JPS62192411A - Tetrafluoroethylene-hexafluoropropylene copolymer reformed with perfluoropropylvinyl ether - Google Patents
Tetrafluoroethylene-hexafluoropropylene copolymer reformed with perfluoropropylvinyl etherInfo
- Publication number
- JPS62192411A JPS62192411A JP62031649A JP3164987A JPS62192411A JP S62192411 A JPS62192411 A JP S62192411A JP 62031649 A JP62031649 A JP 62031649A JP 3164987 A JP3164987 A JP 3164987A JP S62192411 A JPS62192411 A JP S62192411A
- Authority
- JP
- Japan
- Prior art keywords
- autoclave
- tfe
- tetrafluoroethylene
- hfp
- added
- 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.)
- Pending
Links
- 229920001577 copolymer Polymers 0.000 title description 13
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 title 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 48
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 25
- 229920001897 terpolymer Polymers 0.000 claims description 17
- KHXKESCWFMPTFT-UHFFFAOYSA-N 1,1,1,2,2,3,3-heptafluoro-3-(1,2,2-trifluoroethenoxy)propane Chemical compound FC(F)=C(F)OC(F)(F)C(F)(F)C(F)(F)F KHXKESCWFMPTFT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000006185 dispersion Substances 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 8
- 238000005259 measurement Methods 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002835 absorbance Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000498 cooling water Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 239000012986 chain transfer agent Substances 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- -1 Fluorocarbon acyl peroxides Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910001347 Stellite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- AHICWQREWHDHHF-UHFFFAOYSA-N chromium;cobalt;iron;manganese;methane;molybdenum;nickel;silicon;tungsten Chemical compound C.[Si].[Cr].[Mn].[Fe].[Co].[Ni].[Mo].[W] AHICWQREWHDHHF-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical compound CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- DASQIKOOFDJYKA-UHFFFAOYSA-N CCIF Chemical compound CCIF DASQIKOOFDJYKA-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 101001012040 Pseudomonas aeruginosa (strain ATCC 15692 / DSM 22644 / CIP 104116 / JCM 14847 / LMG 12228 / 1C / PRS 101 / PAO1) Immunomodulating metalloprotease Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007707 calorimetry Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000012674 dispersion polymerization Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000007870 radical polymerization initiator Substances 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
- C08F214/262—Tetrafluoroethene with fluorinated vinyl ethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
光」f吐U旧江豊遣−
テトラフルオロエチレン(TFE)及びヘキサフルオロ
プロピレン(HFP)の共重合体は多年にわたり市販さ
れてきた。該共重合体(下文ではしばしばTFE/HF
Pと称する)は高温における安定性、耐薬品性及び優れ
た電気的性質を有することによって著名である。同様に
TFEとペルフルオロ(プロピルビニルエーテル)(P
PVE)との共重合体く下文ではTFE/PPVEと称
する)はTF E/HF Pの総ての好ましい性質を有
し、更にT F E/HF Pよりも一層高い温度で長
期間にわたって使用できる。TFE、RFP及びPPV
Eの三元共重合体はTFE/HFP及びT F E/P
PVIF、の中間の高温的性質、例えば引っ張り強度を
有している。DETAILED DESCRIPTION OF THE INVENTION Copolymers of tetrafluoroethylene (TFE) and hexafluoropropylene (HFP) have been commercially available for many years. The copolymer (hereinafter often referred to as TFE/HF
P) is notable for its stability at high temperatures, chemical resistance and excellent electrical properties. Similarly, TFE and perfluoro(propyl vinyl ether) (P
The copolymer with TFE/PPVE) (referred to below as TFE/PPVE) has all the favorable properties of TFE/HFP and can further be used at higher temperatures and for longer periods of time than TFE/HFP. . TFE, RFP and PPV
The terpolymers of E are TFE/HFP and TFE/P
It has high temperature properties, such as tensile strength, intermediate to that of PVIF.
T F E/HF Pの主な用途は、特殊な設計のダイ
を用いて高温で作動する押出機によって、迅速に移動す
る電線上に溶融した共重合体を塗布することにより製造
される電線及びケーブルの絶縁物及び外被のようなもの
である。電線被覆作業系統の速度を最大にするためには
、溶@重合体の粘度は、押出し速度を最大にするために
出来るだけ低い方が有利である。しかしTFE/HFP
又はTFE/PPVE重合体の溶融粘度(MV)を低く
すると、MIT曲げ亀裂寿命(flex 1ife)
によって都合良く測定できる応力亀裂抵抗(SCR,)
も又低下する。亀裂抵抗が低いことは、冷却後恐らく数
年たった後に電線又はケーブルの絶縁に亀裂が生じる結
果を招くことによって明示される。SCRはタンクの内
張り及びバルブ、管材料、フィルム等のような′rFE
/HFPの他の重要な用途に対しても同様に重要である
。The primary use of TFE/HFP is in electrical wires and wires produced by applying the molten copolymer onto rapidly moving electrical wires by extruders operating at high temperatures using specially designed dies. Such as cable insulation and jacket. To maximize the speed of the wire coating system, it is advantageous for the viscosity of the melt@polymer to be as low as possible to maximize extrusion speed. However, TFE/HFP
Or, by lowering the melt viscosity (MV) of TFE/PPVE polymer, the MIT flexural crack life (flex 1ife)
Stress crack resistance (SCR,) can be conveniently measured by
It also decreases. Low crack resistance is manifested by the resultant cracking of the wire or cable insulation, perhaps several years after cooling. SCR includes 'rFE such as tank linings and valves, tubing, films, etc.
