Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From halogenated hydrocarbon reactant
Reexamination Certificate
2000-09-13
2002-03-26
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From halogenated hydrocarbon reactant
C525S200000, C525S199000, C525S191000, C428S690000, C528S397000
Reexamination Certificate
active
06362310
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to novel 2,7-dihalofluorenes which are substituted at the 9-position and methods for the preparation of such 9-substituted-2,7-dihalofluorenes. This invention further relates to oligomers and polymers of such fluorene compounds. This invention also relates to films and coatings prepared from such fluorenes, oligomers and polymers, processes for preparing such films and coatings, and light-emitting diodes comprised of one or more layers of polymer films at least one of which is derived from the oligomers and polymers of the invention.
Polymers and oligomers of fluorenes substituted by alkyl groups at the 9-carbon position have been reported by Fukuda et al. in
Japanese Journal of Applied Physics
, Vol. 28, pp. L1433-L1435 (1989). Such polymers are disclosed as useful as luminescent materials in the preparation of light-emitting diodes. These polymers were prepared by the Kovacic procedure wherein the appropriate fluorene monomers were treated for several days with a large excess of oxidizing metal salts such as ferric chloride. The structures are represented as poly(fluorene-2,7′-diyl)s. In a later article, Fukuda disclosed that the procedure used resulted in significant crosslinking and mislinking reactions during the polymerization. See Fukuda et al.,
Journal of Polymer Science, Polymer Chemistry Edition
, Vol. 31, pp. 2465-2471 (1993). Brown et al.,
Journal of Polymer Science, Polymer Chemistry Edition
, Vol. 24, pp. 255-267 (1989) disclosed the presence of substantial chemical defects in the polymers formed by oxidative coupling polymerization of aromatic compounds under the reaction conditions of the Kovacic procedure, resulting in non-regioselective coupling and a significant number of polynuclear structures. Thus, it may be expected that oxidative coupling of fluorenes may frequently occur through other, non-desirable, positions, such as the 3,5′- and 3,6′-positions. In addition, it is possible that branching may occur as a result of attachment of more than two other fluorene molecules to a given fluorene molecule, thereby creating multifunctional sites for growth of branches. The presence of such by-products can result in low molecular weight oligomers and polymers with low degrees of polymerization. Such materials demonstrate a high polydispersity and low glass transition temperatures, properties that are detrimental to film quality. Indeed, Fukuda's polyfluorenes prepared by oxidative coupling have high polydispersity and low glass transition temperatures. Furthermore, the oxidative coupling process is very slow.
SUMMARY OF THE INVENTION
In one aspect, this invention is a compound of the formula:
and compounds of the formulas:
wherein R
1
is independently in each occurrence C
1-20
hydrocarbyl or C
1-20
hydrocarbyl containing one or more S, N, O, P or Si atoms, C
4-16
hydrocarbyl carbonyloxy, C
4-16
aryl(trialkylsiloxy) or both R
1
may form with the 9-carbon on the fluorene ring a C
5-20
ring structure or a C
4-20
ring structure containing one or more heteroatoms of S, N or O;
R
2
is independently in each occurrence C
1-20
hydrocarbyl, C
1-20
hydrocarbyloxy, C
1-20
thioether, C
1-20
hydrocarbylcarbonyloxy or cyano;
R
3
is independently in each occurrence C
1-20
hydrocarbyl or C
1-20
hydrocarbyl substituted with di(C
1-20
alkyl)amino, C
1-20
hydrocarbyloxy or C
1-20
hydrocarbyl or tri(C
1-10
alkyl)siloxy;
a is independently in each occurrence 0 or 1;
X is independently in each occurrence a halogen moiety; and
Z is independently in each occurrence —B(OH)
2
, —B(OR
4
)
2
or
wherein R
4
is independently in each occurrence a C
1-10
alkyl group and R
5
is independently in each occurrence a C
2-10
alkylene group.
In a second aspect, this invention is a composition containing polymers which have at least ten groups of the formula:
and a polydispersity of less than 5.
