JPH02167242A - Fluorine-containing divinyl ether and production thereof - Google Patents
Fluorine-containing divinyl ether and production thereofInfo
- Publication number
- JPH02167242A JPH02167242A JP32058088A JP32058088A JPH02167242A JP H02167242 A JPH02167242 A JP H02167242A JP 32058088 A JP32058088 A JP 32058088A JP 32058088 A JP32058088 A JP 32058088A JP H02167242 A JPH02167242 A JP H02167242A
- Authority
- JP
- Japan
- Prior art keywords
- fluorine
- compound
- formula
- integer
- reaction
- 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
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 24
- 239000011737 fluorine Substances 0.000 title claims description 24
- 229910052731 fluorine Inorganic materials 0.000 title claims description 24
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 title claims description 14
- 229960000834 vinyl ether Drugs 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 6
- 150000002009 diols Chemical class 0.000 claims abstract description 5
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 5
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 abstract description 23
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000011248 coating agent Substances 0.000 abstract description 3
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000005871 repellent Substances 0.000 abstract description 3
- 239000000010 aprotic solvent Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 abstract description 2
- 150000004678 hydrides Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 9
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- -1 divinyl compound Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000000862 absorption spectrum Methods 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- 229920006037 cross link polymer Polymers 0.000 description 3
- 238000000921 elemental analysis Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002940 repellent Effects 0.000 description 2
- 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 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- JMGNVALALWCTLC-UHFFFAOYSA-N 1-fluoro-2-(2-fluoroethenoxy)ethene Chemical compound FC=COC=CF JMGNVALALWCTLC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000013032 Hydrocarbon resin Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- OEERIBPGRSLGEK-UHFFFAOYSA-N carbon dioxide;methanol Chemical compound OC.O=C=O OEERIBPGRSLGEK-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006270 hydrocarbon resin Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 229940029284 trichlorofluoromethane Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、新規な含フツ素ジビニルエーテル及びその製
造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel fluorine-containing divinyl ether and a method for producing the same.
（従来技術及び発明が解決ｌ−ようとする課題）架橋構
造を有する炭化水素系の樹脂は、その優れた特性から多
くの分野で利用されているが、高度にフッ素化された架
橋重合体に関する報告は余りｔｘい。例えば、特開昭６
２−５９６１０号公報には、ジビニル化合物として
を用いた含フツ素架橋重合体の製造方法が開示されてい
るが、二重結合が充分架橋に利用されず、一部環化構造
が生成すること、又他の含フツ素モノマーと共重合した
場合、ジビニル化合物が５０モル％以上でたいと高い重
合率で架橋樹脂が得られたいことが記載されている。又
、他のジビニル化合物としてｃＦ２−ＣＦＣＦ’−ＣＦ
２ の重合に関しては、ジャーナル オブ ポリマー
サイエンス Ｂ ６ｔａ６３９〜６４２頁（１９５８
）に記載があるが、とのジビニル化合物は重合性が悪（
，６０℃で１週間重合しても重合率が１５〜１８％であ
る。(Prior art and problems to be solved by the invention) Hydrocarbon resins having a crosslinked structure are used in many fields due to their excellent properties, but highly fluorinated crosslinked polymers The report is too tx. For example, JP-A-6
Publication No. 2-59610 discloses a method for producing a fluorine-containing crosslinked polymer using divinyl compound, but double bonds are not sufficiently utilized for crosslinking and a partially cyclized structure is generated. It is also described that when copolymerized with other fluorine-containing monomers, a crosslinked resin with a divinyl compound content of 50 mol % or more and a very high polymerization rate is desired. In addition, as other divinyl compounds, cF2-CFCF'-CF
Regarding the polymerization of 2, see Journal of Polymer Science B 6ta 639-642 (1958
), but the divinyl compound with has poor polymerizability (
Even if the polymerization is carried out at 60° C. for one week, the polymerization rate is 15 to 18%.
