U.S. patent application number 09/850843 was filed with the patent office on 2001-10-04 for (co)polymers based on vinyl units and use thereof in electroluminescent devices.
Invention is credited to Chen, Yun, Dujardin, Ralf, Elschner, Andreas, Wehrmann, Rolf.
Application Number | 20010026879 09/850843 |
Document ID | / |
Family ID | 7754616 |
Filed Date | 2001-10-04 |
United States Patent
Application |
20010026879 |
Kind Code |
A1 |
Chen, Yun ; et al. |
October 4, 2001 |
(Co)polymers based on vinyl units and use thereof in
electroluminescent devices
Abstract
This invention relates to (co)polymers which contain at least
one repeat chain unit of the general formula (1) or (2) and
optionally contain repeat units of the general formula (3) 1 in
which L.sup.1 and L.sup.2 mean a photoluminescent residue, wherein
the proportion of structural units of the formulae (1) and/or (2)
is in each case 0.5 to 100 mol.%, and (3) 0 to 99.5 mol.%, and the
molar percentages add up to 100, to the use thereof for the
production of electroluminescent devices and to the
electroluminescent devices.
Inventors: |
Chen, Yun; (Krefeld, DE)
; Wehrmann, Rolf; (Krefeld, DE) ; Elschner,
Andreas; (Mulheim, DE) ; Dujardin, Ralf;
(Willich, DE) |
Correspondence
Address: |
Robert G. McMorrow, Jr.
Connolly Bove Lodge & Hutz LLP
1220 Market Street
P.O. Box 2207
Wilmington
DE
19899
US
|
Family ID: |
7754616 |
Appl. No.: |
09/850843 |
Filed: |
May 8, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09850843 |
May 8, 2001 |
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08599581 |
Feb 9, 1996 |
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6248457 |
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Current U.S.
Class: |
428/690 ;
252/301.35; 313/504; 313/506; 428/523; 428/917; 526/256; 526/259;
526/266; 526/280 |
Current CPC
Class: |
H05B 33/14 20130101;
C09K 11/06 20130101; C08F 246/00 20130101; Y10T 428/31938 20150401;
Y10S 428/917 20130101; C09B 69/10 20130101 |
Class at
Publication: |
428/690 ;
428/917; 428/523; 313/504; 313/506; 252/301.35; 526/256; 526/259;
526/266; 526/280 |
International
Class: |
H05B 033/14; C09K
011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 21, 1995 |
DE |
19505942-5 |
Claims
1. (Co)polymers which contain at least one repeat chain unit of the
general formula (1) or (2) and optionally contain repeat units of
the general formula (3) 56in which R.sup.1, R.sup.2 and R.sup.3
mutually independently mean hydrogen or C.sub.1-C.sub.6 alkyl, M
denotes CN or C.sub.1-C.sub.30 alkoxycarbonyl, C.sub.1-C.sub.30
(di)alkyl-aminocarbonyl- , C.sub.1-C.sub.30 alkylcarbonyl, which
may each be substituted by hydroxy or C.sub.1-C.sub.6
alkoxycarbonyl and furthermore denotes phenyl, naphthyl,
anthracenyl, pyridyl or carbazolyl, which may each be substituted
by residues from the group halogen, hydroxy, silyl,
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl, C.sub.1-C.sub.30
alkoxy, C.sub.1-C.sub.30 alkoxycarbonyl, C.sub.1-C.sub.30 acyloxy
and C.sub.1-C.sub.30 alkylcarbonyl, L.sup.1 and L.sup.2 mean a
photoluminescent residue, wherein the proportion of structural
units of the formulae (1) and/or (2) is in each case 0.5 to 100
mol.%, and (3) 0 to 99.5 mol.%, and the molar percentages add up to
100.
2. (Co)polymers according to claim 1, wherein L.sup.1 and L.sup.2
mutually independently denote a photoluminescent residue which is
based on the skeleton of a fluorescent dye which is selected from
the group of coumarins of the formula (4) 57pyrenes of the formula
(5) 581,8-naphthalimides of the formula (6)
591,8-naphthaloylene-1,2-benzimid- azoles of the formulae (7a) and
(7b) 60phenothiazines or phenoxazines of the formula (8) 61with X=O
or S, benzopyrones of the formula (9) 62carbazoles, fluorenes,
dibenzothiophenes and -furans of the formula (10) 63with
X.sup.2=NR.sup.23, CH.sub.2, S or O, wherein R.sup.23 denotes
hydrogen or C.sub.1-C.sub.6 alkyl, oxazoles, 1,3,4-oxadiazoles of
the formula (1I) 64with X.sup.3=CH or N benzoquinolines of the
formula (12) 659,10-bis-(phenylethynyl)anthracenes of the formula
(13) 66fluorones of the formula (14) 679,10-diphenylanthracene of
the formula (15) 682-styrylbenzazole of the formula (16) 69with
X.sup.4=O, S, Se or CH.sub.2, wherein R.sup.4 denotes hydrogen,
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24
aralkyl or C.sub.1-C.sub.30 alkoxy or 70wherein R.sup.43 and
R.sup.44 mutually independently denote hydrogen, C.sub.1-C.sub.30
alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl, which may
each be substituted by hydroxy, amino, carboxy or C.sub.1-C.sub.4
alkoxycarbonyl, or R.sup.43 and R.sup.44, together with the
nitrogen atom to which they are attached, may mean a morpholine,
piperidine, pyrrolidine or piperazine ring, which may bear one or
two substituents from the group methyl, ethyl and phenyl, R.sup.5
denotes hydrogen, cyano, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18
aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30 alkoxy,
C.sub.2-C,.sub.2 acyl, C.sub.1-C.sub.12 alkoxycarbonyl,
C.sub.1-C.sub.12 (di)-alkylaminocarbonyl- , R.sup.6 denotes
hydrogen, cyano, C.sub.1-C.sub.30 alkyl, C.sub.6-Cl8 aryl,
C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30 alkoxy or 71wherein Z
denotes a group OR.sup.45 or 72and R.sup.45, R.sup.46 and R.sup.47
mutually independently denote C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24 aralkyl, wherein the
aromatic rings may additionally be further substituted by halogen,
C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy, R.sup.7, R.sup.5 and
R.sup.9 mutually independently mean hydrogen, C.sub.1-C.sub.30
alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl,
C.sub.1-C.sub.30 alkoxy, cyano, C.sub.2-C.sub.12 alkoxycarbonyl,
C.sub.1-C.sub.12 (di)alkylaminocarbonyl or an amino group with one
or two C.sub.1-C.sub.6 alkyl groups, R.sup.10 means hydrogen,
cyano, C.sub.1-C.sub.30 alkyl, C.sub.6-Cl, aryl, C.sub.7-C.sub.24
aralkyl, C.sub.1-C.sub.30 alkoxy, amino, an amino group with one or
two C.sub.1-C.sub.6 alkyl groups, C.sub.2-C.sub.12 acyl,
C.sub.1-C.sub.12 alkoxycarbonyl, C.sub.1-C.sub.12
(di)alkylaminocarbonyl, R.sup.11 denotes hydrogen, halogen, nitro,
C.sub.1-C.sub.4 alkoxycarbonyl, C.sub.1-C.sub.4 acyl,
C.sub.8-C.sub.24 aralkenyl, unsubstituted amino, or amino
identically or differently mono- or disubstituted by
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24
aralkyl, R.sup.11 furthermore denotes morpholinyl, piperidinyl,
pyrrolidinyl or piperazinyl, which may bear one or two substituents
selected from methyl, ethyl and/or phenyl, R.sup.12 denotes
hydrogen, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl,
C.sub.7-C.sub.24 aralkyl or C.sub.1-C.sub.30 alkoxy, R.sup.13
denotes hydrogen, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18, aryl,
C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30 alkoxy or 73wherein
R.sup.49 and R.sup.50 mutually independently denote
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24
aralkyl or R.sup.49 and R.sup.50, together with the nitrogen atom
to which they are attached, moreover denote a morpholinyl,
piperidinyl, pyrrolidinyl or piperazinyl, which may bear one or two
identical or different substituents selected from methyl, ethyl and
phenyl, R.sup.14 and R.sup.15 mutually independently mean hydrogen,
cyano, halogen, nitro, C.sub.1-C.sub.30 alkyl, C.sub.1-C.sub.30
alkoxy, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24 aralkyl,
C.sub.1-C.sub.12 alkoxycarbonyl, C.sub.2-C.sub.12 acyl,
C.sub.1-C.sub.12 (di)alkylaminocarbonyl, C.sub.1-C.sub.6
(di)alkylamino, R.sup.17 means hydrogen, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24 aralkyl and R.sup.16,
R.sup.18 to R.sup.22 and R.sup.24 to R.sup.40 mutually
independently mean hydrogen, cyano, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30
alkoxy, an amino group with one or two C.sub.1-C.sub.6 alkyl
groups, unsubstituted amino, C.sub.2-C.sub.12 acyl,
C.sub.1-C.sub.12 alkoxycarbonyl or C.sub.1-C.sub.12
(di)alkylaminocarbonyl, wherein the aliphatic carbon chains, such
as, for example, alkyl, alkoxy, alkylamino, aralkyl, in the
residues R.sup.4 to R.sup.13, R.sup.16 to R.sup.40 may be
interrupted by one or more, preferably one or two heteroatoms
selected from oxygen, nitrogen and sulphur and/or by one or more,
preferably one or two, phenylene rings, which may be substituted by
C.sub.1-C.sub.4 alkyl and/or halogen, and wherein furthermore the
luminophore is attached to the polymer side chains via an oxygen, a
hydroxy or carboxy group or a nitrogen of an amino or primary amino
on the above-stated substituents.
