JPS61209A - Production of fluorine-containing polymer - Google Patents
Production of fluorine-containing polymerInfo
- Publication number
- JPS61209A JPS61209A JP11991784A JP11991784A JPS61209A JP S61209 A JPS61209 A JP S61209A JP 11991784 A JP11991784 A JP 11991784A JP 11991784 A JP11991784 A JP 11991784A JP S61209 A JPS61209 A JP S61209A
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- Prior art keywords
- formula
- fluorine
- polymerization
- polymer
- catalyst
- Prior art date
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Abstract
Description
【発明の詳細な説明】
本発明はフッ素系アクリレートまたはフッ素系メタクリ
レートなどのフッ素系不飽和エステルモノマーを有機リ
チウム触媒の存在下重合することを特徴とする含フツ素
重合体の製造に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of a fluorine-containing polymer, which is characterized by polymerizing a fluorine-containing unsaturated ester monomer such as a fluorine-containing acrylate or a fluorine-containing methacrylate in the presence of an organolithium catalyst. .
（産業上の利用分野）
含フツ素アクリレートあるいは含フツ素メタクリレート
類は工業的に重要なポリマーを与える。特にフッ素系の
機能性が生かされる分野。(Industrial Application Field) Fluorine-containing acrylates or fluorine-containing methacrylates provide industrially important polymers. Fields where the functionality of fluorine-based compounds is particularly useful.
たとえばフッ素系の撥水撥油機能を生かした繊維処理剤
、耐薬品性および耐熱性を生かしたフツ素系ゴムあるい
はプラスチック材料、耐候性を生かしたフィルム材料や
塗料、低屈折性を生かした光学繊維などの光学材料、そ
の他レジスト材料や医用材料への応用が検討され実用化
されているものも多い。For example, fiber treatment agents that take advantage of fluorine-based water and oil repellency, fluorine-based rubber or plastic materials that take advantage of their chemical and heat resistance, film materials and paints that take advantage of their weather resistance, and optics that take advantage of their low refractive properties. Applications to optical materials such as fibers, resist materials, and medical materials have been studied and many have been put into practical use.
（従来の技術）
現在、実用化されている前記モノマーの重合方式はラジ
カル重合によるものである。たとえばベンゾイルパーオ
キシドのような油溶性過酸化物、アゾビスイソブチロニ
トリルのようなアゾ化合物、過硫酸アンモニウム、！！
１酸化水素のような無機過酸化物などを使用して、有機
媒体中で溶液重合、水系で懸濁重合あるいは乳化重合を
行う方法が一般的である。(Prior Art) The polymerization method of the monomers currently in practical use is radical polymerization. For example, oil-soluble peroxides like benzoyl peroxide, azo compounds like azobisisobutyronitrile, ammonium persulfate,! !
Common methods include solution polymerization in an organic medium, suspension polymerization or emulsion polymerization in an aqueous system using an inorganic peroxide such as hydrogen monoxide.
（発明が解決しようとする問題点）
一方、炭化水素のアクリレートあるいはメタクリレート
類はｎ−ブチルリチウムなどの有機） □Ｍ、によ
、ア＝オフ□オ、６ｅ、！＝ｄｉｌｐゎている。たとえ
ばメタクリル酸メチルは、ｎ −ブチルリチウム触媒に
よルトルエン中でアニオン重合し、ポリマーを与える。(Problems to be solved by the invention) On the other hand, hydrocarbon acrylates or methacrylates are organic compounds such as n-butyllithium) □M, yo, a=off □o, 6e,! = dilpwa. For example, methyl methacrylate undergoes anionic polymerization in letoluene with an n-butyllithium catalyst to give a polymer.
しかし、フッ累系のアクリレートあるいはメタクリレー
ト類をアニオン重合した試みは数少ない。However, there have been only a few attempts to anionically polymerize fluorine-based acrylates or methacrylates.
以上のような事実をふまえ、我々は前記含フツ素アクリ
レートおよび含フツ素メタクリレートモノマーに対して
１種々のアニオン重合触媒を応用して検討した結果、あ
る種類の有機リチウム触媒が重合活性があることを見出
し、本発明を完成するに到った。Based on the above facts, we investigated the application of various anionic polymerization catalysts to the fluorine-containing acrylate and fluorine-containing methacrylate monomers, and found that a certain type of organolithium catalyst has polymerization activity. They discovered this and completed the present invention.