そこで１本発明の目的は、従来公知のジビニル化合物の
問題点に鑑み重合性の良好な含フツ素重合体の架橋剤と
して、又、撥水処理剤、コーティング剤等の有用に中間
原料として有用な新規な含フツ素ジビニル化合物を提供
することにある。Therefore, in view of the problems of conventionally known divinyl compounds, it is an object of the present invention to be useful as a crosslinking agent for fluorine-containing polymers with good polymerizability, and as an intermediate raw material for water repellent agents, coating agents, etc. An object of the present invention is to provide a novel fluorine-containing divinyl compound.
（課題を解決するための手段）
本発明者等は、重合性の良好？ｊ含フッ素ジビニル化合
物の化学構造と重合性の関連について鋭意研究を重ねた
結果、新規なジビニル化合物の合成に成功し、該化合物
が上記目的を達成できる化合物であることを見出した。(Means for Solving the Problems) The present inventors have found that the present inventors have good polymerizability. j As a result of extensive research into the relationship between the chemical structure and polymerizability of fluorine-containing divinyl compounds, we succeeded in synthesizing a new divinyl compound and found that this compound is a compound that can achieve the above objectives.
即ち、本発明は下記−紋穴ＣＩ’）
ＣＦ’２−ＣＦＯＣＨ２ＲｆＣＨ２０ＣＦ＝ＣＦ２
［Ｉ］の前記−紋穴〔Ｉ〕に示される化合物中に存在す
る特定の原子団を知ることができる。That is, the present invention provides the following - Monana CI') CF'2 - CFOCH2RfCH20CF=CF2
It is possible to know the specific atomic groups present in the compound shown in the above-mentioned pattern [I] of [I].
前記−紋穴［１１で示される化合物の代表例として下記
式
で示される含フツ素ジビニルエーテルである。A representative example of the compound represented by the above-mentioned -Momonen [11] is a fluorine-containing divinyl ether represented by the following formula.
上記−紋穴〔■〕中、ｋ及びｍは、夫々０以上の整数で
あるが、原料の入手の困難さ、両末端のパーフルオロビ
ニル基の重合性及び重合時の副反応の防止等を勘案する
と、０〜２の整数であることが好資しい。豊た、前記−
紋穴〔１〕中、ｔは２以上の整数であればよいが、上記
と同様の理由により２〜６の整数であることが好！しい
。In the above-mentioned hole [■], k and m are each integers of 0 or more, but due to the difficulty of obtaining raw materials, the polymerizability of the perfluorovinyl groups at both ends, and the prevention of side reactions during polymerization, etc. Taking this into consideration, it is preferable that it is an integer between 0 and 2. Toyota, above-
In Monana [1], t may be an integer of 2 or more, but for the same reason as above, it is preferably an integer of 2 to 6! Yes.
本発明の前記−紋穴〔■〕で示される化合物は、新規化
合物であり、その構造は次の手段によって確認すること
ができろ。The compound indicated by the above-mentioned mark [■] of the present invention is a new compound, and its structure can be confirmed by the following means.
（イ）赤外線吸収スペクトル（以下、ＩＲと略称する。(a) Infrared absorption spectrum (hereinafter abbreviated as IR).
）を測定することにより、本発明で示される化合物のＩ
Ｒチャートを第１図に示した。) of the compound shown in the present invention by measuring
The R chart is shown in FIG.
（ａ） 質ｔスペクトル（以下、ＭＳと略称する）を
測定し、観察された各ピーク（一般にはイオン質量Ｍを
イオンの荷電数ｅで除したＭ／ｅで表わされる値）に相
当するＩ１１或式を算出する事により、測定に供した化
合物の分子量からびに、該分子内にかける各原子団の結
合様式を知る事ができる。(a) Measure the quality t spectrum (hereinafter abbreviated as MS) and calculate the I11 value corresponding to each observed peak (generally expressed as M/e, which is the ion mass M divided by the ion charge number e). By calculating a certain formula, it is possible to know the molecular weight of the compound subjected to measurement and the bonding mode of each atomic group within the molecule.
