with dichloromethane,
cleaned repeatedly, dried, filtered, and separated by column
chromatography. 2.41 g (yield 69%) of a product was obtained.
.sup.1H NMR (CDCl.sub.3, 300 MHz) .delta. 8.67 (d, 1H), 8.64 (d,
1H), 8.11 (d, 1H), 7.82 (d, 4H), 7.74-7.52 (m, 6H). 7.19 (d, 4H),
1.38 (s, 9H).
Example 30
Synthesizing of
4-N-(4-(4'-bromostyryl)phenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphtha-
limide
[0151]
4-N-(4-aldophenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimid-
e (0.20 g, 0.38 mmol), 4-bromo-tributylphosphine bromide methylene
benzene (0.17 g, 0.38 mmol) were dissolved in chloroform (8 ml),
then a solution (3 ml) of metallic sodium (0.030 g, 1.30 mmol) in
ethanol was dropped in. After reacting at room temperature for 10
hr, a diluted HCl solution was added to stop the reaction. The
reaction product was extracted by chloroform, washed repeatedly,
dried, filtered, and separated by column chromatography. 0.19 g
(yield 74%) of a product was obtained. .sup.1H NMR (CDCl.sub.3, 300
MHz) .delta. 8.59 (d, 1H), 8.54 (t, 1H), 8.20 (d, 1H), 7.58-7.53
(m, 3H), 7.48-7.34 (m, 11H). 7.24-6.88 (m, 11H), 6.58-6.47 (m, 1H),
1.38 (s, 9H).
Example 31
Synthesizing of
4-N-(4-methylphenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide
[0152] Under the protection of N.sub.2 gas,
4-bromo-9-(4-t-butylphenyl)-1,8-naphthalimide (5.00 g, 12.30 mmol),
4-methyl-diphenylamine (2.47 g, 13.50 mmol), anhydrous potassium
carbonate (1.86 g, 13.50 mmol), cuprous iodide (0.24 g, 1.23 mmol),
and 18-crown-6 (0.31 g, 1.23 mmol) were dissolved in DMPU solvent
(3 ml). After reacting while magnetic stirring at 190.degree. C.
for 20 hr, the reaction product was extracted with dichloromethane,
washed with acid, washed with ammonia liquor, washed with water
repeatedly, and separated by column chromatography. 1.87 g (yield
30%) of an orange red solid (as pure intermediate product)
4-N-(4-methylphenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalimide
was obtained. .sup.1H NMR (300 MHz, CDCl.sub.3): .delta. 8.57 (d,
1H), 8.52 (d, 1H), 8.20 (d, 1H), 7.57-7.24 (m, 9H), 7.30-6.87 (d,
6H), 2.31 (s, 3H), 1.38 (s, 9H).
Example 32
Synthesizing of
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide
[0153]
4-N-(4-methylphenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphthalim-
ide (0.54 g, 1.06 mmol), tetra-n-butylammonium tribromide (0.55 g,
1.14 mmol) were dissolved in dichloromethane (10 ml). After
reacting at room temperature for 20 min, the reaction product was
poured into water, and the organic layer, after washed with water
repeatedly, was separated by column chromatography. 0.61 g (yield
98%) of an orange red solid (as a pure final product)
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide was obtained. .sup.1HNMR (300 MHz, CDCl.sub.3): .delta. 8.59
(d, 1H), 8.54 (d, 1H), 8.21 (d, 1H), 7.58-7.52 (m, 3H), 7.38-7.21
(m, 5H), 7.12-6.85 (d, 6H), 2.31 (s, 3H), 1.38 (s, 9H).
Example 33
Synthesis of
4-N-(4-methylphenyl)-4-N-(4-tolyl-4'-phenylamino)phenyl-9-(4-tributylphen-
yl)-1, 8-naphthalimide
[0154] Under the protection of N.sub.2 gas, a mixture of
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-tributylphenyl)-1,8-naphtha-
limide (0.59 g, 1.0 mmol),
4-methyl-4'-trimethylene-borate-yl-trianilino (0.75 g, 2.2 mmol),
anhydrous potassium carbonate (1.78 g, 11.0 mmol), toluene (10 ml),
water (10 ml) and palladium catalyst (30 mg) was reacted at
80.degree. C. for 48 hr. The product was extracted with
CH.sub.2Cl.sub.2, washed with water, dried, and separated by column
chromatography to obtain a red solid of
4-N-(4-methylphenyl)-4-N-(4-tolyl-4'-phenylamino)phenyl-9-(4-tributylphen-
yl)-1, 8-naphthalimide (0.50 g, yield, 65%). .sup.1HNMR (300 MHz,
CDCl.sub.3): .delta. 8.57 (d, 1H), 8.51 (d, 1H), 8.20 (d, 1H),
7.56-7.50 (m, 3H), 7.38-7.18 (m, 11H), 7.10-6.78 (m, 13H), 2.31 (s,
3H), 2.27 (s, 3H), 1.38 (s, 9H).