/HFP's other important applications are equally important.
同じMVでTFE/HFPの応力亀裂抵抗を増大させる
か、又は反対にSCRを高い水準に保ちながら一層速く
押出しすことができるようにTFE/HF PのMVを
低下させることは極めて利益あることと思われる。It would be extremely beneficial to increase the stress cracking resistance of TFE/HFP at the same MV or, conversely, to lower the MV of TFE/HFP so that it can be extruded faster while keeping the SCR at a high level. Seem.
1哩へ4扛
以上の目的はTFE/HFP重合体鎖中に0.2ないし
2%のPPVEを組み込むことによって達成される。そ
の結果後られるTFE/HFP/PPVEの三元共重合
体は、従来かような三元共重合体において得られたより
も少ないPPVE含量のものを提供する。HFP含量は
9ないし17重量%である1本発明の三元共重合体はT
FE/HF P共重合体よりも著しく高い応力亀裂抵抗
を有している。The objective of 4 to 100 grams or more is achieved by incorporating 0.2 to 2% PPVE into the TFE/HFP polymer chain. The resulting TFE/HFP/PPVE terpolymers provide lower PPVE contents than previously obtained in such terpolymers. The terpolymer of the present invention has a HFP content of 9 to 17% by weight.
It has significantly higher stress cracking resistance than FE/HF P copolymers.
九黙α礼吸
本発明の三元共重合体は米国特許第3,528゜954
号及び第4.029.868号に記載された非水重合法
によって製造することができる。この方法においては加
圧反応器、例えばステンレス鋼オートクレーブが普通使
用される。ペルフルオロ(プロピルビニルエーテル)及
び連鎖移動剤を含む溶剤が添加される1通常溶剤は1,
1.24リクロロー1.2.2−)リフルオロエタン(
F−113)であるが、1−4個の炭素原子、及び好適
には1−2個の炭素原子を有するクロロフルオロアルカ
ン又はクロロフルオロヒドロアルカンであることができ
る0例としてCCI□F2、CCI。The terpolymer of the present invention is disclosed in U.S. Patent No. 3,528°954.
and No. 4.029.868. Pressurized reactors, such as stainless steel autoclaves, are commonly used in this process. A solvent containing perfluoro(propyl vinyl ether) and a chain transfer agent is added.1 Usually the solvent is 1,
1.24 Lichloro1.2.2-) Lifluoroethane (
F-113), which can be a chlorofluoroalkane or chlorofluorohydroalkane having 1-4 carbon atoms, and preferably 1-2 carbon atoms, as examples: CCI□F2, CCI .
F 、CCI F 2 H、CCl□FCC1,F、C
C1,FCCIF2及びCCI F t CCI F
zが含まれる。F, CCI F 2 H, CCl□FCC1, F, C
C1, FCCIF2 and CCI F t CCIF
Contains z.
連鎖移動剤は好適にはメタノールであるが、2−ヒドロ
へブタフルオロプロパン、シクロヘキサン、クロロホル
ム、イソプロパツール、ジクロロメタン、エタノール等
であることができる。The chain transfer agent is preferably methanol, but can be 2-hydrohebutafluoropropane, cyclohexane, chloroform, isopropanol, dichloromethane, ethanol, and the like.
次いで所望量のヘキサフルオロプロピレンを添加して、
オートクレーブを所望の反応温度に加熱する;該温度は
通常は45℃−65℃であるが、時により30℃−80
℃である0反応器を次いでテトラフルオロエチレンで加
圧する0反応は約0.3から3.4 M Paの圧力で
行うことができる。then adding the desired amount of hexafluoropropylene,
Heat the autoclave to the desired reaction temperature; the temperature is usually 45°C-65°C, but sometimes 30°C-80°C.
The reaction in which the reactor is then pressurized with tetrafluoroethylene can be carried out at a pressure of about 0.3 to 3.4 MPa.
次いで開始剤を添加する。Then the initiator is added.
開始剤は溶剤に可溶で、使用される反応温度で高い活性
を有しているものでなければならない。The initiator must be soluble in the solvent and have high activity at the reaction temperature used.
下記式
但し XはH又はFであり、nは1−10の整数である
、
のフルオロカーボンアシルペルオキシドが好適である。Fluorocarbon acyl peroxides of the following formula, where X is H or F, and n is an integer from 1 to 10, are preferred.
好適な開始剤はビス(ベルフルオロビプロビオニル)ペ
ルオキシドである。好適には開始剤の溶液はその最初の
装填後、少なくともその分解速度に等しい速度で反応器
中に連続的に注入される。反応混合物中の開始剤の濃度
は普通0.5X10−4ないし5X10−’ g /
xlである。A preferred initiator is bis(perfluorobiprobionyl) peroxide. Preferably, the initiator solution is continuously injected into the reactor after its initial charge at a rate at least equal to its decomposition rate. The concentration of initiator in the reaction mixture is usually between 0.5X10-4 and 5X10-' g/
It is xl.
反応時の圧力は反応の間テトラフルオロエチレン単量体
を用いて再加圧することにより一定に保たれる。The pressure during the reaction is kept constant by repressurizing with tetrafluoroethylene monomer during the reaction.