（問題点を解決するための手段）
本発明に使用されるフッ累系アクリレートおよびフッ素
系メタクリレ〜トモツマ−は一般式ｎはθ〜５の整数。(Means for Solving the Problems) The fluorine-based acrylates and fluorine-based methacrylates used in the present invention have a general formula where n is an integer of θ to 5.
Ｒｆは炭素数１〜２０個を有するポリフルオロアルキル
基。Ｒ１は低級アルキル基、ＨまたはＲｆ基。〕
で示される化合物でオシ、具体的には２．２．２−）リ
フルオロエチルアクリレ−）、２．２．２−トリフルオ
ロエチルメタクリレ−） 、 Ｈ（、ＩＨ，３Ｈ−テ
トラフルオログロビルアクリレート、 ＩＨ，ＩＨ；
３Ｈ−テトラフルオログロピルメタクリレート、ヘキサ
ヘプタフルオロブチルメタクリレート、ヘプタフルオロ
イソグロビルアクリレート、ヘプタフルオロイソプロピ
ルメタクリレート、 ＩＨ，、ＩＨ，５Ｈ−オクタフ
ルオロペンチルアクリレ−）、ＩＨ。Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms. R1 is a lower alkyl group, H or Rf group. ] A compound represented by the following, specifically 2.2.2-)lifluoroethyl acrylate), 2.2.2-trifluoroethyl methacrylate), H(,IH,3H-tetrafluoro Globyl acrylate, IH, IH;
3H-tetrafluoroglopyl methacrylate, hexaheptafluorobutyl methacrylate, heptafluoroisoglobyl acrylate, heptafluoroisopropyl methacrylate, IH,, IH, 5H-octafluoropentyl acrylate), IH.
ＩＨ，５Ｈ−オクタフルオロペンチルメタクリレ−）
、 ＩＨ，ＩＨ，７Ｈ−ドデカフルオロへブチルアク
リレート、ＩＨ，ＩＨ，７Ｈ−ドデカフルオロへプチル
メｐクリｖ −）、 ＩＨ，ＩＨ−ペンタデカフルオ
ロオクチルアクリレート、＋ａ、ｔａ−ペンタデカフル
オロオクチルメタクリレートなどがあげられる。IH, 5H-octafluoropentyl methacrylate)
, IH, IH, 7H-dodecafluoroheptyl acrylate, IH, IH, 7H-dodecafluoroheptyl methacrylate, IH, IH-pentadecafluorooctyl acrylate, +a, ta-pentadecafluorooctyl methacrylate, etc. can give.
重合触媒である有機リチウム化合物は一般式％式％
水素またはフェニル基２ｍは１以上の整数。ｐルリチウ
ムとジフェニルエチレンの反応によって得られる１、１
−ジフェニルヘキシルリチウム。The organic lithium compound that is a polymerization catalyst has the general formula % where hydrogen or phenyl group 2m is an integer of 1 or more. 1,1 obtained by the reaction of p-lulithium and diphenylethylene
-Diphenylhexyllithium.
ｎ−ブチルリチウムとスチレンの反応によって得られる
１−フェニルヘキシルリチウムおよびポリスチリルリチ
ウム化合物、ｎ−ブチルリチウムとα−メチルスチレン
の反応によって得られるｌ−フェニル−１−メチルヘキ
シルリチウムおよびポリ−α−メチルスチリルリチウム
、リチウム金属とα−メチルスチレンとの反応により生
成するａ−メチルスチレン四量体リチウム塩などがあげ
られる。これらの有機リチウム化合物は通常ｎ−ヘキサ
ン、ｎ−へブタン、ベンゼン、トルエンなどの炭化水素
溶液として使用する。1-phenylhexyllithium and polystyryllithium compounds obtained by the reaction of n-butyllithium and styrene, l-phenyl-1-methylhexyllithium and poly-α- obtained by the reaction of n-butyllithium and α-methylstyrene Examples include methylstyryllithium and a-methylstyrene tetramer lithium salt produced by a reaction between lithium metal and α-methylstyrene. These organolithium compounds are usually used in the form of a hydrocarbon solution such as n-hexane, n-hebutane, benzene, or toluene.
本発明の製造方法について以下詳細に述べる。The manufacturing method of the present invention will be described in detail below.
含フツ素アクリレートおよび含７ツ累メタクリレートは
窒素あるいはヘリウム気流下で蒸留精製し、完全に脱酸
素した純度９９．５４以上のものが使用される。微量の
水分は重合を抑制するためモレキュラーシーブスなどで
脱水した方が好ましい。The fluorine-containing acrylate and the fluorine-containing methacrylate are purified by distillation under a stream of nitrogen or helium, and those having a purity of 99.54 or higher and completely deoxidized are used. It is preferable to dehydrate trace amounts of water using molecular sieves or the like in order to suppress polymerization.