Example 34
Synthesis of
4-N-(4-methylphenyl)-4-N-(4-methyl-4'-bromophenylamino)phenyl-9-(4-tribut-
yl phenyl)-1,8-naphthalimide
[0155]
4-N-(4-methylphenyl)-4-N-(4-tolyl-4'-phenylamino)phenyl-9-(4-tribu-
tylphenyl)-1, 8-naphthalimide (0.77 g, 1.0 mmol) and
tetrabutylammonium bromide (0.49 g, 1.0 mmol) were dissolved in
CH.sub.2Cl.sub.2 (10 ml) and reacted at room temperature for 10
min. The reaction mixture was poured into water, and the resulting
organic layer was washed repeatedly with water. Then the product
was separated by column chromatography to obtain a pure product of
4-N-(4-methylphenyl)-4-N-(4-tolyl-4'-bromophenylamino)phenyl-9-(4-tributy-
lphenyl)-1, 8-naphthalimide as an orange-red solid (0.83 g, yield
98%). .sup.1HNMR (300 MHz, CDCl.sub.3): .delta. 8.58 (d, 1H), 8.53
(d, 1H), 8.22 (d, 1H), 7.58-7.50 (m, 3H), 7.39-7.20 (m, 11H),
7.12-6.77 (m, 12H), 2.32 (s, 3H), 2.29 (s, 3H), 1.39 (s, 9H).
Example 35
Synthesis of
4-N-(4-aldophenyl)-4-N-p-bromophenyl-9-(4-tributylphenyl)-1,8-naphthalimi-
de
[0156]
4-N-(4-aldophenyl)-4-N-phenyl-9-(4-tributylphenyl)-1,8-naphthalimi-
de (0.52 g, 1.0 mmol) and tributylammonium bromide (0.52 g, 1.07
mmol) were dissolved in CH.sub.2Cl.sub.2 (10 ml) and reacted at
room temperature for 20 min. The reaction mixture was poured into
water, and the resulting organic layer was washed repeatedly with
water. Then the product was separated by column chromatography to
obtain a pure product of
4-N-(4-aldophenyl)-4-N-bromophenyl-9-(4-tributylphenyl)-1,8-naphthalim-
ide as an orange-yellow solid (0.59 g, yield 98%). .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta. 9.86 (s, 1H), 8.61 (d, 2H), 8.19 (d,
1H), 7.73 (d, 2H), 7.62 (t, 1H), 7.55 (t, 3H), 7.37 (t, 2H),
7.19-7.26 (m, 4H), 7.00 (d, 2H), 1.38 (s, 9H).
Example 36
Synthesis of
4-N-p-bromophenyl-4-N-(4-styryl)phenyl-9-(4-tributylphenyl)-1,8-naphthali-
mide
[0157]
4-N-(4-aldophenyl)-4-N-bromophenyl-9-(4-tributylphenyl)-1,8-naphth-
alimide (0.48 g, 0.80 mmol) and tributylphosphinemethylene benzene
chloride (0.29 g, 0.88 mmol) were dissolved in chloroform (15 ml).
Then, a solution of metal sodium (0.055 g, 2.40 mmol) in ethanol (3
ml) was dropped in. The reaction was carried out for 10 hr. A
diluted hydrochloride solution was added to stop the reaction. Then
extracted with chloroform, washed with water, dried, and separated
by column chromatography to obtain
4-N-bromophenyl-4-N-(4-styryl)phenyl-9-(4-tributylphenyl)-1,8-naphthalimi-
de as an orange-red solid product (0.38 g, yield 72%). .sup.1H NMR
(CDCl.sub.3, 300 MHz) .delta. 8.56 (m, 2H), 8.21 (m, 1H), 6.45-7.57
(m, 20H), 1.38 (s, 9H).
Example 37
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P1
[0158] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.56 g, 2.0 mmol), 2,2'-bipyridine
(0.22 g, 2.0 mmol), 1,5-cyclooctadiene (0.32 g, 2.0 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour, then a solution (5 ml) of 9,9'-dioctyl-2,7-dibromofluorene
(0.4937 g, 0.90 mmol) and
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.066 g, 0.10 mmol) in toluene was added. After reacting at
100.degree. C. for 5 days, the reaction product was poured into a
mixture of methanol (100 ml)/acetone (100 ml)/concentrated HCl
solution (100 ml) with stirring for 2 hr, filtered, precipitated
thrice with methanol, extracted with acetone for 1 day in a Soxhlet
extractors, and vacuum dried. 0.24 g (yield 59%) of an orange
yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3): .delta.
7.86-7.68 (m, Ar--H), 2.17-1.15 (m, CH.sub.2), 0.84-0.79 (m,
CH.sub.3). Product performances: number average molecular weight
(Mn), 12,000; maximum UV-absorption (film), 380 nm; solid
fluorescence emissions, 576 nm.
[0159] The assembling conditions of single-layer device
(ITO/PEDOT/Polymer/Ca/Al) were as follows: the pre-cleaned ITO
glass was used as anode, then a layer (40 nm) of conducting
polymer, polythiophene derivative (PEDOT), was spin-coated on the
anode. The ITO coated with PEDOT was vacuum dried at 110.degree. C.
for 1 hr. Then the chloroform solution containing 10 mg/ml of the
polymer was spin-coated on the surface of ITO at 1500 rpm. Then,
under high vacuum condition, metallic calcium (10 nm) and metallic
aluminum (100 nm) were coated by vaporization. The performances of
said single-layer electroluminescent device were as follows:
starting voltage, 5.8V; maximum luminance, 2870 cd/m.sup.2; maximum
efficiency of electroluminescence, 0.8 cd/A; color coordinate,
(0.54, 0.35).
Example 38
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P2
[0160] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.84 g, 3.00 mmol), 2,2'-bipyridine
(0.33 g, 3.0 mmol), 1,5-cyclooctadiene (0.48 g, 3.00 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour, then a solution (5 ml) of 9,9'-dioctyl-2,7-dibromofluorene
(0.543 g, 0.990 mmol) and
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.0067 g, 0.010 mmol) in toluene was added. Reacted at 50.degree.