（−９１９Ｆ−核磁気共鳴スペクトル（以下、１９Ｆ−
ＮＭＲと略称する。）（トリクロロフルオロメタン基準
：高磁場側を正としｐｐｍで表わす）を測定する事によ
り、前記一般式ＣＩＩで示される化合物中に存在するフ
ッ素原子の結合様式を知ることができる。筐た１Ｈ−核
磁気共鳴スペクトル（以下、ＩＨ−ＮＭＲと略称する。(-919F- nuclear magnetic resonance spectrum (hereinafter referred to as 19F-
It is abbreviated as NMR. ) (trichlorofluoromethane standard: positive on the high magnetic field side and expressed in ppm), it is possible to know the bonding mode of the fluorine atoms present in the compound represented by the general formula CII. 1H-nuclear magnetic resonance spectrum (hereinafter abbreviated as IH-NMR).
）（テトラメチルシラン基準；低磁場側を正とし、ｐｐ
ｍで表わす）を測定する事により該化合物中に存在する
水素原子の結合様式を知ることができる。) (tetramethylsilane standard; low magnetic field side is positive, pp
The bonding mode of the hydrogen atoms present in the compound can be determined by measuring the amount (represented by m).
本発明の前記−紋穴〔Ｉ〕で示される化合物の代表例と
して、下式
前記−紋穴ＣＩ〕で示される本発明の化合物の製法はど
のような方法であっても良いが、以下に述べる方法が好
適である。As a representative example of the compound represented by the above-mentioned -Momona [I] of the present invention, the compound of the present invention represented by the following formula -Momona CI] may be produced by any method, but the following method may be used. The method described is preferred.
即ち、下記式〔■〕
ＨＯＣＨ２ＪＣＨ２０Ｈｃｎ〕
ＣＦ２＝ＣＦＯＣＨ２ＣＦＯＣＦ２ＣＦ２０ＣＦＣＨ２
０ＣＦ＝ＣＦ２で示される化合物の１９Ｆ−ＮＭＲチャ
ートを第２図に＋ ＩＨ−ＮＭＲチャートを第３図に
示した。That is, the following formula [■] HOCH2JCH20Hcn] CF2=CFOCH2CFOCF2CF20CFCH2
The 19F-NMR chart of the compound represented by 0CF=CF2 is shown in FIG. 2, and the IH-NMR chart is shown in FIG. 3.
（・・）元素分析によって、炭素、水素、及びフッ素の
各重量％を求め、さらに認知された各元素の重量％の和
を１００から減じる事により酸素の重量％を算出する事
ができ、従って、該化合物の組成式を決定する事ができ
る。(...) Through elemental analysis, the weight percent of carbon, hydrogen, and fluorine can be determined, and the weight percent of oxygen can be calculated by subtracting the sum of the weight percent of each recognized element from 100. , the compositional formula of the compound can be determined.
で示される含フツ素ジオールをアルカリ金属又はアルカ
リ金属水素化物と反応させ、次いで、テトラフルオロエ
チレンと反応させる方法である。This is a method in which a fluorine-containing diol represented by is reacted with an alkali metal or an alkali metal hydride, and then reacted with tetrafluoroethylene.
上記−紋穴〔■〕で示される含フツ素ジオールを、まず
アルカリ金属又はアルカリ金属水素化物と反応させる（
以下、この反応をアルコラード化反応と呼ぶ。）。ここ
でアルカリ金属は、Ｌｌ ｓ Ｎａ ＋ Ｋ等が、アル
カリ金属水素化物は、ＬｉＨ、ＮａＨ、ＫＨ等が用いら
れる。The fluorine-containing diol shown in the above-marked hole [■] is first reacted with an alkali metal or an alkali metal hydride (
Hereinafter, this reaction will be referred to as an alcoholade reaction. ). Here, the alkali metal used is Ll s Na + K, and the alkali metal hydride used is LiH, NaH, KH, etc.
アルカリ金属又はアルカリ金属水素化物は、前記−紋穴
［１１で示される含フツ素ジオールに対して、通常−２
モル以上、好！シ〈は２〜４モルの範囲で使用されろ。The alkali metal or alkali metal hydride is usually -2 for the fluorine-containing diol represented by the above-mentioned
Better than a mole! Sh is used in a range of 2 to 4 moles.