次いで所望の重合度が得られるまで反応を進行させる0
次いで反応器の内容物を排出し、乾燥して溶剤を除く、
乾燥は普通の方法、例えば加熱空気炉中で乾燥すること
によって行なわれる。The reaction is then allowed to proceed until the desired degree of polymerization is obtained.
The contents of the reactor are then drained and dried to remove the solvent.
Drying is carried out in the usual manner, for example by drying in a heated air oven.
本発明の三元共重合体は又周知のような水性エマルジョ
ン又は分散重合によっても製造できる。The terpolymers of the present invention can also be prepared by aqueous emulsion or dispersion polymerization, as is well known.
反応混合物は水、単量体、分散剤、遊離基重合開始剤、
及び場合により単量体の拡散を促進するための、或いは
開始剤を溶解するための反応しないフルオロカーボン相
及び低分子量炭化水素のような連鎖移動剤から成ってい
る620℃ないし140℃の重合温度を使用することが
でき、1.4−7.0MPaの圧力が通常使用される。The reaction mixture contains water, monomers, dispersant, free radical polymerization initiator,
and optionally a chain transfer agent such as an unreacted fluorocarbon phase and a low molecular weight hydrocarbon to promote monomer diffusion or to dissolve the initiator. Pressures of 1.4-7.0 MPa are commonly used.
トIFP及びPPVEを最初に反応器に総て装填するこ
とができ、又は総てのRFPを最初に装填し、一方TF
EとPPVEの両者は最初に装填され且つ反応の間中連
続的に供給されることが好ましい。The IFP and PPVE can all be loaded into the reactor first, or all the RFP can be loaded first while the TF
Preferably, both E and PPVE are charged initially and fed continuously throughout the reaction.
反応器の圧力は一般には反応期間の間TFE単量体を供
給することにより一定に保たれる。単産体は所望の鰻終
分散固体ft(15−50%)に達するまで供給される
。反応器中の撹拌機の速度は重合の間一定に保つことが
でき、或いは単藍体の拡散及びそれによる反応速度を調
節するため可変とすることができる。Reactor pressure is generally kept constant during the reaction period by feeding TFE monomer. The monomer is fed until the desired final dispersed solids ft (15-50%) is achieved. The speed of the stirrer in the reactor can be kept constant during the polymerization or can be varied to control the diffusion of the monomer and thus the reaction rate.
開始剤としては一般に過tI!酸アンモニウム又はカリ
ウムのような遊離基開始剤が使用される0分散剤は水性
媒体の重量当たり0.01ないし0.5パーセント、好
適には0.05ないし0.2パーセントの量で存在する
。As an initiator, it is generally used as an initiator. The dispersant, in which a free radical initiator such as ammonium or potassium acid is used, is present in an amount of 0.01 to 0.5 percent, preferably 0.05 to 0.2 percent, based on the weight of the aqueous medium.
溶融粘度はASTM D−1238−52T及びD2
116−81法に従い、それを下記のように変更して測
定したニジリンダ−、オリフィス及びピストンの先端は
ハイネス ステライト(Haynes S tell
iLe)社により製造された耐食性の合金、ハイネス
ステライト19から出来ている。Melt viscosity is ASTM D-1238-52T and D2
The tip of the cylinder, orifice, and piston was measured according to the Haynes Stellite method according to the method No. 116-81 with the following modifications.
Highness, a corrosion-resistant alloy manufactured by iLe)
Made from Stellite 19.
5.0gの試料を372±1℃に保持された内径9.5
3avのシリンダーに装填する。試料をシリンダーに装
填した5分後に、直径2.1Ozz 、長さ8.00v
の角形の側面を持ったオリフィスを通して、5.0kg
の荷重(ピストン及び分銅により)をかけて押し出す。A 5.0 g sample was kept at 372 ± 1°C with an inner diameter of 9.5
Load into a 3av cylinder. 5 minutes after loading the sample into the cylinder, the diameter is 2.1Ozz and the length is 8.00V.
5.0kg through an orifice with square sides.
Push out by applying a load (by piston and weight).
これは44゜8KPaの剪断応力に相当する。Pa−5
で示す溶融粘度は、H/sinで表した押出し速度実測
値により5317を割った値として計算される。This corresponds to a shear stress of 44°8 KPa. Pa-5
The melt viscosity is calculated as 5317 divided by the measured extrusion speed expressed in H/sin.
赤外測定に使用されるフィルムは、350℃で加圧して
圧縮成形し、氷水中でフィルムを急冷することにより調
製される。厚さ0 、1 myのフィルムが使用された
。赤外測定はニコレット(N ico[et)5DX型
フ一リエ変換赤外分光器により行なわれた。赤外法はF
1核磁気共鳴装置によって較正された。The film used for infrared measurements is prepared by compression molding under pressure at 350° C. and rapidly cooling the film in ice water. Films with thicknesses of 0 and 1 my were used. Infrared measurements were performed using a Nicoret 5DX type Fourier transform infrared spectrometer. Infrared method is F
1 nuclear magnetic resonance apparatus.