有機リチウム化合物は市販のあるいは常法によシ合成し
たｎ−ブチルリチウムなどのアルキルリチウムと精製し
た１、１−ジフェニルエチレン、スチレンなどとの反応
によシ合成される。The organolithium compound is synthesized by reacting a commercially available or synthesized alkyllithium such as n-butyllithium with purified 1,1-diphenylethylene, styrene, or the like.
有機リチウム化合物は空気や空気中の水分と敏感に反応
するため、窒素系の密封容器内に保存するが、好ましく
は合成後、早期に使用する。Since organolithium compounds react sensitively with air and moisture in the air, they are stored in a sealed nitrogen-based container, but preferably used early after synthesis.
溶媒中でアルキルリチウムと反応試剤を反応し、所期の
有機リチウム化合物を合成し１次に含フツ素不飽和エス
テルモノマーを添加する方法が適当である。A suitable method is to react an alkyllithium with a reaction reagent in a solvent to synthesize the desired organolithium compound, and then first add a fluorine-containing unsaturated ester monomer.
溶媒は触媒調整およびポリマー製造の重合活性の面で、
芳香族炭化水素または脂肪族炭化水（素が好１しく・同
様な非７°ＯＦ７糸有機溶媒１もジエチルエーテル、テ
トラヒドロフランなどの極性溶媒では重合が進まない。Solvents are important in terms of catalyst adjustment and polymerization activity in polymer production.
Polymerization does not proceed with aromatic hydrocarbons or aliphatic hydrocarbons (preferably bare) and similar non-7°OF7 organic solvents 1 with polar solvents such as diethyl ether and tetrahydrofuran.
重合温度、触媒調整温度は一７８〜１００℃、好ましく
は一２０〜８０℃が適当である。重合時間は限定されず
、有機リチウム触媒の種類または不飽和エステルモノマ
ーと触媒との組み合わせによシ決定される。重合を終了
させるためには。The appropriate polymerization temperature and catalyst adjustment temperature are -78 to 100°C, preferably -20 to 80°C. The polymerization time is not limited and is determined by the type of organolithium catalyst or the combination of unsaturated ester monomer and catalyst. In order to terminate the polymerization.
メタノール、エタノール、イソプロパツールなどのプロ
トン系有機溶媒を重合系へ少量添加する。生成ポリマー
はメタノールなどの有機溶媒で洗浄、濾過をくシ返し、
乾燥する。A small amount of a protic organic solvent such as methanol, ethanol, or isopropanol is added to the polymerization system. The generated polymer is washed with an organic solvent such as methanol, filtered, and then
dry.
（作用）
以上のような含７ツ素エステルモノマーの重合は、単独
あるいは２種以上を共重合させてもヨく、炭化水素のス
チレン、ブタジェンなどの有機リチウム化合物で重合す
るモノマー類と共重合させてもよい。さらに本重合系の
有機リチウム触媒はポリスチリルリチウムなどのポリマ
ー触媒にも拡大でき、ポリスチレンのポリマー鎖に含フ
ッ素不飽和エステルモノマー鎖を接続場せるなどのブロ
ック共重合体も製造可能である。(Function) The above-mentioned hepta-containing ester monomers can be polymerized singly or in combination of two or more, and can be copolymerized with monomers that are polymerized with organic lithium compounds such as hydrocarbons styrene and butadiene. You may let them. Furthermore, the organolithium catalyst of this polymerization system can be extended to polymer catalysts such as polystyryllithium, and it is also possible to produce block copolymers such as those in which a fluorine-containing unsaturated ester monomer chain is connected to a polystyrene polymer chain.
このように、含フツ素重合体の用途例とじては、撥水撥
油剤、レジスト材料、シートおよびフィルムなどの成形
材料、含フツ素ゴム、塗料。As described above, examples of uses of fluorine-containing polymers include water and oil repellents, resist materials, molding materials such as sheets and films, fluorine-containing rubbers, and paints.
接着剤などがあけられる。Adhesive etc. can be used.
以下実施例により本発Ｅ！Ａを具体的に説明する。The following examples are based on this E! A will be explained specifically.
実施例】
容量５０ｍｇのガラス反応管を乾燥および窒素置換し、
窒素気流下精製したトルエン２０ゴ。Example: A glass reaction tube with a capacity of 50 mg was dried and replaced with nitrogen.