アルコラード化反応にかいては、溶媒を使用する事が好
ましい。溶媒として好適に使用されるものを例示すれば
、ジエチルエーテル。In the alcoholade reaction, it is preferable to use a solvent. An example of a solvent suitably used is diethyl ether.
ジブチルエーテル、ジオキサン、モノプラム。Dibutyl ether, dioxane, monopram.
ジグライム、テトラグライム等の非プロトン性溶媒が挙
げられる。反応温度は特に制限されるものではｋいが、
好適には一り０℃〜５０゛Ｃハ範囲から選ばれる。反応
時間は、一般には数分〜数時間の範囲から選ばれる。Examples include aprotic solvents such as diglyme and tetraglyme. Although the reaction temperature is not particularly limited,
Preferably, the temperature is selected from the range of 0°C to 50°C. The reaction time is generally selected from the range of several minutes to several hours.
次に、上記のアルコラード化反応で得られた生成物にテ
トラフルオロエチレンを反応させる（以下、この反応を
ビニルエーテル化反応と呼ぶ。）ビニルエーテル化反応
は、前記アルコラード化反応に引き続き同一反応器にテ
トラブルオロエチレンを導入してかとなっても良いし、
アルコラード化反応とは別の反応器を用い、アルコラー
ド化反応で得られた生成物の溶液を反応器に移したのち
テトラフルオロエチレンを導入してかこｋっても良い。Next, the product obtained in the above alcoholation reaction is reacted with tetrafluoroethylene (hereinafter, this reaction is referred to as vinyl etherification reaction). It may be possible to introduce trouble oleoethylene,
A reactor separate from that for the alcoholation reaction may be used, and after the solution of the product obtained in the alcoholation reaction is transferred to the reactor, tetrafluoroethylene may be introduced therein.
該反応において使用される溶媒としては、例えば、前述
したアルコラード化反応の溶媒を挙げることができる。Examples of the solvent used in this reaction include the solvent for the alcoholation reaction described above.
該反応において導入するテトラフルオロエチレンの圧力
は、通常３〜５０１’に／、−ｓ（、好普しくは５〜３
０陶／−の範囲から選ばれる。該反応にかける反応温度
は特に制限されるものではたいが、好適には０℃〜１４
０℃の範囲から選ばれる。反応時間は原料の種類によっ
て異なるが、通常１０分〜７日間、好さしくは３時間〜
４日間の範囲から選ばれる。The pressure of the tetrafluoroethylene introduced in the reaction is usually 3 to 501'/, -s (, preferably 5 to 3
Selected from the range 0/-. The reaction temperature for this reaction is not particularly limited, but is preferably 0°C to 14°C.
Selected from the range of 0°C. The reaction time varies depending on the type of raw material, but is usually 10 minutes to 7 days, preferably 3 hours to
Selected from a 4-day period.
反応終了後過剰に存在するテトラフルオロエチレンを放
出した。のち必要によっては８０〜１６０℃の範囲で熱
処理しても良し。After the reaction was completed, the excess tetrafluoroethylene was released. If necessary, heat treatment may be performed in the range of 80 to 160°C.
このようにして本発明の含フツ素ジビニルエーテルを製
造することができる。In this way, the fluorine-containing divinyl ether of the present invention can be produced.
