JPS63159336A - Novel iodine compound and production thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel iodine compound and a method for producing the same.

[Conventional technology]

Linear polyethers having repeating units similar to the iodine compounds of the present invention are already known.

(Unexamined Japanese Patent Publication No. 60-137928, Unexamined Japanese Patent Publication No. 1983-137928,
However, the iodine compound of the present invention and its production method are not known.

[Purpose of the invention]

An object of the present invention is to provide a novel iodine compound and a method for producing the same.

[Structure of the invention]

The iodine compound of the present invention has the formula %) [wherein a, b, c, d, e and f are each O or a positive integer, and 2≦a+b+c+d+e+f≦200
and l≦a+c+d+f. ] It is characterized by having an iodine atom at one or both ends of the polymer chain. Note that the arrangement of repeating units in the polymer chain is homogeneous or random.

The iodine compound of the present invention is 2-(CH*CFtCFxO)--(CHCICPiCh
O) b-(CChChCF*O) c-(CIIFC
PzCFtO) a-(CFCIChCFtO) --
(CFzCFRChO) t- [wherein, a * b +
C+ d + 8 and r have the same meanings as above, and can be obtained by reacting a metal salt of a mono- or dicarboxylic acid containing a polymer chain represented by ] with iodine. The metal salt is preferably an alkali metal salt or a salt of a copper group element, the alkali metal salt is preferably a sodium salt or a potassium salt, and the copper group element salt is preferably a copper salt or a silver salt. In the case of an acid salt, an iodine compound having an iodine atom at one end is obtained, and in the case of a dicarboxylate salt, an iodine compound having an iodine atom at both ends is obtained. The bond between the polymer chain and the iodine atom is usually −〇CF
zChl, but -0CFtl, -0CFzChC
In some cases, it is h1 etc.

The above-mentioned carboxylic acid salt, which is a raw material, is obtained by preparing the mono- or dicarboxylic acid containing the above-mentioned polymer chain by a known method.
It can be obtained by forming it into a metal salt, for example, an alkali metal salt or a salt of a copper group element.

The mono- or dicarboxylic acid can be obtained by hydrolyzing a compound containing an acyl fluoride at one or both ends of the polymer chain (see JP-A-61-113616, etc.) using a known method. easily obtained.

Note that the other end of the novel iodine compound of the present invention (
For example, in the polymerization of 2,2,3,3-tetrafluorooxetane, As an initiator, CO
Acyl fluorides such as Fg, RvCOP (Re is a straight chain or M fluoroalkyl group and also includes chlorine-containing CFtc+cpc+cp, etc.) are common, but C
Molecular species containing hydrocarbon chains such as ll5CFtCOF and CIzllxsChCOP can also be used. In addition to the competing functional molecular species as mentioned above, F(COF)f, CF!
(C0F) z, R' t (CFO) z (R'
t is a fluorine-containing alkylene group and is α.

Polyfunctional molecular species such as H and CI may be bonded at positions other than the α° position can also be used (Japanese Patent Application Laid-Open No. 60-137928
When a monofunctional molecular species is used as an initiator, one end of the molecule is a residue of this initiator (for example,
When using the above-mentioned R, COF, Ro-) is occupied, and when a polyfunctional molecular species is used, both ends of the molecule are occupied by -CFO, and the initiator residue is at the center of the molecule. occupy

The temperature at which the carboxylic acid salt and iodine are reacted is usually in the range of 150 to 250°C, preferably 180 to 250°C.
The temperature range is 230°C.

The reaction is usually carried out in the presence of a solvent, and preferred reaction vehicles include trichlorotrifluoroethane, tetrachlorodifluoroethane, CI(CFzCFCl)t.

Examples include N(C3F?)3.

The reaction time may vary depending on the reaction temperature, etc., but is usually 1.5
~15 hours.

The ratio of the carboxylate to iodine is not particularly limited, but is usually 0.001 to 0.
．． For each mole, 1 mole of iodine is used.