ここに記載された共重合体及び三元共重合体中のHFP
含量は982cm−’における赤外吸光度と2367c
z−’の赤外吸光度との比を測定することにより定量さ
れる。三元共重合体の場合は、993ci+−’に吸収
極大を有するPPVE吸収帯による干渉があるので、H
FP%の計算に補正を加えなければならない、使用され
る式は下記の通りである:
ここに記載された三元共重合体のPPVE含量は133
5ci−’の赤外吸光度と2367ci−’の赤外吸光
度との比の測定によって定量される。HFP in the copolymers and terpolymers described herein
The content is infrared absorbance at 982 cm-' and 2367 c
It is quantified by measuring the ratio of z-' to infrared absorbance. In the case of a terpolymer, there is interference due to the PPVE absorption band which has an absorption maximum at 993ci+-', so H
Corrections must be made in the calculation of FP%, the formula used is as follows: The PPVE content of the terpolymer described here is 133
It is quantified by measuring the ratio of the infrared absorbance at 5 ci-' and the infrared absorbance at 2367 ci-'.
1335cm−’における基線の補正は試料フィルムと
ほぼ同じHFP含量と厚さを持つが、PP■Eを含まな
い参照標準フィルムを用いて定量される。計算式は下記
の通りであるニ
ジ!! −(jaw)の開きが0.2511である A
STM D−2176−63Tに記載されたMIT折
り畳み耐久試験機(folding enduranc
e tester)が曲げ亀裂寿命の測定に使用された
。測定は厚さ約0.19ziないし0.23ii+の氷
水急冷フィルムを用いて行なわれた。長さ約9On、幅
12,7履1の試験片を折り曲げ試験機のジョーに締め
付けし、1.2kgの荷重を掛ける。MIT折り曲げ試
験機は一分間約175サイクルの割合で右へ約135°
、左へ約135°の角度でフィルムを折り曲げる。破損
までのサイクルの数が機械上のカウンターに記録された
。測定は三回繰り返して行なった。三回の測定値の平均
を記録した。The baseline correction at 1335 cm-' is quantified using a reference standard film with approximately the same HFP content and thickness as the sample film, but without PP■E. The calculation formula is as follows.Niji! ! -(jaw) difference is 0.2511 A
MIT folding endurance tester described in STM D-2176-63T
e tester) was used to measure flexural crack life. Measurements were made using ice-water quenched films approximately 0.19zi to 0.23ii+ thick. A test piece with a length of about 9 On and a width of 12.7 mm is clamped into the jaws of a bending tester, and a load of 1.2 kg is applied. The MIT bending tester rotates approximately 135 degrees to the right at a rate of approximately 175 cycles per minute.
, fold the film to the left at an angle of approximately 135°. The number of cycles to failure was recorded on a counter on the machine. Measurements were repeated three times. The average of three measurements was recorded.
溶融点はデュポン(De Pont)の990型熱分
析機(Thermal Analyzer)を用いて
示差走査熱量法(Differential Sca
nning Calorimetry)によって測定
された0MIT曲げ亀裂寿命を測定網るのに用いたのと
同じフィルムから12ないし14zgの試料を採取した
。The melting point was determined by differential scanning calorimetry using a De Pont 990 Thermal Analyzer.
A 12-14 zg sample was taken from the same film used to measure the 0MIT flexural crack life measured by Ninning Calorimetry.
1 び リ 方 −一!き、シε−3−
KB−5(ミ]kLイタ1−−−−」2−
容8361 の清潔な、ステンレス鋼製の、水平な撹
拌機付きオートクレーブ中に22.7kgの脱塩水と2
3gのアンモニウム・ペルフルオロカプリレートを入れ
た。オートクレーブを閉じ、95゛Cに加熱し、N2で
4.1MPaの圧力を掛け、漏れを試験した。温度が6
5℃となるまでオートクレーブを充分に冷却する。オー
トクレーブを真空とし、テトラフルオロエチレン(T
F E )で三回洗浄し再度減圧とした。オートクレー
ブを30℃に冷却した。次いでオートクレーブに601
1のペルフルオロ(プロピルビニルエーテルHp p
vE)を添加した。撹拌機を始動し、38rp−で回転
させた。オートクレーブの温度を95℃に上げた。1 Biri Ho-ichi! Ki, Shi ε-3-
In a clean, stainless steel, horizontal, stirred autoclave with a volume of 8361, 22.7 kg of demineralized water and 2
3g of ammonium perfluorocaprylate was charged. The autoclave was closed, heated to 95°C, pressurized to 4.1 MPa with N2, and tested for leaks. temperature is 6
Cool the autoclave sufficiently until the temperature reaches 5°C. The autoclave was evacuated and tetrafluoroethylene (T
It was washed three times with F E ) and the pressure was reduced again. The autoclave was cooled to 30°C. Then autoclave 601
1 perfluoro(propyl vinyl ether Hp p
vE) was added. The stirrer was started and rotated at 38 rpm. The temperature of the autoclave was increased to 95°C.
オートクレーブをヘキサフルオロプロピレン(HFl)
)で2 、9 M P aに加圧し、次いでTFEで最
終圧力4 、1 M P aまで加圧した。脱塩水に溶
かして新しく調製した0、0088Mの過硫酸アンモニ
ウム溶液を12分間にわたって50 xl /111i
nの速度でオートクレーブにポンプ給送した0重合が開
始した(70KPaの圧力低下で検出される)後、反応
期間全体を通じて0.044Mの過硫酸カリウムの溶液
を10 x1/ll1inの速度でポンプ給送した。又
1−’ f) V Eを反応期間全体にわたって0.2
i1/ninの速度で添加した。’1” F Eは4.
