Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From phosphorus-containing reactant
Reexamination Certificate
1999-08-13
2001-11-13
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From phosphorus-containing reactant
C528S223000, C528S242000, C428S640000, C428S524000, C428S917000
Reexamination Certificate
active
06316591
ABSTRACT:
There is a great industrial need for large-area solid-state light sources for a series of applications, predominantly in the field of display elements, VDU technology and lighting technology. The demands made of these light sources can at present not be met fully satisfactorily by any of the existing technologies.
As alternatives to conventional display and lighting elements, e.g. incandescent lamps, gas discharge lamps and non-self-illuminating liquid crystal display elements, use has been made for some time of electroluminescence (EL) materials and devices such as light-emitting diodes (LEDs).
WO 90/13148 and EP-A 0 443 861 describe electroluminescence devices comprising a film of a conjugated polymer as light-emitting layer (semiconductor layer). Such devices offer numerous advantages such as the opportunity to produce large-area, flexible displays simply and inexpensively. In contrast to liquid crystal displays, electroluminescence displays are self-illuminating and therefore require no additional backward illumination source.
According to WO 90/13148, poly(p-phenylene-vinylene) (PPV) is used as polymeric material for the light-emitting layer and it is proposed that the phenyl group in such a material be substituted or be replaced by other carbocyclic or heterocyclic aromatic ring systems.
Poly(p-phenylene-vinylene) derivatives for use as electroluminescence materials are also known from, for example, WO/A 96/10617 and PCT/EP 96/01066.
Although good results have been achieved with such materials, the property profile of these polymers is still capable of a great deal of improvement.
Since, in addition, the development of electroluminescence materials, particularly those based on polymers, can in no way be regarded as being concluded, the manufacturers of lighting and display devices are still interested in a wide variety of electroluminescence materials for such devices.
One reason for this is that only the interaction of the electroluminescence material with the other components of the devices allows conclusions to be drawn as to the suitability of the electroluminescence material.
It is therefore an object of the present invention to provide new electroluminescence materials which are suitable, when used in lighting or display devices, for improving the property profile of these devices.
It has now surprisingly been found that certain ordered poly(arylene-vinylene) terpolymers are particularly suitable as electroluminescence materials.
The invention accordingly provides a terpolymer comprising repeating units of the formula (I),
where the symbols have the following meanings:
Ar
1
, Ar
2
, Ar
3
are identical or different and are monocyclic or polycyclic, substituted or unsubstituted aryl or heteroaryl groups which may be linked via one or more, preferably one, bridge or be fused and preferably have from 2 to 100, particularly preferably from 2 to 50, very particularly preferably from 2 to 20, carbon atoms;
R
1
, R
2
, R
3
, R
4
, R
5
, R
6
, R
7
R
8
are identical or different and are each H or a hydrocarbon radical having from 1 to 22 carbon atoms which may be substituted, preferably by F, and may also contain heteroatoms, preferably O;
with the proviso that ═CR
1
—Ar
1
—CR
2
═, ═CR
3
—Ar
2
—CR
4
═ and CR
5
—Ar
3
—CR
6
═ are each different from one another.
For the purposes of the invention, different means that they are at least regioisomers or stereoisomers or the radicals Ar
1
, Ar
2
, Ar
3
at least have different substitution patterns.
Terpolymers in the context of the invention are ternary copolymers.
The polymers of the invention generally have from 2 to 1000, preferably from 3 to 500, particularly preferably from 4 to 300, repeating units, preferably of the formula (I).
Preference is given to polymers consisting of repeating units of the formula (I).
Preference is also given to polymers comprising repeating units of the formula (I) in which R
7
and R
8
are, pairwise, identical to R
3
and R
4
respectively.