The reaction product can be recovered by a conventional method, for example, by adding a solvent to the product, filtering out insoluble matter, and then distilling off the solvent.

The iodine compounds of the present invention are useful as prepolymers in producing various block copolymers useful in greases and waxes. That is, since the carbon-iodine bond of the iodine compound of the present invention is a relatively weak bond, it is easily cleaved in the presence of a radical source and an olefin, and the olefin is added and grown to produce various block copolymers. I can do it.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.

Example 1 F(CFIChCFzO)llCFtCFtCOOH(
Average of n = 26) 80 cc of potassium hydroxide aqueous solution (containing 4.87 g of potassium hydroxide) was added to 200 g (4,46 x 10-" moles) of trichlorotrifluoroethane 10
It was added with stirring in the presence of 0 cc to form a potassium salt. -C- at 1770 am-' in the JR spectrum
0) The peak showing 1 is completely -C- at 1680 cm-'
It was confirmed that the peak had shifted to OK.

After drying the synthesized potassium salt under vacuum at 100°C and granulating it, 200 g (0,044 mol) of this potassium salt was dispersed in 600 cc of trichlorotrifluoroethane under a nitrogen stream, and 100 g (0,394 mol) of iodine was dispersed in 600 cc of trichlorotrifluoroethane. )added. Then, this mixture was heated to 200°C and 1
．． The pre-reaction potassium salt, which was held for 5 hours to perform terminal iodination, was a granular solid, whereas the reaction product was a cloudy oil. 168 in the IR spectrum
The peak indicating -C-OK at 0 cm-' completely disappeared,
It was confirmed that a peak indicating -CFICFII was generated at 910 rm-'. Furthermore, when the F-order NMR of the produced oil was measured, a peak appeared at -12.5 ppm, confirming the production of -0CF, cp, and +.

When the cloudy oil is dissolved in trichlorotrifluoroethane and left to stand at -20℃, the white cloudy substance sinks to the bottom and the precipitate is filtered out from the clear supernatant liquid, and the trichlorotrifluoroethane is distilled off. Transparent F (CFIChcho) - CF
176 g of iChl (average n=26) was obtained.

Example 2 F (CFzCF, ChO), lCF, CF, COOH (
Average of n = 26) 87g (4,46XIO-” mole)
249 g (1,07x to-" moles) of silver oxide and 120 cc of trichlorotrifluoroethane were added to 3
The reaction was allowed to take place with stirring for a period of time. 177 in the IR spectrum
The peak indicating -C-OH of 0C1m-' is 1680cs
It was confirmed that the peak of -' shifted to -C-OAg.

After drying the synthesized silver salt under vacuum at 50℃ and making it into granules,
This i 艮 Salt 101. By dispersing Og in 300cc of trichlorotrifluoroethane, 100.1g of iodine (0
, 39 mol) was added. Then, this mixture was heated to 170°C and held for 2 hours to perform terminal iodination. Trichlorotrifluoroethane was added to the reaction mixture and insoluble matter was filtered out, and then trichlorotrifluoroethane was removed from the soluble matter. The fluoroethane was distilled off and the product F (CFIChChO), ICF
xCFd (average of n=26) 90.1g was collected and 1
Also. -C- at 1630 cm-' in the IR spectrum
A peak indicating OAg appeared at 91Qcm-'-C
F,CF! It was confirmed that a peak indicating I was generated. Also, in the NMR spectrum, a peak indicating -CFtChl was generated at -12.4 ppm.
I did m.

Example 3 F(ChCFzCFiO), IChChCOOH (average n, 26) 260 g (6,05 x lO-'' moles) to 4.90 g of sodium methoxide (9,08 x lO-'' moles)
mol) was added with stirring in the presence of 250 cc of methanol to form the sodium salt. In the IR spectrum, the peak indicating -C-OH of 1770 (J-' is 1680
It was confirmed that the peak of -C-ONa at 1J-' had shifted.