1MPaの一定圧力に保つために反応期間全体にわたっ
て添加され、’1” F Eの添加速度を0.050k
g/winに保持するために撹拌機の速度を変化させた
。7.93kgのTFEがオートクレーブに添加された
後(重合の開始後)、TFE、PPVE及び過硫酸カリ
ウムの添加を総て停止した。撹拌機を停め、オートクレ
ーブのジャケットに冷却水を添加し、反応器のガス抜き
を行った0次いでオートクレーブをN1で洗浄して残留
する単量体を除去し、水性分散物をオートクレーブから
排出した。Autoclave hexafluoropropylene (HFl)
) to 2.9 MPa and then pressurized with TFE to a final pressure of 4.1 MPa. A freshly prepared 0,0088M ammonium persulfate solution in demineralized water was added at 50 xl/111i for 12 minutes.
After polymerization had started (detected by a pressure drop of 70 KPa), a solution of 0.044 M potassium persulfate was pumped into the autoclave at a rate of 10 x 1/llin throughout the reaction period. Sent. and 1-' f) VE of 0.2 throughout the reaction period.
It was added at a rate of i1/nin. '1' F E is 4.
'1'' was added throughout the reaction period to maintain a constant pressure of 1 MPa, increasing the addition rate of 0.050 k
Stirrer speed was varied to maintain g/win. After 7.93 kg of TFE was added to the autoclave (after initiation of polymerization), all additions of TFE, PPVE, and potassium persulfate were stopped. The stirrer was stopped, cooling water was added to the autoclave jacket, the reactor was degassed, the autoclave was then rinsed with N1 to remove residual monomer, and the aqueous dispersion was discharged from the autoclave.
激しく撹拌して分散物を凝固させ、フック(fluff
)状の三元共重合体を生成させた。Stir vigorously to coagulate the dispersion, then use a hook (fluff) to solidify the dispersion.
)-like terpolymer was produced.
フック状物を加圧下に絞って部分的に脱水し、次いで1
50℃で乾燥して残りの水分を除去した。The hooks are partially dehydrated by squeezing them under pressure, then 1
The remaining moisture was removed by drying at 50°C.
次いでフック状物を空気及び水の存在で2時間350−
370℃に加熱し、TFE/HFP/PPVE三元共重
合体の発泡状塊を得た6回転するナイフ状刃を持つ切断
機を用いて、この塊を小片に細断した。総ての試験はこ
うして得られた細断物について行なわれた。The hook was then heated at 350°C for 2 hours in the presence of air and water.
The mass was heated to 370° C. to obtain a foamed mass of TFE/HFP/PPVE terpolymer and shredded into small pieces using a cutting machine with a knife blade with 6 revolutions. All tests were carried out on the shreds thus obtained.
ル事」口1倒−」−
容Nl361 の清潔な、ステンレス鋼製の、水平な
撹拌機付きオートクレーブ中に22.7kgの脱塩水と
23gのアンモニウム・ペルフルオロカプリレートを入
れた。オートクレーブを閉じ、95℃に加熱し、N2で
4 、1M P aの圧力を掛け、漏れを試験した。温
度が65℃となるまでオートクレーブを充分に冷却した
。オートクレーブを真空とし、テトラフルオロエチレン
(T F E )で三回洗浄し再度減圧とした。撹拌機
を始動し、38rpnで回転させた。オートクレーブの
温度を95°Cに上げた。オートクレーブをヘキサフル
オロプロピレン(HFP)で2 、9 M P aに加
圧し、次いでTFEで最終圧力4.1MPaまで加圧し
た。脱塩水に溶かして新しく調製した0、0074Mの
過硫酸カリウム溶液を、12分間にわたって’30+1
/winの速度でオートクレーブにポンプ給送した。22.7 kg of demineralized water and 23 g of ammonium perfluorocaprylate were placed in a clean, stainless steel, horizontal, stirred autoclave having a volume of 361 Nl. The autoclave was closed, heated to 95°C, pressurized to 4,1 MPa with N2, and tested for leaks. The autoclave was sufficiently cooled until the temperature reached 65°C. The autoclave was evacuated, washed three times with tetrafluoroethylene (TFE), and evacuated again. The stirrer was started and rotated at 38 rpm. The temperature of the autoclave was increased to 95°C. The autoclave was pressurized to 2.9 MPa with hexafluoropropylene (HFP) and then pressurized with TFE to a final pressure of 4.1 MPa. A freshly prepared 0.0074M potassium persulfate solution in demineralized water was added to the '30+1 solution for 12 minutes.
The autoclave was pumped at a rate of /win.
重合が開始した(70KPaの圧力低下で検出される)
後、反応期間全体を通じて0.063Mの過硫酸カリウ
ムの溶液を10wl /winの速度でポンプ給送した
。TFEは4 、1 M P aの一定圧力に保つため
に反応期間全体にわたって添加され、′f” F Eの
添加速度を0 、050 kg/ ll1inに保持す
るために撹拌機の速度を変化させた。7.93kFtの
TFEがオートクレーブに添加された後(重合の開始後
)、T F E及び過硫酸カリウム溶液の添加を停止し
た。Polymerization has started (detected by a pressure drop of 70 KPa)
Afterwards, a solution of 0.063 M potassium persulfate was pumped at a rate of 10 wl/win throughout the reaction period. TFE was added throughout the reaction period to maintain a constant pressure of 4,1 MPa, and the stirrer speed was varied to maintain the addition rate of 'f'FE at 0,050 kg/ll1 in. After 7.93 kFt of TFE was added to the autoclave (after initiation of polymerization), the addition of TFE and potassium persulfate solution was stopped.