Preference is likewise given to polymers comprising repeating units of the formula (I) in which the symbols have the following meanings:
Ar
1
, Ar
2
, Ar
3
are identical or different and are
where
Ar
1
, Ar
2
, Ar
3
may be substituted by one or more identical or different radicals R
9
-R
14
as substituents
and the above proviso applies;
m is from 1 to 20, preferably 1, 2 or 3, particularly preferably 1;
X, Z are identical or different and are each a single bond, —O—, —S—, —SO—, —SO
2
—, —CO—, —CO
9
R
10
—, —CR
11
═CR
12
—, —CHR
13
—, —CHR
14
—, —NR
15
—;
Y is —O—, —S— or —NR
15
—;
R
9
-R
14
are identical or different and are each H, —CF
3
, —Ph, —O—Ph, —S—Ph, —SO—Ph, —SO
2
—Ph, F, Cl, Br, I, —CN or an alkyl group having from 1 to 22, preferably from 1 to 12, carbon atoms, where one or two nonadjacent CH
2
groups may also be replaced by —O—, —S—, —CO—, —CO—O—, —O—OC— or —Si(CH
3
)
2
—;
R
15
is as defined for R
1
and may be identical to or different from R
1
;
n is 0, 1 or 2, preferably 0 or 1, particularly preferably 0.
Particular preference is given to polymers comprising repeating units of the formula (I) in which the symbols and indices have the following meanings:
Ar
1
, Ar
2
, Ar
3
are identical or different and are
where the above proviso applies;
m is from 1 to 20, preferably 1, 2 or 3, particularly preferably 1;
R
16
-R
23
are identical or different and are each F, Cl, C
6
-C
10
-aryl, a straight-chain or branched alkyl or alkoxy group having from 1 to 22, preferably from 1 to 12, carbon atoms and R
19-22
can also be H.
Very particular preference is given to the case where
Ar
1
, Ar
2
and Ar
3
are identical or different and are
where the above proviso applies and
R
24
, R
25
are identical or different and are straight-chain or branched alkyl groups having from 1 to 22, preferably from 1 to 12, carbon atoms.
In the polymers of the invention, it is preferred that:
R
1
═R
2
, R
3
═R
4
═R
7
═R
8
, R
5
═R
6
.
The polymers of the invention can be prepared by reacting a dicarbonyl compound of the formula (II),
with at least two equivalents of an organophosphorus compound of the formula (III),
in the presence of a basic condensation agent, i.e. a base, and polymerizing the predominant intermediate of the formula (IV)
with a dicarbonyl compound of the formula (V)
in the presence of a base to give a polymer according to the invention comprising repeating units of the formula (I), where the symbols have the same meanings as in the formula (I) and Z are alkoxy radicals having from 1 to 16 carbon atoms, preferably ethoxy, or aryl radicals having from 6 to 10 carbon atoms, preferably phenyl.
This process is likewise a subject matter of the invention.
Similarly, it is naturally possible and subject matter of the invention to start from an organophosphorus compound of the formula (III) and react this with two equivalents of a carbonyl compound of the formula (II), which leads to an intermediate of the formula (IVa) which correspondingly bears carbonyl end groups and is polymerized with a further organophosphorus compound of the formula (IIIa) (with R
5
and R
6
instead of R
3
and R
4
).
The condensation steps are carried out by action of a base, preferably a strong base, for example an alkoxide such as an alkali metal alkoxide or a hydride such as sodium hydride, preferably potassium tert-butoxide.
The polycondensation is advantageously carried out by initially charging a mixture of the starting components in a solvent and, under an inert gas atmosphere and while stirring, introducing preferably at least molar amounts of condensation agent in solution or suspension.
In another variant of the procedure, it is also possible for the condensation agent to be initially charged alone or together with the diketone (II) or (V) in a solvent and for the organophosphorus compound to be added. As solvents, preference is given to using hydrocarbons, particularly preferably aromatic hydrocarbons such as benzene, toluene or xylenes, or polar aprotic solvents, preferably amides such as N-methylpyrrolido
Hartmann Annett
Horhold Hans-Heinrich
Kreuder Willi
Rost Henning
Aventis Research & Technologies GmbH & Co. KG
Frommer & Lawrence & Haug LLP
Truong Duc
LandOfFree
Ordered poly(arylene-vinylene) terpolymers, method for the... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Ordered poly(arylene-vinylene) terpolymers, method for the..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Ordered poly(arylene-vinylene) terpolymers, method for the... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2586961