20 grams of toluene purified under a nitrogen stream.
トリフルオロエチルメタクリレート２０ｍモル、１．１
−ジフェニルヘキシルリチウム０．４ｍモルを順に仕込
み、〜２０℃で５日間重合を行った。20 mmol of trifluoroethyl methacrylate, 1.1
0.4 mmol of -diphenylhexyllithium was sequentially charged, and polymerization was carried out at ~20°C for 5 days.
重合停止は重合系をメタノールへ開放後、生成ポリマー
を濾過し真空乾燥を行った。ポリマー収量は２．０ｙ、
収率は５９．４チであった。２５℃クロロホルム溶液で
測定したポリマーの極限粘度〔η〕は０．１０５であっ
た。ポリマーの赤外吸収スペクトルは１７４０ｃｔｎ”
に（１！ ＝ ０ 、 １１００ Ｎ＋４０００＋１”
にＯ−Ｆの吸収が認められた。重水素化アセトン溶液の
’Ｈ−ＮＭＲスペクトル（：ＴＭＳ）は、 １．ｌｐ
ｐｍに−ＯＨ。To terminate the polymerization, the polymerization system was opened to methanol, and the resulting polymer was filtered and vacuum-dried. Polymer yield is 2.0y,
The yield was 59.4 cm. The intrinsic viscosity [η] of the polymer measured in a chloroform solution at 25° C. was 0.105. The infrared absorption spectrum of the polymer is 1740ctn"
to (1! = 0, 1100 N+4000+1”
Absorption of O-F was observed. The 'H-NMR spectrum (:TMS) of the deuterated acetone solution is as follows: 1. lp
-OH to pm.
２、ｌｐｐｍに主鎖の一〇Ｈ，−１４．４ ｐｐｍに側
鎖の−ＯＨ，−のビークを示し、それらの面積比は３：
２：２であった。2. The peak of 10H of the main chain is shown at lppm, and the peak of -OH, - of the side chain is shown at -14.4 ppm, and their area ratio is 3:
The ratio was 2:2.
実施例２
実施例１と同様にして６０℃で１１日間の重合を行った
。ポリマー収量は１．１３Ｆ、収率は３３．７チであっ
た。Example 2 Polymerization was carried out at 60° C. for 11 days in the same manner as in Example 1. The polymer yield was 1.13F and the yield was 33.7F.
以上実施例１および２で得られたポリマーの熱分解開始
温度はいずれも２００℃以上、ガラス転移温度は約７８
℃であった。The thermal decomposition initiation temperatures of the polymers obtained in Examples 1 and 2 are both 200°C or higher, and the glass transition temperature is approximately 78°C.
It was ℃.
比較例１
実施例！および２と同様にして、溶媒をテトラヒドロン
ランに変え重合を行ったがポリマーは生成しなかった。Comparative Example 1 Example! Polymerization was carried out in the same manner as in 2 and 2, changing the solvent to tetrahydronerane, but no polymer was produced.
比較例２
実施例１と同様にして１．１−ジフェニルヘキシルリチ
ウムに変えｎ−ブチルリチウムを触媒として重合を行っ
たが、ポリマー収量は０．１４５ｉＥ、収率は４．２チ
であった。Comparative Example 2 Polymerization was carried out in the same manner as in Example 1 using n-butyllithium as a catalyst instead of 1.1-diphenylhexyllithium, but the polymer yield was 0.145 iE and 4.2 iE.
実施例５
実施例１と同様にしてトルエン２０ ｄ 、ヘキサフル
オロイングロビルメタクリレート２０ｍモル、ｓ、ｓ−
ジフェニルヘキシルリチウム０．４ｍモルを順に仕込み
、−２０℃で６日間重合を行った。ポリブー収量は３．
２４５Ｆ、収率は６８．７チであった。２５℃、クロロ
ホルム溶液で測定したポリマーの極限粘度〔η〕は、
０．０１５であった。ポリマーの赤外吸収スペクトル
は、 １７６０Ｃ２１１にＯ＝ ０ 、 １１００〜１
４００ｃｒＩｖ”にＯ−Ｆの吸収が認められた。重水素
化アセトン溶液の’Ｈ−ＮＭＲスペクト＃（：７Ｍ８）
は１ 、２ ｐｐｍに一〇Ｈ３，２、２ｐｐｍに−ＯＨ
，−１６、４ｐｐｍに−ａＨぐのピークを示し、それら
の面積比は３：２：１であった。Example 5 In the same manner as in Example 1, 20 d of toluene, 20 mmol of hexafluoroinglovyl methacrylate, s, s-
0.4 mmol of diphenylhexyllithium was sequentially charged, and polymerization was carried out at -20°C for 6 days. Polybou yield is 3.
