Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Polymers from only ethylenic monomers or processes of...
Reexamination Certificate
2002-12-02
2004-06-29
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Polymers from only ethylenic monomers or processes of...
C526S072000, C526S247000, C526S253000, C568S683000, C568S685000
Reexamination Certificate
active
06756458
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a fluorinated diene having two unsaturated bonds, a method for its production and a polymer thereof.
BACKGROUND ART
As a fluorinated diene having two carbon—carbon unsaturated double bonds (hereinafter referred to as unsaturated bonds), CF
2
═CF(CF
2
)
k
OCF═CF
2
(wherein k is an integer of from 1 to 3) has been known (JP-A-1-14843). By cyclopolymerization of this compound, an amorphous polymer can be obtained, and such a polymer has high elastic modulus, yield and breaking extension and is tough and excellent in impact resistance. Further, its transparency is also high, and it can be used for an optical material such as optical fiber or optical waveguide. However, it has a drawback that when this polymer is used to make an optical material, the glass transition temperature (Tg) is low, and if it is used at a high temperature for a long period of time, the optical properties will change. Accordingly, it has been desired to develop a base material having a higher Tg.
It is an object of the present invention to provide a polymer which maintains the mechanical properties which the above amorphous polymer has, and has a higher glass transition temperature, so that it can be an optical resin material excellent in heat resistance, and to provide a fluorinated diene having two unsaturated bonds, which is capable of presenting such a polymer.
DISCLOSURE OF THE INVENTION
The present invention is the following invention relating to a fluorinated diene represented by the formula 1, a method for its production and a polymer thereof.
A fluorinated diene represented by the formula 1.
A method for producing a fluorinated diene represented by the formula 1, which comprises dehalogenating Z
1
and Z
2
of a fluorinated compound represented by the formula 2.
A polymer comprising monomer units formed by polymerization of a fluorinated diene represented by the formula 1.
CF
2
═CF(CF
2
)
n
C(CF
3
)ROCF═CF
2
Formula 1
CF
2
Z
1
CFZ
2
(CF
2
)
n
C(CF
3
)ROCF═CF
2
Formula 2
wherein R is a fluorine atom or a trifluoromethyl group, each of Z
1
and Z
2
which are independent of each other, is a halogen atom other than a fluorine atom, and n is an integer of from 1 to 3.
BEST MODE FOR CARRYING OUT THE INVENTION
The fluorinated diene represented by the formula 1 can be obtained by dehalogenating Z
1
and Z
2
of the fluorinated compound represented by the formula 2. Each of Z
1
and Z
2
which are independent of each other, is a halogen atom other than a fluorine atom, preferably a chlorine atom or a bromine atom, and particularly preferably, each is a chlorine atom. By the dehalogenation of these halogen atoms, a double bond will be formed, and a fluorinated diene represented by the formula 1 will be formed.
The dehalogenation is carried out by having a dehalogenating agent acted in a polar solvent. The dehalogenating agent is a reaction agent having a function to act on halogen atoms in a substrate thereby to withdraw the halogen atoms. As such a dehalogenating agent, zinc, sodium, magnesium, tin, copper, iron or other metals are preferred. From the viewpoint of such a reaction condition that a relatively low reaction temperature can be employed, zinc is preferred as such a dehalogenating agent. As the polar solvent, an organic polar solvent such as dimethylformamide, 1,4-dioxane, diglyme or methanol, or water, may, for example, be preferably employed.
The molar ratio of the dehalogenating agent to the fluorinated compound represented by the formula 2, is preferably from 1 to 10 times, more preferably from 2 to 3 times. The reaction temperature is usually from 40 to 100° C., preferably from 50 to 70° C. Usually, the reaction is carried out by dropwise adding the fluorinated compound represented by the formula 2, in the presence of the dehalogenating agent and the solvent, and isolation of the reaction product is carried out by withdrawing the reaction product from the reaction system by distillation promptly after the reaction.
