2,7-aryl-9-substituted fluorenes and 9-substituted fluorene...

Details 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene... 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene...

2001-01-05

2003-07-15

Truong, Duc (Department: 1711)

Synthetic resins or natural rubbers -- part of the class 520 ser

Synthetic resins

From halogenated hydrocarbon reactant

C528S401000, C521S082000, C428S421000, C427S407100

Reexamination Certificate

active

06593450

ABSTRACT:

SUMMARY OF THE INVENTION
The invention relates to 2,7-substituted-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers. The fluorenes, oligomers and polymers are substituted at the 9-position with two hydrocarbyl moieties which may optionally contain one or more of sulfur, nitrogen, oxygen, phosphorous or silicon heteroatoms; a C
5-20
ring structure formed with the 9-carbon on the fluorene ring or a C
4-20
ring structure formed with the 9-carbon containing one or more heteroatoms of sulfur, nitrogen or oxygen; or a hydrocarbylidene moiety. In one embodiment, the fluorenes are substituted at the 2- and 7-positions with aryl moieties which may further be substituted with moieties which are capable of crosslinking or chain extension or a trialkylsiloxy moiety. The fluorene polymers and oligomers may be substituted at the 2- and 7′-positions. The monomer units of the fluorene oligomers and polymers are bound to one another at the 2- and 7′-positions. The 2,7′-aryl-9-substituted fluorene oligomers and polymers may be further reacted with one another to form higher molecular weight polymers by causing the optional moieties on the terminal 2,7′-aryl moieties, which are capable of crosslinking or chain extension, to undergo chain extension or crosslinking.
In another embodiment, the invention relates to 9-substituted fluorene oligomers and polymers which are terminated at the terminal 2- and 7′-positions with a hydrogen or halogen wherein the oligomers and polymers have weight average molecular weights of about 10,000 or greater and polydispersities of about 3.0 or less.
The polymers and oligomers do not contain a significant amount of misformed polynuclear structures or bonding through positions other than the 2- and 7′-positions. The fluorene polynuclear rings can further be substituted at the 3-, 4-, 5- or 6-positions with substituents which do not adversely affect the properties of the 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers and polymers or subsequent processing of such materials for their intended uses.
Another embodiment of the invention involves a process for the preparation of 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers. The process comprises contacting one or more 2,7-dihalo-9-substituted fluorenes with a haloaromatic compound or haloaromatic compounds, being further substituted with a reactive group capable of crosslinking or chain extension or a trialkylsiloxy moiety, in the presence of a catalytic amount of a divalent nickel salt, at least a stoichiometric amount of zinc powder and a trihydrocarbylphosphine in a polar solvent, under conditions such that a 2,7-aryl-9-substituted fluorene or a 9-substituted fluorene oligomer or polymer is prepared. The 9-substituted fluorene oligomers and polymers terminated at the terminal 2- and 7′-positions with hydrogen or a halogen are prepared by the process described above in the absence of a haloaromatic compound.
In another embodiment, the invention comprises films or coatings comprising 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers or polymers. Such films may be prepared by applying a composition comprising the 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers or polymers to a substrate and exposing the applied composition to conditions such that a film is prepared.
Further, the 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers or polymers may be B-staged, partially crosslinked or chain extended, to prepare a composition which may be used to prepare coatings or films as described hereinbefore.
The 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers or polymers demonstrate fluorescence, high glass transition temperatures or liquid-crystalline properties and facilitate the preparation of films which have high heat resistance and solvent resistance. The 9-substituted fluorene oligomers and polymers demonstrate low polydispersities. Polymers based on 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers which have high molecular weights can be prepared if desired. The 2,7-aryl-9-substituted fluorenes or 9-substituted fluorene oligomers or polymers may be used to prepare films or coatings which may be used in polymeric light-emitting diodes, preferably as the emitting layer. Additionally, such films or coatings may be used as protective layers in electronic devices or as fluorescent coatings in a wide variety of uses.
DETAILED DESCRIPTION OF THE INVENTION
In a preferred embodiment, the 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers or polymers correspond to Formula 1,
wherein substantially all of the monomer units are connected to end moieties or other monomer units through the 2- and 7-carbon atoms.
In Formula 1, E is halogen, hydrogen or an aryl moiety which may optionally be substituted with a reactive group capable of undergoing chain extension or crosslinking or a trialkylsiloxy. As used herein, a reactive group capable of undergoing chain extension or crosslinking refers to any group which is capable of reacting with another of the same group or another group so as to form a link to prepare oligomers or polymers. Preferably, such reactive group is a hydroxy, glycidyl ether, acrylate ester, methacrylate ester, ethenyl, ethynyl, maleimide, nadimide, trifluorovinyl ether moiety or a cyclobutene moiety fused to one of the aromatic rings. E is preferably halogen, aryl or aryl substituted with a reactive group capable of undergoing chain extension or crosslinking or a trialkylsiloxy moiety. E is even more preferably aryl or aryl substituted with a reactive group capable of undergoing chain extension or crosslinking or a trialkylsiloxy. E is most preferably phenol, a cyano-substituted phenyl or a benzylcyclobutene moiety.
R
1
is independently in each occurrence C
1-20
hydrocarbyl or C
1-20
hydrocarbyl containing one or more heteroatoms of S, N, O, P or Si or both of R
1
together with the 9-carbon on the fluorene may form a C
5-20
ring structure or a C
4-20
ring structure containing one or more heteroatoms of S, N, or O. Preferably, R
1
is C
1-12
alkyl, C
6-10
aryl or alkyl-substituted aryl, C
4-16
hydrocarbyl carboxylate or (C
9-16
aryl)trialkylsiloxy moiety. 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
straight- or branched-ring structure or a C
4-20
straight- or branched-chain 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.
R
2
is independently in each occurrence C
1-20
hydrocarbyl, C
1-20
hydrocarbyloxy, C
1-20
thioether, C
1-20
hydrocarbyloxycarbonyl, C
1-20
hydrocarbylcarbonyloxy or cyano. R
2
is preferably C
1-12
alkyl, C
6-10
aryl or alkyl-substituted aryl, C
6-10
aryloxy or alkyl-substituted aryloxy, C
1-12
alkoxycarbonyl, C
6-10
aryloxycarbonyl or alkyl-substituted aryloxycarbonyl, C
1-12
alkoxy, C
1-12
alkylcarbonyloxy, C
6-10
arylcarbonyloxy or alkyl-substituted arylcarbonyloxy, cyano or C
1-20
alkylthio. Even more preferably, R
2
is C
1-4
alkoxy, phenoxy, C
1-4
alkyl, phenyl 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. R
3
is preferably a C
1-20
straight- or branched-chain aliphatic, a C
1-20
straight- or branched-chain aliphatic containing one or more cycloaliphatic rings or a phenyl moiety and such moiety may optionally be substituted with a di(C
1-20
alkyl)amino, C
1-20
hydrocarbyl, tri(C
1-10
alkyl)siloxy or C
1-20
hydrocarbyloxy moiety. R
3
is more preferably a C
3-10
aliphatic, a C
3-10
aliphatic containing one or more cycloaliphatic moieties, pheny

Affiliated with

Also associated with

Rating

2,7-aryl-9-substituted fluorenes and 9-substituted fluorene... does not yet have a rating. At this time, there are no reviews or comments for this patent.

If you have personal experience with 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene... will most certainly appreciate the feedback.

Rate now

Comments { 0 }

Profile ID: LFUS-PAI-O-3038565