After drying the synthesized sodium salt under vacuum at 100°C and granulating it, 261 g of this sodium salt was (CF zCF
CI), (average n = 2) 261 g (0.03 mol) of iodine was added to the solution by dispersing it in 250 cc. Then, this mixture was heated to 240°C and held for 5.2 hours to perform terminal iodination. Trichlorotrifluoroethane was added to the reaction mixture to filter out insoluble materials, and then trichlorotrifluoroethane was removed from the soluble materials. The fluoroethane is distilled off to produce product F
(CFICFgChO)-CFzChI (mean of n=
26) 54.0g was collected. In the IR spectrum, it was confirmed that the peak indicating -C-0Na at 1680 cm-' disappeared and the peak indicating ChChl at 910 cm-' was generated.

Example 4 F(CFtCFtCF!0)-CF*CFgCOOR(
Average of n = 26) 50.0 g (1,12X10-" mol) NiM conversion -m6.0 (4,19X10-" mol)
was added with stirring in the presence of 50 cc of trichlorotrifluoroethane to form a copper salt. In the IR spectrum, it was confirmed that the peak indicating -c-on at 1770 cm-' had completely shifted to the peak of -C-OCu at 1680 cm-'.

After drying the synthesized copper salt under vacuum at 100°C and granulating it, 10.8 g of this copper salt was dispersed in 50 cc of trichlorotrifluoroethane to obtain 10.2 g of iodine (4,0
2×104 moles) were added. Then, add this mixture to 21
Trichlorotrifluoroethane was added to the reaction mixture heated to 0°C and held for 2.0 hours to perform terminal iodination, and insoluble matter was filtered off. Trichlorotrifluoroethane was then distilled from the soluble matter. to give product F (ChCFzCh
O), CFtCFgl (average of n = 26) 5.4g
was recovered. 1680 cm-' in the IR spectrum
The peak indicating -C-0Cu disappears and the peak at 910 cm-'
It was confirmed that peaks representing -CF, CF, and 1 were generated.

〔Effect of the invention〕

According to the present invention, there are provided a new iodine compound useful as a prepolymer for various block copolymers that can be used in greases, waxes, etc., and a method for producing the same.

that's all Voluntary writing of procedural amendments) May 2nd, 1986

Claims (1)

[Claims] 1. Formula -(CH_2CF_2CF_2O)_a-(CHClC
F_2CF_2O)_b-(CCl_2CF_2CF_
2O)_c-(CHFCF_2CF_2O)_d-(C
FClCF_2CF_2O)_e-(CF_2CF_2
CF_2O)_f- [wherein a, b, c, d, e and f
are each 0 or a positive integer, and 2≦a+b+c+
The number satisfies d+e+f≦200 and 1≦a+c+d+f. A novel iodine compound comprising a polymer chain represented by the following formula and having an iodine atom at one or both ends thereof. 2. Formula -(CH_2CF_2CF_2O)_a-(CHClC
F_2CF_2O)_b-(CCl_2CF_2CF_
2O)_c-(CHFCF_2CF_2O)_d-(C
FClCF_2CF_2O)_e-(CF_2CF_2
CF_2O)_f- [wherein a, b, c, d, e and f
are each 0 or a positive integer, and 2≦a+b+c+
The number satisfies d+e+f≦200 and 1≦a+c+d+f. ] -(CH_2CF_2CF_2O)_a-(CHClC
F_2CF_2O)_b-(CCl_2CF_2CF_
2O)_c-(CHFCF_2CF_2O)_d-(C
FClCF_2CF_2O)_e-(CF_2CF_2
CF_2O)_f- [wherein a, b, c, d, e and f
has the same meaning as above. ] A method for producing a novel iodine compound containing a polymer chain represented by the following formula and having an iodine atom at one or both ends thereof. 3. The method for producing a novel iodine compound according to claim 2, wherein the metal salt is an alkali metal salt or a salt of a copper group element.