（効 果）
一般式〔■〕で示される含フツ素ジビニルエーテルは、
パーフルオロジビニルエーテルＣＦ２−ＣＦ’ＯＲ’ｆ
ＯＣＦ−ＣＦ２ （Ｒ’ｆはパーフルオロアルキレン基
）やパーフルオロジビニル化合物、例えば、ＣＦ ２−
ＣＦＣＦ’−Ｃ’Ｆ ２ 等の公知化合物に較べ、非
常に良好な重合性を示す。又と＜ ｉｃ他ノモノマー、
例、ｔば、パーフルオロモノビニルエーテルＣＦ ２−
ＣＦＯＲ′ｆ（Ｒ”ｆはパーフルオロアルキル基）；パ
ーフルオロオレフィン、例えば、ＣＦ２−ＣＦ２ 、
ＣＦ５ＣＦ−ＣＦ２ ：フルオロオレフイン、 例ｔバ
ー ｃｔｃＦ−ｃｍ２゜ＣＦ ２−Ｃ’ＨＦ 等との共
重合においても広い組成において高い重合率で重合し、
含フツ素架橋重合体を得ることができる。(Effect) The fluorine-containing divinyl ether represented by the general formula [■] is
Perfluorodivinyl ether CF2-CF'OR'f
OCF-CF2 (R'f is a perfluoroalkylene group) and perfluorodivinyl compounds, such as CF2-
It shows very good polymerizability compared to known compounds such as CFCF'-C'F 2 . Matato < ic other monomers,
Example, perfluoromonovinyl ether CF2-
CFOR'f (R"f is a perfluoroalkyl group); perfluoroolefins, such as CF2-CF2,
CF5CF-CF2: Fluoroolefin, e.g. ctcF-cm2゜CF2-C'HF It polymerizes at a high polymerization rate in a wide range of compositions,
A fluorine-containing crosslinked polymer can be obtained.
従って１本発明の含フツ素ジビニルエーテルは架橋剤と
して有用であるほか、反応活性な二重結合を利用して撥
水剤、コーティング剤等の含フツ素化合物の合成原料と
して有用である。Therefore, the fluorine-containing divinyl ether of the present invention is useful not only as a crosslinking agent but also as a raw material for the synthesis of fluorine-containing compounds such as water repellents and coating agents by utilizing the reactive double bond.
（実施例）
本発明を更に具体的に説明するため、以下に実施例を挙
げて説明するが、本発明はこれらの実施例に限定される
ものではｋい。(Examples) In order to explain the present invention more specifically, examples will be described below, but the present invention is not limited to these examples.
実施例 １
３００−のステンレス製オートクレーブにＮａＨｌ、８
．９及び予め乾燥したジオキサン３０―を入れたのち、
ＨＯＣＨ２ＣＦＯＣＦ２ＣＦ２０ＣＦＣＨ２０Ｈ９，６
９を２０ｓｄのジオキサンに予め溶解した溶液を攪拌し
つつ２０℃で１０分間かけて添加した。添加終了後、テ
トラフルオロエチレンを２０に４／−ｉｔで導入したの
ち、テトラフルオロエチレンの圧力を２０に！ｉＩ／ｆ
ｆｌに保ちむがら３０℃で４０時間反応をおこｆ、つた
。反応終了後、テトラフルオロエチレンを放出したのち
反応物を水にあけ、エーテルで抽出したのち、エーテル
層を水洗した。次に、このエーテル溶液をＮａ２ＳＯ４
で脱水したのち蒸留し、沸点８０〜８２℃／２０ｍＨ，
ｐの留分７．６１１を得た。核留分の化合物の構造は、
ＩＲ。Example 1 NaHl, 8
．． After adding 9 and pre-dried dioxane 30-, HOCH2CFOCF2CF20CFCH20H9,6
A solution in which 9 was previously dissolved in 20 sd of dioxane was added to the solution at 20° C. over 10 minutes with stirring. After the addition was completed, tetrafluoroethylene was introduced at 4/-it to 20°C, and the pressure of tetrafluoroethylene was increased to 20°C! iI/f
The reaction was carried out at 30° C. for 40 hours while maintaining the temperature at 100° C. After the reaction was completed, tetrafluoroethylene was released, the reaction product was poured into water, extracted with ether, and the ether layer was washed with water. Next, this ether solution was mixed with Na2SO4
After dehydrating with
A fraction 7.611 of p was obtained. The structure of the nuclear fraction compound is
IR.
ＭＳ、１９Ｆ−ＮＭＲ，＋Ｈ−ＮＭＲ及び元素分析によ
り
Ｍ／ｅ：１１１ （ΦＣＨ２０ＣＦ−Ｃ’Ｆ’２）ハ
）ＩＨ−ＮＭＲ，＋９Ｆ−ＮＭＲ（第２図及び第５図に
チャートを示した。）
ＣＦ２−ＣＦＯＣＨ２ＣＦＯＣＦ２ＣＦ２０ＣＦＣＨ２
０ＣＦ−ＣＦ２である事が確認された。M/e: 111 (ΦCH20CF-C'F'2) c) IH-NMR, +9F-NMR (charts are shown in FIGS. 2 and 5) by MS, 19F-NMR, +H-NMR and elemental analysis. ) CF2-CFOCH2CFOCF2CF20CFCH2
It was confirmed that it was 0CF-CF2.