撹拌機を停め、オートクレーブのジャケットに冷却水を
添加し、反応器のガス抜きを行った0次いでオートクレ
ーブをN2で洗浄して残留する単量体を除き、水性分散
物をオートクレーブから排出した。The stirrer was stopped, cooling water was added to the autoclave jacket, and the reactor was degassed.The autoclave was then flushed with N2 to remove residual monomer and the aqueous dispersion was discharged from the autoclave.
激しく撹拌して分散物を凝固させフラフ状の共重合体を
生成させた。フック状物を加圧下に絞って部分的に脱水
し、次いで150℃で屹燥して残りの水分を除去した。Vigorous stirring solidified the dispersion to form a fluffy copolymer. The hooks were partially dehydrated by squeezing under pressure and then dried at 150° C. to remove remaining water.
次いでフラフ状物念空気及び水の存在で2時間350−
370℃に加熱し、TFE/HFP共重合体の発泡状塊
を得た。回転するナイフ状刃を持つ切Ir機を用いて、
この塊を小片に細断した。総ての試験はこうして得られ
た細断物について行なわれた。Then 350-min for 2 hours in the presence of fluffy air and water.
It was heated to 370°C to obtain a foamed mass of TFE/HFP copolymer. Using a cutting machine with a rotating knife-shaped blade,
This mass was shredded into small pieces. All tests were carried out on the shreds thus obtained.
実施例1の三元共重合体及び比較実施例Aの共重合体の
性質は第1表に示されている。又米国特許第4.029
,868号に記載された組成を有するTFE、、/HF
P/PPVE三元共重合体について得られた性質も、比
較実施例Bとして同表に包含されている。The properties of the terpolymer of Example 1 and the copolymer of Comparative Example A are shown in Table 1. Also, U.S. Patent No. 4.029
TFE, /HF having the composition described in , No. 868
The properties obtained for the P/PPVE terpolymer are also included in the same table as Comparative Example B.
Σ−
=−一
一 く ロ
実施例 2及び比較実施例 C
容積36N の清潔な、ステンレス鋼製の、水平な撹
拌機付きオートクレーブ中に22.7kgの脱塩水と2
0gのペルフルオロカプリレート(C,−C,s)−エ
タンスルポン酸(平均=C1)の混合物を水で450g
に希釈して入れた。オートクレーブを閉じ、95℃に加
熱し、N2で4.IMPaの圧力を掛け、漏れを試験し
た。温度が65℃となるまでオートクレーブを充分に冷
却する。Example 2 and Comparative Example C In a clean, stainless steel, horizontal, stirred autoclave with a volume of 36 N, 22.7 kg of demineralized water and 2
A mixture of 0g perfluorocaprylate (C,-C,s)-ethanesulfonic acid (average = C1) was mixed with 450g of water.
It was diluted and added. Close the autoclave, heat to 95°C and flush with N2 4. A pressure of IMPa was applied and leakage was tested. Cool the autoclave sufficiently until the temperature reaches 65°C.
オートクレーブを真空とし、テトラフルオロエチレン(
T F E >で三日洗浄し再度減圧とした。オートク
レーブを30°Cに冷却した1次いでオートクレーブに
60mfのペルフルオロ(プロピルビニルエーテル)(
PPVE)を添加した。撹拌機を始動し、38rp!+
1で回転させた。オートクレーブの温度を95℃に上げ
た。オートクレーブをヘキサフルオロプロピレン(RF
P)で2 、9 M P aに加圧し、次いで’T”
F Eで最終圧力4 、1 M P aまで加圧した。Evacuate the autoclave and add tetrafluoroethylene (
After washing for three days at T F E >, the pressure was reduced again. The autoclave was cooled to 30°C and then 60 mf of perfluoro(propyl vinyl ether) (
PPVE) was added. Start the stirrer, 38 rpm! +
Rotated at 1. The temperature of the autoclave was increased to 95°C. Autoclave with hexafluoropropylene (RF
P) to 2.9 MPa, then 'T'
The pressure was increased to a final pressure of 4.1 MPa using FE.
脱塩水に溶かして新しく調製した0、0175Mの過[
6アンモニウム溶液を6分間にわたって50xl/wi
nの速度でオートクレーブにポンプ給送した。重合が開
始した(70KPaの圧力低下で検出される)後、反応
期間全体を通じて0.0891V[の過硫酸カリウムの
溶液を10璽4/sinの速度でポンプ給送した。又P
PVEを4.1MPaの一定圧力に保つために反応期間
全体にわたって0.2 xi /WAinの速度で添加
し、TFEの添加速度を0 、050 kg/ win
に保持するために撹拌機の速度を変化させた。7.93
kgのTFEがオートクレーブに添加されたf&(ff
i合の開始後)、TFE、PPVE及び過硫酸アンモニ
ウム溶液の添加を停止した。撹拌機を停め、オートクレ
ーブのジャフットに冷却水を添加し、反応器のガス抜き
を行った6次いでオートクレーブをN。Freshly prepared 0.0175M filtrate dissolved in demineralized water.