C. for 3 days. The rest steps were the same as those in Example 37.
0.25 g (yield 64%) of an orange yellow solid was obtained. .sup.1H
NMR (300 MHz, CDCl3): .delta. 7.88-7.69 (m, Ar--H), 2.19-1.16 (m,
CH.sub.2), 0.84-0.80 (m, CH.sub.3). Product performances: number
average molecular weight (Mn), 20,000; maximum UV-absorption
(film), 382 nm; solid fluorescence emissions, 425, 448 and 550
nm.
[0161] The assembling conditions of single-layer device were the
same as those of Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 6.6V;
maximum luminance, 10500 cd/m.sup.2; maximum efficiency of
electroluminescence, 2.8 cd/A; color coordinate, (0.34, 0.48).
Example 39
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P3
[0162] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol) and 4-N,N-di
(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide (0.0033 g,
0.0050 mmol) in toluene was added. Reacted at 80.degree. C. for 1
day. The rest steps were the same as those in Example 37. 0.28 g
(yield 72%) of an orange yellow solid was obtained. .sup.1H NMR
(300 MHz, CDCl3): .delta. 7.87-7.67 (m, Ar--H), 2.15-1.12 (m,
CH.sub.2), 0.86-0.79 (m, CH.sub.3). Product performances: number
average molecular weight (Mn), 17,000; maximum UV-absorption
(film), 380 nm; solid fluorescence emissions, 438, 461 and 550
nm.
[0163] The assembling conditions of single-layer device were the
same as those of Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.8V;
maximum luminance, 18300 cd/m.sup.2; maximum efficiency of
electroluminescence, 3.8 cd/A; color coordinate, (0.29, 0.45).
Example 40
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P4
[0164] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for 1 hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.546 g, 0.997 mmol) and
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.0020 g, 0.0030 mmol) in toluene was added. Reacted at 80.degree.
C. for 2 days. The rest steps were the same as those in Example 37.
0.27 g (yield 70%) of an orange yellow solid was obtained. .sup.1H
NMR (300 MHz, CDCl3): .delta. 7.86-7.66 (m, Ar--H), 2.18-1.15 (m,
CH.sub.2), 0.86-0.79 (m, CH.sub.3). Product performances: number
average molecular weight (Mn), 19,000; maximum UV-absorption
(film), 382 nm; solid fluorescence emissions, 426, 444 and 542
nm.
[0165] The assembling conditions of single-layer device were the
same as those of Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.4V;
maximum luminance, 12900 cd/m.sup.2; maximum efficiency of
electroluminescence, 4.2 cd/A; color coordinate, (0.29, 0.45).
Example 41
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P5
[0166] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
85.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.548 g, 0.9995 mmol) and
4-N,N-di(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.00033 g, 0.00050 mmol) in toluene was added. Reacted at
80.degree. C. for 1 day. The rest steps were the same as those in
Example 37. 0.30 g (yield 77%) of an orange yellow solid was
obtained. .sup.1H NMR (300 MHz, CDCl3): .delta. 7.85-7.68 (m,
Ar--H), 2.16-1.15 (m, CH.sub.2), 0.84-0.78 (m, CH.sub.3). Product
performances: number average molecular weight (Mn), 30,000; maximum
UV-absorption (film), 384 nm; solid fluorescence emissions, 433,
447 and 540 nm.
[0167] The assembling conditions of the single-layer
electroluminescent device were the same as those of Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 4.8V; maximum luminance, 8820
cd/m.sup.2; maximum efficiency of electroluminescence, 3.9 cd/A;
color coordinate for a white light, (0.30, 0.40).
Example 42
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P6
[0168] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.20 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-di(4-octyloxy)phenyl-2,7-dibromofluorene (0.5088 g, 0.695
mmol),
9,9-di(10'-(p-(5''-phenyl-1'',3'',4''-oxadiazole-2''-)phenyloxy)decyloxy)-
-2,7-dibromofluorene (0.3228 g, 0.30 mmol) and 4-N,N-di
(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthalimide (0.0033 g,
0.0050 mmol) in toluene was added. Reacted at 85.degree. C. for 4
days. The rest steps were the same as those in Example 37. 0.31 g
(yield 46%) of an orange yellow solid was obtained. .sup.1H NMR
(CDCl.sub.3, 300 MHz): .delta. 8.10-7.42 (m, Ar--H), 6.98 (b,
Ar--H), 4.20-3.75 (b, OCH.sub.2), 2.61-1.14 (m, CH.sub.2),
1.03-0.80 (m, CH.sub.3). Product performances: number average
molecular weight (Mn), 22,000; maximum UV-absorption (film), 382
nm; solid fluorescence emissions, 421, 447 and 558 nm.
[0169] The assembling conditions of said single-layer
electroluminescent device were the same as those of Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.8V; maximum luminance, 9330
cd/m.sup.2; maximum efficiency of electroluminescence, 1.8 cd/A;
color coordinate for a white light, (0.30, 0.46).
Example 43
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P7
[0170] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol) and
4-N,N-di(4-bromostyryl)-9-(4-t-butylphenyl)-1,8-naphthalimide
(0.0043 g, 0.0050 mmol) in toluene was added. Reacted at 80.degree.
