JPS63159336A - Novel iodine compound and production thereof - Google Patents
Novel iodine compound and production thereofInfo
- Publication number
- JPS63159336A JPS63159336A JP31039886A JP31039886A JPS63159336A JP S63159336 A JPS63159336 A JP S63159336A JP 31039886 A JP31039886 A JP 31039886A JP 31039886 A JP31039886 A JP 31039886A JP S63159336 A JPS63159336 A JP S63159336A
- Authority
- JP
- Japan
- Prior art keywords
- iodine
- formula
- salt
- polymer chain
- iodine compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000002497 iodine compounds Chemical class 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- -1 alkali metal salt Chemical class 0.000 claims description 4
- 239000011630 iodine Substances 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 150000001336 alkenes Chemical class 0.000 abstract description 4
- 229920001400 block copolymer Polymers 0.000 abstract description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 239000004519 grease Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 16
- 238000002329 infrared spectrum Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 238000001035 drying Methods 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 230000026045 iodination Effects 0.000 description 4
- 238000006192 iodination reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 159000000000 sodium salts Chemical group 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 150000001265 acyl fluorides Chemical class 0.000 description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- UHCBBWUQDAVSMS-UHFFFAOYSA-N fluoroethane Chemical compound CCF UHCBBWUQDAVSMS-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- SLGOCMATMKJJCE-UHFFFAOYSA-N 1,1,1,2-tetrachloro-2,2-difluoroethane Chemical compound FC(F)(Cl)C(Cl)(Cl)Cl SLGOCMATMKJJCE-UHFFFAOYSA-N 0.000 description 1
- OFWDLJKVZZRPOX-UHFFFAOYSA-N 2,2,3,3-tetrafluorooxetane Chemical compound FC1(F)COC1(F)F OFWDLJKVZZRPOX-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000003709 fluoroalkyl group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002195 soluble material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyethers (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、新規ヨウ素化合物及びその製法に関するに関
するものである。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.
本発明のヨウ素化合物と同様の操り返し単位を有する線
状のポリエーテルはすでに知られている。Linear polyethers having repeating units similar to the iodine compounds of the present invention are already known.
（特開昭６０−１３７９２８号公報、特開昭Ｇｏ−２０
２１２２号公報及び特開昭６１−１１３１３１６号公報
参照）、シかし、本発明のヨウ素化合物及びその製法に
ついては知られていない。(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.
本発明の目的は、新規なヨウ素化合物及びその製法を提
供することにある。An object of the present invention is to provide a novel iodine compound and a method for producing the same.
本発明のヨウ素化合物は、式
％式％）
〔式中、ａ、ｂ、ｃ、ｄ、ｅ及びｆはそれぞれＯ又は正
の整数であって、２≦ａ＋ｂ＋ｃ＋ｄ＋ｅ＋ｆ≦２００
及びｌ≦ａ＋ｃ＋ｄ＋ｆを満足する数である。〕
で示されるポリマー鎖を含み、その片方又は両方の末端
にヨウ素原子を有することを特徴とするものである。な
お、ポリマー鎖中の繰り返し単位の配列はホモ又はラン
ダムである。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.
本発明のヨウ素化合物は弐
−（ＣＨ＊ＣＦｔＣＦｘＯ）−−（ＣＨＣＩＣＰｉＣｈ
Ｏ） ｂ−（ＣＣｈＣｈＣＦ＊Ｏ） ｃ−（ＣＩＩＦＣ
ＰｚＣＦｔＯ） ａ−（ＣＦＣＩＣｈＣＦｔＯ） −−
（ＣＦｚＣＦＲＣｈＯ） ｔ−〔式中、ａ ＊ ｂ ＋
Ｃ＋ ｄ ＋ ８及びｒは前記と同意義、〕で示され
るポリマー鎖を含むモノ又はジカルボン酸の金属塩をヨ
ウ素と反応させることによって得られる。金属塩として
はアルカリ金属塩又は銅族元素の塩が好ましい、アルカ
リ金属塩としてはナトリウム塩又はカリウム塩が、銅族
元素の塩としては銅塩又は銀塩が好ましい、前記カルボ
ン酸塩がモノカルボン酸塩の場合は片方の末端にヨウ素
原子を有するヨウ素化合物が得られ、ジカルボン酸塩の
場合は両方の末端にヨウ素を有するヨウ素化合物が得ら
れる。ポリマー鎖とヨウ素原子の結合は、通常−〇ＣＦ
ｚＣｈｌであるが、−０ＣＦｔｌ、 −０ＣＦｚＣｈＣ
ｈ１等の場合もある。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.
