Organic compounds -- part of the class 532-570 series – Organic compounds – Halogen containing
Reexamination Certificate
2000-05-09
2002-04-30
Yoon, Tae H. (Department: 1714)
Organic compounds -- part of the class 532-570 series
Organic compounds
Halogen containing
C570S183000, C570S190000, C558S046000
Reexamination Certificate
active
06380445
ABSTRACT:
The present invention relates to unsubstituted and substituted poly(9,9′-spirobisfluorenes); a process for their preparation; a composition comprising a support material and a layer of an unsubstituted or substituted poly(9,9′-spirobisfluorene), which may, if desired, further comprise a luminophore; a composition comprising an unsubstituted or substituted poly(9,9′-spirobisfluorene) which comprises a luminophore; and the use of the compositions or the poly(9,9′-spirobisfluorenes) as fluorophores, for example in light-emitting diodes or electrodes in display applications, and also 2,2′-dihalo-7,7′-disubstituted 9,9′-bisfluorenes.
In recent times, materials which emit fluorescent radiation have attracted greatly increased interest for display elements or photodiodes. In Adv. Mater. 1994, 6, No. 3, pages 190 to 198, J. M. Tour describes polyphenylenes which are known to emit blue fluorescent light. The good mechanical and thermal properties of the polyphenylenes are known. The insolubility in organic solvents and the associated unsatisfactory processibility and also the instability of doped polyphenylenes greatly impairs commercial utilization. There is a great need for blue-fluorescing and processible materials based on aromatic hydrocarbons, which materials have excellent thermal and mechanical properties (for example thermal stabilities above 200° C.); the polymers should be able to be prepared easily and, in particular, the targeted preparation of defined polymers should be possible. Furthermore, it is desirable for the polymers to be suitable as matrix for the incorporation of small amounts of different fluorophores in order to obtain fluorescent emissions over the entire visible spectrum.
It has now surprisingly been found that 9,9′-bisfluorenes can be polymerized to give blue-fluorescing polymers which are soluble in many solvents and are therefore also readily processible, for example by means of customary coating processes. The polymers have excellent thermal and mechanical stabilities and are excellent matrix systems for the incorporation of molecular fluorophores which can be used in fluorescent displays and in electroluminescent displays.
The invention provides, firstly, soluble poly(bis-9,9′-fluorenes) comprising identical or different structural repeating units of the formula I,
where
the two R
1
s are, independently of one another, H, C
1
-C
18
alkyl, C
6
-C
14
aryl, C
7
-C
15
aralkyl, C
1
-C
18
alkoxy, R
2
—(O—C
n
H
2n
)
m
—O—, C
1
-C
18
alkylthio, C
1
-C
18
dialkylamino, —C(O)OH, —C(O)O—C
1
-C
18
alkyl, —C(O)—N(C
1
-C
18
alkyl)
2
, —SO
3
H, —SO
3
—C
1
-C
18
alkyl, —SO
2
—N(C
1
-C
18
alkyl)
2
, C
1
-C
17
alkyl -C(O)—O— or C
1
-C
17
alkyl-C(O)—, R
2
is H or C
1
-C
12
alkyl, n is from 2 to 6 and m is from 1 to 12.
The alkyl groups in alkyl, alkoxy, alkylthio, diaminoalkyl, carboxylic ester or sulfonic ester, carboxamide or sulfonamide, alkyl-CO
2
— and alkyl-C(O)— radicals R
1
can be linear or branched and preferably contain from 1 to 12, particularly preferably from 1 to 8, C atoms. Some examples of alkyl are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl.
Aryl radicals R
1
preferably contain from 6 to 10 C atoms. Some examples are naphthyl, biphenylyl and, particularly preferably, phenyl.
Aralkyl radicals R
1
preferably contain from 7 to 12 C atoms and the alkylene group in the aralkyl radical preferably contains 1 or 2 C atoms. A preferred example is benzyl and also phenylethyl.
Halogen atoms R
1
are preferably F, Cl or Br.
Alkyl radicals R
2
preferably contain from 1 to 8 and particularly preferably from 1 to 4 C atoms. They can be linear or branched. Some examples are methyl, ethyl, n-propyl and n-butyl.