C. for 5 days. The rest steps were the same as those in Example 37.
0.25 g (yield 64%) of an orange yellow solid was obtained. .sup.1H
NMR (300 MHz, CDCl3): .delta. 7.85-7.66 (m, Ar--H), 2.15-1.11 (m,
CH.sub.2), 0.83-0.78 (m, CH.sub.3). Product performances: number
average molecular weight (Mn), 22,000; maximum UV-absorption
(film), 382 nm; solid fluorescence emissions, 435, 451 and 551
nm.
[0171] The assembling conditions of the single-layer
electroluminescent device were the same as those of Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 4.8V; maximum luminance, 12400
cd/m.sup.2; maximum efficiency of electroluminescence, 2.7 cd/A;
color coordinate for a white light, (0.29, 0.33).
Example 44
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P8
[0172] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.493 g, 0.899 mmol),
N,N'-di(4-methyl-phenyl)-N,N'-di(4-bromophenyl)-1,4-phenylenediamine
(0.0672 g, 0.10 mmol) and
4-N,N-(4,4'-di-(4-p-tolyl-4-bromophenylamino)-9-(4-t-butylphenyl)-1,8-nap-
hthalimide (0.0058 g, 0.0001 mmol) in toluene was added. Reacted at
80.degree. C. for 3 days. The rest steps were the same as those in
Example 37. 0.30 g (yield 75%) of an orange yellow solid was
obtained. .sup.1H NMR (300 MHz, CDCl3): .delta. 7.81-7.56 (m,
Ar--H), 7.23-7.14 (m, Ar--H), 2.36 (b, CH.sub.3), 2.03 (b,
CH.sub.2), 1.19-1.06 (m, CH.sub.2), 0.88-0.79 (m, CH.sub.3).
Product performances: number average molecular weight (Mn), 35,000;
maximum UV-absorption (film), 382 nm; solid fluorescence emissions,
428, 450 and 552 nm.
[0173] The assembling conditions of said single-layer
electroluminescent device were the same as those of Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.4V; maximum luminance, 8880
cd/m.sup.2; maximum efficiency of electroluminescence, 1.8 cd/A;
color coordinate for white light, (0.25, 0.34).
Example 45
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P9
[0174] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.2713 g, 0.495 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.50
mmol),
4-N,N-(4,4'-di-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9-(4-t-butylphenyl)-
-1,8-naphthalimide (0.00012 g, 0.0001 mmol), anhydrous potassium
carbonate (0.4140 g, 3 mmol), and tetrakis(triphenylphosphine)
palladium (0) (0.0060 g, 0.0005 mmol) were added into a reacting
flask, then toluene (4 ml) and water (1.5 ml) were added. The
reaction system reacted at 100.degree. C. for 24 hr. The reaction
mixture was poured into methanol to obtain a black solid and
filtered. The black solid was dissolved by chloroform, washed
repeatedly with water, dried by anhydrous Na.sub.2SO.sub.4,
concentrated, precipitated in methanol for three times, and
extracted with acetone for 24 hr. 0.26 g (yield 65%) of a light
yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3): .delta.
7.86-7.68 (m, Ar--H), 2.18-1.15 (m, CH.sub.2), 0.85-0.79 (m,
CH.sub.3). Product performances: Mn, 30,600; maximum UV-absorption
(solid), 382 nm; solid fluorescence emissions, 424, 442 and 550
nm.
[0175] The assembling conditions of the single-layer device were
the same as those in Example 37. The performances of said
single-layer electroluminescent device were as follows: starting
voltage, 5.2V; maximum luminance, 7950 cd/m.sup.2; maximum
efficiency of electroluminescence, 2.0 cd/A; color coordinate,
(0.24, 0.31).
Example 46
Synthesizing and Characterizing of Polymeric Electroluminescent
Material
[0176] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.1096 g, 0.195 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.50
mmol),
N,N'-di(4-methylphenyl)-N,N'-di(4-bromophenyl)-1,4-phenylenediamine
(0.2016 g, 0.30 mmol) and
4-N,N-(4,4'-di-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9-(4-t-butylphenyl)-
-1,8-naphthalimide (0.0058 g, 0.0050 mmol), anhydrous potassium
carbonate (0.4140 g, 3 mmol), and tetrakis(triphenylphosphine)
palladium (0) (0.0060 g, 0.0005 mmol) were added into a reacting
flask, then toluene (4 ml) and water (1.5 ml) were added. The
reaction system reacted at 50.degree. C. for 120 hr. The other
conditions and steps were the same as those in Example 45. 0.26 g
(yield 65%) of a light yellow solid was obtained. .sup.1H NMR (300
MHz, CDCl3): .delta. 7.83-7.59 (m, Ar--H), 7.24-7.11 (m, Ar--H),
2.35 (b, CH.sub.3), 2.01 (b, CH.sub.2), 1.18-1.02 (m, CH.sub.2),
0.86-0.79 (m, CH.sub.3). Product performances: Mn, 30,600; maximum
UV-absorption (solid), 382 nm; solid fluorescence emissions, 424,
442 and 561 nm.
[0177] The assembling conditions of the single-layer
electroluminescent device were the same as those in Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.2V; maximum luminance, 7950
cd/m.sup.2; maximum efficiency of electroluminescence, 2.0 cd/A;
color coordinate, (0.34, 0.39).