原料物質となる前記のカルボン酸塩は、前記のポリマー
鎖を含むモノ又はジカルボン酸を公知の方法によって、
金属塩、例えば、アルカリ金属塩又は銅族元素の塩等に
することによりて得られる。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.
なお、前記のモノ又はジカルボン酸は、前記のポリマー
鎖を含む片方又は両方の末端がアシルフルオライドであ
る化合物（特開昭６１−１１３６１６号公報等参照）を
公知の方法により加水分解することによって容易に 得
られる。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.
なお、本発明の新規ヨウ素化合物のもう一方の片末端（
ヨウ素原子でない方の片末端）は、前記の末端がアシル
フルオライド等のポリマーを製造する際に使用する重合
開始剤によって異なる０例えば、２，２，３．３−テト
ラフルオロオキセタンの重合では、開始剤として、ＣＯ
Ｆｇ、ＲｖＣＯＰ（Ｒｅは直鎖又は分Ｍのフルオロアル
キル基で、塩素を含有したＣＦｔｃ＋ｃｐｃ＋ｃｐ、等
も含む）等のアシルフルオライドが一般的であるが、Ｃ
ｌｌ５ＣＦｔＣＯＦ、ＣＩｚｌｌｘｓＣｈＣＯＰ等の炭
化水素鎖を含む分子種も使用できる。又、前記のような
争官能性分子種のみでなく 、Ｆ（ＣＯＦ）ｆ、ＣＦ！
（Ｃ０Ｆ） ｚ、 Ｒ’ ｔ （ＣＦＯ） ｚ （Ｒ’
ｔは含フツ素アルキレン基でα。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.
α°位以外にＨ，ＣＩを結していてもよい）のような多
官能性分子種も使用できる（特開昭６０−１３７９２８
号公報等参照）、開始剤として単官能性分子種を使用し
た場合、分子の片末端は、この開始剤の残基（例えば、
前記のＲ，ＣＯＦを使用した場合であればＲｏ−）が占
め、多官能性分子種を使用した場合は、分子の両末端は
、−ＣＦＯが占め開始剤の残基は分子の中央部を占める
。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
前記のカルボン酸塩とヨウ素を反応させる際の温度は通
常１５０〜２５０℃の範囲であり、好ましくは１８０〜
２３０℃の範囲である。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.
反応は通常溶媒存在下で行われ、好ましい反応を容媒と
しては、トリクロロトリフルオロエタン、テトラクロロ
ジフルオロエタン、 ＣＩ（ＣＦｚＣＦＣｌ）ｔ。The reaction is usually carried out in the presence of a solvent, and preferred reaction vehicles include trichlorotrifluoroethane, tetrachlorodifluoroethane, CI(CFzCFCl)t.
Ｎ（Ｃ３Ｆ？）３等を挙げることができる。Examples include N(C3F?)3.
反応時間は反応温度等により変化しうるが、通常１．５
〜１５時間の範囲である。The reaction time may vary depending on the reaction temperature, etc., but is usually 1.5
~15 hours.
前記カルボン酸塩とヨウ素の使用割合は特に限定される
ものではないが、通常前記カルボン酸塩０．００１〜０
．１モルに対して、ヨウ素１モルが使用される。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.
反応生成物は、通常の方法で回収することができ、例え
ば、生成物に溶媒を加えて不溶物を濾別したのち、溶媒
を留去することによって回収できる。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.
本発明のヨウ素化合物は、グリースやワックスに有用な
種々のブロックコポリマーを製造する際のプレポリマー
として有用である。すなわち、本発明のヨウ素化合物の
炭素−ヨウ素の結合が比較的弱い結合であるため、ラジ
カル発生源とオレフィンの存在で容易に開裂し、オレフ
ィンを付加生長せしめて、各種のブロックコポリマーを
製造することができる。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.
以下、参考例及び実施例により本発明を更に詳細に説明
する。Hereinafter, the present invention will be explained in more detail with reference to Reference Examples and Examples.