In the radical R
2
—(O—C
n
H
2n
)
m
—O—, n is preferably from 2 to 4, particularly preferably 2 or 3.
In the radical R
2
—(O—C
n
H
2n
)
m
—O—, m is preferably from 1 to 8, particularly preferably from 1 to 6.
In a preferred embodiment of the invention, the two R
1
s in the polymers of the formula I are identical radicals as defined above.
In a preferred embodiment of the invention, each R
1
in the polymers of the formula I is H, C
1
-C
12
alkyl-C(O)— or C
1
-C
12
alkoxy.
The polymers of the invention can be crosslinked, which depends essentially on the method of preparation. The degree of crosslinking can be so high that a virtually only crosslinked low molecular weight polymer, which is, however, still soluble, is obtained. Such polymers comprise structural units of the formula Ia, Ib or both structural units,
where R
1
is as defined above.
Structural units of the formula Ia are formed from monosubstituted 9,9′-bisfluorenes and structural units of the formula Ib are formed from unsubstituted 9,9′-bisfluorene.
The degree of polymerization (number of structural repeating units) can be from 2 to 100, more preferably from 3 to 50, even more preferably from 3 to 40 and particularly preferably from 5 to 30. The term polymers thus also encompasses oligomers. In general, the polymers of the invention comprise polymer chains having different degrees of polymerization (chain lengths).
The polymers of the invention can be prepared by methods known per se and by methods analogous to those described in the literature.
The invention further provides a process for preparing poly(bis-9,9′-fluorenes) comprising identical or different structural repeating units of the formula I,
and, if desired, identical or different structural units of the formulae
where R
1
is as defined above, which process comprises cationically-oxidatively polymerizing a) at least one halogen-free 9,9′-bisfluorene of the formula II,
where R
1
is as defined above,
in the presence of an inert solvent.
Examples of suitable solvents are N,N-disubstituted carboxamides and N-substituted lactams (dimethylformamide, N-methylpyrrolidone), esters (butyl acetate), ethers (dibutyl ether), sulfoxides (dimethyl sulfoxide), sulfones (tetramethylene sulfone), aliphatic and aromatic hydrocarbons (toluene, xylene), halogenated or nitrated aliphatic and aromatic hydrocarbons (carbon tetrachloride, tetrachloroethane) and carbon disulfide.
The cationic-oxidative polymerization has been described for benzene by P. Kovacic et al. in Tetrahedron Letters No. 11, pages 467 to 469 (1962) and can also be employed analogously for the polymerization of 9,9′-spirobisfluorenes.
The polymerization is carried out, for example, using oxidizing Lewis acids such as FeCl
3
or using Lewis acids, mainly metal halides such as AlCl
3
, AlBr
3
, BF
3
or BCl
3
, in combination with an oxidizing agent such as a metal compound having a relatively high oxidation state. Use is frequently made of CuCl
2
. Oxidizing agents such as KMnO
4
, Fe
+3
salts and benzoquinone derivatives such as tetrachlorobenzoquinone can also be used. It is also possible to employ electrochemical oxidation in a suitable organic solvent for effecting the polymerization.
The molar ratio of spirobisfluorene to catalyst or Lewis acid can be from 1:0.2 to 1:2, preferably from 1:0.4 to 1:1.5 and particularly preferably from 1:0.5 to 1:1.2. The molar ratio of Lewis acid to oxidizing agent can be, for example, from 1:0.2 to 1:1, preferably from 1:0.3 to 1:0.8 and particularly preferably from 1:0.4 to 1:0.6.
The reaction temperature is preferably from 200° C. to 200° C., more preferably from 20° C. to 150° C., particularly preferably from 20° C. to 100° C. and most particularly preferably from 30° C. to 80° C.
The reaction can be carried out, for example, by adding the catalyst to the dissolved spirobisfluorene, if desired heating the mixture and allowing it to react for some time (for example up to 24 hours) while stirring. The polymer formed can then be precipitated and filtered off or the solvent can be removed. To remove the Lewis acids/oxidizing agents, the residues can be washed with water, dried and then treated with solvents such as methylene chloride
Rietz Ralf-Roman
Wernet Wolfgang
Lyon & Lyon LLP
Vantico Inc.
Yoon Tae H.
LandOfFree
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