245F, yield was 68.7%. The intrinsic viscosity [η] of the polymer measured in chloroform solution at 25°C is:
It was 0.015. The infrared absorption spectrum of the polymer is O = 0 at 1760C211, 1100~1
Absorption of O-F was observed at 400 crIv''.'H-NMR spectrum of deuterated acetone solution #(:7M8)
-OH to 1, 2 ppm -OH to 3, 2, 2 ppm
-aH peaks were observed at , -16 and 4 ppm, and their area ratio was 3:2:1.
実施例４
実施例３と同様にして、室温で１１日間の重合を行った
。ポリマー収量は２．５２ノ、収率は５３．４チであっ
た。Example 4 Polymerization was carried out in the same manner as in Example 3 at room temperature for 11 days. The polymer yield was 2.52 mm, and the yield was 53.4 mm.
以上実施例３および４で得られたポリマーの熱分解開始
温度はいずれも３００℃以上、ガラス） 転移温
度は約８５℃であった。The thermal decomposition initiation temperature of the polymers obtained in Examples 3 and 4 was 300°C or higher, and the glass transition temperature was about 85°C.
比較例５
実施例３および鴫と同様にして、溶媒をテトラヒドロフ
ランに変え重合を行ったがポリマーは生成しなかった。Comparative Example 5 Polymerization was carried out in the same manner as in Example 3 and Shizu, changing the solvent to tetrahydrofuran, but no polymer was produced.
比較例４
実施例１と同様にして１．１−ジフェニルヘキシルリチ
ウムに変えｎ−ブチルリチウムを触媒として重合を行っ
たが、ポリマー収量は０．７２ノ、収率は１５．３％で
あった。Comparative Example 4 Polymerization was carried out in the same manner as in Example 1 using n-butyllithium as a catalyst instead of 1.1-diphenylhexyllithium, but the polymer yield was 0.72 and the yield was 15.3%. .
実施例５
容量１００．ｄのガラス反応管を乾燥および窒素置換し
、窒素気流下精製したトルエン５０ｄ１スチレン２０ｍ
モル、ｎ−７’チルリチウム２ｍモルを順に仕込み、室
温で１日間重合しポリスチルリチウム化合物を生成させ
た。次にこの重合系に窒素気流下精製したトリフルオロ
エチルメタクリレート２０ｆｆ１モルを添加し重合をさ
らに５日間続けた。重合停止は１重合系をメタノールへ
開放後、生成ポリマーを濾過洗浄し、真空乾燥を行った
。ポリマー収量は５．３５Ｅ、収率は７７．９％であっ
た。生成ポリマーの工Ｒスペクトルはトリフルオロエチ
ルメタクリレートポリマーおよびポリスチレン両者のピ
ークを示した。Example 5 Capacity 100. The glass reaction tube of d was dried and replaced with nitrogen, and purified toluene 50d1 styrene 20m
mol and 2 mmol of n-7' chilllithium were charged in this order and polymerized at room temperature for one day to produce a polystillithium compound. Next, 20ff1 mole of trifluoroethyl methacrylate purified under a nitrogen stream was added to this polymerization system, and the polymerization was continued for another 5 days. Polymerization was terminated by opening the polymerization system to methanol, filtering and washing the resulting polymer, and vacuum drying. The polymer yield was 5.35E, and the yield was 77.9%. The engineered R spectrum of the resulting polymer showed both trifluoroethyl methacrylate polymer and polystyrene peaks.
実施例６
実施例１と同様にしてトルエン２０ｔｔｌ、ト’）フル
オロエチルアクリレート２０ｍモル、１．１−ジフェニ
ルヘキシルリチウム０．４ｍモル’ｋ ＩＩ Ｋ仕込み
、−２０℃で６日間重合を行った。ポリマー収量は０．
３７ｆ、収率は１２％であった。Example 6 In the same manner as in Example 1, 20 ttl of toluene, 20 mmol of t')fluoroethyl acrylate, and 0.4 mmol of 1,1-diphenylhexyllithium 'k II K were charged, and polymerization was carried out at -20°C for 6 days. Polymer yield is 0.
37f, yield was 12%.