3. (Co)polymers according to claim 1, wherein the proportion of
structural units of the formulae (1) and/or (2) is 0.5 to 60 mol.%
and optionally of the formula (3) 40 to 99.5 mol.%.
4. (Co)polymers according to claim 1, wherein L denotes a
fluorescent dye selected from the group of coumarins of the formula
(4), pyrenes of the formula (5), 1,8-naphthalimides of the formula
(6), 1,8-naphthoyl-ene-1',2'-benzimidazoles of the formula (7),
phenothiazines or phenoxazines of the formula (8), carbazoles and
fluorenes of the formula (10).
5. Process for the production of (co)polymers of the formula (1)
according to claim 1, wherein monomers of the formula (20) or (21)
are produced 74from a fluorescent dye functionalised with an OH,
COOH or NH group, which dye contains the structure of L, and a
styrene or acrylic acid derivative of the formulae (22) and (23)
75in which R.sup.1 and R.sup.2 have the above-stated range of
meaning and R.sup.41 denotes halogen, R.sup.42 denotes halogen, a
hydroxy or C.sub.1-C.sub.6 alkoxy group, in the presence of a base
and these monomers are then polymerised, optionally in the presence
of units of the formula (3) as comonomers.
6. Use of the (co)polymers of the formula (1) according to claim 1
for the production of electroluminescent devices.
7. Electroluminescent device which contains (co)polymers according
to claim 1 as the electroluminescent substance.
8. Electroluminescent device according to claim 7 containing two
electrodes, between which is located an electroluminescent layer,
which contain the (co)polymers as the electroluminescent layer, and
wherein one or more interlayers may be arranged between the
electroluminescent layer and the electrodes.
Description
[0001] Light-emitting components for electronics and photonics are
today mainly developed using inorganic semiconductors, such as
gallium arsenide. Punctual display elements may be produced using
such substances. Devices of a large area are not possible.
[0002] In addition to semiconductor light emitting diodes,
electroluminescent devices based on vapour-deposited low molecular
weight organic compounds are also known (U.S. Pat. No. 4,539,507,
U.S. Pat. No. 4,769,262, U.S. Pat. No. 5,077,476P). With these
materials too, as a consequence of the production process, it is
only possible to produce small LEDs. Furthermore, these
electroluminescent devices have elevated production costs and only
a very short service life.
[0003] Polymers such as poly(p-phenylenes) and
poly(p-phenylene-vinylenes) are described as electroluminescent:
Adv. Mater. 4 (1992) no. 1; J. Chem. Soc., Chem. Commun. 1992,
pages 32-34; Polymer, 1990, volume 31, 1137; Physical Review B,
volume 42, no. 18, 11670 or WO 90/13148.
[0004] In contrast to the fully conjugated polymers, non fully
conjugated polycondensation products with luminescent structural
units are described in electroluminescent devices (Macromol. Chem.
Phys. 195, 2023-2037 (1994)).
[0005] The present invention provides polymers for the production
of electroluminescent devices, which polymers are based on a well
known basic structure, such as polystyrene and polyacrylate, with
covalently bonded luminophoric units in the side chains. Due to
their simple production process and ready processability, such
polymers are of great technical interest with regard to use as
electroluminescent materials. Electroluminescent devices containing
these (co)polymers are distinguished by elevated light intensities
and a broad range of colour hues. The advantages of the
(co)polymers according to the invention are, for example, that
[0006] 1. light intensity may purposefully be modified by varying
the concentration of luminophore,
[0007] 2. colour hues may be adjusted by combining different
monomers containing luminophores,
[0008] 3. the morphology and electrical properties of the polymer
layers may be optimised by the incorporation of suitable side chain
units.
[0009] The present invention relates to (co)polymers which contain
at least one repeat chain unit of the general formula (1) or (2)
and optionally contain repeat units of the general formula (3)
2
[0010] in which
[0011] R.sup.1, R.sup.2 and R.sup.3 mutually independently mean
hydrogen or C.sub.1-C.sub.6 alkyl,
[0012] M denotes CN or C.sub.1-C.sub.30 alkoxycarbonyl,
C.sub.1-C.sub.30 (di)alkyl-aminocarbonyl, C.sub.1-C.sub.30
alkylcarbonyl, which may each be substituted by hydroxy or
C.sub.1-C.sub.6 alkoxycarbonyl, and furthermore denotes phenyl,
naphthyl, anthracenyl, pyridyl or carbazolyl, which may each be
substituted by residues from the group halogen, hydroxy, silyl,
C.sub.1-C.sub.30 alkyl, C.sub.6-C,.sub.8 aryl, C.sub.1-C.sub.30
alkoxy, C.sub.1-C.sub.30 alkoxycarbonyl, C.sub.1-C.sub.30 acyloxy
and C.sub.1-C.sub.30 alkylcarbonyl,
[0013] L.sup.1 and L.sup.2 mean a photoluminescent residue,
[0014] wherein the proportion of structural units of the formula
(3) is 0 to 99.5, preferably 40 to 99.5 mol.% and the proportion of
structural units (1) and/or (2) is in each case 0.5 to 100,
preferably 0.5 to 60 mol.% and the molar proportions add up to
100%.
[0015] In the above-stated formulae, R.sup.1, R.sup.2 and R.sup.3
mutually independently preferably mean hydrogen, methyl or
ethyl.
[0016] M preferably denotes CN or C.sub.1-C.sub.15 alkoxycarbonyl,
C.sub.1-C.sub.15 (di)alkylaminocarbonyl, C.sub.1-C.sub.15
alkylcarbonyl, which may each be substituted by hydroxy or
methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxycarbonyl, and
furthermore denotes phenyl, naphthyl, anthracenyl, pyridyl or
carbazolyl, which may each be substituted by residues from the
group chlorine, bromine, hydroxy, silyl, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, C.sub.1-C.sub.6 alkoxycarbonyl,
C.sub.1-C.sub.6 acyloxy and C.sub.1-C.sub.6 alkylcarbonyl, phenyl
optionally substituted by methyl, ethyl, n- or iso-propyl.