The fluorinated compound represented by the formula 2 is a novel compound, and a compound (formula 2-1) wherein R is a fluorine atom, can be produced, for example, from a known fluorinated compound represented by the formula 3-1. Further, a fluorinated compound (formula 2-2) represented by the formula 2 wherein R is a trifluoromethyl group, can be produced, for example, from a known fluorinated compound represented by the formula 4-1.
CF
2
Z
1
CFZ
2
(CF
2
)
n
CF(CF
3
)OCF═CF
2
Formula 2-1
CF
2
Z
1
CFZ
2
(CF
2
)
n
CF═CF
2
Formula 3-1
CF
2
Z
1
CFZ
2
(CF
2
)
n
C(CF
3
)
2
OCF═CF
2
Formula 2-2
CF
2
Z
1
CFZ
2
(CF
2
)
n
COF Formula 4-1
Firstly, a method for producing the fluorinated compound represented by the formula 2-1 will be described. The unsaturated group in the fluorinated compound represented by the formula 3-1 is epoxidized to an epoxy compound (formula 3-2), and this epoxy compound is isomerized and converted to a fluorinated ketone compound (formula 3-3). To this fluorinated ketone compound, hexafluoropropylene oxide is added to obtain a fluorinated ether compound (formula 3-4), and then, the fluorinated ether compound is pyrolyzed to obtain a fluorinated compound (formula 2-1) represented by the formula 2 wherein R is a fluorine atom.
For the production of the epoxy compound (formula 3-2), it is possible to apply a method of employing oxygen as disclosed in “Chemistry of organic fluorine compound”, 1962 edition, pp. 168-169, edited by Hudlicky, a method of employing hydrogen peroxide as disclosed in JP-B-44-2963, or a method of employing a hypochlorite aqueous solution in the presence of a phase-transfer catalyst.
Particularly preferred is a method of employing a sodium hypochlorite aqueous solution in the presence of a phase-transfer catalyst.
In the case of the method of employing a hypochlorite aqueous solution, the reaction temperature is at least the melting point of the hypochlorite aqueous solution, usually within a range of from −20 to 60° C., preferably from −20 to 30° C., although it may vary depending upon the phase-transfer catalyst to be used or its amount. The amount of the phase-transfer catalyst is preferably from 0.01 to 20 mass %, particularly preferably from 0.05 to 10 mass %, based on the compound represented by the formula 3-1. As the hypochlorite, an alkali metal salt or an alkaline earth metal salt, such as NaClO, KClO, Ca(ClO)
2
or NaBrO, may be mentioned. From the industrial viewpoint, use of NaClO is preferred. The effective concentration of the hypochlorite in the hypochlorite aqueous solution is preferably from 1 to 20 mass %.
As the phase-transfer catalyst, a quaternary ammonium salt, a quaternary phosphonium salt, a quaternary arsonium salt, a sulfonium salt or a crown ether, known as a phase-transfer catalyst, may, for example, be used. Among them, a quaternary ammonium salt and a quaternary phosphonium salt are preferred. As an organic group to be bonded to the nitrogen atom or the phosphorous atom, an alkyl group, an aryl group or an aralkyl group may, for example, be preferred, and as an anion, a halogen ion such as a chlorine ion, or a mineral acid ion such as a sulfate ion, is preferred. A particularly preferred phase-transfer catalyst is a tetraalkylammonium salt.
The epoxy compound (formula 3-2) is subjected to an isomerization reaction in a gas phase or in a liquid phase using a metal compound such as a metal oxide, a metal oxyhalide or a metal halide as a catalyst, whereby a fluorinated ketone compound (formula 3-3) can be obtained. As the metal component of the catalyst, Al, Zr, Ti, Fe, Co, Ni or Cr may, for example, be mentioned, and particularly preferred is aluminum. A reaction wherein a fluorinated epoxide is isomerized in the presence of a catalyst such as aluminum oxide or aluminum chloride to obtain a fluorinated ketone, is known and is disclosed, for example, in U.S. Pat. No. 3,391,119.
In the present invention, when the above isomerization reactio
Kaneko Isamu
Kashiwagi Kimiaki
Ogawa Gen
Oharu Kazuya
Sato Masakuni
Asahi Glass Company Limited
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Wu David W.
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