Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2001-09-07
2004-02-10
Keys, Rosalynd (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S636000, C568S637000
Reexamination Certificate
active
06689919
ABSTRACT:
TECHNICAL FIELD
The present invention relates to catalysts for the oxidative polymerization of fluorophenols and a method for the oxidative polymerization of fluorophenols wherein such catalysts are used. More particularly, this invention relates to catalysts for the oxidative polymerization of fluorophenols useful for the synthesis of engineering plastics, such as fluoropolyarylene ether, with excellent heat resistance and flame resistance, as well as small friction factor, and a method for the oxidative polymerization of fluorophenols wherein such catalysts are used.
Further, the present invention relates to poly(oxyfluorophenylene) compounds. More particularly, the present invention relates to soluble poly(oxyfluorophenylene) compounds with excellent heat resistance, membrane-formability and chemical stability.
BACKGROUND ART
Polyarylene ethers are known as engineering plastics having characteristics such as excellent heat resistance, mechanical strength, drug resistance, dimensional stability, electric performance, and workability, and are used in various industrial fields, such as mechanical parts, gas separating membranes, conductive resins, and functional rubbers.
In addition, they are also known as being prepared by the oxidative coupling of for example, 2,6-dimethylphenol, using various copper-amine complex catalyst and oxygen.
More specifically, polyarylene ether, particularly poly (2,6-dimethyl-1,4-arylene)ether is prepared by the oxidative coupling of 2,6-dimethylphenols using a tertiary amine (for example, pyridine, tetramethylene diamine, triethylamine, etc.) and a copper (I) salt (e.g. cuprous chloride) which is capable of forming a complex therewith, as a catalyst. This reaction is a less expensive reaction system, since it uses dissolved oxygen as the oxidizing agent and produces water. However, for phenols (such as 2,6-difluorophenol), which contain an electron withdrawing substituent, due to its high oxidation potential, oxidation by copper complex catalysts is difficult, and reports on polymers obtained by oxidative polymerization are scarce. The only method reported so far on the oxidative polymerization of 2,6-difluorophenol involves the use of oxidase as a catalyst (Ryohei Ikeda, Hozumi Tanaka, Hiroshi Uyama and Shiro Kobayashi, 76
th
Spring Annual Meeting of Japan Chemical Society) However, the degree of polymerization for the polymer product is extremely low, because enzymatic reactions require the use of water as the solvent, making the method unpractical.
Thus, the objective of the present invention is to provide a novel catalyst useful for the oxidative polymerization of fluorophenols, which does not require the use of water as solvent, and enables the polymerization of fluoropolyarylene ether in high degree, and to provide a novel method of the oxidative polymerization of fluorophenols.
Further, another objective of the present invention is to provide poly(oxyfluorophenylene) compounds which have so far been deemed impossible to synthesize.
DISCLOSURE OF THE INVENTION
In order to overcome the above objectives, the present invention firstly provides, a copper complex catalyst for the oxidative polymerization of fluorophenols that contain at least one hydrogen atom as well as a fluorine atom bonded to the carbon atoms constituting the benzene ring, which has an oxidation potential in the range of −1V to 2V.
Further, the invention of the present application secondly provides the above copper complex catalysts for the oxidative polymerization of fluorophenols, wherein the ligand is at least one compound chosen from aliphatic cyclic amines and alkylene cross-linked compounds thereof. The invention thirdly provides a copper complex catalyst for the oxidative polymerization of fluorophenols, wherein the ligand is at least one compound chosen from alkylenediamines and alkylene cross-linked compounds thereof. Fourthly, the present invention provides the copper complex catalysts for the oxidative polymerization of fluorophenols according to any one of claims 1 to 3, wherein the complex is a mononuclear or a binuclear copper complex.
Further, the invention of the present application fifthly provides a method for the oxidative polymerization of fluorophenols that contain at least one hydrogen atom as well as fluorine atoms bonded to the carbon atoms constituting the benzene ring, wherein the copper complex catalyst according to any one of the above-described first to fourth inventions is used. The present invention sixthly provides a method for the oxidative polymerization of fluorophenols represented by the following formula (II):
(wherein R
1
, R
2
, R
3
and R
4
each represents a hydrogen atom, a hydrocarbon group or a fluorine atom, at least one of R
1
, R
2
, R
3
and R
4
being a fluorine atom), according to the aforesaid fifth invention.
The invention or the present application seventhly provides a poly(oxyfluorophenylene) compound represented by the following formula (I):
wherein R
1
, R
2
, R
3
and R
4
each represents a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom, and n is an integer larger than or equal to 2, which represents the degree of polymerization.
Furthermore, the invention of the present application eighthly provides the above-described poly(oxyfluorophenylene) compounds prepared by the oxidative polymerization of the fluorophenol represented by the following formula (II):
wherein R
1
, R
2
, R
3
and R
4
each represent a hydrogen atom or a fluorine atom, at least one of which is a fluorine atom. The invention of the present application ninthly provides a poly(oxyfluorophenylene) compound obtained by the re-polymerization of the oligomers of the seventh or eighth inventions.
The invention of the present application tenthly provides poly(oxyfluoro-1,4-phenylene-cooxy-1,4-arylene) compounds obtained by the oxidative polymerization of the fluorophenols represented by formula (II) of the eighth invention, with substituted phenols.
Further, the present invention eleventhly provides a method for producing poly(oxyphenylene) compounds, wherein the method for the oxidative polymerization of the eighth invention is performed in the presence of a copper complex catalyst selected from the group consisting of a mononuclear copper complex containing an aliphatic cyclic amine-type multidentate ligand, a mononuclear copper complex containing an alkylenediamine ligand and a binuclear copper complex containing either an aliphatic cyclic amine-type multidentate ligand or a binuclear ligand wherein an alkylenediamine ligand is linked by an alkyl chain.
Furthermore, a method to produce poly(oxyfluoro-1,4-phenylene-cooxy-1,4-arylene) by the oxidative polymerization method according to the ninth invention, in the presence of a catalyst selected from the group consisting of a mononuclear copper complex containing an aliphatic cyclic amine-type multidentate ligand, a mononuclear copper complex containing an alkylenediamine ligand and a binuclear copper complex containing either an aliphatic cyclic amine-type multidentate ligand or a binuclear ligand wherein an alkylenediamine ligand is linked by an alkyl chain is provides as the twelfth invention.
Moreover, as the thirteenth invention, a method for producing poly(oxyphenylene) compounds with substituted phenyl ether as a side chain, which comprises reacting any one of the aforesaid poly(oxyphenylene)compounds with a substituted phenol to replace the fluorine group with a substituted phenyl ether group is provided.
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention has the features described above. Further embodiments of the present invention are discussed below in detail.
The copper complex catalyst used as a catalyst for the oxidative polymerization of fluorophenols of the present invention is composed of a ligand or a group of ligands, and copper (Cu). The ligand in this case should be chosen so that the oxidation potential of the copper complex is in the range of −1V to 2V. It is important that this requirement is fulfilled, and examples of preferab
Kumaki Yosuke
Oyaizu Kenichi
Saito Kei
Tsuchida Eishun
Japan Science and Technology Corporation
Keys Rosalynd
Wenderoth , Lind & Ponack, L.L.P.
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