ィ）ＩＲ（第１図にチャートを示した。）２９７５ ｃ
ｍ−’ （−ＣＨ２−）１８３５備−’
（−０ＣＦ−ＣＦ２）１０５０〜１４００傭−
”（−ＣＦ２−）９４５ ｃｍ−’ （−０
ＣＨ２−）１ ２７．２ ｐｐｍ
１ ２１．５ ｐｐｍ
１ ３８．９ ｐｐｍ
、ｉ、、ｉ ３ ｐＴ）ｍ
１ ３６．０１）１）ｍ
８３、Ｏｐｐｍ
８６．８ ｐｐｍ
０′５
実施例 ２
実施例１にわいて、ＮａＨのかわりにＮａを用いたほか
は実施例１と同様な操作を行ｆｘＩＡ、ＨＯＣＨ２ＣＦ
２ＣＦ２Ｃ’ｌ’ｉ’２０Ｆ２Ｃ’Ｈ２０ＨからＣ”Ｆ
２−Ｃ沁Ｊ２ＣＦ２α２α２ＣＦ２ＣＨ２加−ＣＦ２
を得た。b) IR (Chart shown in Figure 1) 2975 c
m-'(-CH2-)1835Bi-'
(-0CF-CF2) 1050~1400 yen-
”(-CF2-)945 cm-' (-0
CH2-)1 27.2 ppm 1 21.5 ppm 1 38.9 ppm, i,, i 3 pT) m 1 36.01) 1) m 83, Oppm 86.8 ppm 0'5 Example 2 Example 1, the same operation as in Example 1 was carried out except that Na was used instead of NaH. fxIA, HOCH2CF
2CF2C'l'i'20F2C'H20H to C"F
2-C 沁J2CF2α2α2CF2CH2加-CF2
I got it.
生成物の構造は、 Ｉ Ｒ、Ｍ Ｓ １１９Ｆ−ＮＭＲ
。The structure of the product is: IR, MS 119F-NMR
.
’Ｈ−ＮＭＲ及び元素分析により確認した。Confirmed by 'H-NMR and elemental analysis.
イ） Ｉ Ｒ２９７５ｆｆｉ−’ （−
ＣＨ２−）１８４５ ｃｍ−’ （−００Ｆ−
ＣＦ２）１０５０〜１４００ｃｒＲ−’ （−ＣＦ２−
）９４５ｍ−’ （−〇〇Ｈ２−）０） Ｍ
Ｓ Ｍ／ｅ ： ３１１ （Ｃ’Ｆ２−ＣＦＯ
Ｃ［（２Ｃ’ｌ’ｉ”２ＣＦ’２Ｃ’Ｆ２ＣＦ２°）Ｍ
／ｅ：１１１ （■ＣＨ２０ＣＦ−ＣＦ２）実施例
３
実施例１及び２で詳細に説明したのと同様た方法により
、第１表に記載した含フツ素ジビニルエーテルを合成し
た。ｋか、第１表には合成した含フツ素ジビニルエーテ
ルの赤外吸収スペクトルにおける特性吸収値及びＭＳの
結果も併記した。b) I R2975ffi-' (-
CH2-)1845 cm-' (-00F-
CF2) 1050-1400crR-' (-CF2-
)945m-' (-〇〇H2-)0) M
S M/e: 311 (C'F2-CFO
C[(2C'l'i"2CF'2C'F2CF2°)M
/e:111 (■CH20CF-CF2) Example
3 The fluorine-containing divinyl ethers listed in Table 1 were synthesized by the same method as described in detail in Examples 1 and 2. Table 1 also lists the characteristic absorption values and MS results in the infrared absorption spectrum of the synthesized fluorine-containing divinyl ether.