[0017] L.sup.1 and L.sup.2 mutually independently denote a
photoluminescent residue which is based on the skeleton of a
fluorescent dye which is selected from the group of coumarins of
the formula (4) 3
[0018] pyrenes of the formula (5) 4
[0019] 1,8-naphthalimides of the formula (6) 5
[0020] 1,8-naphthaloylene-1,2-benzimidazoles of the formulae (7a)
and (7b) 6
[0021] phenothiazines or phenoxazines of the formula (8) 7
[0022] with X.sup.1=O or S,
[0023] benzopyrones of the formula (9) 8
[0024] carbazoles, fluorenes, dibenzothiophenes and -furans of the
formula (10) 9
[0025] with X.sup.2=NR.sup.23, CH.sub.2, S or O, wherein R.sup.23
denotes hydrogen or C.sub.1-C.sub.6 alkyl, preferably hydrogen or
C.sub.1-C.sub.4 alkyl,
[0026] oxazoles, 1,3,4-oxadiazoles of the formula (11) 10
[0027] with X.sup.3=CH or N
[0028] benzoquinolines of the formula (12) 11
[0029] 9,10-bis-(phenylethynyl)anthracenes of the formula (13)
12
[0030] fluorones of the formula (14) 13
[0031] 9,10-diphenylanthracene of the formula (15) 14
[0032] 2-styrylbenzazole of the formula (16) 15
[0033] with X.sup.4=O, S, Se or CH.sub.2,
[0034] wherein
[0035] R.sup.4 denotes hydrogen, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18, aryl, C.sub.7-C.sub.24 aralkyl or
C.sub.1-C.sub.30 alkoxy or 16
[0036] wherein
[0037] R.sup.43 and R.sup.44 mutually independently denote
hydrogen, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl,
C.sub.7-C.sub.24 aralkyl, which may each be substituted by hydroxy,
amino, carboxy or C.sub.1-C.sub.4 alkoxycarbonyl, or
[0038] R.sup.43 and R.sup.44, together with the nitrogen atom to
which they are attached, may mean a morpholine, piperidine,
pyrrolidine or piperazine ring, which may bear one or two
substituents from the group methyl, ethyl and phenyl,
[0039] R.sup.5 denotes hydrogen, cyano, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C30
alkoxy, C.sub.2-C.sub.12 acyl, C.sub.1-C.sub.12 alkoxycarbonyl,
C.sub.1-C.sub.12 (di)alkylaminocarbonyl,
[0040] R.sup.6 denotes hydrogen, cyano, C.sub.1-C.sub.30 alkyl,
C.sub.6-C, aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30 alkoxy
or 17
[0041] wherein Z denotes a group OR.sup.45 or 18
[0042] R.sup.45, R.sup.46 and R.sup.47 mutually independently
denote C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl or
C.sub.7-C.sub.24 aralkyl, wherein the aromatic rings may
additionally be further substituted by halogen, C.sub.1-C.sub.6
alkyl, C.sub.1-C.sub.6 alkoxy,
[0043] R.sup.7, R.sup.8 and R.sup.9 mutually independently mean
hydrogen, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl,
C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30 alkoxy, cyano,
C.sub.2-C.sub.12 acyl, C.sub.1-C.sub.12 alkoxycarbonyl,
C.sub.1-C.sub.12 (di)alkyl-aminocarbonyl or an amino group with one
or two C.sub.1-C.sub.6 alkyl groups,
[0044] R.sup.10 means hydrogen, cyano, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30
alkoxy, amino, C.sub.2-C.sub.12 acyl, C.sub.1-C.sub.12
alkoxycarbonyl, C.sub.1-C.sub.12 (di)alkylaminocarbonyl,
[0045] R.sup.11 denotes hydrogen, halogen, nitro, C.sub.1-C.sub.4
alkoxycarbonyl, C.sub.1-C.sub.4 acyl, C.sub.8-C.sub.24 aralkenyl,
unsubstituted amino, or amino identically or differently mono- or
disubstituted by C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl or
C.sub.7-C.sub.24 aralkyl,
[0046] R.sup.11 furthermore denotes morpholinyl, piperidinyl,
pyrrolidinyl or piperazinyl, which may bear one or two substituents
selected from methyl, ethyl and/or phenyl,
[0047] R.sup.12 denotes hydrogen, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl or C.sub.1-C.sub.30
alkoxy,
[0048] R.sup.13 denotes hydrogen, C.sub.1-C.sub.30 alkyl,
C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl, C.sub.1-C.sub.30
alkoxy or 19
[0049] wherein
[0050] R.sup.49 and R.sup.50 mutually independently denote
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl, C7-C.sub.24 aralkyl
or
[0051] R.sup.49 and R.sup.50, together with the nitrogen atom to
which they are attached, moreover denote a morpholinyl,
piperidinyl, pyrrolidinyl or piperazinyl, which may bear one or two
identical or different substituents selected from methyl, ethyl and
phenyl,
[0052] R.sup.14 and R.sup.15 mutually independently mean hydrogen,
cyano, halogen, nitro, C.sub.1-C.sub.30 alkyl, C.sub.1-C.sub.30
alkoxy, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24 aralkyl,
C.sub.1-C.sub.12 alkoxycarbonyl, C.sub.2-C.sub.12 acyl,
C.sub.1-C.sub.12 (di)alkylaminocarbonyl, C.sub.1-C.sub.6
(di)alkylamino,
[0053] R.sup.17 and R.sup.23 mutually independently mean hydrogen,
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24
aralkyl and
[0054] R.sup.16, R.sup.18 to R.sup.23 and R.sup.24 to R.sup.40
mutually independently mean hydrogen, cyano, C.sub.1-C.sub.30
alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl,
C.sub.1-C.sub.30 alkoxy, an amino group with one or two
C.sub.1-C.sub.6 alkyl groups, unsubstituted amino, C.sub.2-C.sub.12
acyl, C.sub.1-C.sub.12 alkoxycarbonyl or C.sub.1-C.sub.12
(di)alkylaminocarbonyl, wherein the aliphatic carbon chains, such
as, for example, alkyl, alkoxy, alkylamino, aralkyl, in the
residues R.sup.4 to R.sup.13, R.sup.16 to R.sup.40 may be
interrupted by one or more, preferably one or two heteroatoms
selected from oxygen, nitrogen and sulphur and/or by one or more,
preferably one or two, phenylene rings, which may be substituted by
C.sub.1-C.sub.4 alkyl and/or halogen,
[0055] and wherein furthermore the luminophore is attached to the
polymer side chains via an oxygen, a hydroxy or carboxy group or a
nitrogen of an amino or primary amino on the above-stated
substituents.
[0056] In the above-stated residues R.sup.4 to R.sup.40, at least
one aliphatic, aromatic or heterocyclic carbon chain per
fluorescent dye bears at least one hydroxy, carboxy or optionally
an amino group, preferably hydroxy, by means of which the covalent
bond to the monomer is formed by the reaction of these groups with
a reactive group (for example halogen) located on the monomer, c.f.
production process. In the case of monomer (1), this attachment
site is the methylene group on the phenyl ring (--CH.sub.2--Cl
reacts). In the case of monomer (2), the attachment site is the
carbonyl group (via --CO--Cl).
[0057] M in particular denotes phenyl, naphthyl, anthracenyl,
pyridyl or carbazolyl, which may each be substituted by hydroxy,
silyl, C.sub.1-C.sub.4 alkyl, optionally by phenyl substituted by
methyl, ethyl, n- or iso-propyl, by C.sub.1-C.sub.4 alkoxy,
C.sub.1-C.sub.6 alkoxycarbonyl, C.sub.1-C.sub.6 acyloxy or
C.sub.1-C.sub.6 alkylcarbonyl.
[0058] L.sup.1 and L.sup.2 in particular mutually independently
denote a fluorescent dye residue selected from the group of
coumarins of the formula (4), pyrenes of the formula (5),
1,8-naphthalimides of the formula (6),
1,8-naphthaloylene-1,2-benzimidazoles of the formula (7),
phenothiazines or phenoxazines of the formula (8), carbazoles and
fluorenes of the formula (10).
[0059] R.sup.4 preferably presents C.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.10 aryl or C]-C.sub.6 alkoxy or 20
[0060] wherein
[0061] R.sup.43 and R.sup.44 preferably independently represent
C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.10 aryl which may each be
substituted by hydroxy and/or amino or
[0062] R.sup.43 and R.sup.44 together with the nitrogen atom to
which they are attached may mean a morpholine, piperidine,
pyrrolidine or piperazine ring which may bear one or two
substituents from the group methyl, ethyl and phenyl.
[0063] R.sup.5 preferably denotes hydrogen or cyano,
[0064] R.sup.6 preferably denotes hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.10 aryl oder C.sub.1-C.sub.6 alkoxy or 21
[0065] wherein Z denotes a group OR.sup.45 or 22
[0066] and
[0067] R.sup.45, R.sup.46 and R.sup.47 independently preferably
represent C.sub.1-C.sub.6 alkyl or C.sub.6-C.sub.10 aryl, in
particular phenyl or naphthyl,
[0068] R.sup.7, R.sup.5 and R.sup.9 independently preferably
represent hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.1O aryl,
C.sub.1-C.sub.6 alkoxy or cyano,
[0069] R.sup.10 preferably denotes hydrogen, cyano, C.sub.1-C.sub.6
alkyl, C.sub.6-C.sub.10 aryl, in particular phenyl or naphthyl,
C.sub.2-C.sub.4 acyl oder C.sub.1-C.sub.6 alkoxycarbonyl,
[0070] R.sup.11 preferably denotes hydrogen, halogen, nitro,
C.sub.1-C.sub.4 alkoxycarbonyl, C.sub.1-C.sub.4 acyl,
C.sub.8-C.sub.24 aralkenyl or amino identically or differently
mono- or disubstituted by C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.10
aryl, in particular phenyl or naphthyl,
[0071] R.sup.11 furthermore denotes morpholinyl, piperidinyl,
pyrrolidinyl or piperazinyl which may bear one or two substituents
selected from methyl, ethyl or phenyl,
[0072] R.sup.12 preferably denotes C.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.10 aryl, in particular phenyl or naphthyl, or
C.sub.7-C.sub.12 aralkyl.