Example 47
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P11
[0178] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.2166 g, 0.40 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.50
mmol), and
4-N,N-(4,4'-di-(4-p-tolyl-4-bromophenyl-amino)phenyl)-9-(4-t-butylphe-
nyl)-1,8-naphthalimide (0.116 g, 0.10 mmol), anhydrous potassium
carbonate (0.4140 g, 3 mmol), and tetrakis(triphenylphosphine)
palladium (0) (0.0060 g, 0.0005 mmol) were added into a reacting
flask, then toluene (4 ml) and water (1.5 ml) were added. The
reaction system reacted at 85.degree. C. for 48 hr. The other
conditions and steps were the same as those in Example 45. 0.26 g
(yield 65%) of a light yellow solid was obtained. .sup.1H NMR (300
MHz, CDCl3): .delta. 8.60-8.31 (m, Ar--H), 7.85-7.43 (m, Ar--H),
7.27-7.02 (m, Ar--H), 2.88-2.69 (b, CH.sub.3), 2.17-1.13 (m,
CH.sub.2 and CH.sub.3), 0.84-0.79 (b, CH.sub.3). Product
performances: Mn, 30,600; maximum UV-absorption (solid), 382 nm;
solid fluorescence emissions, 581 nm.
[0179] The assembling conditions of the single-layer
electroluminescent device were the same as those in Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.2V; maximum luminance, 1950
cd/m.sup.2; maximum efficiency of electroluminescence, 1.0 cd/A;
color coordinate, (0.60, 0.36).
Example 48
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P12
[0180] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.548 g, 0.9995 mmol) and
4-N,N-(4,4'-di(4-p-tolyl-4-bromophenyl-amino)carbazolyl)-9-(4-t-butylphen-
yl)-1,8-naphthalimide (0.0006 g, 0.0005 mmol) in toluene was added.
The reaction system reacted at 85.degree. C. for 5 days. The other
conditions and steps were the same as Example 37. 0.22 g (yield
57%) of a yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 7.88-7.68 (m, Ar--H), 2.17-1.14 (m, CH.sub.2), 0.84-0.78
(m, CH.sub.3). Product performances: Mn, 21,200; maximum
UV-absorption (solid), 385 nm; solid fluorescence emissions, 428,
442 and 525 nm.
[0181] The assembling conditions of the single-layer device were
the same as Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.0V;
maximum luminance, 6550 cd/m.sup.2; maximum efficiency of
electroluminescence, 2.1 cd/A; color coordinate for white light,
(0.35, 0.40).
Example 49
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P13
[0182] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a toluene solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol), and
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-
-naphthalimido)-2,7-dibromofluorene (0.0050 g, 0.0049 mmol) was
added. The reaction system reacted at 80.degree. C. for 5 days. The
other conditions and steps were the same as Example 37. 0.24 g
(yield 62%) of a yellow solid was obtained. .sup.1H NMR (300 MHz,
CDCl3): .delta. 7.86-7.69 (m, Ar--H), 2.18-1.15 (m, CH.sub.2),
0.84-0.79 (m, CH.sub.3). Product performances: Mn, 27,000; maximum
UV-absorption (solid), 385 nm; solid fluorescence emissions, 428,
442 and 532 nm.
[0183] The assembling conditions of the single-layer device were
the same as Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.8V;
maximum luminance, 9050 cd/m.sup.2; maximum efficiency of
electroluminescence, 2.8 cd/A; color coordinate for white light,
(0.27, 0.32).
Example 50
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P14
[0184] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.1070 g, 0.195 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.50
mmol), N,N'-di(4-methylphenyl)-N,N'-di(4-bromophenyl)-1,4-phenylene
diamine (0.2016 g, 0.30 mmol),
9-phenyl-9-((4-N-(4-(4'-styryl)phenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-
-naphthalimido)-2,7-dibromofluorene (0.0050 g, 0.0050 mmol),
anhydrous potassium carbonate (0.4140 g, 3 mmol) and
tetrakis(triphenylphosphine) palladium (0) (0.0060 g, 0.0005 mmol)
were added into a reacting flask, then toluene (5 ml) and water
(2.0 ml) were added. The reaction system reacted at 80.degree. C.
for 96 hr. The other conditions and steps were the same as Example
45. 0.25 g (yield 65%) of a light yellow solid was obtained.
.sup.1H NMR (300 MHz, CDCl3): .delta. 7.81-7.55 (m, Ar--H),
7.25-7.14 (m, Ar--H), 2.36 (b, CH.sub.3), 2.02 (b, CH.sub.2),
1.17-1.05 (m, CH.sub.2), 0.86-0.78 (m, CH.sub.3). Product
performances: Mn, 25,600; maximum UV-absorption (solid), 382 nm;
solid fluorescence emissions, 424, 442 and 531 nm.
[0185] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.6V; maximum luminance, 9970
cd/m.sup.2; maximum efficiency of electroluminescence, 1.7 cd/A;
color coordinate, (0.26, 0.33).
Example 51
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P15
[0186] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.2739 g, 0.4999 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.5
mmol),
2-(6'-(4'-N,N-diphenylamino-1',8'-naphthalimido-9'-alkyl)hexoxy)-5-hexoxy-
-1,4-dibromobenzene (0.00081 g, 0.0001 mmol), anhydrous potassium
carbonate (0.4140 g, 3 mmol), and tetrakis(triphenylphosphine)
palladium (0) (0.0060 g, 0.0005 mmol) were added into a reacting
flask, then toluene (4 ml) and water (3 ml) were added. The
reaction system reacted at 100.degree. C. for 24 hr. The other
conditions and steps were the same as Example 45. 0.21 g (yield
54%) of a light yellow solid was obtained. .sup.1H NMR (300 MHz,
CDCl3): .delta. 7.85-7.66 (m, Ar--H), 2.16-1.15 (m, CH.sub.2),
0.84-0.79 (m, CH.sub.3). Product performances: Mn, 23,000; maximum
UV-absorption (solid), 378 nm; solid fluorescence emissions, 435
and 510 nm.