実施例１
Ｆ（ＣＦＩＣｈＣＦｚＯ）ｌｌＣＦｔＣＦｔＣＯＯＨ（
ｎの平均＝２６） ２００ｇ（４，４６Ｘ１０−”モル
）に水酸化カリウム水溶液８０ｃｃ（水酸化カリウムを
４．８７ｇ含む）をトリクロロトリフルオロエタン１０
０ｃｃの存在下、攪拌しながら加えて、カリウム塩とし
た。ＪＲスペクトルにおいて１７７０ａｍ−’の−Ｃ−
０）１を示すピークが完全に１６８０ｃｍ−’の−Ｃ−
ＯＫを示すピークに移行したのを確認した。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.
合成したカリウム塩を１００℃真空下で乾燥し粒状にし
たあと、このカリウム塩２００ ｇ （０，０４４モル
）をトリクロロトリフルオロエタン６００ｃｃで窒素気
流下分散させ、ヨウ素を１００ ｇ （０，３９４モル
）加えた。そして、この混合物を２００℃に加熱し、１
．５時間保持して末端のヨウ素化を行った０反応前カリ
ウム塩は粒状固体であったのに対して、反応生成物は白
濁したオイルであった。ＩＲスペクトルにおいて１６８
０ｃｍ−’の−Ｃ−ＯＫを示すピークが完全に消えて、
９１０ｒｍ−’に−ＣＦＩＣＦＩＩを示すピークが生成
しているのを確認した。又生成したオイルについてＦ目
ＮＭＲを測定してみると、−１２，５ｐｐｍにピークが
出来ており、−０ＣＦ、ｃｐ、＋の生成を確認した。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 +.
白濁したオイルをトリクロロトリフルオロエタンに溶解
させ一２０℃で静置しておくと、白濁物は下に沈み透明
な上澄液から沈澱物を濾別し、トリクロロトリフルオロ
エタンを留去して透明なＦ（ＣＦＩＣｈｃｈｏ）−ＣＦ
ｉＣｈｌ （ｎの平均＝２６） １７６ｇを得た。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.
実施例２
Ｆ（ＣＦｚＣＦ、ＣｈＯ）、ｌＣＦ、ＣＦ、Ｃ０ＯＨ（
ｎの平均＝２６） ８７ｇ（４，４６ＸＩＯ−”モル）
に酸化銀２４９ ｇ （１，０７ｘ ｔｏ−”モル）と
トリクロロトリフルオロエタン１２０ｃｃを加えて、３
時間攪拌下反応させた。ＩＲスペクトルにおいて１７７
０Ｃ１ｍ−’の−Ｃ−ＯＨを示すピークが１６８０ｃｓ
−’の−Ｃ−ＯＡｇのピークに移行したのを確認した。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.
合成した銀塩を５０℃真空下で乾燥し粒状にしたあと、
このｉ艮塩１０１．Ｏｇをトリクロロトリフルオロエタ
ン３００ｃｃに分散させて、ヨウ素を１００．１ｇ（０
，３９モル）加えた。そして、この混合物を１７０℃に
加熱し、２時間保持して末端のヨウ素化を行うた０反応
部合物にトリクロロトリフルオロエタンを加えて不溶物
を濾別したあと、可溶物からトリクロロトリフルオロエ
タンを留去し、生成物Ｆ（ＣＦＩＣｈＣｈＯ）、ＩＣＦ
ｘＣＦｄ （ｎの平均＝２６） ９０．１ｇを回収し１
ま
た。ＩＲスペクトルにおいて１６３０ｃｍ−’の−Ｃ−
ＯＡｇを示すピークがン肖えて、９１Ｑｃｍ−’に−Ｃ
Ｆ、ＣＦ！Ｉを示すピークが生成しているのを確認した
。又ＮＭＲスペクトルにおいても−１２，４ｐｐｍに一
０ＣＦｔＣｈｌを示すピークが生成していることをｉｌ
ｍした。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.
実施例３
Ｆ（ＣｈＣＦｚＣＦｉＯ）、ＩＣｈＣｈＣＯＯＨ（ｎの
平均、２６） ２６０ｇ（６，０５ｘｌＯ−”モル）に
ナトリウムメトキシド４．９０ｇ（９，０８ｘｌＯ−”
モル）をメタノール２５０ｃｃの存在下、攪拌しながら
加えて、ナトリウム塩とした。ＩＲスペクトルにおいて
１７７０（Ｊ−’の−Ｃ−ＯＨを示すピーりが１６８０
１Ｊ−’の−Ｃ−ＯＮａのピークに移行したのを確認し
た。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.