6 ammonium solution at 50xl/wi for 6 minutes
The autoclave was pumped at a rate of n. After the polymerization started (detected by a pressure drop of 70 KPa), a solution of potassium persulfate at 0.0891 V was pumped at a rate of 10 g/sin throughout the reaction period. Also P
PVE was added at a rate of 0.2 xi/WAin throughout the reaction period to maintain a constant pressure of 4.1 MPa, and the TFE addition rate was 0.050 kg/win.
The stirrer speed was varied to maintain a 7.93
kg of TFE was added to the autoclave f&(ff
After the start of the reaction), the addition of TFE, PPVE and ammonium persulfate solution was stopped. The stirrer was stopped, cooling water was added to the autoclave's Jacuzzi, and the reactor was degassed.6 Then, the autoclave was heated to N.
で洗浄して残留する単産体を除き、水性分散物をオート
クレーブから排出した。The aqueous dispersion was removed from the autoclave by washing to remove residual monoproducts.
激しく撹拌して分散物を凝固させフッフ状の三元共重合
体を生成させた。フッフ状物を加圧下に絞って部分的に
脱水し、次いで150℃で乾燥して残りの水分を除去し
た0次いでフラノ状物を空気及び水の存在で2時間35
0−370℃に加熱し、TFE/f(FP/PPVE三
元共重合体の発泡軟塊を得た。回転するナイフ状刃を持
つ切断機を用いて、この塊を小片に細断した。総ての試
験はこうして得られた細断物について行なわれた。The dispersion was solidified by vigorous stirring to form a fluffy terpolymer. The fluff was partially dehydrated by squeezing it under pressure and then dried at 150°C to remove any remaining moisture.
It was heated to 0-370° C. to obtain a foamed soft mass of TFE/f (FP/PPVE terpolymer). This mass was shredded into small pieces using a cutting machine with a rotating knife-like blade. All tests were carried out on the shreds thus obtained.
比、 Hc−
容積361 の清潔な、ステンレス鋼製の、水平な撹拌
機付きオートクレーブ中に、22.7kgの脱塩水と2
0 g のペルフルオロカブリレート(C= C
ps)−エタンスルホン酸(平均=C1)の混合物を水
で450gに希釈して入れた。オートクレーブを閉じ、
95℃に加熱し、N2で4.1MPaの圧力を掛け、漏
れを試験した。温度が65℃となるまでオートクレーブ
を充分に冷却する。In a clean, stainless steel, horizontal, stirred autoclave of volume 361, 22.7 kg of demineralized water and 2
0 g perfluorocabrylate (C=C
ps)-ethanesulfonic acid (average=C1) diluted to 450 g with water. Close the autoclave and
It was heated to 95° C., pressured to 4.1 MPa with N2, and tested for leaks. Cool the autoclave sufficiently until the temperature reaches 65°C.
オートクレーブを真空とし、テトラフルオロエチレン(
TFE)で三日洗浄し再度減圧とした。撹拌機を始動し
、38「p−で回転させた。オートクレーブの温度を9
5℃に上げた。オートクレーブをヘキサフルオロプロピ
レン(HFP)で2.9MPaに加圧し、次いでTFE
で最終圧力4.1MPaまで加圧した。脱塩水に溶かし
て新しく調製した0、0175Mの過硫酸アンモニウム
溶液を6分間にわたって50 x1/minの速度でオ
ートクレーブにポンプ給送した。重合が開始した(70
KPaの圧力低下で検出される)後、反応期間全体を通
じて0.059Mの過硫酸カリウムの溶液を10 ml
/+*inの速度でポンプ給送した。’T” F E
は4 、1 M P aの一定圧力に保つために反応期
間全体にわたって添加され、T FEの添加速度を0
、050 kg/ sinに保持するために撹拌機の速
度を変化させた。7.93kgのTFEがオートクレー
ブに添加されたf&(重合の開始後)、TFE及び過硫
酸カリウム溶液の添加を停止した。撹拌機を停め、オー
トクレーブのジャケットに冷却水を添加し、反応器のガ
ス抜きを行った0次いでオートクレーブをN2で洗浄し
て残留する単量体を除き、水性分散物をオートクレーブ
から排出した。Evacuate the autoclave and add tetrafluoroethylene (
After washing with TFE for three days, the pressure was reduced again. The stirrer was started and rotated at 38"p. The temperature of the autoclave was increased to 9".
The temperature was raised to 5°C. The autoclave was pressurized to 2.9 MPa with hexafluoropropylene (HFP), then TFE
The pressure was increased to a final pressure of 4.1 MPa. A freshly prepared 0.0175 M ammonium persulfate solution in demineralized water was pumped into the autoclave at a rate of 50 x 1/min for 6 minutes. Polymerization started (70
10 ml of a solution of 0.059 M potassium persulfate throughout the reaction period (detected by a pressure drop of KPa).
Pumped at a rate of /+*in. 'T' F E
was added throughout the reaction period to maintain a constant pressure of 4, 1 M Pa, and the addition rate of TFE was reduced to 0.