[0187] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.8V; maximum luminance, 13080
cd/m.sup.2; maximum efficiency of electroluminescence, 6.6 cd/A;
color coordinate, (0.13, 0.50).
Example 52
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P16
[0188] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.56 g, 2.0 mmol), 2,2'-bipyridine
(0.22 g, 2.0 mmol), 1,5-cyclooctadiene (0.32 g, 2.0 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour, then a toluene solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.3288 g, 0.60 mmol),
2-(6'-(4'-N,N-diphenylamino-1',8'-naphthalimide-9'-alkyl)hexoxyl)-5-hexox-
yl-1,4-dibromobenzene (0.88 g, 0.1 mmol) and
N,N'-di(4-methyl-phenyl)-N,N'-di(4-bromophenyl)-1,4-phenylenediamine
(0.20162 g, 0.30 mmol) was added. The reaction system reacted at
100.degree. C. for 1 day. The other conditions and steps were the
same as Example 37. 0.24 g (yield 60%) of a yellow solid was
obtained. .sup.1HNMR 8.60-8.52 (b, Ar--H), 8.28-8.18 (b, Ar--H),
7.85-7.55 (b, Ar--H), 7.20-6.85 (b, Ar--H), 4.22-4.14 (b,
--OCH.sub.2), 2.30-1.15 (b, CH.sub.2), 0.88-0.78 (b, CH.sub.3).
Product performances: Mn, 26,000; maximum UV-absorption (solid),
375 nm; solid fluorescence emissions, 519 nm.
[0189] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.2V; maximum luminance, 8450
cd/m.sup.2; maximum efficiency of electroluminescence, 1.2 cd/A;
color coordinate for white light, (0.26, 0.68).
Example 53
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P17
[0190] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.844 g, 3.0 mmol), 2,2'-bipyridine
(0.33 g, 3.0 mmol), 1,5-cyclooctadiene (0.48 g, 3.0 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour, then a toluene solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.548 g, 0.9999 mmol), and
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4'-dianilino-biphenyl-4-)amino-1,8-napht-
halimide-9-)-hexoxyl)benzene (0.13 g, 0.0001 mmol) was added. The
reaction system reacted at 50.degree. C. for 5 day. The other
conditions and steps were the same as Example 37. 0.24 g (yield
60%) of an orange solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 7.88-7.69 (m, Ar--H), 2.18-1.15 (m, CH.sub.2), 0.85-0.79
(m, CH.sub.3). Product performances: Mn, 24,800; maximum
UV-absorption (solid), 375 nm; solid fluorescence emissions, 435
and 551 nm.
[0191] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.0V; maximum luminance, 15400
cd/m.sup.2; maximum efficiency of electroluminescence, 4.2 cd/A;
color coordinate for white light, (0.27, 0.34).
Example 54
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P18
[0192] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a toluene solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.54534 g, 0.995 mmol), and
1,4-dibromo-2-hexoxyl-5-(6-(4-di(4-styrylphenyl-1-)amino-1,8-naphthalimid-
e-9-)-hexoxyl)benzene (0.0050 g, 0.005 mmol) was added. The
reaction system reacted at 80.degree. C. for 3 days. The other
conditions and steps were the same as Example 37. 0.24 g (yield
60%) of an orange solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 7.87-7.68 (m, Ar--H), 2.17-1.15 (m, CH.sub.2), 0.83-0.77
(m, CH.sub.3). Product performances: Mn, 24,800; maximum
UV-absorption (solid), 375 nm; solid fluorescence emissions, 440
and 552 nm.
[0193] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 4.8V; maximum luminance, 12400
cd/m.sup.2; maximum efficiency of electroluminescence, 2.2 cd/A;
color coordinate for white light, (0.30, 0.34).
Example 55
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P19
[0194] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.844 g, 3.0 mmol), 2,2'-bipyridine
(0.33 g, 3.0 mmol), 1,5-cyclooctadiene (0.48 g, 3.0 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour, then a toluene solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.545 g, 0.995 mmol) was added.
The reaction system reacted at 100.degree. C. for 1 day. A solution
(0.5 ml) of
4-N-(4-(4'-bromostyryl)phenyl)-4-N-phenyl-9-(4-t-butylphenyl)-1,8-naphtha-
limide (0.0034 g, 0.0050 mmol) in toluene was then added. The
reaction system reacted at 80.degree. C. for further 1 hr. The
other conditions and steps were the same as Example 37. 0.28 g
(yield 72%) of a light yellow solid was obtained. .sup.1H NMR (300
MHz, CDCl3): .delta. 7.86-7.68 (m, Ar--H), 2.16-1.14 (m, CH.sub.2),
0.83-0.77 (m, CH.sub.3). Product performances: Mn, 19,600; maximum
UV-absorption (solid), 383 nm; solid fluorescence emissions, 425,
447 and 528 nm.
[0195] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.2V; maximum luminance, 16880
cd/m.sup.2; maximum efficiency of electroluminescence, 2.6 cd/A;
color coordinate for white light, (0.25, 0.38).