[0073] R.sup.13 preferably denotes hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.6-C.sub.10 aryl, in particular phenyl or naphthyl, or
C.sub.1-C.sub.6 alkoxy or 23
[0074] wherein
[0075] R.sup.49 and R.sup.50 independently preferably denote
C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.10 aryl, in particular phenyl
or naphthyl, or
[0076] R.sup.49 und R.sup.50 together with the nitrogen atom to
which they are attached, moreover denote a morpholinyl,
piperidinyl, pyrrolidinyl or piperazinyl, which may bear one or two
identical or different substituents selected from methyl, ethyl and
phenyl,
[0077] R.sup.14 and R.sup.15 independently preferably represent
hydrogen, cyano, halogen, nitro, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, C.sub.6-C.sub.10 aryl, in particular phenyl
or naphthyl,
[0078] R.sup.17 and R.sup.23 independently preferably represent
hydrogen, C.sub.1-C.sub.6 alkyl, C.sub.6-C.sub.10 aryl.
[0079] R.sup.16, R.sup.18 to R.sup.22 and R.sup.24 to R.sup.40
independently preferably represent hydrogen, cyano, C.sub.1-C.sub.6
alkyl, C.sub.6-C.sub.10 aryl, C.sub.1-C.sub.6 alkoxy, amino
substituted by one or two C.sub.1-C.sub.6 alkyl groups,
unsubstituted amino,
[0080] wherein the aliphatic carbon chains such as e.g. alkyl,
alkoxy, Alkylamino, aralkyl, in the residues of R.sup.4 to
R.sup.13, R.sup.16 to R.sup.40 may be interrupted by a heteroatom,
selected from oxygen, nitrogen and sulphur and/or a phenyl
ring.
[0081] Alkyl residues, for example, in alkyl, alkoxy,
alkoxycarbonyl or (di)alkylamino are exemplified by methyl, ethyl,
n- or iso-propyl, n-, iso- or tert.-butyl. Aryl represents in
particular phenyl and naphthyl. Aralkyl represents in particular
phenyl-C.sub.1-C.sub.4-alkyl, z.B. phenylmethyl, phenylethyl or
naphthyl-C.sub.1-C.sub.4-alkyl, e.g. naphthylmethyl,
naphthylethyl.
[0082] The present invention furthermore relates to a process for
the production of the above-stated (co)polymers which contain at
least one repeat chain unit of the general formula (1) or (2) and
optionally repeat units of the general formula (3), 24
[0083] wherein the residues have the above-stated meanings,
[0084] wherein the corresponding monomers of the formula (20) or
(21) are produced 25
[0085] from a fluorescent dye functionalised with an OH, COOH or NH
group, which dye contains the structure of L,
[0086] and a styrene or acrylic acid derivative of the formulae
(22) and (23) 26
[0087] in which
[0088] R.sup.1 and R.sup.2 have the above-stated range of meaning
and
[0089] R.sup.41 denotes a halogen atom, preferably Cl or Br,
[0090] R.sup.42 denotes a halogen atom, preferably Cl or Br, a
hydroxy or C.sub.1-C.sub.6 alkoxy group,
[0091] in the presence of a base, preferably triethylamine,
pyridine or an alkali metal alkoxide and these monomers are then
polymerised, optionally in the presence of units of the formula (3)
as comonomers.
[0092] The reaction of the fluorescent dyes functionalised with an
OH, carboxyl or NH group generally proceeds at temperatures of
-30.degree. C. to 100.degree. C., preferably from 0.degree. C. to
60.degree. C.
[0093] Polymerisation processes are described in the literature.
They may proceed by ionic or free-radical polymerisation. Anionic
polymerisation may, for example, be initiated by initiators such as
butyllithium or lithiumnapthalide. Free-radical polymerisation may
be initiated by, for example, free-radical initiators, such as for
example azo initiators or peroxides, preferably AIBN
(azoisobutyro-nitrile) or dibenzoyl peroxide. The polymers may be
produced using bulk methods or in suitable solvents such as
benzene, toluene, tetrahydrofuran, dioxane, ethyl acetate, xylene,
chlorobenzene, 1-methoxy-2-propyl acetate, chlorinated
hydrocarbons, acetone etc., at temperatures of 20-250.degree.
C.
[0094] Production of the (co)polymers according to the invention is
illustrated by way of example by the following reaction scheme:
27
[0095] In this scheme, the methacrylate (26) is initially produced
starting from 3-(6-hydroxyhexoxycarbonyl)-7-diethylamino-coumarin
(24) and methacryloyl chloride (25) together with triethylamine at
0.degree. C. to room temperature. The methacrylate (26) may be
polymerised in chlorobenzene at 100.degree. C. in the presence of
n-butyl acrylate (27) as a comonomer together with AIBN as
free-radical initiator to form the copolymer (28). The preferred
molar percentage x of comonomer (26) is between 0.5 and 60%.
[0096] Production of the polymers or copolymers according to the
invention may furthermore be illustrated by way of example by the
following reaction scheme: 28
[0097] In this scheme, the styrene derivative (31) is first
produced at 0.degree. C. to room temperature in a phase transfer
catalysed reaction starting from phenothiazine (29) and
m/p-vinylbenzene chloride (30) together with sodium hydroxide and
tributylammonium hydrogen sulphite in a catalytic quantity. The
styrene derivative (31) may be polymerised in toluene at 80.degree.
C. to 100.degree. C. in the presence of m/p-methylstyrene (32) as
comonomer together with AIBN as free-radical initiator to form the
copolymer (33). The preferred molar percentage x of comonomer (31)
is between 0.5 and 60%.
[0098] Production of the polymers or copolymers according to the
invention may furthermore be illustrated by way of example by the
following reaction scheme: 29
[0099] In this scheme, the methacrylate (35) is first produced at
0.degree. C. to room temperature starting from
4/5-(N-methyl-N-hydroxyeth- yl)amino-1,8-naphthoylene-
1',2'-benzimidazole (34) (only 4-isomer shown) and methacryloyl
chloride (25) together with triethylamine. The methacrylate (35)
may be polymerised in chlorobenzene at 80.degree. C in the presence
of N-vinylcarbazole (36) as comonomer together with AIBN as
free-radical initiator to form the copolymer (37). The preferred
molar percentage x of comonomer (35) is between 0.5 and 60%.
[0100] Production of the polymers or copolymers according to the
invention may furthermore be illustrated by way of example by the
following reaction scheme: 30
[0101] In this scheme, the styrene derivative (39) is first
produced at room temperature in tetrahydrofuran starting from
N-isoamyl-4-(N-methyl-N- -hydroxyethyl)amino-1,8-naplithalimide
(38) and mip-vinylbenzyl chloride (30) together with potassium
tert.-butylate. The styrene derivative (39) may be polymerised in
toluene at 100.degree. C. together with AIBN as free-radical
initiator to form the homopolymer (40).
[0102] The styrene derivative (39) may also be copolymerised with a
comonomer such as, for example, N-vinylcarbazole, styrene, n-butyl
acrylate etc..
[0103] (Co)polymers of the present invention have molecular
weights, determined by gel permeation chromatography, in the range
from 500 to 1 million g/mol, preferably of 800 to 500000 g/mol.
[0104] Some of the fluorescent dyes functionalised with OH, SH or
NH (c.f. definition of residue L), which are necessary for the
production of the (co)polymers according to the invention, are
known.
[0105] The coumarin derivatives of the following formula (4a) are
novel: 31
[0106] wherein
[0107] R.sup.43 and R.sup.44 mutually independently denote
hydrogen, C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl,
C.sub.7-C.sub.24 aralkyl, which may each be substituted by hydroxy,
amino, carboxy or C.sub.1-C.sub.4 alkoxycarbonyl or
[0108] R.sup.43 and R.sup.44, together with the nitrogen atom to
which they are attached, may mean a morpholine, piperidine,
pyrrolidine or piperazine ring, which may bear one or two
substituents from the group methyl, ethyl and phenyl, and
[0109] Z denotes a group OR.sup.45 or 32
[0110] wherein
[0111] R.sup.45 means C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl
or C.sub.7-C.sub.24 aralkyl, which are each substituted by at least
one hydroxy group and wherein the aromatic rings may additionally
be substituted by halogen, C.sub.1-C.sub.6 alkyl C.sub.1-C.sub.6
alkoxy and
[0112] R.sup.46 and R.sup.47 mutually independently denote
C.sub.1-C.sub.30 alkyl C.sub.6-C.sub.18 aryl or C.sub.7-C.sub.24
aralkyl, each optionally hydroxy-substituted, wherein at least one
of the residues R.sup.46 or R.sup.47 has a hydroxy group and
wherein the aromatic rings may additionally be substituted by
halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy.
