Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
2002-05-15
2003-12-30
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S685000, C570S125000, C570S128000, C570S138000, C570S142000, C526S072000, C528S397000, C528S401000, C528S422000, C528S503000
Reexamination Certificate
active
06670511
ABSTRACT:
The present invention relates to a fluorine-containing diene having two unsaturated bonds, its production method and its polymer.
As a fluorine-containing 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 cyclic polymerization of this compound, an amorphous polymer can be obtained, which has high elastic modulus, yield elongation in tension and breaking extension, which is less likely to break and is excellent in impact resistance. It also has a high transparency, and it can thereby be used as a material for optical components or optical devices such as optical waveguides or optical fibers. However, in a case where an optical resin material is obtained by using this polymer, since the polymer has a low glass transition temperature, the optical properties tend to change by a long-term use at a high temperature.
It is an object of the present invention to provide a polymer which maintains mechanical properties of the above amorphous polymer and has a higher glass transition temperature, and can thereby be an optical resin material excellent in heat resistance, and a fluorine-containing diene having two unsaturated bonds to give such a polymer.
The present invention provides a fluorine-containing diene represented by the following formula 1, its production method and its polymer, a fluorine-containing compound represented by the following formula 2, a method of producing the fluorine-containing diene represented by the following formula 1, which comprises dehalogenating the fluorine-containing compound represented by the formula 2, and a polymer which contains a polymer formed by polymerization of the fluorine-containing diene represented by the formula 1 in monomer units:
CF
2
═CF(CF
2
)
n
CXYOCF═CF
2
Formula 1
CF
2
Z
1
CFZ
2
(CF
2
)
n
CXYOCFZ
3
CF
2
Z
4
Formula 2
wherein each of X and Y which are independent of each other, is an atom selected from a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, provided that X and Y are neither simultaneously hydrogen atoms nor simultaneously fluorine atoms, each of Z
1
, Z
2
, Z
3
and Z
4
which are independent of one another, is a halogen atom selected from a chlorine atom, a bromine atom and an iodine atom, and n is an integer of from 1 to 3.
With respect to X and Y in the formulae 1 and 2, preferably at least one is a chlorine atom, particularly preferably both are chlorine atoms or one is a chlorine atom and the other is a fluorine atom. Particularly preferably, one is a chlorine atom and the other is a fluorine atom. Further, with respect to Z
1
, Z
2
, Z
3
and Z
4
, preferably at least one is a chlorine atom, particularly preferably all are chlorine atoms. A chlorine atom strongly connects with a carbon atom as compared with a bromine atom and an iodine atom, such being favorable in view of stability of a compound, and in synthesis of the compound of the present invention and in polymerization of the fluorine-containing diene represented by the formula 1, a reaction such as release of a halogen atom is less likely to take place. Further, the desired dehalogenation reaction can easily be carried out as compared with a case of a fluorine atom or a hydrogen atom. Here, the carbon atom to which X and Y are bonded, is adjacent to an oxygen atom and a difluoromethylene group, whereby a dehalogenation reaction hardly takes place, and the stability is high even if X or Y is a chlorine atom.
The fluorine-containing compound represented by the formula 2 (hereinafter sometimes referred to as a fluorine compound (2)), wherein each of X, Y, Z, Z
2
, Z
3
and Z
4
is a chlorine atom, can be produced, for example, by the following method. Namely, iodine chloride and trifluorochloroethylene are reacted at a low temperature to produce a compound (a) represented by the formula 3, which is reacted with a predetermined amount of tetrafluoroethylene in the presence of a radical initiator to produce a compound (b) represented by the formula 4, which is oxidized by fuming sulfuric acid to obtain a compound (c) represented by the formula 5, followed by alkylesterification to produce a compound (d) represented by the formula 6 (wherein R is an alkyl group).