Example 56
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P20
[0196] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.56 g, 2.0 mmol), 2,2'-bipyridine
(0.22 g, 2.0 mmol), 1,5-cyclooctadiene (0.32 g, 2.0 mmol) and DMF
(5 ml) in a reacting flask was reacted at 80.degree. C. for half an
hour. Then a solution (5 ml) of 9,9'-dioctyl-2,7-dibromofluorene
(0.545 g, 0.995 mmol) in toluene was added. After reacting at
50.degree. C. for 5 days, a solution (0.5 ml) of
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide (0.0029 g, 0.0049 mmol) in toluene were added. The reaction
system reacted at 50.degree. C. for further 2 days. The other
conditions and steps were the same as Example 37. 0.27 g (yield
70%) of a yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 7.86-7.68 (m, Ar--H), 2.17-1.15 (m, CH.sub.2), 0.85-0.79
(m, CH.sub.3). Product performances: Mn, 22,450; maximum
UV-absorption (solid), 380 nm; solid fluorescence emissions, 430,
451 and 523 nm.
[0197] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 6.8V; maximum luminance 19280
cd/m.sup.2; maximum efficiency of electroluminescence, 7.4 cd/A;
color coordinate, (0.34, 0.50).
Example 57
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P21
[0198] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.2714 g, 0.495 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.5
mmol), anhydrous potassium carbonate (0.4140 g, 3 mmol), and
tetrakis(triphenylphosphine) palladium (0) (0.0060 g, 0.0005 mmol)
were added into a reacting flask, then toluene (4 ml) and water
(1.5 ml) were added. After reacting at 100.degree. C. for 24 hr,
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide (0.0029 g, 0.005 mmol) was added. The reaction system reacted
at 100.degree. C. for further 1 hr. The other conditions and steps
were the same as Example 45. 0.21 g (yield 54%) of a light yellow
solid was obtained. .sup.1H NMR (300 MHz, CDCl3): .delta. 7.84-7.65
(m, Ar--H), 2.16-1.12 (m, CH.sub.2), 0.85-0.77 (m, CH.sub.3).
Product performances: Mn, 20,300; maximum UV-absorption (solid),
387 nm; solid fluorescence emissions, 435, 443 and 525 nm.
[0199] The assembling conditions of the single-layer device were
the same as Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 6.4V;
maximum luminance, 17780 cd/m.sup.2; maximum efficiency of
electroluminescence, 7.2 cd/A; color coordinate, (0.34, 0.52).
Example 58
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P22
[0200] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.1096 g, 0.1999 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.5
mmol),
N,N'-di(4-methyl-phenyl)-N,N'-di(4-bromophenyl)-1,4-phenylenediamine
(0.2016 g, 0.30 mmol), anhydrous potassium carbonate (0.4140 g, 3
mmol), and tetrakis(triphenylphosphine) palladium (0) (0.0060 g,
0.0005 mmol) were added into a reacting flask, then toluene (4 ml)
and water (1.5 ml) were added. After reacting at 50.degree. C. for
120 hr,
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide (0.00058 g, 0.0001 mmol) was added. The reaction system
reacted at 50.degree. C. for further 48 hr. The other conditions
and steps were the same as Example 45. 0.26 g (yield 59%) of a
light yellow solid was obtained. .sup.1H NMR (CDCl.sub.3, 300 MHz):
.delta. 7.81-7.56 (m, Ar--H), 7.23-7.10 (m, Ar--H), 2.34 (b,
CH.sub.3), 2.00 (b, CH.sub.2), 1.19-1.06 (m, CH.sub.2), 0.86-0.77
(m, CH.sub.3). Product performances: Mn, 23,400; maximum
UV-absorption (solid), 385 nm; solid fluorescence emissions, 435,
443 and 520 nm.
[0201] The assembling conditions of the single-layer device were
the same as Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.2V;
maximum luminance, 7980 cd/m.sup.2; maximum efficiency of
electroluminescence, 2.2 cd/A; color coordinate, (0.23, 0.28).
Example 59
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P23
[0202] Under the protection of N.sub.2 gas,
2,7-dibromo-9,9-dioctylfluorene (0.2192 g, 0.40 mmol),
9,9-dioctylfluorene-2,7-bis(trimethyleneborate) (0.2792 g, 0.5
mmol), anhydrous potassium carbonate (0.4140 g, 3 mmol), and
tetrakis(triphenylphosphine) palladium (0) (0.0060 g, 0.0005 mmol)
were added into a reacting flask, then toluene (4 ml) and water
(1.5 ml) were added. After reacting at 50.degree. C. for 120 hr,
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide (0.058 g, 0.10 mmol) was added. The reaction system reacted
at 50.degree. C. for further 48 hr. The other conditions and steps
were the same as Example 45. 0.21 g (yield 53%) of a light yellow
solid was obtained. .sup.1H NMR (300 MHz, CDCl3): .delta. 8.62-8.33
(m, Ar--H), 7.85-7.43 (m, Ar--H), 7.24-7.02 (m, Ar--H), 2.85-2.75
(b, CH.sub.3), 2.18-1.11 (m, CH.sub.2 and CH.sub.3), 0.85-0.78 (b,
CH.sub.3). Product performances: Mn, 7,400; maximum UV-absorption
(solid), 380 nm; solid fluorescence emissions, 535 nm.
[0203] The assembling conditions of the single-layer device were
the same as Example 37. The performances of said single-layer
electroluminescent device were as follows: starting voltage, 5.4V;
maximum luminance, 1770 cd/m.sup.2; maximum efficiency of
electroluminescence, 0.82 cd/A; color coordinate, (0.40, 0.58).