[0113] The coumarin derivatives of the formula (4a) according to
the invention bear at least one hydroxy group by means of which
they may be chemically bonded to the polymer side chains.
[0114] In the formula (4a), R.sup.43 and R.sup.44 mutually
independently preferably denote hydrogen or C.sub.1-C.sub.16 alkyl,
optionally substituted by hydroxy, amino, carboxy and/or
C.sub.1-C.sub.4 alkoxycarbonyl, each unsubstituted, or phenyl,
naphthyl, phenyl-C.sub.1-C.sub.4-alkyl or
naphthyl-C.sub.1-C.sub.4-alkyl substituted by C.sub.1-C.sub.4
alkyl, hydroxy, amino, carboxy, C.sub.1-C.sub.4 alkoxycarbonyl,
chlorine and/or bromine.
[0115] R.sup.43 and R.sup.44 in particular denote C.sub.1-C.sub.6
alkyl or phenyl optionally substituted by hydroxy, amino or
carboxy,
[0116] Z in the above-stated formula (4a) denotes OR.sup.45 or
NR.sup.46R.sup.47, wherein R.sup.45 preferably denotes
C.sub.1-C.sub.16 alkyl, phenyl, naphthyl,
phenyl-C.sub.1-C.sub.4-alkyl or naphthyl-C.sub.1-C.sub.4-alkyl,
which are each substituted by at least one hydroxy group, and
wherein the aromatic rings may additionally be substituted by
halogen, C.sub.1-C.sub.6 alkyl, C.sub.1-C.sub.6 alkoxy,
[0117] R.sup.46 and R.sup.47 mutually independently preferably
denote C.sub.1-C.sub.16 alkyl, phenyl, naphthyl,
phenyl-C.sub.1-C.sub.4-alkyl or naphthyl-C.sub.1-C.sub.4-alkyl,
each optionally substituted by hydroxy, wherein at least one of the
residue R.sup.46 or R.sup.47 has a hydroxy group and the aromatic
rings may additionally also be substituted by halogen,
C.sub.1-C.sub.6 alkyl C.sub.1-C.sub.6 alkoxy
[0118] R.sup.45 particularly preferably denotes a C.sub.1-C.sub.12
alkyl substituted by a hydroxy group.
[0119] R.sup.46 and R.sup.47 mutually independently particularly
preferably denote C.sub.1-C.sub.12 alkyl optionally substituted by
a hydroxy group, wherein at least one of the residues R.sup.46 and
R.sup.47 has a hydroxy group.
[0120] The novel coumarin derivatives of the formula (4a), 33
[0121] wherein R.sup.43, R.sup.44 and Z have the above-stated
meaning, may be produced by,
[0122] a) in the event that Z denotes --OR.sup.45, producing the
malonic acid derivative of the formula (III) 34
[0123] preferably in a single vessel process from the Meldrums acid
of the formula (I) 35
[0124] and an alcohol of the formula (II)
R.sup.45--OH (II)
[0125] optionally in the presence of a diluent, such as for example
toluene, xylene or mesitylene with catalysis by, for example,
p-toluenesulphonic acid at temperatures in the range from 20 to
250.degree. C., preferably from 80 to 150.degree. C.,
[0126] and then reacting this malonic acid derivative with a
salicylic aldehyde of the formula (IV) 36
[0127] wherein R.sup.43, R.sup.44, R.sup.45 have the above-stated
meaning,
[0128] optionally in the presence of a diluent, such as for example
toluene, xylene, mesitylene, with catalysis by, for example,
piperidine acetate at temperatures of 50 to 250.degree. C.,
preferably of 80 to 140.degree. C., and,
[0129] b) in the event that Z denotes 37
[0130] by reacting a salicylic aldehyde of the formula (IV), a
secondary amine of the formula (V) and a malonic acid derivative of
the formula (VI) 38
[0131] in which
[0132] R.sup.43, R.sup.44, R.sup.46 and R.sup.47 have the
above-stated meaning and
[0133] R.sup.48 denotes C.sub.1-C.sub.6 alkyl,
[0134] optionally in the presence of a diluent, such as for example
toluene, xylene or mesitylene, with catalysis by, for example,
piperidine acetate at temperatures of 50 to 250.degree. C.,
preferably of 80 to 140.degree. C.
[0135] When performing the process a) according to the invention,
2-10 mol, preferably 3-6 mol of alcohol of the formula (1I) are
generally used for each mol of Meldrums acid, and 0.5-1.0,
preferably 0.9-1.0 mol of salicylic aldehyde of the formula (IV) is
generally used for each mol of malonic acid derivative of the
formula (III).
[0136] When performing the process b) according to the invention,
2-20, preferably 5-10 mol of secondary amine and 1-2, preferably
1.2-1.5 mol of malonic acid derivative of the formula (VI) are
generally used per mol of salicylic aldehyde of the formula
(IV).
[0137] Production of the coumarin derivatives of the formula (4a)
according to the invention, where Z=OR.sup.45, by way of a
Knoevenagel condensation reaction and subsequent cyclisation is
illustrated by way of example by the following reaction scheme:
39
[0138] In this scheme, bis-(6-hydroxyhexyl) malonate is first
produced by reacting the Meldrums acid and 1,6-hexanediol in the
presence of catalytic quantities of p-toluene-sulphonic acid with
elimination of acetone and water. The bis-(6-hydroxyhexyl) malonate
is then combined with 4-diethylaminosalicylic aldehyde in the
presence of catalytic quantities of piperidine acetate to form the
desired 3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin.
[0139] Production of the coumarin derivatives of the formula (4a)
according to the invention, where Z=NR.sup.46R.sup.47, is
illustrated by way of example by the following reaction scheme:
40
[0140] In this scheme, 4-diethylaminosalicylic aldehyde is reacted
with diethyl malonate and 2-(methylamino)ethanol in the presence of
catalytic quantities of piperidine acetate. The desired
3-[(N-hydroxyethyl-N-methyl-
)aminocarbonyl]-7-diethylamnino-coumarin is obtained.
[0141] The starting products of the formulae (I), (II), (III),
(IV), (V) and (VI) are compounds which are generally known in
organic chemistry.
[0142] The following 1,8-naphthalimide derivatives of the formulae
(6a), (7a-1) and (7b-1) are also novel: 41
[0143] in which
[0144] R.sup.11' denotes hydrogen, halogen, nitro, C.sub.1-C.sub.4
alkoxycarbonyl, C.sub.1-C.sub.4 acyl, C.sub.8-C.sub.24 aralkenyl,
unsubstituted amino or amino identically or differently mono- or
disubstituted by C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl,
C.sub.7-C.sub.24 aralkyl, wherein the above-stated carbon chains
may themselves be substituted by hydroxy and/or carboxy,
[0145] R.sup.11' furthermore denotes morpholinyl, piperidinyl,
pyrrolidinyl or piperazinyl, which may bear one or two substituents
selected from methyl, ethyl and/or phenyl,
[0146] R.sup.12' denotes hydrogen or C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24
aralkyl, which may be mono- or polysubstituted by hydroxy and/or
carboxy,
[0147] and at least one of the residues R.sup.11 or R.sup.12 has a
hydroxy or carboxy group,
[0148] R.sup.49' and R.sup.50' mutually independently denote
C.sub.1-C.sub.30 alkyl, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24
aralkyl, which may be substituted by hydroxy, wherein at least one
of the residues R.sup.49 or R.sup.50' has a hydroxy or carboxy
group.
[0149] R.sup.49' and R.sup.50', together with the nitrogen atom to
which they are attached, moreover denote morpholinyl, piperidyl,
pyrrolidyl or piperazinyl, which may bear one or two identical or
different substituents selected from methyl, ethyl and phenyl and
have at last one hydroxy or carboxy group,
[0150] R.sup.14 and R.sup.15 mutually independently mean hydrogen,
halogen, cyano, nitro, C.sub.1-C.sub.30 alkyl, C.sub.1-C.sub.30
alkoxy, C.sub.6-C.sub.18 aryl, C.sub.7-C.sub.24 aralkyl,
C.sub.1-C.sub.12 alkoxycarbonyl, C.sub.2-C.sub.12 acyl or
C.sub.1-C.sub.6 (di)alkylamino.