合成したナトリウム塩を１００℃真空下で乾燥し粒状に
したあと、このナトリウム塩２６１ｇを（ＣＦ ｚＣＦ
ＣＩ）、 （ｎの平均＝２） ２５０ｃｃに分散させて
、ヨウ素２６１ ｇ （０，０３モル）加えた。そして
、この混合物を２４０℃に加熱し、５．２時間保持して
末端のヨウ素化を行った０反応混合物にトリクロロトリ
フルオロエタンを加えて不溶物を濾別したあと、可溶物
からトリクロロトリフルオロエタンを留去し、生成物Ｆ
（ＣＦＩＣＦｇＣｈＯ）−ＣＦｚＣｈＩ （ｎの平均＝
２６） ５４．０ｇを回収した。ＩＲスペクトルにおい
て１６８０ｃｍ−’の−Ｃ−０Ｎａを示すピークが消え
て、９１０ｃｍ−’ニーＣｈＣｈｌを示すピークが生成
しているのを確認した。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.
実施例４
Ｆ（ＣＦｔＣＦｔＣＦ！０）−ＣＦ＊ＣＦｇＣＯＯＲ（
ｎの平均＝２６）５０．０ ｇ（１，１２Ｘｌ０−”モ
ル） ニＭ化第−ｍ６．０（４，１９Ｘ１０−”モル）
をトリクロロトリフルオロエタン５０ｃｃの存在下、攪
拌しながら加えて、銅塩とした。ＩＲスベクトルにおい
て１７７０ｃｍ−’の−ｃ−ｏｎを示すピークが完全に
１６８０ｃｍ−’の−Ｃ−ＯＣｕのピークに移行したの
を確認した。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-'.
合成した銅塩を１００℃真空下で乾燥し粒状にしたあと
、この銅塩１０．８ｇをトリクロロトリフルオロエタン
５０ｃｃに分散させて、ヨウ素１０．２ ｇ （４，０
２Ｘ１０４モル）を加えた。そして、この混合物を２１
０℃に加熱して、２．０時間保持して末端のヨウ素化を
行った０反応混合物にトリクロロトリフルオロエタンを
加えて不溶物を濾別したあと、可溶物からトリクロロト
リフルオロエタンを留去し、生成物Ｆ（ＣｈＣＦｚＣｈ
Ｏ）、ＣＦｔＣＦｇｌ （ｎの平均＝２６） ５．４ｇ
を回収した。ＩＲスペクトルにおいて１６８０ｃｍ−’
の−Ｃ−０Ｃｕを示すピークが消えて、９１０ｃｍ−’
に−ＣＦ、ＣＦ、１を示すピークが生成しているのを確
認した。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.
本発明によれば新規でグリースやワックス等に使用可能
な種々のブロックコポリマーのプレポリマーとして有用
なヨウ素化合物及びその製法が提供される。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.
以上 手続補正書く自発） 昭和６２年５月２つ日that's all Voluntary writing of procedural amendments) May 2nd, 1986
Claims (1)
Ｆ＿２ＣＦ＿２Ｏ）＿ｂ−（ＣＣｌ＿２ＣＦ＿２ＣＦ＿
２Ｏ）＿ｃ−（ＣＨＦＣＦ＿２ＣＦ＿２Ｏ）＿ｄ−（Ｃ
ＦＣｌＣＦ＿２ＣＦ＿２Ｏ）＿ｅ−（ＣＦ＿２ＣＦ＿２
ＣＦ＿２Ｏ）＿ｆ−〔式中、ａ、ｂ、ｃ、ｄ、ｅ及びｆ
はそれぞれ０又は正の整数であって、２≦ａ＋ｂ＋ｃ＋
ｄ＋ｅ＋ｆ≦２００及び１≦ａ＋ｃ＋ｄ＋ｆを満足する
数である。〕で示されるポリマー鎖を含み、その片方又
は両方の末端にヨウ素原子を有することを特徴とする新
規ヨウ素化合物。 ２、式 −（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−〔式中、ａ、ｂ、ｃ、ｄ、ｅ及びｆ
はそれぞれ０又は正の整数であって、２≦ａ＋ｂ＋ｃ＋
ｄ＋ｅ＋ｆ≦２００及び１≦ａ＋ｃ＋ｄ＋ｆを満足する
数である。〕で示されるポリマー鎖を含む、モノ又はジ
カルボン酸の金属塩をヨウ素と反応させることを特徴と
する式 −（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−〔式中、ａ、ｂ、ｃ、ｄ、ｅ及びｆ
は前記と同意義。〕で示されるポリマー鎖を含み、その
片方又は両方の末端にヨウ素原子を有する新規ヨウ素化
合物の製法。 ３、金属塩がアルカリ金属塩又は銅族元素の塩である特
許請求の範囲第２項記載の新規ヨウ素化合物の製法。[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.
