Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – From halogenated hydrocarbon reactant
Reexamination Certificate
1999-05-21
2001-07-03
Truong, Duc (Department: 1711)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
From halogenated hydrocarbon reactant
C528S407000, C521S082000, C428S421000, C427S407100
Reexamination Certificate
active
06255447
ABSTRACT:
This invention relates to 2,7-aryl-9-substituted fluorenes and 9-substituted fluorene oligomers and polymers prepared therefrom. The invention further relates to processes for the preparation of such fluorenes, oligomers and polymers. The invention also relates to films and coatings prepared from such fluorenes, oligomers and polymers and processes for preparing such films and coatings.
Polymers and oligomers of fluorenes substituted by alkyl groups at the 9-carbon position have been reported by Fukuda et al.,
Japanese Journal of Applied Physics,
Vol. 28, pp. L1433-L1435 (1989). 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′-diyls). In a later article, Fukuda discloses 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) disclose the presence of substantial chemical defects under the reaction conditions of the Kovacic procedure, in particular, a significant number of polynuclear structures and substitutions at positions other than the 2,7-position result. In addition, the oxidative polymerization is not regiospecific and the coupling of fluorenes through other positions, such as the 3,5′- and 3,6′-positions, frequently occurs. 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 trifunctional materials which could crosslink during the preparation process. The presence of such by-products can result in low molecular weight oligomers and polymers with low degrees of polymerization. Further, such materials demonstrate a high polydispersity and low glass transition temperatures. Such problems result in poor film formation properties and poor properties in any films prepared in that such films may demonstrate unacceptable mechanical properties and low heat resistance. Furthermore, the oxidative coupling process is very slow.
Fukuda et al., supra, disclose that the poly(9-alkylfluorenes-2,7′-diyls) may be used to prepare polymeric light-emitting diode devices. The materials prepared according to the teachings of Fukuda demonstrate low heat resistance and a low degree of polymerization. Thus, light-emitting diode devices using such materials would demonstrate inferior durability.
In order to successfully prepare such materials on a commercial scale, a faster and more efficient process for the preparation of such materials is needed. What is further needed are 9-substituted fluorenes which enable the preparation of polymers having low polydispersity, high molecular weights and degrees of polymerization. Further, what is needed are such materials which can readily prepare films which have high solvent and heat resistance. What is further needed are such materials which have such properties and continue to demonstrate good fluorescence ability. What is further needed is a procedure for the preparation of such materials. What is also needed are procedures for preparing high heat resistant and solvent resistant films from such materials.
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
5-2
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
Inbasekaran Michael
Roof Gordon R.
Shiang William R.
Woo Edmund P.
The Dow Chemical Company
Truong Duc
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