[0151] The 1,8-naphthalimide derivatives of the formulae (6a),
(7a-1) and (7b-1) according to the invention bear at least one
hydroxy or one carboxy group, preferably a hydroxy group, by means
of which they may be chemically bonded to the polymer side
chains.
[0152] In the above-stated formula (6a),
[0153] R.sup.11' preferably denotes hydrogen, chlorine, bromine,
nitro, methoxycarbonyl, ethoxycarbonyl, n- or iso-propoxy-carbonyl,
methylcarbonyl, ethylcarbonyl, n- or iso-propylcarbonyl, amino,
amino identically or differently mono- or disubstituted by
C.sub.1-C.sub.15 alkyl, phenyl, naphthyl,
phenyl-C.sub.1-C.sub.4-alkyl or naphthenyl-C.sub.1-C.sub.4-alkyl,
in each case optionally substituted by methyl and/or ethyl, wherein
the above-stated carbon chains may themselves by substituted by
hydroxy, R.sup.11' furthermore preferably denotes morpholinyl,
piperidinyl, pyrrolidinyl or piperazinyl, which may bear one or two
substituents selected from hydroxy, methyl, ethyl and/or
phenyl.
[0154] R.sup.12' preferably denotes C.sub.1-C.sub.15 alkyl, phenyl
or phenyl-C.sub.1-C.sub.6-alkyl, which may be substituted by
hydroxy and the aromatic rings may additionally be substituted by
halogen, C.sub.1-C.sub.6 alkyl and/or C.sub.1-C.sub.6 alkoxy.
[0155] R.sup.11' in particular denotes chlorine, bromine, amino
which is identically or differently mono- or disubstituted by
C.sub.1-C.sub.15 alkyl, morpholinyl, piperidinyl, pyrrolidinyl or
piperazinyl, wherein the above-stated carbon chains may themselves
by substituted by hydroxy.
[0156] R.sup.12' in particular denotes C.sub.1-C.sub.12 alkyl,
phenyl optionally substituted by halogen, C.sub.1-C.sub.6 alkyl,
C.sub.1-C.sub.6 alkoxy, which may bear a hydroxy group.
[0157] At least one of the residues R.sup.11' and R.sup.12' must
have a hydroxy group.
[0158] R.sup.49' and R.sup.50' in the formulae (7a-1) and (7b-1)
mutually independently preferably denote C.sub.1-C.sub.15 alkyl,
phenyl, phenyl-C.sub.1-C.sub.6-alkyl, naphthyl,
naphthyl-C.sub.1-C.sub.6-alkyl, which may be mono- or poly-, in
particular monosubstituted by hydroxy, wherein at least one of the
residues R.sup.49' or R.sup.50' has a hydroxy group.
[0159] R.sup.49' and R.sup.50', together with the nitrogen atom to
which they are attached, moreover preferably denote piperidinyl or
piperazinyl, which may bear one or two identical or different
substituents selected from methyl, ethyl and phenyl and have at
least one hydroxy or carboxy group,
[0160] R.sup.14 and R.sup.15 in the formulae (7a-1) and (7b-1)
mutually independently preferably denote hydrogen, halogen,
C.sub.1-C.sub.15 alkyl, C.sub.1-C.sub.15 alkoxy, C.sub.1-C.sub.4
alkoxycarbonyl, C.sub.1-C.sub.4 acyl or
di(C.sub.1-C.sub.6-alkyl)amino, phenyl,
phenyl-C.sub.1-C.sub.6-alkyl, naphthyl or
naphthyl-C.sub.1-C.sub.6-alkyl in each case substituted by methyl
and/or ethyl.
[0161] R.sup.49' and R.sup.50' in particular denote
C.sub.1-C.sub.12 alkyl, phenyl, phenyl-C.sub.1-C.sub.6 alkyl, which
may be substituted by a hydroxy group, wherein at least one of the
residues R.sup.49' or R.sup.50' has a hydroxy group.
[0162] R.sup.14 and R.sup.15 in particular denote hydrogen,
halogen, C.sub.1-C.sub.12 alkyl, C.sub.1-C.sub.12 alkoxy,
di(C.sub.1-C.sub.6-alkyl- )amino, phenyl.
[0163] The number of hydroxy groups and/or carboxy groups is at
least one, but there may also be up to four hydroxy and/or carboxy
groups.
[0164] The aromatic rings in the above-stated residues may be
identically or differently mono- to penta-, preferably mono- to
trisubstituted by the stated substituents.
[0165] The aliphatic carbon chains, such as for example alkyl,
alkoxy, alkylamino, aralkyl in R.sup.43, R.sup.44, R.sup.45,
R.sup.46 and R.sup.47, R.sup.11', R.sup.12', R.sup.45', R.sup.50'
may be interrupted by one or more, preferably one or two
heteroatoms selected from oxygen, nitrogen and sulphur, and/or by
one or more, preferably one or two phenylene rings, which may be
substituted by C.sub.1-C.sub.4 alkyl and/or halogen.
[0166] A process for the production of novel 1,8-naphthalimide
derivatives of the formula (6a) 42
[0167] in which
[0168] R.sup.11' and R.sup.12' have the above-stated meaning,
[0169] is characterised in that either
[0170] a) a 1,8-naphthalic anhydride of the formula (VII) and a
primary amine of the formula (VIII), 43
[0171] are reacted together at 50 to 250.degree. C., preferably at
90 to 140.degree. C., optionally in the presence of diluents, such
as for example acetic acid, butanol, chlorobenzene, toluene or
xylene or,
[0172] b) in the event that R.sup.11' in formula (6a) means an
unsubstituted, mono- or disubstituted amino or cyclic amino, a
1,8-naphthalimide of the formula (6a-1) 44
[0173] in which
[0174] R.sup.11' denotes halogen, preferably chlorine, bromine or
iodine, or nitro,
[0175] which is produced from a 1,8-naphthalic anhydride of the
formula (VIIA) and a primary amine of the formula (VIII) 45
[0176] in which R.sup.11' and R.sup.12' have the above stated
meaning,
[0177] at temperatures of 50 to 250.degree. C., preferably of 90 to
140.degree. C., optionally in the presence of diluents, such as for
example acetic acid, butanol, chlorobenzene, toluene or xylene,
[0178] and the resultant compound of the formula (6a-1) is then
reacted with a primary or secondary amine or piperidine,
morpholine, pyrrolidine or piperazine, which may bear one or two
substituents selected from methyl, ethyl and/or phenyl, or with an
aqueous ammonia solution, optionally in the presence of solvents,
such as for example methoxy-ethanol or butanol, optionally with
catalysis by, for example, a copper(II) salt at temperatures of 50
to 250.degree. C., preferably of 100 to 150.degree. C.
[0179] A process for the production of novel 1,8-naphthalimide
derivatives of the formula (7a-1) and (7b-1) (process C), 46
[0180] in which
[0181] R.sup.14, R.sup.15, R.sup.49' and R.sup.50' have the
above-stated meaning,
[0182] wherein a 1,8-naphthalimide derivative of the formula (IXa
and b), 47
[0183] in which
[0184] R.sup.14, R.sup.15 and R.sup.11" have the above range of
meaning,
[0185] is produced from a 1,8-naphthalic anhydride of the formula
(VIIa) 48
[0186] in which R.sup.11" has the above-stated meaning,
[0187] and an o-phenylenediamine of the formula (X) 49
[0188] in which R.sup.14 and R.sup.15 have the above-stated
meanings, at temperatures of 50 to 250.degree. C., preferably of 90
to 140.degree. C., optionally in the presence of solvents, such as
for example acetic acid, butanol, chlorobenzene, toluene or xylene
and the 1,8-naphthalimide derivative of the formula (IXa and b) is
then reacted with a secondary amine of the formula (XI), 50
[0189] in which R.sup.49' and R.sup.50' have the above-stated
meaning,
[0190] with catalysis by, for example, a copper(II) salt at
temperatures of 50 to 250.degree. C., preferably of 100 to
150.degree. C., optionally in the presence of a solvent, such as
for example methoxyethanol or butanol.
[0191] When performing the process a) according to the invention
for the production of the 1,8-naphthalimide derivatives of the
formula (6a), 1 to 1.8 mol, preferably 1.2 to 1.4 mol of primary
amine of the formula (VIII) are generally used per mol of compound
of the formula (VII).