In a third aspect, this invention is a composition containing polymers, wherein an average of at least 10 percent by weight of each polymer is of the formula:
In a fourth aspect, this invention is a process for preparing polymers having at least three fluorene groups in it backbone, which comprises heating compounds of the formulas:
or a mixture thereof, optionally in the presence of other compounds containing aryl halide groups, under reaction conditions sufficient to form a polymers having at least three groups of Formula (IV) or (V), or a combination thereof.
In a fifth aspect, this invention is a process for preparing polymers having at least three fluorene groups in its backbone, which comprises heating a mixture of compounds of the formulas:
X—A—X (VII)
and
Z—A—Z (VIII);
wherein A is independently in each occurrence a conjugated group, provided that A, in at least three occurrences, is a unit of Formula (IV) or (V); under reaction conditions sufficient to form the corresponding alternating copolymer.
In a sixth aspect, this invention is a film prepared from the polymers of this invention.
In a seventh aspect, this invention is a light-emitting diode comprised of one or more layers of polymer films, at least one of which is derived from the oligomers and polymers of the invention.
The compounds of the invention are useful in the preparation of the polymers of the second and third aspects of the invention. The polymers and oligomers of the invention do not contain a significant amount of misformed polynuclear structures or bonding through positions other than the 2- and 7′-positions, and they can be converted into films that are useful as light-emitting or carrier transport layers in light-emitting diodes. The polymers have good solubility characteristics and relatively high glass transition temperatures, which facilitates their fabrication into coatings and films that are relatively thin, thermally stable, and relatively free of defects. If the polymers contain end groups which are capable of being crosslinked, the crosslinking of such groups after the films or coating is formed increases the solvent resistance thereof, which is beneficial in applications wherein one or more solvent-based layers of material are deposited thereon. These and other advantages of the invention will be apparent from the description which follows.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Preferred Substituents
“Hydrocarbyl” as used herein shall mean any organic moiety containing only hydrogen and carbon unless specified otherwise, and may include aromatic, aliphatic, cycloaliphatic and moieties containing two or more of aliphatic, cycloaliphatic and aromatic moieties.
R
1
is preferably C
1-12
alkyl, C
6-10
aryl or alkyl-substituted aryl, C
4-16
hydrocarbylcarbonyloxy, (C
9-10
aryl)trialkylsiloxy, a poly(alkyleneoxy) group having a terminal hydroxy, C
1-10
hydrocarbyloxy, or a group of the formula: —(CH
2
)
b
CO
2
R
6
, —(CH
2
)
b
SO
3
R
6
, —(CH
2
)
b
N(R
1
)
2
, —(CH
2
)
b
N
+
(R
1
)3, or —(CH
2
)
b
—CN, wherein R
6
is a C
1-6
hydrocarbyl, H, Li
+
, Na
+
, or K
+
. In the embodiment where the two R
1
form a ring structure with the 9-carbon atom of the fluorene ring, the ring structure formed is preferably a C
5-20
ring structure or a C
1-20
ring structure containing one or more heteroatoms of S, N or O; even more preferably a C
5-10
aliphatic ring or a C
4-10
aliphatic ring containing one or more of S or O; and most preferably a C
5-10
cycloalkyl or C
4-10
cycloalkyl containing oxygen.
The fluorene groups of the compounds of Formulas (I), (II), (III), and (IV) as well as the fluorene groups of other compounds used in the processes described herein can further be substituted at the 3-, 4-, 5- or 6-positions with substituents (R
2
) which do not adversely affect the formation of oligomers of polymers therefrom, nor the subsequent processing of the oligomers or polymers for their intended uses. Preferably, R
2
is C
1-4
alkoxy, phenoxy, C
1-4
alkyl, phenyl or cyano. “a” is preferably 0. R
3
is preferably a C
1-20
straight- or branched-chain aliph
Bernius Mark T.
Inbasekaran Michael
Roof Gordon R.
Shiang William R.
Woo Edmund P.
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