特許出願人 セントラル硝子株式会社手 続 補
正 書
昭和６０年に月／／日Patent Applicant: Central Glass Co., Ltd. Procedures Amendment: Month//Day, 1985
Claims (1)
式、表等があります▼ｎは０〜５の整数。Ｒ＿ｆは炭素
数１〜２０個を有するポリフルオロアルキル基。Ｒ＾１
は低級アルキル基、ＨまたはＲ＿ｆ基〕 で示される含フッ素不飽和エステルモノマーを有機リチ
ウム触媒の存在下重合することを特徴とする含フッ素重
合体の製造方法。 ２）一般式 Ｒ＿ｘＲ＿ｙ＾■Ｌｉ＾■ 〔但し、Ｒ＿ｘはＣｍＨ＿２＿ｍ＿＋＿１−（ＣＺ＿１
Ｚ＿２−ＣＨ＿２）−＿ｐ、Ｚ＿１、Ｚ＿２は水素また
はフェニル基、ｍは１以上の整数。 ｐは０または１以上の整数。Ｒ＿ｙは ▲数式、化学式、表等があります▼、Ｚ＿１は水素また
はフェニル基。〕で示される有機リチウム触媒を使用す
ることを特徴とする特許請求の範囲第１項記載の方法。 ３）重合溶媒として芳香族炭化水素または脂肪族炭化水
素を使用することを特徴とする特許請求の範囲第１項お
よび第２項記載の方法。[Claims] 1) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [However, in the formula, R_1=H or CH_3, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ n is an integer from 0 to 5. R_f is a polyfluoroalkyl group having 1 to 20 carbon atoms. R^1
is a lower alkyl group, H or R_f group] A method for producing a fluoropolymer, which comprises polymerizing a fluorine-containing unsaturated ester monomer represented by the following in the presence of an organolithium catalyst. 2) General formula R_xR_y^■Li^■ [However, R_x is CmH_2_m_+_1-(CZ_1
Z_2-CH_2)-_p, Z_1, and Z_2 are hydrogen or phenyl groups, and m is an integer of 1 or more. p is an integer of 0 or 1 or more. R_y has ▲numerical formula, chemical formula, table, etc.▼, Z_1 is hydrogen or phenyl group. The method according to claim 1, characterized in that an organolithium catalyst represented by the following formula is used. 3) The method according to claims 1 and 2, characterized in that aromatic hydrocarbons or aliphatic hydrocarbons are used as the polymerization solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11991784A JPS61209A (en) | 1984-06-13 | 1984-06-13 | Production of fluorine-containing polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11991784A JPS61209A (en) | 1984-06-13 | 1984-06-13 | Production of fluorine-containing polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61209A true JPS61209A (en) | 1986-01-06 |
| JPH0430409B2 JPH0430409B2 (en) | 1992-05-21 |
Family
ID=14773377
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11991784A Granted JPS61209A (en) | 1984-06-13 | 1984-06-13 | Production of fluorine-containing polymer |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61209A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01152179A (en) * | 1987-09-28 | 1989-06-14 | Daikin Ind Ltd | Adhesive composition for biotic material |
| US5175790A (en) * | 1989-04-13 | 1992-12-29 | Hoechst Aktiengesellschaft | Transparent thermoplastic molding compound made of 2,3-difluoroacrylic acid esters |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56106907A (en) * | 1979-12-26 | 1981-08-25 | Daicel Chem Ind Ltd | Novel optically active high-molecular-weight substance |
| JPS5755743A (en) * | 1980-09-17 | 1982-04-02 | Nippon Electric Co | Power source |
-
1984
- 1984-06-13 JP JP11991784A patent/JPS61209A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56106907A (en) * | 1979-12-26 | 1981-08-25 | Daicel Chem Ind Ltd | Novel optically active high-molecular-weight substance |
| JPS5755743A (en) * | 1980-09-17 | 1982-04-02 | Nippon Electric Co | Power source |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01152179A (en) * | 1987-09-28 | 1989-06-14 | Daikin Ind Ltd | Adhesive composition for biotic material |
| US5175790A (en) * | 1989-04-13 | 1992-12-29 | Hoechst Aktiengesellschaft | Transparent thermoplastic molding compound made of 2,3-difluoroacrylic acid esters |
| US5283303A (en) * | 1989-04-13 | 1994-02-01 | Hoechst Aktiengesellschaft | Transplant thermoplastic molding compound made of 2,3-difluoroacrylic acid esters |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0430409B2 (en) | 1992-05-21 |
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