[0192] When performing the process b) according to the invention
for the production of the 1,8-naphthalimide derivatives of the
formula (6a-1), I to 1.8 mol, preferably 1.2 to 1.4 of the primary
amine of the formula (VIII) are generally used per mol of compound
of the formula (VIIa) and 1.2 to 5 mol, preferably 2 to 2.5 mol of
the corresponding primary, secondary or cyclic amine are use per
mol of compound of the formula (6a-1).
[0193] Production of the 1,8-naphthalimide derivatives of the
formula (6a), processes (a) and (b), according to the invention is
illustrated by way of example by the following reaction scheme:
51
[0194] In this scheme, the
4-chloro-N-hydroxyethyl-1,8-naphthalimide is first produced by the
reaction of 4-chloronaphthalic anhydride and 2-aminoethanol. The
4-chloro-N-hydroxyethyl-1,8-naphthalimide is then combined with
piperidine in the presence of a catalytic quantity of a copper(II)
salt to form the desired N-hydroxyethyl-4-piperidino-1,8-napht-
halimide.
[0195] When performing the process C) according to the invention
for the production of the 1,8-naphthalimide derivatives of the
formula (7a-1) and (7b-1), 1 to 1.8 mol, preferably 1.2 to 1.4 mol
of the o-phenylenediamine of the formula (X) are generally used per
mol of compound of the formula (VIIa) and 1.2 to 5 mol, preferably
2 to 2.5 mol of the secondary amine of the formula (XI) per mol of
compound (IXa-b).
[0196] Production of the 1,8-naphthalimide derivatives according to
the invention of the formulae (7a-1 and 7b-1) is illustrated by way
of example by the following reaction scheme: 52
[0197] In this scheme, the
4/5-chloro-1,8-naphthoylene-1',2'-benzimidazole- , which occurs as
an isomeric mixture (approximately 3:1), is first produced by the
reaction of 4-chloronaphthalic anhydride and o-phenylenediamine.
The 4/5-chloro-1,8-naphthoylene-1',2'-benzimidazole is then
combined with 2-(methylamino)ethanol in the presence of a catalytic
quantity of a copper(II) salt to form the desired
4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1',2'-benzimidazole.
[0198] The starting products of the formulae (VII), (VIII), (VIIa),
(X) and (XI) for the production of the compounds according to the
invention of the formula are compounds which are generally known in
organic chemistry.
[0199] The styrene and acrylic acid derivatives of the formulae
(22) and (23) which are also necessary for the production of the
(co)polymers according to the invention are generally known
compounds.
[0200] The (co)polymers according to the invention are
distinguished by their luminescent properties and film-forming
capacity and may be applied onto suitable substrates by casting,
knife coating or spin coating. The products exhibit
photoluminescence on irradiation both in solutions and as films.
The (co)polymers of the present invention are suitable for the
production of electroluminescent displays.
[0201] The invention thus relates to the use of the (co)polymers
described above in the luminescent layer of an electroluminescent
device, which is characterised in that
[0202] an electroluminescent layer is located between two
electrodes,
[0203] at least one of the two electrodes is transparent in the
visible range of the spectrum,
[0204] light in the frequency range of 200 to 2000 nm is emitted
when a direct voltage in the range of 0.1 to 100 volts is
applied,
[0205] one or more interlayers may additionally be arranged between
the electroluminescent layer and the electrodes.
[0206] These interlayers are known from the literature (c.f. Appl.
Phys. Lett., 57, 531 (1990)) and are described therein as HTL (hole
transport layer) and ETL (electron transport layer). The purpose of
such interlayers is inter alia to increase the intensity of
electroluminescence.
[0207] The electroluminescent polymers according to the invention
may also be used in the electroluminescent layer as a mixture with
each other or with at least one further material. This further
material may be an inert binder, charge transporting substances as
described in EP-A 532 798 or EP-A 564 224, or mixture of inert
binders and charge transporting substances.
[0208] The mixtures of the polymers according to the invention and
a further material are distinguished inter alia that they are
film-forming and may be applied in large areas onto suitable
substrates by casting, knife coating or spin coating. Suitable
substrates are transparent supports such as glass or plastic films
(for example polyester, such as polyethylene terephthalate or
polyethylene naphthalate, polycarbonate, polysulphone, polyimide
films).
[0209] The inert binder preferably comprises soluble, transparent
polymers, such as for example polycarbonates, polystyrene,
polyvinylpyridine, polymethylphenylsiloxane and polystyrene
copolymers such as SAN, polysulphones, polyacrylates,
polyvinylcarbazole, polymers and copolymers of vinyl acetate and
vinyl alcohol.
EXAMPLES
Example 1
[0210] 1. Production of
3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin- , formula (24)
in the reaction scheme
[0211] A solution of bis-(6-hydroxyhexyl) malonate in
1,6-hexanediol is prepared by heating a mixture of 21.6 g (0.15
mol) of Meldrums acid, 59 g (0.50 mol) of 1,6-hexanediol and 0.28 g
(1.5 mmol) of p-toluene-sulphonic acid monohydrate for 2 hours at
140.degree. C.
[0212] The resultant solution is then combined with 26.0 g (0.135
mol) of 4-diethylaminosalicylic aldehyde, 0.7 ml of piperidine and
0.1 ml of acetic acid. The reaction mixture is stirred for 3 hours
at 110.degree. C. and, once cool, combined with 300 ml of water.
The suspension is extracted with dichloromethane. The organic phase
is evaporated and the residue recrystallised from toluene.
[0213] 40.2 g (83% of theoretical) of
3-(6-hydroxyhexoxy-carbonyl)-7-dieth- ylaminocoumarin are obtained
as yellow crystals with a melting point of 85 to 86.degree. C.
[0214] 2. Production of the
3-(6-methacryloxyhexoxycarbonyl)-7-diethylamin- ocoumarin, formula
(26) in the reaction scheme
[0215] 8.36 g (0.08 mol) of methacryloyl chloride (25) are added
dropwise with stirring and cooling with iced water to a solution of
16.3 g (0.045 mol) of
3-(6-hydroxyhexoxycarbonyl)-7-diethylaminocoumarin (24) and 10.0 g
(0.10 mol) of freshly distilled triethylamine in 50 ml of dry
tetrahydrofuran. The reaction mixture is stirred for 5 hours at
room temperature. The reaction mixture is then treated with 200 ml
of water and 200 ml of methylene chloride. Once the phases have
separated, the aqueous phase is extracted twice more with 100 ml
portions of methylene chloride. The combined organic extracts are
washed until neutral and dried with sodium sulphate. Once the
solvent has been removed by vacuum distillation, the residue is
adsorptively filtered through a short silica gel column with
diethyl ether as the mobile solvent. Once the solvent has been
removed by distillation, 17.6 g (92% of theoretical) of a pale
yellow oil are obtained.
[0216] 3. Production of the copolymer according to formula (28) in
the reaction scheme with x=13 mol.%, y=87 mol.%
[0217] A solution of 5.0 g (0.012 mol) of
3-(6-methacryloxy-hexoxycarbonyl- )-7-diethylaminocoumarin (26),
10.0 g (0.078 mol) of n-butyl acrylate (27) and 0.15 g (0.91 mmol)
of AIBN in 80 ml of dry chlorobenzene are degassed under a vacuum
and then stirred for 3 hours at 100.degree. C under nitrogen. The
polymerisation mixture is then reinitiated with 0.15 g (0.91 mmol)
of AIBN in three portions within 3 hours. The solution is then
added dropwise to 100 ml of methanol with stirring and the
suspension is then suction filtered. The crude product is
precipitated twice more from a methylene chloride/methanol mixture.
Yield 12.7 g (85% of theoretical).
Example 2
[0218] 1. Production of N-(m/p-vinylbenzyl)phenothiazine, formula
(31)
[0219] 100 ml of 45% sodium hydroxide solution is added with
stirring at 0.degree. C. to a mixture of 20 g (0.10 mol) of
phenothiazine (29), 18.4 g (0.12 mol) of m/p-vinylbenzyl chloride
(30) and 3.39 g (0.01 mol) of tributylammonium hydrogen sulphite in
100 ml of isobutyl methyl ketone. The reaction mixture is
vigorously stirred for 4 hours at room temperature and then diluted
with 100 ml of water and 150 ml of isobutyl methyl ketone. Once the
phases have separated, the organic solution is washed until neutral
and dried with sodium sulphate. The solution is then adsorptively
filtered through a short silica gel column with diethyl ether as
the mobile solvent. Once the solvent has been removed, 30 g (95% of
theoretical) of a pale yellow oil are obtained.