The compound (d) is reduced by e.g. sodium borohydride to produce a compound (e) represented by the formula 7, then this compound (e) is reacted with a metal hydride, and the resulting metal alkoxide is reacted with tetrafluoroethylene to produce a compound (f) represented by the formula 8. The compound (f) is chlorinated so that every hydrogen atom in the compound (f) is replaced by a chlorine atom, and chlorine atoms are added to the unsaturated bond to obtain the desired fluorine-containing compound represented by the formula 9 i.e. the fluorine-containing compound represented by the formula 2, wherein each of X, Y, Z
1
, Z
2
, Z
3
and Z
4
is a chlorine atom (hereinafter referred to as a compound (g)). Here, in this method, by making tetrafluoroethylene react with the compound (a) to produce the compound (b), the desired compound wherein n is 1 or 3 can be obtained. The desired compound wherein n is 2 can be obtained by another known method to produce the compound represented by the formula 5 wherein n is 2, and then conducting the same operation as mentioned above.
CF
2
ClCFClI Formula 3
CF
2
ClCFCl(CF
2
)
n+1
I Formula 4
CF
2
ClCFCl(CF
2
)
n
COF Formula 5
CF
2
ClCFCl(CF
2
)
n
COOR Formula 6
CF
2
ClCFCl(CF
2
)
n
CH
2
OH Formula 7
CF
2
ClCFCl(CF
2
)
n
CH
2
OCF═CF
2
Formula 8
CF
2
ClCFCl(CF
2
)
n
CCl
2
OCFClCF
2
Cl Formula 9
Further, by changing conditions of the chlorination in the chlorination step to obtain the compound (g), the chlorine-containing compound represented by the formula 2, wherein X is a hydrogen atom, Y is a chlorine atom, and each of Z
1
, Z
2
, Z
3
and Z
4
is a chlorine atom (a compound represented by the following formula 10), can be produced. For example, by partial chlorination by adjusting the feed amount of a chlorine gas or the ultraviolet irradiation intensity in the chlorination step as mentioned hereinafter, one of the two hydrogen atoms in the compound (f) can be replaced by a chlorine atom. Further, by partial fluorination of the compound (g) represented by the formula 9, the fluorine-containing compound represented by the formula 2, wherein X is a fluorine atom, Y is a chlorine atom and each of Z
1
, Z
2
, Z
3
and Z
4
is a chlorine atom (a compound represented by the following formula 11, hereinafter sometimes referred to as a compound (h)) can be produced.
CF
2
ClCFCl(CF
2
)
n
CHClCOFClCF
2
Cl Formula 10
CF
2
ClCFCl(CF
2
)
n
CFClOCFClCF
2
Cl Formula 11
By the reaction of iodine chloride and trifluorochloroethylene is carried out by a method disclosed in a literature (J. Am. Chem. Soc., 83, 2495 (1981)) at a low temperature, preferably from −8° C. to 0° C., the compound (a) is selectively formed. The reaction of the compound (a) and tetrafluoroethylene is carried out in the presence of a radical initiator such as a peroxide or an azo compound, usually at from 20 to 150° C., preferably from 60 to 100° C., while keeping tetrafluoroethylene under at most 1 MPa, preferably at most 0.5 MPa, to obtain the compound (b).
The production of the compound (c) by oxidation of the compound (b) is carried out, for example, by fuming sulfuric acid. The concentration of fuming sulfuric acid may optionally be selected. The reaction temperature varies depending upon the concentration of the fuming sulfuric acid, but is from 40 to 100° C., preferably from 60 to 80° C., when the concentration is 60 mass %, for example. The alkylesterification of the compound (c) is carried out by dropwise adding the compound (c) to an alkanol, for example. By reacting an alkanol with the compound (c) at a low temperature, preferably at from 0° C
Kashiwagi Kimiaki
Murofushi Hidenobu
Sato Masakuni
Sugiyama Norihide
Watakabe Atsushi
Asahi Glass Company Limited
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
Richter Johann
Witherspoon SiKarl A.
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