Example 60
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P24
[0204] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.3835 g, 0.6999 mmol) and
N,N'-di(4-methylphenyl)-N,N'-di(4-bromophenyl)-1,4-phenylenediamine
(0.2016 g, 0.30 mmol) in toluene was added. After reacting at
80.degree. C. for 3 days, a solution (0.5 ml) of
4-N-(4-methylphenyl)-4-N-(4-bromophenyl)-9-(4-t-butylphenyl)-1,8-naphthal-
imide (0.00058 g, 0.0001 mmol) in toluene was added. Reacted at
80.degree. C. for 1 day. The other steps and conditions are the
same as those in Example 37. 0.27 g (yield 47%) of a yellow solid
was obtained. .sup.1H NMR (CDCl.sub.3, 300 MHz): .delta. 7.82-7.58
(m, Ar--H), 7.24-7.12 (m, Ar--H), 2.37 (b, CH.sub.3), 2.02 (b,
CH.sub.2), 1.18-1.05 (m, CH.sub.2), 0.85-0.79 (m, CH.sub.3).
Product performances: number average molecular weight (Mn), 26,700;
maximum UV-absorption (solid), 380 nm; solid fluorescence
emissions, 430, 441 and 525 nm.
[0205] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 6.0V; maximum luminance, 4350
cd/m.sup.2; maximum efficiency of electroluminescence, 1.8 cd/A;
color coordinate, (0.23, 0.21).
Example 61
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P25
[0206] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.5453 g, 0.995 mmol) in toluene
was added. After reacting at 80.degree. C. for 3 days, a solution
(0.5 ml) of
4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-bromophenylamino)phenyl-9-(4--
t-butylphenyl)-1,8-naphthalimide (0.0042 g, 0.005 mmol) in toluene
was added. Reacted at 80.degree. C. for 1 day. The other steps and
conditions are the same as those in Example 37. 0.25 g (yield 64%)
of a yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 7.87-7.70 (m, Ar--H), 2.19-1.15 (m, CH.sub.2), 0.84-0.79
(m, CH.sub.3). Product performances: number average molecular
weight (Mn), 20,700; maximum UV-absorption (solid), 381 nm; solid
fluorescence emissions, 433 and 545 nm.
[0207] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 6.0V; maximum luminance, 10950
cd/m.sup.2; maximum efficiency of electroluminescence, 4.3 cd/A;
color coordinate, (0.28, 0.32).
Example 62
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P26
[0208] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.4932 g, 0.90 mmol) in toluene
was added. After reacting at 80.degree. C. for 3 days, a solution
(0.5 ml) of
4-N-(4-methylphenyl)-4-N-(4-methylphenyl-4'-bromophenylamino)phenyl-9-(4--
t-butylphenyl)-1,8-naphthalimide (0.084 g, 0.1 mmol) in toluene was
added. Reacted at 80.degree. C. for 1 day. The other steps and
conditions are the same as those in Example 37. 0.26 g (yield 60%)
of a yellow solid was obtained. .sup.1H NMR (300 MHz, CDCl3):
.delta. 8.61-8.32 (m, Ar--H), 7.82-7.41 (m, Ar--H), 7.28-7.00 (m,
Ar--H), 2.86-2.68 (m, CH.sub.3), 2.16-1.11 (m, CH.sub.2 and
CH.sub.3), 0.84-0.78 (b, CH.sub.3). Product performances: number
average molecular weight (Mn), 6,700; maximum UV-absorption
(solid), 381 nm; solid fluorescence emissions, 553 nm.
[0209] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.4V; maximum luminance, 2950
cd/m.sup.2; maximum efficiency of electroluminescence, 1.3 cd/A;
color coordinate, (0.43, 0.56).
Example 63
Synthesizing and Characterizing of Polymeric Electroluminescent
Material P27
[0210] Under the protection of N.sub.2 gas, a mixture of
bis(1,5-cyclooctadienyl)nickel (0.619 g, 2.20 mmol),
2,2'-bipyridine (0.24 g, 2.2 mmol), 1,5-cyclooctadiene (0.352 g,
2.20 mmol) and DMF (5 ml) in a reacting flask was reacted at
80.degree. C. for half an hour, then a solution (5 ml) of
9,9'-dioctyl-2,7-dibromofluorene (0.5453 g, 0.995 mmol) in toluene
was added. After reacting at 80.degree. C. for 3 days, a solution
(0.5 ml) of
4-N-p-bromophenyl-4-N-(4-styryl)phenyl-9-(4-t-butylphenyl)-1,8-naphthalim-
ide (0.0034 g, 0.005 mmol) in toluene was added. Reacted at
80.degree. C. for 1 day. The other steps and conditions are the
same as those in Example 37. 0.22 g (yield 57%) of a yellow solid
was obtained. .sup.1H NMR (300 MHz, CDCl3): .delta. 7.88-7.68 (m,
Ar--H), 2.17-1.15 (m, CH.sub.2), 0.86-0.80 (m, CH.sub.3). Product
performances: number average molecular weight (Mn), 19,200; maximum
UV-absorption (solid), 376 nm; solid fluorescence emissions, 433
and 540 nm.
[0211] The assembling conditions of the single-layer
electroluminescent device were the same as Example 37. The
performances of said single-layer electroluminescent device were as
follows: starting voltage, 5.0V; maximum luminance, 9940
cd/m.sup.2; maximum efficiency of electroluminescence, 3.3 cd/A;
color coordinate for white light, (0.27, 0.33).
* * * * *