Priority Applications (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31039886A JPS63159336A (en) | 1986-12-23 | 1986-12-23 | Novel iodine compound and production thereof |
| US07/136,916 US4861836A (en) | 1986-12-23 | 1987-12-22 | Novel, iodine-containing compound, preparation thereof and block copolymer comprising the same |
| EP92109052A EP0501532B1 (en) | 1986-12-23 | 1987-12-23 | Novel block copolymer and preparation thereof |
| DE3752293T DE3752293T2 (en) | 1986-12-23 | 1987-12-23 | New block copolymers and their production |
| EP87119110A EP0272698B1 (en) | 1986-12-23 | 1987-12-23 | Novel iodine-containing compound and preparation thereof |
| DE3789431T DE3789431T2 (en) | 1986-12-23 | 1987-12-23 | Compound containing iodine and its preparation. |
| EP19920109061 EP0501533A3 (en) | 1986-12-23 | 1987-12-23 | Grease |
| CA000555380A CA1318690C (en) | 1986-12-23 | 1987-12-24 | Iodine-containing compound, preparation thereof and block copolymer comprising the same |
| US07/345,571 US4962236A (en) | 1986-12-23 | 1989-05-01 | Novel iodine-containing compound, preparation thereof and block copolymer comprising the same |
| US07/487,865 US5198136A (en) | 1986-12-23 | 1990-03-05 | Iodine-containing compound, preparation thereof and block copolymer comprising the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31039886A JPS63159336A (en) | 1986-12-23 | 1986-12-23 | Novel iodine compound and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63159336A true JPS63159336A (en) | 1988-07-02 |
| JPH0588691B2 JPH0588691B2 (en) | 1993-12-24 |
Family
ID=18004780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31039886A Granted JPS63159336A (en) | 1986-12-23 | 1986-12-23 | Novel iodine compound and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63159336A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007862A1 (en) | 2009-07-16 | 2011-01-20 | ダイキン工業株式会社 | Process for production of fluorine-containing block copolymer |
| WO2013125736A1 (en) * | 2012-02-24 | 2013-08-29 | Daikin Industries, Ltd. | Fluororubber composition |
| US9403954B2 (en) | 2012-01-20 | 2016-08-02 | Daikin Industries, Ltd. | Fluororubber composition and method for producing same |
| US9499678B2 (en) | 2012-02-24 | 2016-11-22 | Daikin Industries, Ltd. | Fluororubber composition |
| US11898661B2 (en) | 2012-02-24 | 2024-02-13 | Daikin Industries, Ltd. | Fluororubber composition |
-
1986
- 1986-12-23 JP JP31039886A patent/JPS63159336A/en active Granted
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011007862A1 (en) | 2009-07-16 | 2011-01-20 | ダイキン工業株式会社 | Process for production of fluorine-containing block copolymer |
| US9403954B2 (en) | 2012-01-20 | 2016-08-02 | Daikin Industries, Ltd. | Fluororubber composition and method for producing same |
| WO2013125736A1 (en) * | 2012-02-24 | 2013-08-29 | Daikin Industries, Ltd. | Fluororubber composition |
| JP2015512954A (en) * | 2012-02-24 | 2015-04-30 | ダイキン工業株式会社 | Fluoro rubber composition |
| US9499678B2 (en) | 2012-02-24 | 2016-11-22 | Daikin Industries, Ltd. | Fluororubber composition |
| US9976016B2 (en) | 2012-02-24 | 2018-05-22 | Daikin Industries, Ltd. | Fluororubber composition |
| US11898661B2 (en) | 2012-02-24 | 2024-02-13 | Daikin Industries, Ltd. | Fluororubber composition |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0588691B2 (en) | 1993-12-24 |
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