実施例 ４
実施例１〜３で得られたそれぞれの含フツ素ジビニルエ
ーテルとＣＦ２−ＣＦＯＣＦ２ＣＦ２ＣＦ３との共重合
を行なった。Example 4 Each of the fluorine-containing divinyl ethers obtained in Examples 1 to 3 was copolymerized with CF2-CFOCF2CF2CF3.
ガラス製のアンプルに本発明の含フツ素ジビニルエーテ
ルが３０．５０．７０及び９０ｍｏｌｅ％の組成の上記
コモノマーとの混合物をそれぞれ加え、さらに重合開始
剤として（ＣＦ、ＣＦ２Ｃｏ２）−を含フツ素ジビニル
エーテル及びコモノマーの合計量に対し２ ｍｏｌｅ％
となるように加えた。次にアンプルをドライアイス−メ
タノール中に浸漬し、真空ポンプで窒素を大気圧封入し
た。アンプルを２０℃のオイルバスに震盪下に２４時間
浸漬した。その後オイルバスの温度を１００℃にあげ５
時間重合を続けた。アンプルの内容物はいずれも半透明
白色固化物とｔｘつた。得られた各重合物をアンプルか
ら取出し、トリクロルトリフルオロエタンに還流下に５
時間浸漬して未重合モノマー及び低重合物を抽出した。Mixtures of the fluorinated divinyl ether of the present invention with the above comonomers having compositions of 30.50.70 and 90 mole% were added to glass ampoules, and (CF, CF2Co2)- was added as a polymerization initiator. 2 mole% based on the total amount of vinyl ether and comonomer
I added it so that Next, the ampoule was immersed in dry ice-methanol and filled with nitrogen at atmospheric pressure using a vacuum pump. The ampoule was immersed in a 20° C. oil bath with shaking for 24 hours. After that, raise the temperature of the oil bath to 100℃ 5
Polymerization was continued for hours. The contents of the ampoules were all translucent white solids. Each of the obtained polymers was taken out from the ampoule and diluted with trichlorotrifluoroethane under reflux for 5 minutes.
Unpolymerized monomers and low polymers were extracted by soaking for a period of time.
その後１００℃で減圧乾燥した後、各重合物の重さを測
り、アンプルに仕込んだ時の重さから各重合物について
重合率を下記式により求めた。After drying under reduced pressure at 100°C, the weight of each polymer was measured, and the polymerization rate of each polymer was determined from the weight when charged into an ampoule using the following formula.
得られた結果を次表に示す。The results obtained are shown in the table below.
比較として本発明の含フツ素ジビニルエーテルに代えて
ＣＦ２−ＣＦ’０ＣＦ２ＣＦ２００Ｆ−ＣＦ２ を用
いて上記と同様に重合を行にい、その結果を表に併記し
た。For comparison, polymerization was carried out in the same manner as above using CF2-CF'0CF2CF200F-CF2 in place of the fluorine-containing divinyl ether of the present invention, and the results are also shown in the table.
表 つた。）table Ivy. )
第１図は実施例１で得られた化合物の赤外吸収スペクト
ルであり、第２図及び第３図は。
実施例１で得られた化合物の１９ｐ−核磁気共鳴スペク
トル及び１Ｈ−核磁気共鳴スペクトルである。
昭和６３年１２月み日FIG. 1 shows the infrared absorption spectrum of the compound obtained in Example 1, and FIGS. 2 and 3 show the infrared absorption spectrum of the compound obtained in Example 1. 1 is a 19p-nuclear magnetic resonance spectrum and a 1H-nuclear magnetic resonance spectrum of the compound obtained in Example 1. December 1986
Claims (2)
＿２ 〔但し、Ｒ＿ｆは、 ▲数式、化学式、表等があります▼ 〔但し、ｊ及びｎはそれぞれ０又は１であり、ｋ及びｍ
はそれぞれ０以上の整数であり（但し、Ｊが０のときは
ｋは０であり、ｎが０のときはｍは０である。）、ｌは
２以上の整数である。〕で示される基である。〕 で示される含フッ素ジビニルエーテル。(1) The following formula CF_2=CFOCH_2R_fCH_2OCF=CF
＿２ [However, R_f is: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, j and n are each 0 or 1, and k and m
are each an integer of 0 or more (however, when J is 0, k is 0, and when n is 0, m is 0), and l is an integer of 2 or more. ] is a group represented by ] A fluorine-containing divinyl ether represented by the following.