, the stirrer speed was varied to maintain it at , 050 kg/sin. 7.93 kg of TFE was added to the autoclave (after initiation of polymerization), and the addition of TFE and potassium persulfate solution was stopped. The stirrer was stopped, cooling water was added to the autoclave jacket, and the reactor was degassed.The autoclave was then flushed with N2 to remove residual monomer and the aqueous dispersion was discharged from the autoclave.
激しく撹拌して分散物を凝固させフッフ状の共重合体を
生成させた。フラノ状物を加圧下に絞って部分的に脱水
し、次いで150℃で乾燥して残りの水分を除去した0
次いでフラノ状物を空気及び水の存在で2時間350−
370℃に加熱し、TFE/HFP共重合体の発泡軟塊
を得た1回転するナイフ状刃を持つ切断機を用いて、こ
の塊を小片に細断した。総ての試験はこうして得られた
細断物について行なわれた。The dispersion was stirred vigorously to coagulate and form a fluffy copolymer. The flannel was partially dehydrated by squeezing it under pressure and then dried at 150°C to remove the remaining moisture.
The flannelate was then heated at 350° C. for 2 hours in the presence of air and water.
A foamed soft mass of TFE/HFP copolymer was obtained by heating to 370° C., and this mass was shredded into small pieces using a cutting machine with a knife-like blade rotating once. All tests were carried out on the shreds thus obtained.
実施例2の三元共重合体及び比較実施例Cの共重合体の
性質は第2表に示されている。The properties of the terpolymer of Example 2 and the copolymer of Comparative Example C are shown in Table 2.
工 −− へQ 杯 蝋ミEngineering −− To Q Cup Waxmi
Claims (1)
ニルエーテル) から成ることを特徴とするペルフルオル化された三元共
重合体組成物。[Scope of Claims] 1. Perfluoroethylene, characterized in that it consists of a) tetrafluoroethylene, b) 9 to 17% by weight of hexafluoropropylene, and c) 0.2 to 2% by weight of perfluoro(propyl vinyl ether). terpolymer composition.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US830850 | 1986-02-18 | ||
US06/830,850 USH130H (en) | 1986-02-18 | 1986-02-18 | Tetrafluoroethylene hexafluoropropylene copolymer modified with perfluoropropyl vinyl ether |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS62192411A true JPS62192411A (en) | 1987-08-24 |
Family
ID=25257816
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP62031649A Pending JPS62192411A (en) | 1986-02-18 | 1987-02-16 | Tetrafluoroethylene-hexafluoropropylene copolymer reformed with perfluoropropylvinyl ether |
Country Status (2)
Country | Link |
---|---|
US (1) | USH130H (en) |
JP (1) | JPS62192411A (en) |
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WO2003059969A1 (en) * | 2002-01-17 | 2003-07-24 | Daikin Industries, Ltd. | Fep pellet |
WO2003059970A1 (en) * | 2002-01-17 | 2003-07-24 | Daikin Industries, Ltd. | Fluorine-containing copolymer |
JP2007072556A (en) * | 2005-09-05 | 2007-03-22 | Yanmar Co Ltd | Pedal structure of traveling vehicle |
JP2010507272A (en) * | 2006-10-12 | 2010-03-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Hinge with insulated wire for electronic devices |
JP2010073144A (en) * | 2008-09-22 | 2010-04-02 | Mazda Motor Corp | Pedal device for vehicle |
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WO2022181840A1 (en) * | 2021-02-26 | 2022-09-01 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190954A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190948A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190955A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190956A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190957A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
WO2023190953A1 (en) * | 2022-03-30 | 2023-10-05 | ダイキン工業株式会社 | Fluorine-containing copolymer |
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Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6541588B1 (en) | 1999-01-29 | 2003-04-01 | 3M Innovative Properties Company | Tetrafluoroethylene/hexafluoropropylene copolymers with higher drawability |
US20040204536A1 (en) * | 2001-06-18 | 2004-10-14 | Toshio Miyatani | Powder coating material |
US6653379B2 (en) * | 2001-07-12 | 2003-11-25 | 3M Innovative Properties Company | Fluoropolymers resistant to stress cracking |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52109588A (en) * | 1976-03-10 | 1977-09-13 | Du Pont | Fluorinated terpolymers |
JPS59166516A (en) * | 1983-02-01 | 1984-09-19 | Daikin Ind Ltd | Fluorine-containing copolymer |
-
1986
- 1986-02-18 US US06/830,850 patent/USH130H/en not_active Abandoned
-
1987
- 1987-02-16 JP JP62031649A patent/JPS62192411A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS52109588A (en) * | 1976-03-10 | 1977-09-13 | Du Pont | Fluorinated terpolymers |
JPS59166516A (en) * | 1983-02-01 | 1984-09-19 | Daikin Ind Ltd | Fluorine-containing copolymer |
Cited By (26)
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US7105619B2 (en) | 2002-01-17 | 2006-09-12 | Daikin Industries, Ltd. | Fluorine-containing copolymer |
US7923519B2 (en) | 2002-01-17 | 2011-04-12 | Daikin Industries, Ltd. | FEP pellet |
US8334351B2 (en) | 2002-01-17 | 2012-12-18 | Daikin Industries, Ltd. | FEP pellet |
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JP2023153017A (en) * | 2022-03-30 | 2023-10-17 | ダイキン工業株式会社 | Fluorine-containing copolymer |
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Also Published As
Publication number | Publication date |
---|---|
USH130H (en) | 1986-09-02 |
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