[0220] 2. Production of the copolymer of the formula (33), with
x=28 mol. %, y=72 mol. %
[0221] 8.0 g (80% of theoretical) of the copolymer (33) may be
produced in a similar manner to the method described in example 1
from 5.0 g (0.016 mol) of N-(m/p-vinylbenzyl)phenothiazine (31),
5.0 g (0.042 mol) of m/p-methylstyrene (32) and a total of 0.15 g
(0.91 mmol) of AIBN with toluene as the solvent.
Example 3
[0222] 1.
4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1',2'-benzim-
idazole is obtained in a similar manner to example 5, section 1
from 4/5-chloro-1,8-naphthoylene-1,2-benzimidazole in an 82% yield
as red-brown crystals of a melting point of 168-169.degree. C.
[0223] 2. Production of
4/5-(N-methyl-N-methacryloxethyl)amino-1,8-naphtho-
ylene-1',2'-benzimidazole, formula (35)
[0224] 6.3 g (90% of theoretical) of the methacrylate (35) are
produced in a similar manner to the process described in example I
starting from 5.83 g (0.017 mol) of
4/5-(N-methyl-N-hydroxyethyl)amino-1,8-naphthoylene-1',2-
'-benzimidazole (34) and 3.24 g (0.031 mol) of methacryloyl
chloride (25). The reaction mixture is worked up by treatment with
water and the resultant suspension is suction filtered. The crude
product is recrystallised from toluene at low temperature.
[0225] 3. Production of the copolymer according to formula (37), in
which x=55 mol. %, y=45 mol. %
[0226] In a similar manner to the method described in example 1,
4.8 g (87% of theoretical) of the copolymer (37) may be produced
from 4.0 g (9.7 mmol) of
4/5-(N-methyl-N-methacryloxyethyl)amino-1,8-naphthoylene-1'-
2'-benzimidazole (35), 1.5 g (7.8 mmol) of N-vinylcarbazole (36)
and a total of 50 mg (0.30 mmol) of AIBN with chlorobenzene as the
solvent.
Example 4
[0227] 1.
N-isoamyl-4-(N-methyl-N-hydroxyethyl)amino-1,8-naphthalamide 53
[0228] is obtained in a similar manner to example 5, section I from
4-chloro-N-isoamyl-1,8-naphthalimide and 2-(methylamino)ethanol in
a 71% yield as yellow to brown crystals of a melting point of
117-118.degree. C.
[0229] 2. Production of the
N-isoamyl-4-(N-methyl-N-m/p-vinylbenzyloxyethy-
l)-amino-1,8-naphthalimide (39)
[0230] A solution of 10.2 g (0.03 mol) of
N-isoamyl-4-(N-methyl-N-hydroxy-- ethyl)amino-1,8-naphthalimide
(38) in 30 ml of dry tetrahydrofuran is added dropwise under
nitrogen at 5.degree. C to a stirred solution of 4.0 g (0.036 mol)
of potassium tert.-butylate in 40 ml of dry tetrahydrofuran. The
mixture is stirred for a further 5 hours at room temperature. 5.0 g
(0.033 mol) of m/p-vinylbenzyl chloride (30) are then added
dropwise at room temperature to the red-brown coloured solution.
After 3 hours, the reaction mixture is treated with 200 ml of water
and 300 ml of methylene chloride. Once the phases have separated,
the aqueous phase is extracted twice more with 100 ml portions of
methylene chloride. The combined organic extracts are washed until
neutral and dried with sodium sulphate. Once the solvent has been
removed by vacuum distillation, the residue is adsorptively
filtered through a short silica gel column with diispropyl ether as
the mobile solvent, wherein an initial run with a small quantity of
mip-vinyl-benzyl chloride is removed. Once the solvent has been
removed by distillation, 9.6 g (70% of theoretical) of a yellow oil
are obtained.
[0231] 3. Production of the homopolymer according to formula
(40)
[0232] In a similar manner to the method described in example 1,
2.3 g (77% of theoretical) of the homopolymer (40) may be produced
from 3.0 g (6.6 mmol) of
N-isoamyl-4-(N'-methyl-N-m/p-vinylbenzyloxyethyl)-amino-1,8-
-naphthalimide (39) and a total of 30 mg (0.18 mmol) of AIBN with
toluene as the solvent.
[0233] 4. Production of the electroluminescent device
[0234] ITO-coated glass (manufactured by Balzers) is cut into
substrates of dimensions 20.times.30 mm and cleaned. Cleaning is
performed in the following sequence of stages:
[0235] 1. 15 minutes rinsing in distilled water and Falterol in
ultrasound bath,
[0236] 2. 2.times.15 minutes' rinsing in ultrasound bath, each time
with fresh distilled water,
[0237] 3. 15 minutes rinsing with ethanol in ultrasound bath,
[0238] 4. 2.times.15 minutes rinsing in ultrasound bath, each time
with fresh acetone,
[0239] 5. drying on lint-free lens cleaning cloths.
[0240] A 1% solution of the polymer according to formula (40)
(example 4) in 1,2-dichloroethane is filtered (0.2 .mu.m filter,
Sartorius). The filtered solution is distributed on the ITO glass
with a spin coater at 1000 rpm. The thickness of the dry film is
110 nm and the R.sub.a value of the surface is 5 nm (Alpha-Step 200
stylus profilometer from Tencor Inst.).
[0241] The film produced in this manner is then provided with Al
electrodes by vapour deposition. To this end, isolated 3 mm
diameter dots of Al are vapour-deposited onto the film using a
perforated mask. A pressure of below 10-5 mbar prevails in the
vapour deposition device (Leybold) during deposition.
[0242] The ITO layer and the Al electrode are connected to an
electrical supply via electrical supply lines. When the voltage is
increased, an electric current flows through the device and the
described layer electroluminesces. Electroluminescence is in the
yellow/green range of the spectrum and occurs with an ITO contact
of positive polarity.
Example 5
[0243] 1. Production of
N-hydroxyethyl-4-piperidinyl-1,8-naphthalimide
[0244] A mixture of 20.0 g (0.073 mol) of
4-chloro-N-hydroxyethyl-1,8-naph- thalimide, 25.8 g (0.30 mol) of
piperidine, 2.0 g of copper(II) sulphate and 200 ml of ethylene
glycol monomethyl ether is refluxed for 2 hours while being
stirred. The solution is cooled to room temperature and then
combined with 1 liter of water. The suspension is extracted with
dichloromethane. The organic phase is evaporated and the residue
recrystallised from toluene. 16 g (68% of theoretical) of brown
crystals of a melting point of 152-153.degree. C. are obtained.
[0245] 2. Production of
N-(m/p-vinylbenyloxyethyl)-4-piperidyl-1,8-naphtha- limide, formula
(42)
[0246] In a similar manner to the method described in example 4,
6.4 g (73% of theoretical) of
N-(m/p-vinylbenzyl-oxyethyl)-4-piperidyl- 1,8-naphthalimide (42)
may be produced from 6.48 g (0.020 mol) of
N-hydroxyethyl-4-piperidyl-1,8-naphthalimide (41) and 3.6 g (0.024
mol) of m/p-vinylbenzyl chloride (30).
[0247] 3. Production of the copolymer of the formula (44) with
x=1.2 mol.% and y=98.8 mol.%
[0248] In a similar manner to the method described in example 1,
2.5 g (79% of theoretical) of the copolymer (44) may be produced
from 0.16 g (0.36 mmol) of
N-(m/p-vinylbenzyloxyethyl)-4-piperidyl-1,8-naphthalimide (42), 3.0
g (28.8 mmol) of styrene (43) and a total of 30 mg (0.18 mmol) of
AIBN with toluene as the solvent. 54
Example 6
[0249] 1. Production of the copolymer of the formula (45) with x=1
mol. % and y=99 mol. %
[0250] In a similar manner to the method described in example 1,
4.15 g (96% of theoretical) of the copolymer (45) may be produced
from 0.10 g (0.22 mmol) of
N-isoamyl-4-(N-methyl-N-m/p-vinylbenzyloxyethyl)amino-1,8--
naphthalimide (39), 4.20 g (21.8 mmol) of N-vinyl-carbazole (36)
and a total of 30 mg (0.18 mmol) of AIBN with toluene as the
solvent. 55
[0251] 2. Production of an electroluminescent device
[0252] Production process as described in example 4. The dry film
thickness of the copolymer of the formula (45) is 144 nm and the
R.sub.a value of the surface is 12 nm. Electroluminescence is in
the yellow-green range of the spectrum.
* * * * *