はそれぞれ０以上の整数であり（但し、ｊが０のときは
ｋは０であり、ｎが０のときはｍは０である。）、ｌは
２以上の整数である。〕で示される基である。〕 で示される含フッ素ジオールをアルカリ金属又はアルカ
リ金属水素化物と反応させ、次いで、テトラフルオロエ
チレンと反応させることを特徴とする特許請求の範囲第
（１）項記載の含フッ素ジビニルエーテルの製造方法。(2) The following formula HOCH_2R_fCH_2OH [However, R_f has ▲ mathematical formula, chemical formula, table, etc. ▼ [However, j and n are each 0 or 1, and k and m
are each an integer of 0 or more (however, when j is 0, k is 0, and when n is 0, m is 0), and l is an integer of 2 or more. ] is a group represented by ] A method for producing a fluorine-containing divinyl ether according to claim (1), which comprises reacting the fluorine-containing diol represented by with an alkali metal or an alkali metal hydride, and then reacting with tetrafluoroethylene. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32058088A JPH0655685B2 (en) | 1988-12-21 | 1988-12-21 | Fluorine-containing divinyl ether and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32058088A JPH0655685B2 (en) | 1988-12-21 | 1988-12-21 | Fluorine-containing divinyl ether and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02167242A true JPH02167242A (en) | 1990-06-27 |
| JPH0655685B2 JPH0655685B2 (en) | 1994-07-27 |
Family
ID=18123009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32058088A Expired - Lifetime JPH0655685B2 (en) | 1988-12-21 | 1988-12-21 | Fluorine-containing divinyl ether and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0655685B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106036A (en) * | 2006-09-29 | 2008-05-08 | Fujifilm Corp | Polymerizable fluorine-containing compound, antireflective membrane using the same, antireflective film, image display device, fluorine-containing alcohol for polyurethane and composition containing the same |
| JP2010053084A (en) * | 2008-08-28 | 2010-03-11 | Fujifilm Corp | Polymerizable fluorine-containing compound, antireflective membrane using the same, antireflective film, image display and fluorine-containing alcohol |
| EP2239284A1 (en) * | 2008-01-28 | 2010-10-13 | Asahi Glass Company, Limited | Curable composition, fluorine-containing cured product, optical material using the cured product, and light-emitting device |
| JP2013035849A (en) * | 2006-09-29 | 2013-02-21 | Fujifilm Corp | Fluorine-containing alcohol and composition for water-repellent polyurethane using the same |
-
1988
- 1988-12-21 JP JP32058088A patent/JPH0655685B2/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008106036A (en) * | 2006-09-29 | 2008-05-08 | Fujifilm Corp | Polymerizable fluorine-containing compound, antireflective membrane using the same, antireflective film, image display device, fluorine-containing alcohol for polyurethane and composition containing the same |
| JP2013035849A (en) * | 2006-09-29 | 2013-02-21 | Fujifilm Corp | Fluorine-containing alcohol and composition for water-repellent polyurethane using the same |
| EP2239284A1 (en) * | 2008-01-28 | 2010-10-13 | Asahi Glass Company, Limited | Curable composition, fluorine-containing cured product, optical material using the cured product, and light-emitting device |
| EP2239284A4 (en) * | 2008-01-28 | 2011-02-16 | Asahi Glass Co Ltd | Curable composition, fluorine-containing cured product, optical material using the cured product, and light-emitting device |
| JP2010053084A (en) * | 2008-08-28 | 2010-03-11 | Fujifilm Corp | Polymerizable fluorine-containing compound, antireflective membrane using the same, antireflective film, image display and fluorine-containing alcohol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0655685B2 (en) | 1994-07-27 |
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